JP6468108B2 - Resin composition, laminate and method for producing laminate - Google Patents

Description

  The present invention relates to a resin composition and a laminate. More specifically, the present invention relates to a resin composition comprising a carbon nanotube, a bright pigment, and a resin. The present invention also relates to a laminate in which carbon nanotube-containing layers containing the composition are laminated.

  A carbon nanotube is a cylindrical carbon material having a diameter of several nanometers to several tens of nanometers. Carbon nanotubes have high electrical conductivity and mechanical strength. For this reason, carbon nanotubes are expected to be used in a wide range of fields including electronic engineering and energy engineering as functional materials. Examples of functional materials include fuel cells, electrodes, electromagnetic shielding materials, conductive resins, field emission display (FED) members, and various gas storage materials such as hydrogen.

  As a development example of the functional material, a conductive transparent film using carbon nanotubes is known. For example, in patent document 1, what laminated | stacked the carbon nanotube electrically conductive film and the transparent protective film on the single side | surface of a transparent base material is proposed. Patent Document 2 also proposes a method of applying a resin solution after applying a carbon nanotube dispersion to a substrate surface and drying the conductive transparent film.

  On the other hand, as examples of the development of the functional material, there are few examples using carbon nanotubes as a coloring material. Carbon black is used as the color material instead of carbon nanotubes. For example, as disclosed in Patent Documents 3 and 4, carbon black is used in order to obtain a jet black resin coated product, film, or molded product. Carbon black is uniformly dispersed in a resin solution or a solid resin.

However, a color material made of carbon black tends to have a high lightness (L ^* ) (that is, gray / white). Further, the chromaticity (a ^* , b ^* ) is in the plus direction (+ a ^* : red, + b ^* : yellow). Here, L ^* , a ^*, and b ^* represent values in the L ^* a ^* b ^* color system defined by JIS Z8729. For this reason, it has been difficult for carbon black to express jet blackness such as so-called “piano black” and “wet crow wings”.

  Further, the color tone of a molded product using carbon black tends to change depending on the primary particle diameter of carbon black. Specifically, when carbon black having a small primary particle diameter is used, bluishness is exhibited while blackness is lowered. Thus, in the conventional black color material, there is a trade-off relationship between blackness and blueness. For this reason, it was difficult to reproduce a color tone having a bluish color and a high blackness, that is, a jet black color tone.

  Patent documents 5, 6 and 7 relate to the adjustment of the blackness of a color material made of carbon black. When adjusting the blackness, for example, colloidal characteristics such as the particle size and aggregate size of carbon black are changed. Further, surface treatment such as ozone oxidation and nitric acid oxidation is applied to the carbon black. By such processing, the dispersion state in the dispersion is changed.

  A method of adding an organic pigment such as phthalocyanine blue to carbon black is also known. By this method, the color material can exhibit a bluish color in addition to black. However, the blackness decreases with the addition of the organic pigment in the coloring material. For this reason, when the molded object containing such a coloring material is observed under direct sunlight, a reddish color is observed on the molded object. This problem is recognized as the occurrence of a so-called bronze phenomenon.

  In Patent Documents 8, 9, and 10, a method of suppressing scattering on the outermost surface is used in order to improve the texture of painting. In such a method, a color base layer using a pigment is formed so as to be superimposed on an underlayer, and then a color clear layer is superimposed. However, since a dye is used for the color base layer, a coating film structure excellent in light resistance and weather resistance cannot be formed.

  In recent years, coatings formed on automobile bodies and the like have been demanded to have a high-quality appearance such as excellent denseness and high flip-flop properties. Here, the dense feeling means a uniform and continuous glitter feeling based on the glitter pigment in the coating film. The fineness is usually excellent when the glittering particles have a small graininess. In addition, the flip-flop property means that the flake-like glitter pigment is oriented parallel to the coating surface in the coating film. As a result, when highlighting (when the coating film is viewed from the front), it reflects light well and becomes high brightness. On the other hand, the shade (when the coating film is viewed obliquely) means that the brightness is low, that is, the property that there is a brightness difference depending on the direction of vision.

  Therefore, in Patent Document 11, a method for forming a glittering base coating film on an object to be coated in two stages and then forming a clear layer, the film thickness of the base coating film of the first stage and the second stage By the glittering coating film forming method in which the ratio is 2/1 to 4/1, glittering unevenness of the glittering coating film is prevented.

  However, in the conventional method for forming a glittering coating film, the orientation of the flake-like glittering pigment tends to be insufficient, and it has not been possible to obtain a glittering coating film with excellent compactness and high flip-flop properties.

JP 2010-192186 A Japanese translation of PCT publication No. 2004-526838 JP 2001-179176 A JP 2004-098033 A Japanese Patent Laid-Open No. 6-122834 JP-A-6-136287 JP 2008-285632 A JP-A-6-15223 Japanese Patent Laid-Open No. 8-71501 JP 2010-279899 A JP 2002-273333 A

  The present invention solves the above conventional problems. That is, an object of the present invention is to provide a resin composition having excellent flip-flop properties and high jetness. Moreover, it is providing the laminated body which has this resin composition.

  The inventors of the present invention have intensively studied to solve the above problems. The inventors have found that by laminating a resin composition containing carbon nanotubes, a luster pigment and a resin, a resin composition excellent in jetness and flip-flop properties and a laminate of the resin composition can be obtained. . The inventors have arrived at the present invention based on such findings.

That is, one embodiment of the present invention is a laminate in which a carbon nanotube-containing layer made of a resin composition containing at least carbon nanotubes, a flake-like glitter pigment, and a resin is laminated on a substrate. ,
The film thickness of the carbon nanotube-containing layer is 10 to 50 μm,
L ^* based on spectral reflectance measured by a multi-angle spectrocolorimeter received at 45 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the stacked surfaces is 10 or less. , A ^* is −2 or more and 2 or less and b ^* is −2 or more and 0.3 or less. L based on the spectral reflectance received at 45 ° with respect to the specularly reflected light of the light incident on the base material at an angle of 45 ° with respect to the perpendicular direction of the laminated surface. ^* Is 10 or less, a ^* is −2 to 2 and b ^* is −2 to 0.3.

In another aspect of the present invention, a clear layer is preferably laminated on the carbon nanotube-containing layer of the laminate. L ^* is 10 or less, a ^* is −2 or more and 2 or less, and is based on the spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the stacked surfaces. b ^* is preferably −2 or more and 0.3 or less.

In the laminated body, L ^* based on the spectral reflectance received at 15 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the laminated surface and the perpendicular of the laminated surface 45 ° angle of the light incident at L ^* ratio based on the spectral reflectance of light received by 110 ° with respect to the specular reflection light (of 15 ° in the L ^* / 110 ° L ^*) of 10 or more with respect to the direction 30 The following is preferable.

  Moreover, it is preferable that the fiber diameter of a carbon nanotube is 8-25 micrometers in the said laminated body.

  In the laminate, the amount of carbon nanotubes in the carbon nanotube-containing layer is preferably 1 to 30% by mass.

  Moreover, in the said laminated body, it is preferable that the film thickness of a clear layer is 5-150 micrometers.

  Moreover, in the said laminated body, when measuring a laminated body from the laminated | stacked surface direction, it is preferable that the average reflectance in wavelength 380-780 nm is 5% or less.

  The base material preferably has an average transmittance of 5% or less at a wavelength of 380 to 780 nm.

  Moreover, it is preferable that the base material includes at least one selected from the group consisting of organic pigments, inorganic pigments, and glitter pigments, and a resin. (However, organic pigments and inorganic pigments exclude bright pigments.)

Another aspect of the present invention is a laminate in which a carbon nanotube-containing layer made of a resin composition comprising at least a carbon nanotube, a bright pigment, and a resin is laminated on a substrate, A manufacturing method of a laminate in which a clear layer is further laminated on a lamination surface of nanotube-containing layers, and is 45 with respect to specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the laminated surface. L ^* is 10 or less, a ^* is −2 or more and 2 or less and b ^* is −2 or more and 0.3 or less.

  By using the resin composition of the present invention, a resin composition having excellent flip-flop properties and high jetness can be obtained. Therefore, it is possible to use the resin composition and laminate obtained in the present invention in various application fields where a high quality appearance is desired.

Hereinafter, the resin composition and laminate of the present invention will be described in detail with reference to embodiments.

(1) Resin composition (a)

  The resin composition (a) of this embodiment contains at least a carbon nanotube (b), a bright pigment (g), and a resin (c).

  In order to obtain the resin composition (a) of the present embodiment, it is preferable to perform a treatment of dispersing the carbon nanotube (b), the glitter pigment (g), and the resin (c) in a solvent. The equipment used for performing such processing is not particularly limited. Examples of equipment include paint conditioner (manufactured by Red Devil), ball mill, sand mill (“Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (“DCP mill” manufactured by Eirich), coball mill, basket mill, homomixer, Examples include homogenizers ("Claremix" manufactured by M Technique Co., Ltd.), wet jet mills ("Genus PY" manufactured by Genus, "Nanomizer" manufactured by Nanomizer), Hoover Mahler, three roll mills, and extruders. It is not limited.

  Moreover, in order to obtain the resin composition (a), a high-speed stirrer can be used. Examples of the high-speed stirrer include, but are not limited to, homodisper (manufactured by PRIMIX), fillmix (manufactured by PRIMIX), dissolver (manufactured by Inoue Seisakusho) and hyper HS (manufactured by Ashizawa Finetech).

