JP2017019251A - Laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body having high jet-blackness.SOLUTION: There is provided a laminated body which has a first layer [A layer] having a film thickness of 30 μm or more and 150 μm or less and Lof 10 or less and a second layer [B layer] formed by laminating a carbon nanotube-containing resin composition containing a carbon nanotube and a resin by a wet coating method, where in the laminate having two layers of at least the first layer and the second layer, Lof the first layer is 10 or less, Lof the laminated body measured from a plane direction in which the second layer is laminated on the first layer is 2.5 or less, a* is -2.0 or more and 2.0 or less and b* is -2.0 or more and 0.5 or less, the second layer is formed by wet coating, and 0.1 mass% to 1 mas% of carbon nanotube is contained in the material constituting the second layer.SELECTED DRAWING: None

Description

  The present invention relates to a laminate. More specifically, the present invention relates to a laminate having high jetness.

  Generally, product designers and consumers are required to impart high design properties to resin molded bodies. In particular, there is a need for a so-called jet-black molded body having a bluish color and a high blackness in order to impart a high-class feeling and high texture to the molded body. Similarly, in general, painting of automobiles and the like is intended to protect the vehicle body and improve durability, but in recent years, there has been an increasing demand for improvement in appearance quality (painting texture) appealing to sensitivity. . In order to improve the coating texture, it is necessary to increase the depth, transparency, and depth, and there is a strong demand for jet blackness and depth black coating as a high-quality coating.

  In general, in order to obtain a jet-black resin coated product, film, or molded product as described above, carbon black uniformly dispersed in a resin solution or a solid resin has been used. However, in this means, the lightness (L *) is in the high (gray / white) direction, and the chromaticity (a *, b *) is in the positive direction (+ a *: red, + b *: Yellow), and it was difficult to express jetness such as so-called “piano black” and “wet crow feathers”.

  The color tone of a molded body using carbon black tends to vary depending on the primary particle diameter of the carbon black compounded. Specifically, when carbon black having a small primary particle diameter is used, a color tone with high blackness but blackness can be obtained. On the contrary, when carbon black having a large primary particle diameter is used, the blackness is lowered although it is bluish. In this way, black coloration using carbon black has a trade-off relationship between blackness and blueness, so it was difficult to reproduce a jet-black color tone that has a blueness and high blackness. .

  In order to improve the coating texture, a black base color layer having a lightness of less than 0.2 on the first layer and a black color containing carbon black in an amount of more than 0.1% by weight and less than 10% by weight. A coating film structure formed by forming a clear layer has been proposed (Patent Document 3).

  However, in the conventional coating film structure, there is a problem that it is difficult to obtain a sufficient jetness and low brightness cannot be obtained.

JP 2001-179176 A JP 2004-098033 A JP-A-6-15223

  This invention is made | formed in view of the said subject, and it aims at providing the laminated body with high jetness, and also a feeling of depth.

The laminate of the present invention is formed by wet coating to form a carbon nanotube-containing resin composition including a first layer [A layer] having a film thickness of 30 μm or more and 150 μm or less and L ^* of 10 or less, and a carbon nanotube and a resin. With the laminate in which the second layer [B layer] is laminated, low brightness can be obtained, and a black coating with a jet black feeling and a deep feeling can be obtained.

That is, in the present invention, a wet coating method is used to form a carbon nanotube-containing resin composition including a first layer [A layer] having a film thickness of 30 μm or more and 150 μm or less and L ^* of 10 or less, and a carbon nanotube and a resin. A laminated body in which the second layer [B layer] is laminated (however, it is a laminated body having two layers of at least a first layer and a second layer, and L * of the first layer is 10 or less, L * of the laminate measured from the plane direction in which the second layer is laminated on the first layer is 2.5 or less, a * is -2.0 or more and 2.0 or less, and b * is -2.0. It is 0.5 or less, the second layer is formed by wet coating, and a laminate containing 0.1% by mass to 1% by mass of carbon nanotubes in the material constituting the second layer is excluded. .

Further, according to the present invention, L ^{* of} the laminate measured from the second layer [B layer] side is 2.5 or less, a ^* is -2.0 or more and 2.0 or less, and b ^* is -2.0 or more and 0. It is related with the said laminated body characterized by being 5 or less.

  Further, the present invention relates to the laminate, wherein the average transmittance of the second layer [B layer] at a wavelength of 380 to 780 nm is 5% or more and 80% or less.

  The present invention also relates to the laminate, wherein the film thickness of the second layer [B layer] is 0.5 μm or more and 50 μm or less.

  The present invention also relates to the laminate, wherein the content of carbon nanotubes in the second layer [B layer] is 1 to 20% by mass.

Moreover, this invention is a manufacturing method of the laminated body which has two layers of at least 1st layer [A layer] and 2nd layer [B layer],
The first layer [A layer] has a film thickness of 30 μm or more and 150 μm or less, and L ^* is 10 or less,
The second layer [B layer] is a method for producing a laminate comprising forming a carbon nanotube-containing resin composition containing carbon nanotubes and a resin by a wet coating method (however, at least the first layer and the second layer). A method for producing a laminate having two layers, wherein the L * of the first layer is 10 or less, and the L * of the laminate measured from the plane direction in which the second layer is laminated on the first layer Is 2.5 or less, a * is −2.0 or more and 2.0 or less, and b * is −2.0 or more and 0.5 or less, and the second layer is formed by wet coating to form the second layer The manufacturing method of the laminated body which contains 0.1 mass%-1 mass% of carbon nanotube in the material to do is related.