  The resin composition (a) may contain a dispersant. As the dispersant, a surfactant or a resin-type dispersant can be used. Surfactants are mainly classified into anionic, cationic, nonionic and amphoteric. Depending on the properties required for the dispersion of the resin (c), a suitable type of dispersant can be appropriately used in a suitable amount. A preferable dispersant is a resin-type dispersant.

  When selecting an anionic surfactant, the kind is not specifically limited. Specifically, fatty acid salt, polysulfonate, polycarboxylate, alkyl sulfate ester salt, alkylaryl sulfonate, alkylnaphthalene sulfonate, dialkyl sulfonate, dialkyl sulfosuccinate, alkyl phosphate, polyoxy Examples include ethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphoric acid sulfonate, glycerol borate fatty acid ester and polyoxyethylene glycerol fatty acid ester. It is not limited to. Specific examples include sodium dodecylbenzenesulfonate, sodium laurate sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene nonylphenyl ether sulfate, and sodium salt of β-naphthalenesulfonic acid formalin condensate. However, it is not limited to these.

  Cationic activators include alkylamine salts and quaternary ammonium salts. Specifically, stearylamine acetate, trimethyl cocoammonium chloride, trimethyl tallow ammonium chloride, dimethyl dioleyl ammonium chloride, methyl oleyl diethanol chloride, tetramethyl ammonium chloride, lauryl pyridinium chloride, lauryl pyridinium bromide, lauryl pyridinium disulfate, cetyl pyridinium bromide , 4-alkylmercaptopyridine, poly (vinylpyridine) -dodecyl bromide, and dodecylbenzyltriethylammonium chloride. Examples of amphoteric surfactants include, but are not limited to, aminocarboxylates.

  Nonionic activators include, but are not limited to, polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and alkyl allyl ethers. Specific examples include, but are not limited to, polyoxyethylene lauryl ether, sorbitan fatty acid ester, and polyoxyethylene octyl phenyl ether.

  The selected surfactant is not limited to a single surfactant. For this reason, it is also possible to use 2 or more types of surfactant in combination. For example, a combination of an anionic surfactant and a nonionic surfactant, or a combination of a cationic surfactant and a nonionic surfactant can be used. The blending amount at that time is preferably set to a suitable blending amount for each surfactant component as described above. As a combination, a combination of an anionic surfactant and a nonionic surfactant is preferable. The anionic surfactant is preferably a polycarboxylate. The nonionic surfactant is preferably polyoxyethylene phenyl ether.

  Specific examples of the resin-type dispersant include polyurethane; polyacrylate ester of polyacrylate; unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid alkylamine salt. , Polysiloxanes, long-chain polyaminoamide phosphates and hydroxyl group-containing polycarboxylic acid esters and modified products thereof; amides formed by reaction with lower alkyleneimine polymers and polyesters having free carboxyl groups or salts thereof Oil-based dispersant: water-soluble as represented by (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol and polyvinylpyrrolidone Resin or water-soluble polymer compound; Poly Ester resins; modified polyacrylate resin, ethylene oxide / propylene oxide addition compound; and phosphate ester-based resin used but not limited thereto. These can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  Among the above dispersants, polymer dispersants having an acidic functional group such as polycarboxylic acid are preferable. This is because such a polymer dispersant lowers the viscosity of the dispersion composition with a small addition amount and increases the spectral transmittance of the dispersion composition. The resin-type dispersant is preferably used in an amount of about 3 to 300% by mass with respect to the carbon nanotube (b). Moreover, it is more preferable to use about 5-100 mass% from a film forming viewpoint.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 manufactured by Big Chemie. 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150 and 2155 or Anti-Terra-U, 203 and 204, or BYK-P104, P104S, 220S and 6919, or Lactimon and Lactimon-WS or Bykumen; SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 1700 manufactured by Japan Lubrizol Corporation 18000, 20000, 21000, 24000, 26000, 27000, 28000, 18845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000 and 76500; manufactured by BASF Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 11 1,120,150,1501,1502 and 1503; and Ajinomoto Fine-Techno Co. AJISPER PA 111, PB711, PB821, but PB822 and PB824 include, but are not limited to.

  The solvent used for obtaining the resin composition (a) is not particularly limited. As the solvent, any of an aqueous solution, an aqueous solvent and an organic solvent can be used.

  Among organic solvents, organic solvents having a boiling point of 50 to 250 ° C. are easy to use. Such an organic solvent is excellent in workability during coating and drying before and after curing. Specific examples of the solvent include alcohol solvents typified by methanol, ethanol and isopropyl alcohol; ketone solvents typified by acetone, butyl diglycol acetate and MEK (methyl ethyl ketone); typified by ethyl acetate and butyl acetate. Ester solvents such as dibutyl ether, ethylene glycol and monobutyl ether; and dipolar aprotic solvents such as N-methyl-2-pyrrolidone, but are not limited thereto. These solvents can be used alone or in admixture of two or more.

  Aromatic hydrocarbon solvents represented by toluene, xylene, Solvesso # 100 (manufactured by Exxon) and Solvesso # 150 (manufactured by Exxon); aliphatic hydrocarbons represented by hexane, heptane, octane and decane Solvents; or amide solvents represented by cellosolve acetate, ethyl cellosolve, and butyl cellosolve can also be used. These solvents can also be used alone or in admixture of two or more.

  Moreover, an additive can be suitably mix | blended with the said solvent in the range which does not inhibit the objective of this embodiment as needed. Examples of additives include pigments, wetting and penetrating agents, anti-skinning agents, ultraviolet absorbers, antioxidants, crosslinking agents, preservatives, antifungal agents, viscosity modifiers, pH adjusters, leveling agents, and antifoaming agents. However, it is not limited to these.

  When the content of the carbon nanotube (b) and the glitter pigment (g) in the resin composition (a) is expressed by PWC, it is 0.1 to 60% by mass. PWC is Pigment Weight Concentration (pigment weight concentration) and is calculated by the following equation.

PWC = [(pigment mass) / (total solid mass)] × 100 (%)

  The content ratio of the carbon nanotube (b) and the glitter pigment (g) in the resin composition (a) is carbon nanotube (b): glitter pigment (g) = 5: 95 to 95: 5 mass%. Is preferred.

(2) Carbon nanotube (b)

  The carbon nanotube (b) has a shape obtained by winding planar graphite into a cylindrical shape. The carbon nanotube (b) may be a single-walled carbon nanotube, a multi-walled carbon nanotube, or a mixture of these. Single-walled carbon nanotubes have a structure in which a single layer of graphite is wound. Multi-walled carbon nanotubes have a structure in which two or more layers of graphite are wound. The carbon nanotube (b) is preferably a multi-walled carbon nanotube from the viewpoint of cost and coloring effect. Further, the side wall of the carbon nanotube (b) may not have a graphite structure. For example, a carbon nanotube having a sidewall having an amorphous structure can be used as the carbon nanotube (b).

  The shape of the carbon nanotube (b) is not limited. Examples of the shape include various forms including a needle shape, a cylindrical tube shape, a fish bone shape (fishbone or cup laminated type), a trump shape (platelet), and a coil shape. Specific examples of the form of the carbon nanotube (b) include, for example, graphite whisker, filamentous carbon, graphite fiber, ultrafine carbon tube, carbon tube, carbon fibril, carbon microtube, and carbon nanofiber. It is not limited. The carbon nanotube (b) may have a single form or a combination of two or more of these.

  In the present embodiment, the form of the carbon nanotube (b) is preferably a form other than a fishbone shape (fishbone or cup laminate type), a trump shape (platelet), and a coil shape.

  The carbon nanotube (b) of this embodiment may be a carbon nanotube manufactured by any method. Carbon nanotubes can be generally produced by laser ablation, arc discharge, thermal CVD, plasma CVD, and combustion, but are not limited thereto. For example, the carbon nanotube (b) can be produced by contacting the carbon source with the catalyst at 500 to 1000 ° C. in an atmosphere having an oxygen concentration of 1% by volume or less. The carbon source may be at least one of a hydrocarbon and an alcohol.

  Any conventionally known material gas can be used as the source gas for the carbon nanotube (b). For example, hydrocarbons typified by methane, ethylene, propane, butane, and acetylene, carbon monoxide, and alcohol can be used as a source gas containing carbon, but the present invention is not limited to these. In particular, from the viewpoint of ease of use, it is desirable to use at least one of hydrocarbon and alcohol as a raw material gas.

  If necessary, after activating the catalyst in a reducing gas atmosphere, it is preferable to cause the source gas and the catalyst to react with each other in an atmosphere having an oxygen concentration of 1% by volume or less. In addition to the reducing gas, the raw material gas may be contacted with the catalyst. The atmosphere having an oxygen concentration of 1% by volume or less is not particularly limited, but an atmosphere of an inert gas typified by a rare gas such as argon gas and a nitrogen gas is preferable. As the reducing gas used for the activation of the catalyst, hydrogen or ammonia can be used, but is not limited thereto. As the reducing gas, hydrogen is particularly preferable.

  Various conventionally known metal oxides can be used as the catalyst. For example, the catalyst which combined the metal used as the active component represented by cobalt, nickel, or iron, and the metal used as the carrying component represented by magnesium or aluminum is mentioned.