  According to the present invention, a laminate with high jetness can be obtained. Therefore, it is possible to use the laminate obtained by the present invention in various application fields where high jetness is required. In particular, since the laminate of the present invention is excellent in appearance, it can be suitably used in applications requiring high design properties.

Hereinafter, the present invention will be described in detail.
<Laminate>
The laminate of the present invention is formed by wet coating to form a carbon nanotube-containing resin composition including a first layer [A layer] having a film thickness of 30 μm to 150 μm and L ^* of 10 or less, and a carbon nanotube and a resin. A laminated body in which the second layer [B layer] is laminated. By such a laminated body, it can be set as the laminated body which is excellent in jet black property, and is excellent also in an external appearance.
Further, another layer may be provided between the first layer [A layer] and the second layer [B layer], and the first layer [A layer] or the first layer is formed on the substrate or the release film. Two layers [B layer] may be formed.
Further, at least one of the first layer [A layer] and the second layer [B layer] may have a third layer [C layer], and the third layer [C layer] is bonded. A layer is preferred. By having the adhesive layer [C layer], it is possible to attach the laminate of the present invention to various adherends and easily impart jetness. When the third layer [C layer] is an adhesive layer, the second layer [B layer] containing the carbon nanotubes is exposed to the outermost surface when the laminate is attached to the adherend. In order to obtain a jet black appearance, the third layer [C layer] is preferably provided on the first layer [A layer] side.

  However, the laminate of the present invention is a laminate having at least two layers of a first layer and a second layer, wherein the L * of the first layer is 10 or less, and the second layer is formed on the first layer. L * of the laminate measured from the laminated plane direction is 2.5 or less, a * is -2.0 or more and 2.0 or less, and b * is -2.0 or more and 0.5 or less, The case where the layer is formed by a wet coat and is a laminate containing 0.1% by mass to 1% by mass of carbon nanotubes in the material constituting the second layer is excluded.

By having such a first layer [A layer] and a second layer [B layer], the L * a * b * color specification defined by JIS Z8729 was measured from the second layer [B layer] side. It is possible to obtain a laminate in which L ^* of the laminate in the system is 2.5 or less, a ^* is −2.0 or more and 2.0 or less, and b ^* is −2.0 or more and 0.5 or less. .

That, ^L * based on JIS Z8729 of the ^laminate, a *, preferably ^{b * L *} is in the color system of 2.5 or less, further preferably 2.0 or less. Further, a ^* is preferably −2.0 or more and 2.0 or less, b ^* is preferably −2.0 or more and 0.5 or less, and more preferably −2.0 or more and 0 or less. Preferably, it is -2.0 or more and -1.0 or less. If it is especially in such a range, the laminated body excellent in jetness will be obtained. A smaller L ^* indicates a higher blackness (lower brightness). It can be said that the closer the value of a ^* and b ^* is to zero (0), the darker the hue. Further, it can be said that the b ^* (blue) has a stronger hue as b ^* is more negative. Therefore, from the viewpoint of jetness, since the case where the color is slightly bluish (blue) is considered to be high jetness, the above numerical range is considered preferable.

The lightness (L ^* ) and chromaticity (a ^* , b ^* ) in the L ^* a ^* b ^* color system defined by JIS Z8729 of the laminate are determined from the second layer [B layer] side by a color difference meter (NIPPONDENSHOKU). It can be obtained by measurement using a spectrocolor meter SE2000 manufactured by the company.

  In the 60 ° gloss of Glossometer GM-26D (manufactured by Murakami Color Research Laboratory), the gloss value is preferably 80 or more, and more preferably 85 or more. Particularly in such a range, L * can be reduced by gloss, and thus a laminate excellent in jetness can be obtained.

  What is necessary is just to select the optimal method for the formation method of the laminated body of this invention by the use etc. of a laminated body. Moreover, the method according to need can be selected according to the formation method and shape of the first layer [A layer].

  Although it does not restrict | limit especially as a formation method of a laminated body, For example, (i) The method of carrying out the layer formation of the 2nd layer [B layer] on the 1st layer [A layer] by the wet coat method, (ii) Base material A method of forming a first layer [A layer] on the first layer [A layer] and then forming a second layer [B layer] on the first layer [A layer] by a wet coating method; A method of forming a layer [A layer], then forming a second layer [B layer] on the first layer [A layer] by a wet coating method, and then peeling and removing the release film; (iv) a release film A method of forming a first layer [A layer] on the second layer [B layer] after forming a second layer [B layer] on the second layer [B layer] on top, and then peeling and removing the release film; Or the like.

  Even when the adhesive layer [C layer] is provided, the formation method is not particularly limited. For example, (I) the first layer [A layer] and the second layer [B layer] obtained by any one of the above methods are laminated. A method of forming an adhesive layer [C layer] by applying a pressure-sensitive adhesive or adhesive on one side of the laminated body, followed by drying by heating and curing, (II) a pressure-sensitive adhesive or adhesive on the release film After coating and drying by heating and curing to form an adhesive layer [C layer], a laminate in which the first layer [A layer] and the second layer [B layer] obtained by any of the above methods are laminated A method of bonding one surface of the body and the adhesive layer [C layer], (III) forming the first layer [A layer] on the release film and forming the adhesive layer [C on the other release film After the layer] and the first layer [A layer] are bonded together, the release film on the first layer [A layer] is peeled off and removed. How second layer [B layer] is formed by a wet coating method on [A layer, it can be formed by a.

By using these methods for forming a laminate, the L ^{* of} the laminate as measured from the second layer [B layer] side is 2.5 or less, a ^* is −2.0 or more and 2.0 or less, and b ^*. Is -2.0 or more and 0.5 or less, and it can be set as the laminated body excellent in jetness.

  The base material is not particularly limited. Metals such as iron, aluminum, copper or alloys thereof, inorganic materials such as glass, cement, concrete, polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer Natural or resin such as resin, polyamide resin, acrylic resin, vinylidene chloride resin, polycarbonate resin, polyurethane resin, polyester resin, epoxy resin, etc., various films, plastic materials such as FRP, wood, fiber materials (paper, cloth, etc.) Examples include synthetic materials.

  Moreover, a peeling film can also be used as a base material. Examples of release films include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin resins such as polypropylene and polyethylene, polyvinyl chloride resins, polycarbonate resins, acrylic resins, cycloolefin resins, triacetyl cellulose, Which of synthetic rubber, polyamide resin, styrene resin, melamine resin, urethane resin, amino resin, fluorine resin, vinylidene fluoride resin, ABS resin, silicone resin, natural rubber, etc. Any one or both surfaces of which a peeling treatment is applied can be used.

  In the 60 ° gloss of Glossometer GM-26D (manufactured by Murakami Color Research Laboratory), the gloss value is preferably 80 or more, and more preferably 85 or more. Particularly in such a range, L * can be reduced by gloss, and thus a laminate (c) having excellent jetness can be obtained.

<First layer [A layer]>
The first layer [A layer] is a layer obtained by using the resin composition (a) described later, and includes at least a black pigment and a resin, a film thickness of 30 μm to 150 μm, and L ^* is 10 or less. It is.
The first layer [A layer] may be formed on the substrate.
In addition, when a black pigment has a carbon nanotube, it does not correspond to 1st layer [A layer], but corresponds to 2nd layer [B layer].

As the method for forming the first layer [A layer], an optimum method may be selected depending on the material to be formed, and dry methods such as heat curing, vacuum deposition, EB deposition, sputter deposition, casting, spin coating, dip Coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, inkjet, etc. wet coating methods, injection molding methods, injection compression molding methods, extrusion molding methods, blow molding General methods such as law can be listed.
Among these, the wet coating method is preferable because of the smoothness of the first layer [A layer] obtained, the film thickness uniformity, and the wide range of film thickness that can be formed.

  The film thickness of the first layer [A layer] is 30 μm or more and 150 μm or less, and more preferably 50 μm or more and 100 μm or less. Excellent jetness and depth can be obtained when the film thickness is 30 μm or more. On the other hand, even if it exceeds 150 μm, jetness and depth are not improved, and production costs are increased, which is not preferable.

L ^* of the first layer [A layer] is a value in the L ^* a ^* b ^* color system defined by JIS Z8729 and is 10 or less. L ^* of the first layer (a) can be measured using a color difference meter from the surface direction of the first layer laminated on the substrate. If it is especially in such a range, the laminated body (c) excellent in jetness will be obtained. A smaller L * indicates a higher blackness (lower brightness).

(Resin composition (a))
The resin composition (a) for forming the first layer [A layer] contains a black pigment other than carbon nanotubes and a resin, and may contain a wax, a solvent or the like as required.

Although it does not specifically limit as a manufacturing method of a resin composition (a), A black pigment is combined with resin and a solvent, wax, etc. as needed, for example,
Paint shaker (manufactured by Red Devil), ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, basket mill, homomixer, homogenizer ( M-Technic Co., Ltd. “Cleamix”, etc.), wet jet mill (Genus Co. “Genus PY”, Nanomizer Co. “Nanomizer”, etc.), Hoover Mahler, 3-roll mill, extruder (double-screw extruder), Henschel It is preferable to perform a dispersion treatment using a mixer or the like. You may add a dispersing agent and an additive as needed.

  Moreover, in order to obtain the resin composition (a), a high-speed stirrer can be used. For example, homodisper (manufactured by PRIMIX), fill mix (manufactured by PRIMIX), dissolver (manufactured by Inoue Seisakusho), hyper HS (manufactured by Ashizawa Finetech) and the like can be mentioned.

"Black pigment"
Examples of the black pigment used for the resin composition (a) include carbon black. As specific examples of carbon black, hydrocarbons such as ketjen black, acetylene black, furnace black, channel black and naphtha are partially oxidized in the presence of hydrogen and oxygen to produce synthesis gas containing hydrogen and carbon monoxide. And carbon black produced as a by-product during oxidation, or carbon black obtained by oxidizing or reducing it.

"Dispersant"
As the dispersant, a surfactant or a resin-type dispersant can be used. Surfactants are mainly classified into anionic, cationic, nonionic, and amphoteric, and suitable types and blending amounts can be appropriately selected and used according to required properties. A resin-type dispersant is preferable.