The fiber diameter of the carbon nanotube (b) is 1 to 500 from the viewpoint of ease of dispersion and hue.
nm is preferable, and 8 to 25 nm is more preferable.

  The fiber diameter of the carbon nanotube (b) is determined as follows. First, the carbon nanotube (b) is observed and imaged with a scanning transmission electron microscope. Next, in the observation photograph, arbitrary 100 carbon nanotubes (b) are selected, and the outer diameter of each is measured. Next, the average particle diameter (nm) of the carbon nanotube (b) is calculated as the number average of the outer diameters.

  The fiber length of the carbon nanotube (b) is preferably 0.1 to 150 μm, and more preferably 1 to 10 μm, from the viewpoint of easy dispersion and hue.

  The carbon purity of the carbon nanotube (b) is represented by the carbon atom content (% by mass) in the carbon nanotube (b). The carbon purity is preferably 85% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more with respect to 100% by mass of the carbon nanotube (b).

  In this embodiment, the carbon nanotube (b) usually exists as secondary particles. The shape of the secondary particles may be, for example, a state where carbon nanotubes (b) that are general primary particles are intertwined in a complicated manner. An aggregate of the carbon nanotubes (b) may be used. Secondary particles, which are aggregates of linear carbon nanotubes (b), are more easily loosened than those intertwined. Moreover, since the linear thing has a good dispersibility compared with the thing intertwined, it can be utilized suitably as a carbon nanotube (b).

  The carbon nanotube (b) may be a carbon nanotube subjected to surface treatment. The carbon nanotube (b) may be a carbon nanotube derivative to which a functional group represented by a carboxyl group is added. Moreover, the carbon nano nanotube (b) which included the substance represented by the organic compound, the metal atom, or fullerene can also be used.

(3) Resin (c)

  The resin (c) is selected from natural resins and synthetic resins. Resin (c) may be a single resin. As the resin (c), two or more kinds of resins may be selected from natural resins and synthetic resins. Two or more kinds of resins can be used in combination.

  Natural resins include, but are not limited to, natural rubber, gelatin, rosin, shellac, polysaccharides and gilsonite. Synthetic resins include phenolic resin, alkyd resin, petroleum resin, vinyl resin, olefin resin, synthetic rubber, polyester, polyamide resin, acrylic resin, styrene resin, epoxy resin, melamine resin, urethane resin, amino resin, amide. Resins, imide resins, fluororesins, vinylidene fluoride resins, vinyl chloride resins, ABS resins, polycarbonates, silicone resins, nitrocellulose, rosin-modified phenol resins, and rosin-modified polyamide resins are exemplified, but not limited thereto.

  Of these resins, it is preferable that the carbon nanotube-containing layer (e) contains at least one of an acrylic resin and a polyester resin from the viewpoint of light resistance. At this time, it is preferable that at least one of an acrylic resin and a polyester resin is also contained in the base paint described later.

  The water-soluble resin used in the emulsion paint is preferably a water-soluble resin having an acid value of 20 to 70 mgKOH / g and a hydroxyl value of 20 to 160 mgKOH / g. Specifically, polyester resin, acrylic resin, and polyurethane resin are particularly preferably used as the water-soluble resin. The polyester resin is a resin using polyhydric alcohol and polybasic acid as raw materials. The acid value of the polyester resin is 20 to 70 mgKOH / g, preferably 25 to 60 mgKOH / g, and particularly preferably 30 to 55 mgKOH / g. The hydroxyl value of the polyester resin is 20 to 160 mgKOH / g, preferably 80 to 130 mgKOH / g.

  In this embodiment, an acid value means the mass (mg) of potassium hydroxide required in order to neutralize 1 g of resin. The hydroxyl value refers to the mass (mg) of potassium hydroxide required to react the hydroxyl group of the resin with phthalic anhydride and neutralize 1 g of the resin with the acid required for the reaction.

  In this embodiment, the acid value and hydroxyl value of the resin can be measured according to the method of JIS K-0070.

  The water-soluble polyester resin can be easily obtained by a known esterification reaction. The water-soluble polyester resin is a resin produced using a polyhydric alcohol and a polybasic acid as raw materials. The raw material may be a compound constituting a normal polyester resin. You may add fats and oils to water-soluble polyester resin as needed.

  Examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and diethylene glycol. Examples include, but are not limited to, propylene glycol, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol and dipentaerythritol. These polyhydric alcohols may be used alone or in combination of two or more. Examples of the polybasic acid include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, maleic anhydride, fumaric acid, itaconic acid and trimellitic anhydride. However, it is not limited to these. These polybasic acids may be used alone or in combination of two or more. Examples of the fats and oils include, but are not limited to, soybean oil, coconut oil, safflower oil, bran oil, castor oil, persimmon oil, linseed oil and tall oil, and fatty acids obtained therefrom.

  The acrylic resin is a resin made from a vinyl monomer. The acid value of the acrylic resin is 20 to 70 mgKOH / g, preferably 22 to 50 mgKOH / g, particularly preferably 23 to 40 mgKOH / g. The acrylic resin is a water-soluble resin having a hydroxyl value of 20 to 160 mgKOH / g, preferably 80 to 150 mgKOH / g.

  The water-soluble acrylic resin can be easily obtained by a known solution polymerization method or other methods. The water-soluble acrylic resin is a resin produced using a vinyl monomer as a raw material. The raw material may be a compound constituting a normal acrylic resin. In the above method, the organic peroxide is used as an initiator for the polymerization reaction.

  Examples of vinyl monomers include ethylenically unsaturated carboxylic acids represented by acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid; methyl, ethyl, propyl, butyl, isobutyl, tertiary butyl, Alkyl esters of acrylic acid or methacrylic acid represented by 2-ethylhexyl, lauryl, cyclohexyl, stearyl; acrylics represented by 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, polyethylene glycol having a molecular weight of 1000 or less Hydroxyalkyl esters of acid or methacrylic acid; amides of acrylic acid or methacrylic acid; or alkyl ethers thereof include, but are not limited to. Examples include, but are not limited to, acrylamide, methacrylamide, N-methylol acrylamide, diacetone acrylamide, diacetone methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide and N-butoxymethyl acrylamide.

  Furthermore, the glycidyl (meth) acrylate which has an epoxy group is mentioned. Also included are monomers containing a tertiary amino group. Examples thereof include, but are not limited to, N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate. In addition, aromatic monomers represented by styrene, α-methylstyrene, vinyltoluene, and vinylpyridine; acrylonitrile; methacrylonitrile; vinyl acetate; and mono- or dialkyl esters of maleic acid or fumaric acid. It is not limited to. Examples of the organic peroxide include acyl peroxides (for example, benzoyl peroxide), alkyl hydroperoxides (for example, t-butyl hydroperoxide and p-methane hydroperoxide), and dialkyl peroxides ( Examples thereof include, but are not limited to, di-t-butyl peroxide.

  The polyurethane resin is a resin made from polyol and polyisocyanate. The acid value of the polyurethane resin is 20 to 70 mgKOH / g, preferably 22 to 50 mgKOH / g, particularly preferably 23 to 35 mgKOH / g. The hydroxyl value of the polyurethane resin is 20 to 160 mgKOH / g, preferably 25 to 50 mgKOH / g.

  The water-soluble polyurethane resin can be easily obtained by addition polymerization of polyol and polyisocyanate. The raw material may be a polyol and a polyisocyanate constituting an ordinary polyurethane resin.

  Polyols include, but are not limited to, polyester polyols, polyether polyols, and acrylic polyols. Polyisocyanates include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate. , Trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, and trimethylhexane diisocyanate, but are not limited thereto.

  Water-soluble polyester resin, acrylic resin and polyurethane resin are imparted with water-solubility by neutralization with a basic substance. Under the present circumstances, it is preferable to use the basic substance of the quantity which can neutralize 40 mol% or more of the acidic group contained in water-soluble resin. Examples of the basic substance include ammonia, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, triethanolamine, N-methylethanolamine, N-aminoethylethanolamine, N-methyldiethanolamine, morpholine, and monoisopropanol. Examples include, but are not limited to amines, diisopropanolamine, and dimethylethanolamine.

  The number average molecular weight of the water-soluble resin is not particularly limited. The number average molecular weight is preferably 500 to 50000, more preferably 800 to 25000, and particularly preferably 1000 to 12000.

  The resin (c) is classified into a curable type and a lacquer type. In the present embodiment, a curable resin is preferably used. The curable resin (c) is used with an amino resin typified by melamine resin or a crosslinking agent typified by (block) polyisocyanate compound amine compound, polyamide compound and polyvalent carboxylic acid. After the resin (c) and the cross-linking agent are mixed, the curing reaction proceeds by being heated or being at room temperature. Moreover, while using resin of the type which does not have curability as resin for film-forming, it can also use together with resin of the type which has curability.

(4) Laminate (d)

  The laminate (d) of the present embodiment is composed of two layers including at least a base layer and a carbon nanotube-containing layer (e). The basic structure of the laminate (d) is a structure in which a base layer is provided under the carbon nanotube-containing layer (e). Another layer may be provided between the base material layer and the carbon nanotube-containing layer (e).