  The anionic surfactant is not particularly limited, and specifically, fatty acid salt, polysulfonate, polycarboxylate, alkyl sulfate ester salt, alkylaryl sulfonate, alkylnaphthalene sulfonate, dialkyl Sulfonates, dialkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl aryl ether sulfates, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phosphate sulfonates, glycerol Late fatty acid esters, polyoxyethylene glycerol fatty acid esters and the like, specifically, sodium dodecylbenzenesulfonate, sodium laurate sulfate, sodium polyoxyethylene lauryl ether sulfate, Polyoxyethylene nonylphenyl ether sulfate, sodium salt of β- naphthalenesulfonic acid formalin condensate and the like.

  Examples of cationic activators include alkylamine salts and quaternary ammonium salts. Specifically, stearylamine acetate, trimethyl cocoammonium chloride, trimethyl tallow ammonium chloride, dimethyldioleyl 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, dodecylbenzyltriethylammonium chloride and the like. Examples of amphoteric surfactants include aminocarboxylates.

  Nonionic activators include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, polyoxyethylene phenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, alkyl allyl ethers, and more specifically, polyoxyethylene Examples include lauryl ether, sorbitan fatty acid ester, polyoxyethylene octyl phenyl ether, and the like.

  The selection of the surfactant is not limited to one type, and two or more surfactants such as an anionic surfactant and a nonionic surfactant, and a cationic surfactant and a nonionic surfactant are used. It can also be used in combination. In this case, the blending amount is preferably set to the blending amount described above for each activator component. Preferably, an anionic surfactant and a nonionic surfactant are used in combination. The anionic surfactant is preferably a polycarboxylate and the nonionic surfactant is preferably polyoxyethylene phenyl ether.

  Specific examples of the resin-type dispersant include polyurethane; polycarboxylic acid ester such as polyacrylate; unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, and modified products thereof; amides and salts thereof formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group Water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin and water-soluble polymer compound; polyester resin, modified Li acrylate resin, an ethylene oxide / propylene oxide adduct, a phosphoric acid ester-based resin and the like are used, they can be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a resin-type dispersant having an acidic functional group such as polycarboxylic acid is preferable because the dispersion composition has a low viscosity and exhibits high spectral transmittance when added in a small amount. The compounding amount of the resin-type dispersant is preferably 3 to 300 parts by mass with respect to 100 parts by mass of the black pigment, and more preferably 5 to 100 parts by mass from the viewpoint of film formability.

  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, 2155 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc .; SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 170 manufactured by Lubrizol Japan 0, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc .; BASF Japan Manufactured by 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, 1 01,120,150,1501,1502,1503, etc .; Ajinomoto Fine-Techno Co. AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

"resin"
The resin used for the resin composition (a) can be used in combination of one or more selected from natural resins and synthetic resins.

  Examples of natural resins include 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. Examples thereof include resins, imide resins, fluorine resins, vinylidene fluoride resins, vinyl chloride resins, ABS resins, polycarbonates, silicone resins, nitrocellulose, rosin-modified phenol resins, and rosin-modified polyamide resins. Among these resins, acrylic resin, polyester, vinyl chloride resin, or urethane resin is preferable for the resin composition (a) from the viewpoint of weather resistance and light resistance. In particular, for example, a two-component clear paint (for example, a two-component curable urethane paint) in which a polyol resin containing a hydroxyl group is used as the main agent and the curing agent is an isocyanate is preferable. This is because the resulting coating film has excellent weather 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.

  Isocyanates used as curing agents include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane. Examples include diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, and trimethylhexane diisocyanate.

  When the emulsion paint is used as the resin composition (a), a water-soluble resin is used. As the water-soluble resin, a water-soluble resin having an acid value of 20 to 70 mgKOH / g and a hydroxyl value of 20 to 160 mgKOH / g is preferable, and specifically, a polyester resin, an acrylic resin, and a polyurethane resin are particularly preferable. The polyester resin suitably used as the water-soluble resin is obtained by using a polyhydric alcohol and a polybasic acid as a resin raw material, and has an acid value of 20 to 70 mgKOH / g, preferably 25 to 60 mgKOH / g, particularly preferably 30 to It is a water-soluble resin having a hydroxyl value of 55 to Kmg / g and a hydroxyl value of 20 to 160 mgKOH / g, preferably 80 to 130 mgKOH / g.

  The water-soluble polyester resin can be easily obtained by a known esterification reaction using a polyhydric alcohol, a polybasic acid and, if necessary, fats and oils constituting a normal polyester resin as a resin raw material. 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 dipropylene. Examples include 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, trimellitic anhydride, and the like. Can do. These polybasic acids may be used alone or in combination of two or more. Examples of the fats and oils include soybean oil, coconut oil, safflower oil, bran oil, castor oil, persimmon oil, linseed oil, tall oil, and fatty acids obtained therefrom.

  The acrylic resin suitably used as the water-soluble resin is obtained by using a vinyl monomer as a resin raw material, and has an acid value of 20 to 70 mgKOH / g, preferably 22 to 50 mgKOH / g, particularly preferably 23 to 40 mgKOH / g. 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 using an organic peroxide as an initiator, using a vinyl monomer constituting a normal acrylic resin as a resin raw material.

  Examples of vinyl monomers include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid, acrylic acid or methacrylic acid methyl, ethyl, propyl, butyl, isobutyl, Alkyl esters such as tertiary butyl, 2-ethylhexyl, lauryl, cyclohexyl, stearyl, hydroxyalkyl such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl of acrylic acid or methacrylic acid, polyethylene glycol having a molecular weight of 1000 or less Esters, amides of acrylic acid or methacrylic acid or their alkyl ethers such as acrylamide, methacrylamide, N-methylol acrylamide, diacetone acrylamide, diacetate Down methacrylamide, N- methoxymethyl acrylamide, N- methoxymethyl methacrylamide, N- butoxymethyl acrylamide.

  Furthermore, glycidyl (meth) acrylate having an epoxy group and monomers containing a tertiary amino group, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate and the like can be mentioned. . In addition, aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, and vinylpyridine, acrylonitrile, methacrylonitrile, vinyl acetate, maleic acid, and mono- or dialkyl esters of fumaric acid can be used.

  Examples of the organic peroxide include acyl peroxides (for example, benzoyl peroxide), alkyl hydroperoxides (for example, t-butyl hydroperoxide, p-methane hydroperoxide), dialkyl peroxides (for example, , Di-t-butyl peroxide) and the like.

  The polyurethane resin suitably used as the water-soluble resin is obtained by using polyol and polyisocyanate as raw materials, and has an acid value of 20 to 70 mgKOH / g, preferably 22 to 50 mgKOH / g, particularly preferably 23 to 35 mgKOH / g. A water-soluble resin having a hydroxyl value of 20 to 160 mgKOH / g, preferably 25 to 50 mgKOH / g.

  The water-soluble polyurethane resin can be easily obtained by addition polymerization using a polyol and a polyisocyanate constituting a normal polyurethane resin as the resin raw material.

  Examples of the polyol include polyester polyol, polyether polyol, acrylic polyol and the like. 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, trimethylhexane diisocyanate and the like.

  Water-soluble polyester resins, acrylic resins, polyurethane resins and the like are usually imparted with water solubility by neutralization with a basic substance. At this time, the basic substance is preferably used in an amount necessary to neutralize 40 mol% or more of the acidic groups contained in the 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 amines, diisopropanolamine, dimethylethanolamine and the like.

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

  In addition, when the resin composition (a) is used as an ultraviolet curable resin composition, an ultraviolet curable resin can be used. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400 (manufactured by Toagosei Co., Ltd.).

  Moreover, you may mix | blend a photoinitiator with ultraviolet curable resin as needed. Specific examples of the photopolymerization initiator include acetophenone series, ketone series, benzophenone series, benzoin series, ketal series, anthraquinone series, disulfide series, thioxanthone series, thiuram series, and fluoroamine series. These photopolymerization initiators can be used alone or in combination of two or more.

  The wax used in the resin composition (a) is one or more selected from polyethylene wax, polypropylene wax, sazol wax, montan wax, paraffin wax, microcrystalline wax, carnauba wax, shrack wax, and the like. Preferably there is. Among these, polyethylene wax or polypropylene wax is more preferable.

"solvent"
The solvent used for the resin composition (a) as needed is not particularly limited, and either water or an organic solvent can be used.

  As the organic solvent, an organic solvent having a boiling point of 50 to 250 ° C. is easy to use from the viewpoint of workability during coating and drying before and after curing. Specific examples of the solvent include alcohol solvents such as methanol, ethanol and isopropyl alcohol, ketone solvents such as acetone, butyl diglycol acetate and MEK, ethyl acetate, butyl acetate and ethyl 3-ethoxypropionate (EEP). Ester solvents such as dibutyl ether, ethylene glycol, monobutyl ether, etc., aromatic solvents such as toluene, xylene, Solvesso 150 (manufactured by TonenGeneral Sekiyu KK), N-methyl-2-pyrrolidone, etc. A protic polar solvent or the like can be used. These solvents can be used alone or in admixture of two or more.

  In addition to the above-mentioned solvents, if necessary, for example, pigments, wetting and penetrating agents, anti-skinning agents, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, cross-linking agents, preservatives, fungicides Additives such as an agent, a viscosity modifier, a pH adjuster, a leveling agent, and an antifoaming agent can be appropriately blended within a range that does not impair the object of the present invention.

<Second layer [B layer]>
The second layer [B layer] is a layer formed by layer-forming a carbon nanotube-containing resin composition (b) containing carbon nanotubes and a resin by a wet coating method.

  Specifically, the wet coating method for forming the second layer [B layer] includes casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, Examples thereof include print transfer and ink jet.

  The average transmittance of the second layer [B layer] at a wavelength of 380 to 780 nm is preferably 5% or more and 80% or less, and more preferably 10% or more and 30% or less. If it is especially in such a range, the laminated body excellent in jetness will be obtained.

  The average transmittance is only the second layer [B layer] obtained from the carbon nanotube-containing resin composition (b) on the PET (polyethylene terephthalate) film (Toray Co., Ltd., Lumirror 100, T60) used as the base material. About the laminated body formed with the bar coater, wavelength 300-1500 nm from the surface which laminated | stacked the 2nd layer [B layer] on the base material using the ultraviolet visible near-infrared spectrophotometer (the Hitachi Ltd. make, UV-3500). Can be calculated by measuring the transmission spectrum in the range of 5 nm and calculating the weighted average value of the respective transmittances at wavelengths of 380 nm to 780 nm.