  The base material used in order to form the laminated body (d) in this embodiment is not specifically limited. Metals typified by alloys such as iron, aluminum and copper or steel, stainless steel, chrome molybdenum steel, brass, bronze, duralumin, tinplate; inorganic materials typified by glass, cement and concrete; Resins typified by polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin and epoxy resin; plastic materials typified by various FRPs; Wood, and natural or synthetic materials, including but not limited to fiber materials (including paper and cloth).

  Of the above materials, metals such as iron, aluminum and copper or steel, stainless steel, chrome molybdenum steel, brass, bronze, duralumin and tin are preferred. In addition, a resin containing an organic pigment, an inorganic pigment, or a bright pigment (g), which has been conventionally used for paints, is also preferable as the color pigment. Examples of organic pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, and the like. Examples of inorganic pigments include yellow iron oxide, red iron oxide, titanium dioxide, carbon black, and carbon nanotube. The average transmittance of these substrates at a wavelength of 380 to 780 nm is preferably 5% or less.

When using resin containing a color pigment for a base material, it is preferable that L ^* of resin containing a color pigment will be 1-40 from a viewpoint of a brightness. More preferably, L ^* is 1-20.

  The average transmittance of the substrate at a wavelength of 380 to 780 nm is preferably 5% or less, and more preferably 3% or less. If the characteristic of a base material exists in such a range, the laminated body (d) excellent in jetness will be obtained.

  The shape of the substrate may be a plate shape, a film shape, a sheet shape, or a molded body shape. For example, an injection molding method such as an insert injection molding method, an in-mold molding method, an overmold molding method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method; Typified by extrusion, multilayer extrusion, coextrusion and extrusion coating; and multilayer blow molding, multilayer calendering, multilayer press molding, slush molding and melt casting. Other molding methods can be used.

  The average transmittance is obtained as follows. As an example, a laminate in which a carbon nanotube-containing layer containing the resin composition is formed on a PET (polyethylene terephthalate) film (Toray Co., Ltd., Lumirror 100, T60) by a bar coater is given. First, using a UV-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., UV-3500), a transmission spectrum at a wavelength of 300 to 1500 nm is measured in a range of 5 nm. The measurement is performed from the surface on the side where the carbon nanotube-containing layer is laminated on the substrate. In the present specification, such a measurement mode may be referred to as “measurement from the direction of stacked surfaces”. Next, the average transmittance can be calculated by obtaining a weighted average value of each transmittance at a wavelength of 380 to 780 nm from the measured value.

  In the method for forming the laminate (d) of the present embodiment, the carbon nanotube-containing layer (e) is formed on the surface of the base material directly or via an underlayer. In the case where the laminate (d) is an automobile body or an automobile part, it is preferable that the base material is preliminarily subjected to chemical conversion treatment, undercoating coating represented by electrodeposition coating, and intermediate coating, but is not limited thereto. This intermediate coating means that a coating film is formed in advance in order to conceal the base, impart chipping resistance, and ensure adhesion with the color clear coating film to be overcoated.

  In order to form the laminate (d) of the present embodiment, after forming a base layer on the substrate, the carbon nanotube-containing layer (e) is formed without heating and curing the base layer, and then the coating film is formed. A heat curing method (wet on wet method) may be used. Moreover, after forming the said base layer on a base material, you may use the method (wet on dry method) which heat-hardens this base layer, and then heat-hardens the carbon nanotube content layer (e).

  As the undercoat layer, a base paint containing an organic pigment, an inorganic pigment, or a bright pigment (g) and a resin (c) can be used. Any organic pigment, inorganic pigment or glittering face can be used as long as it is commercially available or manufactured for coating.

  When the content of the organic pigment, inorganic pigment, or glitter pigment (g) in the base paint is expressed by PWC, it is 5 to 50% by mass, preferably 5 to 30% by mass. PWC is Pigment Weight Concentration (pigment weight concentration) and is calculated by the following equation.

PWC = [(pigment mass) / (total solid mass)] × 100 (%)

  In the laminate (d) of the present embodiment, it is preferable that a clear layer (f) is further formed on the carbon nanotube-containing layer (e). By forming the clear layer (f), a laminate (d) having gloss and excellent jetness is obtained.

L ^* exhibited by the laminate (d) is preferably 10.0 or less, and more preferably 5.0 or less. Here L ^* represents L ^* in the L ^* a ^* b ^* color system defined in JIS Z8729. Moreover, it is preferable that a ^* is -2.0 or more and 2.0 or less. Further, b ^* is preferably −2 or more and 0.3 or less.

When the clear layer (f) is further laminated on the carbon nanotube-containing layer (e), it is preferable that b ^* exhibited by the laminate (d) is −2.0 or more and 0.3 or less, More preferably, it is -2.0 or more and 0 or less. In particular, when b ^* is within such a range, a laminate (d) having excellent jetness can be obtained.

In the above color system, the smaller the L ^* , the higher the blackness. Moreover, it shows that the brightness is so high that L ^* is small. In addition, the closer a ^* and b ^* are to zero (0), the darker the hue. Further, b ^* is negative, and the larger the absolute value, the stronger the blue (blue) hue. Here, it is considered that humans feel that the black color having a slight bluish color (blue) has higher jetness than the black color having no bluish color. For this reason, it is considered that the above numerical range is preferable in terms of jetness presentation.

The lightness (L ^* ) and chromaticity (a ^* , b ^* ) are obtained by measurement using a multi-angle spectrocolorimeter. The measurement is performed from the surface on which the resin composition is laminated on the substrate. As a multi-angle spectrocolorimeter, MA68II manufactured by X-Rite may be used.

  The average reflectance of light having a wavelength of 380 to 780 nm on the surface of the laminate (d) on which the carbon nanotube-containing layer is laminated is preferably 5% or less, and more preferably 3% or less. In particular, when the average reflectance is within such a range, a laminate (d) having excellent jetness can be obtained.

  The average reflectance is obtained as follows. As an example, a coating film formed with a bar coater on a PET (polyethylene terephthalate) film (Toray Co., Ltd., Lumirror 100, T60) is mentioned. First, an absolute reflection spectrum at a wavelength of 300 to 1500 nm is measured in a range of 5 nm using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., UV-3500, using an integrating sphere). The measurement is performed from the surface on which the resin composition (a) is laminated on the substrate. In this specification, such a measurement mode may be expressed as “measurement from the direction of stacked surfaces”. Next, an average reflectance can be calculated by obtaining a weighted average value of each reflectance at a wavelength of 380 to 780 nm from the measured value.

(5) Carbon nanotube-containing layer (e)

  The carbon nanotube-containing layer of the present embodiment includes carbon nanotubes (b), a bright pigment (g), and a resin (c). A substrate is provided under the carbon nanotube-containing layer (e).

  The carbon nanotube-containing layer (e) of the present embodiment can be formed by using a general technique for the resin composition (a). Specific techniques include wet coating methods such as casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, and inkjet. Examples of the method include stacking the resin composition (a) that has been melt-kneaded and molded using a main roll, three-roll, pressure kneader, Banbury mixer, single-screw kneading extruder, or twin-screw kneading extruder. However, it is not limited to these.

  What is necessary is just to select suitably the addition rate of the carbon nanotube (b) in a carbon nanotube content layer (e) according to a use. The addition rate is preferably in the range of 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 2 to 15% by mass. In particular, if the addition rate is within such a range, a laminate having excellent jetness can be obtained.

  Carbon black can be added to the carbon nanotube-containing layer (e) in addition to the carbon nanotube (b) as long as the object of the present invention is not impaired. Specific examples of carbon black include ketjen black, acetylene black, furnace black and channel black. Carbon black may be by-produced when producing a synthesis gas containing hydrogen and carbon monoxide by partially oxidizing a hydrocarbon typified by naphtha in the presence of hydrogen and oxygen. Carbon black may be obtained by oxidizing or reducing such a by-product. The above is not intended to limit the carbon black according to the present invention. These carbon blacks may be used alone or in combination of two or more. From the viewpoint of improving blackness, carbon black having an average particle diameter of 20 nm or less and a DBP oil absorption of 80 ml / 100 g or less is preferably used. In addition, in this embodiment, the DBP oil absorption represents the amount (ml) of dibutyl phthalate (DBP) that can be included per 100 g of carbon black. The DBP oil absorption is a measure for quantifying the structure of carbon black. The structure is a complex aggregated form due to chemical or physical bonding between carbon black particles.

  The average particle diameter of carbon black is determined in the same manner as the fiber diameter of the carbon nanotube (b). Specifically, carbon black is first observed and imaged with a scanning transmission electron microscope. Next, in the observation photograph, arbitrary 100 carbon blacks are selected, and the outer diameter of each is measured. Next, the average particle diameter of carbon black is calculated as the number average of the outer diameters.

  The amount of carbon black used is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and still more preferably 1 to 25 parts by mass with respect to 100 parts by mass of the carbon nanotube (b).

  The average reflectance of the carbon nanotube-containing layer (e) at a wavelength of 380 to 780 nm is preferably 5% or less, and more preferably 3% or less. In particular, when the average reflectance is within such a range, a laminate having a better jetness can be obtained.

  The film thickness of the carbon nanotube-containing layer (e) is preferably 10 μm or more, and preferably 50 μm or less.