  The content of carbon nanotubes contained in the second layer [B layer] is preferably 1 to 20% by mass, and more preferably 1% by mass or more and less than 3.5% by mass. Within this range, excellent jetness and high gloss can be obtained.

  The film thickness of the second layer [B layer] is preferably 0.5 μm or more and 50 μm or less, and more preferably 1 μm or more and 30 μm or less. If it is such a range, the laminated body excellent in jetness will be obtained.

(Resin composition (b))
The resin composition (b) for forming the second layer [B layer] is a carbon nanotube-containing resin composition containing carbon nanotubes and a resin, and may contain a solvent as necessary.

  Although it does not specifically limit as a manufacturing method of a resin composition (b), A carbon nanotube is combined with resin and a solvent as needed, for example, a paint shaker (made by Red Devil), a ball mill, Sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), Attritor, Pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, basket mill, homomixer, homogenizer (such as “Clairemix” manufactured by M Technique) The dispersion treatment is preferably performed using a wet jet mill (“Genus PY” manufactured by Genus, “Nanomizer” manufactured by Nanomizer, etc.), Hoover Mahler, three-roll mill, extruder and the like. You may add a dispersing agent and an additive as needed.

  The resin composition (b) can further contain UV absorbers, light stabilizers, surface conditioners, and the like as necessary, and transparent pigments such as colored pigments, metallic pigments, and mica can be added to the coating film. It can mix | blend to such an extent that sex is not inhibited.

"carbon nanotube"
The carbon nanotube used in the resin composition (b) has a shape in which one surface of graphite is wound into a cylindrical shape, and the single-walled carbon nanotube (SWCNT) has a structure in which the graphite layer is wound in one layer. Multi-walled carbon nanotubes (MWCNT) wound with two or more layers may be mixed, but multi-walled carbon nanotubes (MWCNT) are preferable from the viewpoint of cost and coloring effect. In addition, carbon nanotubes having an amorphous structure on the side wall of the carbon nanotube can be used instead of the graphite structure.

  The shape of the carbon nanotube may be any shape such as a needle shape, a cylindrical tube shape, a fish bone shape (fishbone, cup stack type), a trump shape (platelet), or a coil shape. Specific examples include graphite whiskers, filamentous carbon, graphite fibers, ultrafine carbon tubes, carbon tubes, carbon fibrils, carbon microtubes, and carbon nanofibers. These forms can be used in the form of one or a combination of two or more. The present invention is preferably in a form other than a fishbone shape (fishbone, cup laminate type), a trump shape (platelet), and a coil shape. In the case of fishbone or trump, carbon nanotubes are cut from the laminated surface (xy plane) of the cup and trump-like graphite sheet due to the shear stress generated during the production of the resin composition / molded body. There is a risk that a sufficient network structure cannot be formed, and the light confinement effect is reduced, leading to a decrease in blackness. Similarly, in the case of a coil shape, the three-dimensional structure is easily destroyed during manufacturing, and the coloring effect may be reduced.

  The fiber diameter of the carbon nanotube is preferably 1 to 500 nm, and more preferably 5 to 50 nm, from the viewpoint of easy dispersion and hue.

  The fiber length of the carbon nanotube is preferably from 0.1 to 150 μm, more preferably from 1 to 50 μm, from the viewpoint of ease of dispersion and hue.

  The carbon purity of the carbon nanotube is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more in 100% by mass of the carbon nanotube.

  Carbon nanotubes generally exist as secondary particles. The secondary particle shape may be, for example, a state in which carbon nanotubes, which are general primary particles, are intricately intertwined, or may be an aggregate of carbon nanotubes that are easily loosened and linear. Secondary particles, which are aggregates of linear carbon nanotubes, are preferable because they have better dispersibility than those intertwined.

  The carbon nanotube may be a surface-treated carbon nanotube derivative or a carbon nanotube derivative provided with a functional group such as a carboxyl group. In addition, carbon nano-nanotubes encapsulating organic compounds, metal atoms, fullerenes, and the like can also be used.

"Dispersant"
As the dispersant used for the resin composition (b), the same dispersants as those described for the resin composition (a) are used.

"resin"
As the resin used for the resin composition (b), the same resin as described for the resin composition (a) is used. Also when the resin composition (b) is used as an ultraviolet curable resin composition, an ultraviolet curable resin can be used. Moreover, the photoinitiator may be included as needed.

  In particular, for example, a two-component clear paint (for example, a two-component curable urethane paint) in which a polyol resin containing a hydroxyl group is used as the main agent and the curing agent is an isocyanate is preferable. This is because the resulting clear coating film has 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.

  Isocyanates used as curing agents include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane. Examples include diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate, and trimethylhexane diisocyanate.

"solvent"
The solvent used for the resin composition (b) is not particularly limited, and either water or an organic solvent can be used. As the organic solvent, the same solvents as those described in the resin composition (a) are used.

  As the resin composition (b), in particular, the ketone solvent and the ester solvent are excellent in stability of the carbon nanotube-containing resin composition and the coating property at the time of coating, and the aromatic solvent is excellent in drying property, Since it is easy to obtain a coating film excellent in jetness, it is preferable to use these solvents.