  In order to form the carbon nanotube-containing layer (e) on the base material, an optimal technique may be selected from general techniques according to the base material to be formed. Such techniques are preferably wet coating methods including casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, print transfer, and inkjet. Also preferred is a method in which the resin composition (a) is melt-kneaded and molded using a two-roll, three-roll, pressure kneader, Banbury mixer, single-screw kneading extruder or twin-screw kneading extruder, etc. . By forming the resin composition (a) on the substrate by the above technique, the carbon nanotube-containing layer (e) can be formed.

(6) Clear layer (f)

  The clear layer (f) of the present embodiment has transparency to the extent that a lower layer coating film can be visually recognized. Specific examples of the material include transparent materials such as transparent resin and glass. Transparent resins include polyesters represented by polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, and alicyclic rings. Acrylic resin, cycloolefin resin, triacetyl cellulose, epoxy resin, phenol resin, alkyd resin, petroleum resin, vinyl resin, olefin resin, synthetic rubber, polyamide resin, acrylic resin, styrene resin, melamine resin, urethane resin, amino Resin, fluorine resin, vinylidene fluoride resin, vinyl chloride resin, ABS resin, silicone resin, nitrocellulose, rosin modified phenolic resin, rosin modified polyamide resin, natural rubber , Gelatin, rosin, shellac, it may be mentioned polysaccharides and gilsonite, without limitation. As the glass, ordinary soda glass can be used. A combination of these materials can also be used. Carbon black and carbon nanotubes (b) that can visually recognize the lower coating film may be included in the clear layer (f).

  A two-component clear paint is preferred as the resin for the clear layer (f). An example of the two-part clear paint is a two-part curable urethane paint. The main component of the two-component clear paint is preferably a polyol resin containing a hydroxyl group, and the curing agent is preferably an isocyanate. This is because the clear layer (f) has a good appearance and excellent acid resistance. The polyol resin used as the main agent is not particularly limited, and examples thereof include polyester polyol, polyether polyol, acrylic polyol, polycarbonate polyol, and polyurethane polyol.

  Examples of the isocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, tricyclohexyl diisocyanate. Examples include, but are not limited to, methylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, and trimethylhexane diisocyanate.

  In order to form the clear layer (f) on the carbon nanotube-containing layer (e), an optimal technique may be selected according to the material to be formed. Such techniques include dry methods such as vacuum deposition, EB deposition and sputter deposition, as well as casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, and mold coating. In addition, it can be selected from general methods including a wet coating method typified by print transfer and inkjet. In addition, the clear layer (f) may be laminated in advance. As long as the clear layer (f) is laminated on the carbon nanotube-containing layer (e), these layers may not necessarily adhere to each other.

  The film thickness of the clear layer (f) is 5 to 150 μm, preferably 20 to 50 μm. In particular, if the film thickness is within such a range, a laminate having excellent jetness can be obtained.

  The following transparent protective film may be formed as the clear layer (f). In order to lower the average reflectance of the laminate (d), the refractive index of the transparent protective film is preferably lower than the refractive index of the carbon nanotube-containing layer (e) by 0.3 or more.

  The material of the transparent protective film is not particularly limited as long as it is a substance that falls within the above range. The material may be a single substance. The single substance may be an inorganic compound or an organic compound. Examples of the single substance include inorganic compounds typified by silicon oxide, magnesium fluoride, cerium fluoride, lanthanum fluoride and calcium fluoride, and organic compounds typified by polymers containing silicon element and fluorine element. It is done.

  The transparent protective film may be composed of a composite material containing an inorganic compound and an organic compound. Such a composite material preferably has a cavity inside. The transparent protective film may have fine particles of an inorganic compound. The fine particles may be made of silica or acrylic. The fine particles may have cavities inside. The organic compound may be one or more compounds selected from the group consisting of monofunctional or polyfunctional (meth) acrylic acid esters, siloxane compounds, and polymers obtained by polymerizing monomers having a perfluoroalkyl group. The composite material may be a mixture thereof.

  Specific examples of the silicon oxide include tetraalkoxysilanes represented by tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane; Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltri Methoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxy Lan, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino) Ethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxy Roxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ure Trialkoxysilanes typified by idpropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and vinyltriacetoxysilane; and organo typified by methyltriacetyloxysilane and methyltriphenoxysilane An alkoxysilane is mentioned.

  The transparent protective film may be a sol-gel coating film. The sol-gel coating film is formed using silicon oxide and alcohol, water or acid as raw materials. These raw materials form a sol-gel coating film by hydrolysis reaction and polymerization reaction. The transparent protective film may be a sputter-deposited film of silicon oxide, but is not limited thereto.

  Further, as the transparent protective film, a composite material using silica fine particles having a cavity inside can be used. As such a composite material, Opstar ((registered trademark)) TU-2180 (manufactured by JSR Corporation) or ELCOM ((registered trademark)) P-5024 (manufactured by JGC Catalysts & Chemicals) can be used. It is not limited to.

The jet-blackness herein, based on the L ^* a ^* b ^* color system defined in JIS Z8729, L ^* of the laminate (d) is 10 or less, and b ^* -2 to 0.3 Indicates the value of. L ^* and b ^* are measured from the surface on the side where the carbon nanotube-containing layer (e) is laminated on the substrate.

Further, when the clear layer (f) is further laminated on the lamination surface of the carbon nanotube-containing layer (e), the jetness is L ^* is 10.0 or less and b ^* is −2.0. This indicates that the value is 0.3 or less. The above values are measured by a multi-angle spectrocolorimeter. The multi-angle spectrocolorimeter may be MA68II manufactured by X-Rite.

(7) Bright pigment (g)
The glitter pigment (g) is a pigment having a pearly luster or metallic luster. Specifically, pigments that differ in appearance depending on the viewing angle due to variations in light reflected on the surface of the glitter pigment (g) are shown.

  Examples of the bright pigment (g) include aluminum flakes, metal oxide-coated alumina flakes, metal oxide-coated silica flakes, graphite pigments, metal oxide-coated mica, titanium flakes, stainless steel flakes, plate-like iron oxide pigments, metal plating Examples thereof include glass flakes, metal oxide-coated glass flakes, hologram pigments, and phthalocyanine flakes.

  The average particle diameter of the flaky glitter pigment (g) is usually preferably about 5 to 50 μm, more preferably about 5 to 30 μm. The average thickness is usually preferably from 0.01 to 2 μm, more preferably from about 0.05 to 1.5 μm. The ratio between the average particle diameter and the average thickness is usually preferably about 5 to 500, and more preferably about 20 to 300.

  The glitter pigment (g) is preferably a pearl pigment obtained by coating natural mica with a metal oxide such as titanium oxide or iron oxide. Examples of the pearl pigment include Merck's pearl pigment Iriodin (registered trademark) 100 Silver Pearl, Iriodin (registered trademark) 103 Rutil Sterling Silver, Iriodin (registered trademark) 111 Rutile Fine Satin, Iriodin (registered trademark) 120 Luster Satin, Iriodin (R) 123 Bright Luster Satin, Iriodin (R) 151 Luster Pearl, Iriodin (R) 153 Flash Pearl, Iriodin (R) 163 Shimmer Pearl, Iriodin (R) 183 Supernova White, Iriodin (R) 201 Rutile Fine Gold, Iriodin (registered trademark) 211 Rutile Fine Red, Iriodin (registered trademark) 221 Rutile Fine Blue, Iriodin (registered trademark) 223 Rutile Fine Lilac, Iriodin (registered trademark) 231 Rutile Fine Green, Iriodin (registered trademark) ) 205 Rutile Platinam Gold, Iriodin (R) 215 Rutile Red Pearl, Iriodin (R) 217 Rutile Copper Pearl, Iriodin (R) 219 Rutile Lilac Pearl, Iriodin (R) 225 Rutile Blue Pearl, Iriodin (R) ) 235 Rutile Green Pearl, Iriodin® 249 F lash Gold, Iriodin (registered trademark) 259 Flash Red, Iriodin (registered trademark) 289 Flash Blue, Iriodin (registered trademark) 299 Flash Green, Iriodin (registered trademark) 300 Gold Pearl, Iriodin (registered trademark) 302 Gold Satin, Iriodin ( (Registered trademark) 303 Royal Gold, Iriodin (registered trademark) 306 Olympic Gold, Iriodin (registered trademark) 309 Medallion Gold, Iriodin (registered trademark) 320 Bright Gold Satin, Iriodin (registered trademark) 323 Royal Gold Satinl, Iriodin (registered trademark) 351 Sunny Gold Pearl, Iriodin (registered trademark) 355 Glitter Gold, Iriodin (registered trademark) 500 Bronze, Iriodin (registered trademark) 502 Red Brown, Iriodin (registered trademark) 504 Red, Iriodin (registered trademark) 505 Red Violet, Iriodin ( (Registered trademark) 507 Searab Red, Iriodin (registered trademark) 520 Bronze Satin, Iriodin (registered trademark) 522 Red Brown Satin, Iriodin (registered trademark) 524 Red Satin, Iriodin (registered trademark) 530 Glitter Bronze, Iriodin (registered trademark) 532 Examples include Glitter Red Brown and Iriodin (registered trademark) 534 Glitter Red.

  The paint containing the glitter pigment (g) and the resin (c) can be classified as a metallic paint using metal flakes and a pearl paint using pearl pigments.

  The present invention will be described more specifically with reference to the following examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. In Examples, unless otherwise specified, “part” means “part by mass” and “%” means “mass%”. Further, “carbon nanotube” may be abbreviated as “CNT”, and “carbon black” may be abbreviated as “CB”.

<Method of measuring physical properties>

  The physical properties of the laminates used in Examples and Comparative Examples described later were measured by the following methods.

<Film thickness>

  The film thicknesses of the carbon nanotube-containing layer and the clear layer in the laminate were determined as follows. First, three points in the coating film were measured using a film thickness meter (manufactured by NIKON, DIGIMICRO MH-15M). Next, these average values were made into the said film thickness.

<L ^* a ^* b ^* >

In the laminate, the lightness (L ^* ) and chromaticity (a ^* , b ^* ) in the L ^* a ^* b ^* color system defined by JIS Z8729 were measured. The measurement was performed using a multi-angle spectrocolorimeter (manufactured by X-Rite, MA68II). Moreover, the measurement was performed from the surface where the resin composition was laminated | stacked on the base material.

<Average reflectance>

The average reflectance of the laminate formed on the tin plate was determined. The average reflectance is 45 ° with respect to the perpendicular direction of the stacked surfaces using a multi-angle spectrocolorimeter (manufactured by X-Rite, MA68II).
Measured from the spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of. The average reflectance was calculated by calculating a weighted average value of each reflectance with a wavelength of 400 to 700 nm.

<Average transmittance>

  The average transmittance of the tin plate used for producing the laminate was determined. First, using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., UV-3500), a transmission spectrum at a wavelength of 300 to 1500 nm was measured in a range of 5 nm. The measurement was performed from the surface where the resin composition was laminated on the substrate. Next, the average transmittance was calculated by obtaining a weighted average value of each transmittance at a wavelength of 380 to 780 nm from the measured value. The average transmittance was 0%.

<Carbon nanotube fiber diameter>

  The obtained carbon nanotubes were observed and imaged with a scanning transmission electron microscope (JEM-6700M manufactured by JEOL Ltd.). In the observation photograph, arbitrary 100 carbon nanotubes were selected, and the outer diameter of each was measured. Furthermore, the fiber diameter (nm) of the carbon nanotube was computed by calculating | requiring the number average of a measured value.

<Average particle size of carbon black>

  Carbon black was observed and imaged with a scanning transmission electron microscope (JEM-6700M manufactured by JEOL Ltd.). In the observation photograph, arbitrary 100 carbon blacks were selected, and the outer diameter of each was measured. Furthermore, the average particle diameter (nm) of carbon black was computed by calculating | requiring the number average of a measured value.

<Examples of carbon nanotube synthesis catalyst and carbon nanotube production>

  Catalysts for carbon nanotube synthesis and carbon nanotubes used in Examples and Comparative Examples described later were prepared by the following method.

<Preparation of carbon nanotube synthesis catalyst (A)>

  200 g of cobalt acetate tetrahydrate and 172 g of magnesium acetate tetrahydrate as a supporting component were weighed in a beaker. The weighed material was stirred until uniform. The homogenized material was transferred to a heat resistant container. Using an electric oven, the material in the container was dried to evaporate water at a temperature of 190 ± 5 ° C. for 30 minutes. Thereafter, the dried material was pulverized in a mortar to obtain a precursor of the carbon nanotube synthesis catalyst (A). 100 g of the obtained precursor was weighed in a heat-resistant container. The precursor was baked in a muffle furnace in an atmosphere of 500 ° C. ± 5 ° C. for 30 minutes. Thereafter, the fired product was pulverized in a mortar to obtain a catalyst (A).

<Preparation of carbon nanotube synthesis catalyst (B)>

  74 g of cobalt hydroxide and 172 g of magnesium acetate tetrahydrate as a supporting component were weighed in a beaker. The weighed material was stirred until uniform. The homogenized material was transferred to a heat resistant container. Using an electric oven, the material in the container was dried to evaporate water at a temperature of 190 ± 5 ° C. for 30 minutes. Thereafter, the dried material was pulverized in a mortar to obtain a precursor of the carbon nanotube synthesis catalyst (B). 100 g of the obtained precursor was weighed in a heat-resistant container. The precursor was baked in a muffle furnace in an atmosphere of 500 ° C. ± 5 ° C. for 30 minutes. Thereafter, the fired product was pulverized in a mortar to obtain a catalyst (B).

<Production of carbon nanotube (A1)>

  At the center of the horizontal reaction tube, a quartz glass heat-resistant dish in which 1.0 g of carbon nanotube synthesis catalyst (A) was dispersed was installed. The horizontal reaction tube was pressurizable and could be heated with an external heater, and the internal volume was 10 liters. By exhausting while injecting argon gas into the horizontal reaction tube, the air in the reaction tube was replaced with argon gas. The atmosphere in the horizontal reaction tube after replacement was adjusted to an oxygen concentration of 1% by volume or less. Next, the reaction tube was heated with an external heater until the central temperature in the horizontal reaction tube reached 700 ° C. After the center temperature reached 700 ° C., the catalyst was activated by introducing hydrogen gas into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute to conduct a contact reaction for 1 hour. After completion of the reaction, the reaction tube was cooled until the temperature in the reaction tube became 100 ° C. or lower by replacing the gas in the reaction tube with argon gas. After cooling, the produced carbon nanotubes were collected. The obtained carbon nanotubes were pulverized with an 80-mesh wire mesh and filtered.

<Production of carbon nanotube (A2)>

  At the center of the horizontal reaction tube, a quartz glass heat-resistant dish in which 1.0 g of carbon nanotube synthesis catalyst (A) was dispersed was installed. The horizontal reaction tube was pressurizable and could be heated with an external heater, and the internal volume was 10 liters. By exhausting while injecting argon gas into the horizontal reaction tube, the air in the reaction tube was replaced with argon gas. The atmosphere in the horizontal reaction tube after replacement was adjusted to an oxygen concentration of 1% by volume or less. Next, the reaction tube was heated with an external heater until the central temperature in the horizontal reaction tube reached 700 ° C. After the center temperature reached 700 ° C., the catalyst was activated by introducing hydrogen gas into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute to conduct a contact reaction for 2 hours. After completion of the reaction, the reaction tube was cooled until the temperature in the reaction tube became 100 ° C. or lower by replacing the gas in the reaction tube with argon gas. After cooling, the produced carbon nanotubes were collected. The obtained carbon nanotubes were pulverized with an 80-mesh wire mesh and filtered.

<Production of carbon nanotube (B1)>

  At the center of the horizontal reaction tube, a quartz glass heat-resistant dish in which 1.0 g of carbon nanotube synthesis catalyst (B) was dispersed was installed. The horizontal reaction tube was pressurizable and could be heated with an external heater, and the internal volume was 10 liters. By exhausting while injecting argon gas into the horizontal reaction tube, the air in the reaction tube was replaced with argon gas. The atmosphere in the horizontal reaction tube after replacement was adjusted to an oxygen concentration of 1% by volume or less. Next, the reaction tube was heated with an external heater until the central temperature in the horizontal reaction tube reached 700 ° C. After the center temperature reached 700 ° C., the catalyst was activated by introducing hydrogen gas into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute to conduct a contact reaction for 1 hour. After completion of the reaction, the reaction tube was cooled until the temperature in the reaction tube became 100 ° C. or lower by replacing the gas in the reaction tube with argon gas. After cooling, the produced carbon nanotubes were collected. The obtained carbon nanotubes were pulverized with an 80-mesh wire mesh and filtered.

<Production of carbon nanotube (B2)>

  At the center of the horizontal reaction tube, a quartz glass heat-resistant dish in which 1.0 g of carbon nanotube synthesis catalyst (B) was dispersed was installed. The horizontal reaction tube was pressurizable and could be heated with an external heater, and the internal volume was 10 liters. By exhausting while injecting argon gas into the horizontal reaction tube, the air in the reaction tube was replaced with argon gas. The atmosphere in the horizontal reaction tube after replacement was adjusted to an oxygen concentration of 1% by volume or less. Next, the reaction tube was heated with an external heater until the central temperature in the horizontal reaction tube reached 700 ° C. After the center temperature reached 700 ° C., the catalyst was activated by introducing hydrogen gas into the reaction tube at a flow rate of 0.1 liter per minute for 1 minute. Thereafter, ethylene gas as a carbon source was introduced into the reaction tube at a flow rate of 1 liter per minute to conduct a contact reaction for 2 hours. After completion of the reaction, the reaction tube was cooled until the temperature in the reaction tube became 100 ° C. or lower by replacing the gas in the reaction tube with argon gas. After cooling, the produced carbon nanotubes were collected. The obtained carbon nanotubes were pulverized with an 80-mesh wire mesh and filtered.

<Preparation of CNT coating liquid>

  A method for producing a CNT coating liquid that is one embodiment of the resin composition of the present invention will be described below.

(Production Example 1)

<Production of acrylic melamine coating on carbon nanotube>
Weight ratio of 3.2 g of carbon nanotube (A1), 25.6 g of acrylic resin (Acridic 47-712 manufactured by DIC), solvent (toluene: xylene: butyl acetate: Sorvesso 150 manufactured by TonenGeneral) 3: 3: 2: 2 68.2 g and zirconia beads 150 g were put into a 225 cm ³ glass bottle. These raw materials were dispersed for 2 hours using a paint conditioner manufactured by Red Devil. Then, the dispersion | distribution of the carbon nanotube was obtained by isolate | separating and removing a zirconia bead from the disperse | distributed raw material. In a high-speed stirrer, 100 parts by mass of this dispersion, 119.1 parts by mass of acrylic resin (Acridic 47-712 manufactured by DIC), and 30.3 parts by mass of melamine resin (Super Becamine L-177-60 manufactured by DIC) Stirring to obtain an acrylic melamine paint (A1) of carbon nanotubes.