<Third layer [C layer]>
The laminate of the present invention has a third layer [C layer] in at least one of the first layer [A layer] and the second layer [B layer] depending on the method of use and use of the laminate. The third layer [C layer] is preferably an adhesive layer.
By having the adhesive layer [C layer], it is possible to attach the laminate of the present invention to various adherends and easily impart jetness.

The adhesive layer [C layer] in the present invention expresses adhesiveness by an action such as pressure or heat, and plays a role of joining the laminate of the present invention and the adherend.
The material used for the adhesive layer [C layer] is not particularly limited, and general pressure-sensitive adhesives and adhesives can be used. Specifically, for example, general rubber, synthetic isoprene rubber, recycled rubber, styrene-butadiene rubber, polyisoprene rubber, styrene-isoprene-styrene rubber, etc., rubber adhesive, acrylic adhesive Urethane adhesives and silicon adhesives, hot melt adhesives, ethylene vinyl alcohol adhesives, chlorinated polyolefin adhesives, and the like can be used. In addition, in the pressure-sensitive adhesive and adhesive, for example, additives such as a crosslinking agent, a catalyst, a pigment, a dispersant, a tackifier, a solvent, an ultraviolet absorber, a viscosity modifier, a leveling agent, and an antifoaming agent Can be appropriately blended within a range not impairing the object of the present invention.

  As a method for forming the adhesive layer [C layer], an optimal method may be selected according to the type of material for forming the adhesive layer and the use of the laminate, and the adhesive or A method of heat drying and curing after applying the adhesive, a pressure sensitive adhesive or adhesive applied on the release film, and then heat drying and curing to form an adhesive layer, and either side of the laminate and the surface of the adhesive layer It can be formed by a bonding method or the like. General methods such as wet coating methods such as casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, and screen printing can be used as the method for forming the adhesive layer. Can be mentioned.

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

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

<Film thickness>
The film thickness of each layer in the laminate was measured at three points in the layer using a film thickness meter (manufactured by NIKON, DIGIMICRO MH-15M), and the average value was taken as the film thickness.

<L ^{* of} first layer [A layer]>
The lightness (L *) defined by JIS Z8729 was measured using a color difference meter (manufactured by NIPONDENSHOKU, SpectroColorMeterSE2000) from the surface direction in which the first layer [A layer] was laminated.

<Average transmittance (%) of second layer [B layer]>
Using a PET film (Toray Co., Ltd., Lumirror 100, T60) as a base material, the resin composition is coated on one side using a bar coater so that the film thickness after drying is the target film thickness, and then in an electric oven About the layer dried at 150 ° C. ± 5 ° C. for 60 minutes, an ultraviolet-visible near-infrared spectrophotometer (manufactured by Hitachi, Ltd., UV-3500) is used, and the wavelength is 300 to 1500 nm from the surface where the resin composition is laminated on the substrate. The transmittance spectrum was measured in the range of 5 nm, and the average transmittance was calculated by calculating the weighted average value of each transmittance at wavelengths of 380 nm to 780 nm.

<L ^* , a ^* , b ^* >
From the second layer [B layer] side, using a color difference meter (manufactured by NIPPONDENSHOKU, SpectroColorMeterSE2000), L ^* , a ^* , b ^* lightness (L ^* ) and chromaticity (a ^* ) defined in JIS Z8729 ^* , B ^* ) were measured.

<Resin composition (a)>
(Resin composition (а-1))
3 g of carbon black (manufactured by Degussa, COLOR Black FW-200) as a black pigment, 83 g of acrylic resin (manufactured by DIC, Acridic 47-712) as a resin, melamine resin (manufactured by DIC, Super Becamine L-117-) 60) 17.1 g, Solvesso 150 (manufactured by TonenGeneral Sekiyu K.K.) as a solvent, 8.1 g of toluene, 12.2 g of toluene, 12.2 g of xylene, and 8.1 g of butyl acetate are charged into a 225 cm 3 glass bottle, and paint shaker using zirconia beads as a medium. Was used for 1 hour to obtain a resin composition for forming a first layer (а-1).

(Resin composition (а-2))
Carbon black (manufactured by Mitsubishi Carbon Co., MA-100) 3 g as a black pigment, acrylic resin (manufactured by DIC, Acridic 47-712) 83 g, melamine resin (manufactured by DIC, Super Becamine L-117-60) ) 17.1 g, Solvesso 150 (manufactured by TonenGeneral Sekiyu K.K.) as a solvent, 8.1 g of toluene, 12.2 g of xylene, 12.2 g of xylene, and 8.1 g of butyl acetate are charged into a 225 cm 3 glass bottle, and a paint shaker is used with zirconia beads as a medium. The resulting mixture was dispersed for 1 hour to obtain a resin composition for forming a first layer (а-2).

(Resin composition (а-3))
Carbon black (Degussa, COLOR Black FW-200) 3g as a black pigment, Resin acrylic polyol for aqueous two-component urethane paint (DIC, Vernock WE-300) 74.5g as resin, Isocyanate (DIC, Barnock) DNW-5500) 33 g and 150 g of purified water as a solvent were charged into a 445 cm 3 glass bottle and dispersed for 1 hour using a paint shaker using zirconia beads as a medium to obtain a resin composition (а-3) for forming the first layer. .