(Production Examples 2 to 4)

  Acrylic melamine paints (A2 to B2) of carbon nanotubes were obtained in the same manner as in Production Example 1 except that the types of carbon nanotubes listed in Table 1 were changed.

(Production Example 5)

<Production of acrylic urethane coating on carbon nanotubes>
3.0 g of carbon nanotubes (A1), 24.0 g of acrylic polyol resin (Aclidick A-801-P manufactured by DIC), 88.4 g of solvent (mixed solvent of toluene: butyl acetate in a weight ratio of 7: 3), zirconia beads 150 g was charged into a 225 cm ³ glass bottle. These raw materials were dispersed for 2 hours using a paint conditioner manufactured by Red Devil. Then, the dispersion | distribution of the carbon nanotube was obtained by isolate | separating and removing a zirconia bead from the disperse | distributed raw material. 100 parts by mass of this dispersion, 78.1 parts by mass of acrylic polyol resin (Acricid A-801-P manufactured by DIC) and 29.6 parts by mass of isocyanate resin (Bernock DN-950 manufactured by DIC) were mixed with a high-speed stirrer. By stirring, an acrylic urethane paint (A1) of carbon nanotubes was obtained.

  Table 2 shows the carbon nanotube acrylic urethane paint (A1) produced in Production Example 5.

<Preparation of pearl pigment acrylic melamine paint>

(Production Example 6)

  Pearl pigment (5.5 parts by mass of Iriodin 103 WNT rutile sterling silver manufactured by MERCK, 243.2 parts by mass of acrylic resin (Acridic 47-712 manufactured by DIC), melamine resin (Super Becamine L-177-60 manufactured by DIC) 50.7 mass parts was stirred with the high-speed stirrer, and the acrylic melamine coating material (A) of the pearl pigment was obtained.

<Preparation of acrylic urethane paint for pearl pigment>

(Production Example 7)

  Pearl pigment (5.5 parts by mass of Iriodin 103 WNT rutile sterling silver manufactured by MERCK, 209.3 parts by mass of acrylic polyol resin (Acridick A801-P manufactured by DIC) and isocyanate resin (Bernock DN-950 manufactured by DIC) 62.7 The mass part was stirred with a high-speed stirrer to obtain an acrylic urethane paint (A) of a pearl pigment.

<Transparent acrylic melamine paint production>
(Production Example 8)
Acrylic resin (Acricid 44-179 manufactured by DIC) 100 parts by mass and melamine resin (DIC Superbeccamin L-177-60) 25 parts by mass were stirred with a high-speed stirrer to obtain a transparent acrylic melamine paint. .

<Preparation of transparent acrylic urethane paint>
(Production Example 9)
Immediately before coating, 100 parts by mass of acrylic polyol resin (Aclidick A-801-P manufactured by DIC) and 30 parts by mass of isocyanate resin (Bernock DN-950 manufactured by DIC) were stirred with a high-speed stirrer to obtain a transparent acrylic urethane coating. Got.

<Preparation of acrylic melamine pearl paint of carbon nanotube with pearl pigment>

(Example 1)

  100 parts by mass of the carbon nanotube acrylic melamine paint (A1) produced in Production Example 1 and 68.7 parts of the pearl pigment acrylic melamine paint produced in Production Example 6 were stirred with a high-speed stirrer, An acrylic melamine pearl paint A1 (CNT coating liquid) was obtained.

(Examples 2 to 4)
Acrylic melamine pearl paints A2 to B2 (CNT coating liquid) of pearl pigment-containing carbon nanotubes were obtained in the same manner as in Example 1 except that the acrylic melamine paint of carbon nanotubes listed in Table 3 was used.

<Preparation of acrylic urethane pearl paint of pearl pigment containing carbon nanotube>
(Example 5)

  100 mass parts of acrylic urethane paint of carbon nanotubes and 63.1 mass parts of acrylic urethane paint of pearl pigment were stirred with a high-speed stirrer to obtain acrylic urethane pearl paint A1 (CNT coating liquid) of pearl pigment-containing carbon nanotubes.

  Table 4 shows the acrylic urethane pearl paint A1 of pearl pigment-containing carbon nanotubes obtained in Example 5.

The CNT coating solutions obtained in Examples 1 to 5 were diluted to a viscosity suitable for spray coating with a solvent (toluene: xylene: butyl acetate: mass ratio 3: 3: 2: 2 of Solvesso 150 manufactured by TonenGeneral). The diluted CNT coating solution was spray-coated on the tin plate so that the film thickness of the CNT coating solution was 30 μm. Spray coating was performed using an air spray gun (Anest Iwata W-61-2G). The tin plate was left at room temperature for 30 minutes. Thereafter, the paint is dried at 80 ° C. for 20 minutes in a drier to prepare a laminate, which is measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite, and 45 ° with respect to the perpendicular direction of the laminated surfaces. Colorimetric values were obtained based on spectral reflectances received at 15 °, 45 °, and 110 ° with respect to specularly reflected light incident at an angle of.

Table 5 shows the evaluation results of the laminates produced using the CNT coating solutions produced in Examples 1 to 5. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

(Examples 6 to 9)

The transparent acrylic melamine paint produced in Production Example 8 was diluted to a viscosity suitable for spray coating with a mixed solvent (toluene: xylene: butyl acetate: mass ratio of Solvesso 150 manufactured by TonenGeneral Corp. 3: 3: 2: 2). The diluted transparent acrylic melamine paint was spray-coated on the laminate prepared using the CNT coating liquid prepared in Examples 1 to 4, respectively. Spray coating was performed using an air spray gun (W-61-2G manufactured by Anest Iwata Co., Ltd.) so that the film thickness of the transparent acrylic melamine was 30 μm. After painting, the tin plate was left at room temperature for 30 minutes. Thereafter, the tin plate was baked in a dryer at 140 ° C. for 30 minutes to dry the paint. As described above, acrylic melamine pearl laminates (A1 to B2) containing a pearl pigment and carbon nanotubes with a clear layer laminated thereon were obtained. The obtained laminate was measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite Co., Ltd., and 15 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the perpendicular direction of the laminated surface. Colorimetric values based on spectral reflectances received at 45 ° and 110 ° were obtained.

Table 6 shows the production conditions of the laminates produced in Examples 6 to 9, and Table 7 shows the evaluation results of the laminates produced in Examples 6 to 9. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

(Example 10)
The transparent acrylic urethane paint produced in Production Example 9 was diluted with a mixed solvent (a mixed solvent of toluene: butyl acetate in a weight ratio of 7: 3) to a viscosity suitable for spray coating. On the laminated body produced using the CNT coating liquid produced in Example 5, the diluted transparent acrylic urethane coating was spray-coated. Spray coating was performed using an air spray gun (W-61-2G manufactured by Anest Iwata Co., Ltd.) so that the film thickness of the transparent acrylic urethane was 30 μm. After painting, the tin plate was left at room temperature for 30 minutes. Thereafter, the tin plate was baked in a dryer at 140 ° C. for 30 minutes to dry the paint. Thus, an acrylic urethane pearl laminate (A1) containing a pearl pigment and carbon nanotubes, on which a clear layer was laminated, was obtained. The obtained laminate was measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite Co., Ltd., and 15 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the perpendicular direction of the laminated surface. Colorimetric values based on spectral reflectances received at 45 ° and 110 ° were obtained.

Table 8 shows the production conditions of the laminate produced in Example 10, and Table 9 shows the evaluation results of the laminate produced in Example 10. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

<Preparation of carbon black acrylic melamine paint>

(Production Example 10)

Carbon black (Degussa Color Black FW-200) 3.2 g, acrylic resin (DIC Corporation Acrydic 47-712) 25.6 g, mixed solvent (toluene: xylene: butyl acetate: TonenGeneral's Solvesso 150 mass (Ratio 3: 3: 2: 2) 42.3 g and zirconia beads 150 g were put into a 225 cm ³ glass bottle. These raw materials were dispersed for 2 hours using a paint conditioner manufactured by Red Devil. Thereafter, zirconia beads were separated and removed from the dispersed raw material to obtain a carbon black dispersion. In a high-speed stirrer, 100 parts by mass of this dispersion, 162.5 parts by mass of acrylic resin (Acridic 47-712 manufactured by DIC) and 41.4 parts by mass of melamine resin (Super Becamine L-177-60 manufactured by DIC) Stirring to obtain a carbon black acrylic melamine paint.

<Production of pearl pigment-containing carbon black acrylic melamine pearl paint>

(Comparative Example 1)

  78.5 parts by mass of the carbon black acrylic melamine paint prepared in Preparation Example 10 and 117.8 parts by mass of the pearl pigment acrylic melamine paint prepared in Preparation Example 6 were stirred with a high-speed stirrer, An acrylic melamine pearl paint (CB coating solution) was obtained.

Table 10 shows the pearl pigment-containing carbon black acrylic melamine pearl paint (CB coating solution) obtained in Comparative Example 1.

The CB coating solution obtained in Comparative Example 1 was diluted to a viscosity suitable for spray coating with a solvent (toluene: xylene: butyl acetate: Solvesso 150 mass ratio 3: 3: 2: 2 manufactured by TonenGeneral). The diluted CB coating solution was spray-coated on the tin plate so that the film thickness of the CB coating solution was 30 μm. Spray coating was performed using an air spray gun (Anest Iwata W-61-2G). The tin plate was left at room temperature for 30 minutes. Thereafter, the paint is dried at 80 ° C. for 20 minutes in a drier to prepare a laminate, which is measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite, and 45 ° with respect to the perpendicular direction of the laminated surfaces. Colorimetric values were obtained based on spectral reflectances received at 15 °, 45 °, and 110 ° with respect to specularly reflected light incident at an angle of.

Table 11 shows the production conditions and evaluation results of the laminate produced using the CB coating solution produced in Comparative Example 1. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

(Comparative Example 2)
The transparent acrylic melamine paint was diluted to a viscosity suitable for spray coating with a mixed solvent (toluene: xylene: butyl acetate: Solvesso 150 mass ratio 3: 3: 2: 2 manufactured by TonenGeneral). On the laminated body produced using the CB coating liquid produced in Comparative Example 1, a diluted transparent acrylic melamine paint was spray-coated. Spray coating was performed using an air spray gun (W-61-2G manufactured by Anest Iwata Co., Ltd.) so that the film thickness of the transparent acrylic melamine was 30 μm. After painting, the tin plate was left at room temperature for 30 minutes. Thereafter, the tin plate was baked in a dryer at 140 ° C. for 30 minutes to dry the paint. Thus, an acrylic melamine pearl laminate (A1) containing a pearl pigment and carbon black was obtained. The obtained laminate was measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite Co., Ltd.
Colorimetric values based on spectral reflectances received at 15 °, 45 °, and 110 ° with respect to specularly reflected light incident at an angle of ° were obtained.

Table 12 shows the production conditions of the laminate produced in Comparative Example 2, and Table 13 shows the evaluation results of the laminate produced in Comparative Example 2. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

(Examples 11 to 12)
The CNT coating solution obtained in Example 1 was diluted to a viscosity suitable for spray coating with a solvent (toluene: xylene: butyl acetate: Solvesso 150 mass ratio 3: 3: 2: 2 manufactured by TonenGeneral). The diluted CNT coating solution was spray-coated on the tin plate so that the film thickness of the CNT coating solution was 10 μm or 50 μm. Spray coating was performed using an air spray gun (Anest Iwata W-61-2G). The tin plate was left at room temperature for 30 minutes. Thereafter, the paint is dried at 80 ° C. for 20 minutes in a drier to prepare a laminate, which is measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite, and 45 ° with respect to the perpendicular direction of the laminated surfaces. Colorimetric values were obtained based on spectral reflectances received at 15 °, 45 °, and 110 ° with respect to specularly reflected light incident at an angle of.

Table 14 shows the production conditions of the laminate produced using the CNT coating liquid produced in Examples 11-12, and Table 15 shows the evaluation results of the laminate produced using the CNT coating liquid produced in Examples 11-12. Show. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

(Examples 13 to 14)
The transparent acrylic melamine paint produced in Production Example 8 was diluted to a viscosity suitable for spray coating with a mixed solvent (toluene: xylene: butyl acetate: mass ratio of Solvesso 150 manufactured by TonenGeneral Corp. 3: 3: 2: 2). The diluted transparent acrylic melamine paint was spray-coated on the laminate prepared using the CNT coating liquid prepared in Examples 11 to 12, respectively. Spray coating was performed using an air spray gun (W-61-2G manufactured by Anest Iwata Co., Ltd.) so that the film thickness of the transparent acrylic melamine was 30 μm. After painting, the tin plate was left at room temperature for 30 minutes. Thereafter, the tin plate was baked in a dryer at 140 ° C. for 30 minutes to dry the paint. As described above, acrylic melamine pearl laminates (A1 to B2) containing a pearl pigment and carbon nanotubes with a clear layer laminated thereon were obtained. The obtained laminate was measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite Co., Ltd., and 45 ° with respect to the perpendicular direction of the laminated surface.
Colorimetric values were obtained based on spectral reflectances received at 15 °, 45 °, and 110 ° with respect to specularly reflected light incident at an angle of.

The evaluation result of the laminated body produced using the CNT coating liquid produced in Tables 13-14 in Table 16 is shown. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

(Example 15)
A pearl pigment in which a clear layer is laminated by laminating a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., Lumirror 100, T60) on the laminate produced using the CNT coating solution produced in Example 1. And an acrylic melamine pearl laminate (A1P) containing carbon nanotubes. The obtained laminate was measured with a multi-angle spectrocolorimeter MA68II manufactured by X-Rite Co., Ltd., and 15 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the perpendicular direction of the laminated surface. Colorimetric values based on spectral reflectances received at 45 ° and 110 ° were obtained.

Table 17 shows the evaluation results of the laminate produced using the CNT coating solution produced in Example 15. The evaluation criteria of jetness were as follows: The spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the surface on which the coating film was laminated Based on L ^* of 5.0 or less and b ^* of 0 or less, ++ (excellent), L ^* of 5.1 to 10.0 and b ^* of 0 or less of + (good), L ^* is A value of 10.1 or more and b ^* of 0.1 or more was defined as “-” (defective). The evaluation criteria of the flip-flop property were as follows: spectroscopic light received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the direction perpendicular to the surface on which the coating film was laminated. the ratio of the based on the spectral reflectance of light received by the L ^* and 110 ° based on the reflectance L ^* (15 ° in L ^* / 110 ° of the L ^*) is a ++ those over 20 (excellent), 10 to 19. Nine were rated as + (good), and 9.9 or lower were rated as-(bad).

In the above examples, a resin composition and a laminate including carbon nanotubes, a bright pigment, and a resin were used. In the comparative example, a resin composition and a laminate using carbon black instead of carbon nanotubes were used. In the examples, resin compositions and laminates having a high jetness as compared with the comparative examples were obtained. Further, L ^{* of} 15 ° measured by the multi-angle spectrophotometer MA68II and 11
0 ° in the L ^* a ratio of (the 15 ° in the L ^* / 110 ° L ^*) is large, high resin composition of the flip-flop property and laminates were obtained. From the above, it has been clarified that the present invention can provide a resin composition and a laminate having a jet black property that cannot be realized with carbon black and having a high flip-flop property.

Although the present invention has been described with reference to the exemplary embodiments, the present invention is not limited to the above. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the invention.

Claims (10)

A laminate in which a carbon nanotube-containing layer made of a resin composition comprising at least carbon nanotubes, a flake-like glitter pigment, and a resin is laminated on a substrate,
The film thickness of the carbon nanotube-containing layer is 10 to 50 μm,
L ^* based on spectral reflectance measured by a multi-angle spectrocolorimeter received at 45 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the stacked surfaces is 10 or less. , A ^* is −2 or more and 2 or less and b ^* is −2 or more and 0.3 or less. Furthermore, it is a laminated body in which a clear layer is laminated on a carbon nanotube-containing layer, and is received at 45 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the perpendicular direction of the laminated surface. the following L ^* is 10 based on the spectral reflectance, the laminated body according to claim 1, wherein a ^* -2 to 2 and b ^* is equal to or is -2 0.3. The laminated body according to claim 1 or 2 , wherein the clear layer has a thickness of 5 to 150 µm. L ^* based on spectral reflectance received at 15 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the perpendicular direction of the laminated surface and 45 ° with respect to the perpendicular direction of the laminated surface L ^* ratio (15 ^* L ^* / 110 ^* L ^* ) based on spectral reflectance received at 110 [deg.] With respect to specularly reflected light incident at an angle of 10 to 30 The laminate according to any one of claims 1 to 3 . The laminated body according to any one of claims 1 to 4 , wherein the carbon nanotube has a fiber diameter of 8 to 25 nm. The laminate according to any one of claims 1 to 5 , wherein the content of carbon nanotubes in the carbon nanotube-containing layer is 1 to 30% by mass. The average reflectance at a wavelength of 400 to 700 nm determined from the spectral reflectance received at 45 ° with respect to the specularly reflected light incident at an angle of 45 ° with respect to the perpendicular direction of the stacked surfaces is 5% or less. The laminated body in any one of Claims 1-6 . The laminate according to any one of claims 1 to 7 , wherein an average transmittance of the substrate at a wavelength of 380 to 780 nm is 5% or less. The laminate according to any one of claims 1 to 8 , wherein the base material comprises at least one selected from the group consisting of organic pigments, inorganic pigments and glitter pigments, and a resin. (However, organic pigments and inorganic pigments exclude bright pigments.) On the substrate, a carbon nanotube-containing layer made of a resin composition comprising at least carbon nanotubes, a flake-like glitter pigment, and a resin is laminated so that the carbon nanotube-containing layer has a thickness of 10 to 50 μm. And a method for producing a laminate in which a clear layer is further laminated,
L ^* based on spectral reflectance measured by a multi-angle spectrocolorimeter received at 45 ° with respect to specularly reflected light incident at an angle of 45 ° with respect to the normal direction of the stacked surfaces is 10 or less. , A ^* is −2 or more and 2 or less and b ^* is −2 or more and 0.3 or less.