(Resin composition (а-4))
An epoxy resin solution prepared by dissolving 1.05 g of carbon black (manufactured by Degussa, COLOR Black FW-200) as a black pigment, and an epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER4250) in butyl carbitol acetate as a resin and adjusting the nonvolatile content to 40%. 50 g was kneaded three times with a Hoovermarler under the conditions of a load of 150 lb (= 667 N) and a rotation speed of 100 rpm to obtain a resin composition for forming a first layer (а-4).

(Resin composition (а-5))
Carbon black (Degussa, COLOR Black FW-200) 3.0 g as a black pigment, acrylic polyol resin (Acridic A-801-P, DIC) 24.0 g as a resin, toluene: butyl acetate mass ratio as a solvent 78.4 mixed solvent 88.4 g, resin type dispersant (BYK111, BYK111) 1 g as a dispersant was weighed into a 225 cm3 glass bottle and dispersed using a paint shaker with zirconia beads as a medium for 1 hour. Immediately before coating, 100 parts by mass of this dispersion, 78.1 parts by mass of an acrylic polyol resin (Aclidick A-801-P manufactured by DIC), 29.6 parts by mass of an isocyanate resin (Bernock DN-950 manufactured by DIC) Part is stirred with a high-speed stirrer, and the first layer forming resin composition (а-5) is prepared. Obtained.

(Resin composition (а-6))
A polyester resin (Byron GK-130, manufactured by Toyobo Co., Ltd.) was dissolved as a resin in a mixed solution of methyl ethyl ketone / toluene = 50/50 (mass ratio) to obtain a polyester resin solution having a nonvolatile content of 40%. Next, 3 g of carbon black (manufactured by Degussa, COLOR Black FW-200) as a black pigment, 142 g of the above-mentioned polyester resin solution as a resin, and 50 g of a mixed solution of methyl ethyl ketone / toluene = 50/50 (mass ratio) as a solvent And kneaded 3 times under the conditions of a load of 150 lb (= 667 N) and a rotation speed of 100 rpm, to obtain a resin composition for forming a first layer (а-6).

(Resin composition (а-7))
As a black pigment, 3.0 g of carbon black (manufactured by Degussa, COLOR Black FW-200), 61.5 g of tripropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., Aronix M-220), polyester acrylate (manufactured by Daicel Ornex, Ebecryl 812) ) 28.5 g, cyclohexanenone 12.5 g, photopolymerization initiator (BASF Japan, Irgacure 907) was kneaded 3 times with Hoover Marler under a load of 150 lb (= 667 N) and a rotation speed of 100 rpm for forming the first layer. A resin composition (а-7) was obtained.

(Resin composition (а-8))
1000 g of block polypropylene copolymer (Prime Polymer Co., Prime Polypro 966 HP) as resin, 20 g of carbon black (Mitsubishi Carbon Co., MA-100) as black pigment, polyethylene wax (Sanyo Chemical Industries, Sun Wax 151P, molten) (Viscosity = 130 mPa · s) 1 g was charged into a Henschel mixer, and stirred and mixed for 4 minutes at a stirring blade rotation speed of 300 rpm. This was put into a twin-screw extruder (manufactured by Nippon Steel Co., Ltd., TEX30α) at a set temperature of 220 ° C., and melt kneaded and granulated to obtain a resin composition for forming a first layer (а-8).

<Resin composition (b) and other resin compositions>
(Resin composition (b-1))
Carbon nanotube (manufactured by Nanosil Corporation, NC-7000, MWCNT, fiber length 1.5 μm, fiber diameter 9.5 nm, carbon purity 90%) 1.08 g, acrylic resin as resin (DIC Corporation, Acrydic 44-179) 120 g, 30 g of melamine resin (manufactured by DIC, Super Becamine L-117-60), 10 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene, 10 g of ethyl acetate was charged into a 225 cm 3 glass bottle and dispersed for 1 hour using a paint shaker using zirconia beads as a medium to obtain a resin composition (b-1) for forming a second layer.

(Resin composition (b-2))
2.7 g of carbon nanotube (Nanosil, NC-7000), 120 g of acrylic resin (DIC, Acridick 44-179) as a resin, 30 g of melamine resin (Super Becamine L-117-60, manufactured by DIC) , 10 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene and 10 g of ethyl acetate are charged into a 225 cm ³ glass bottle, and a paint shaker is used with zirconia beads as a medium. Then, dispersion was performed for 1 hour to obtain a resin composition for forming a second layer (b-2).

(Resin composition (b-3))
1.08 g of carbon nanotube (Nanosil, NC-7000), 74.5 g of resin acrylic polyol for aqueous two-component urethane coating (DIC, Vernock WE-300) as resin, isocyanate (DIC, Vernock DNW-5500) ) 33 g and 150 g of purified water as a solvent were charged into a 445 cm 3 glass bottle and dispersed for 1 hour using a paint shaker using zirconia beads as a medium to obtain a resin composition (b-3) for forming a second layer.

(Resin composition (b-4))
Carbon nanotubes (Nanosil, NC-7000) 1.08 g, epoxy resin (Mitsubishi Chemical Co., JER4250) as a resin dissolved in butyl carbitol acetate and adjusted to NV 40%, varnish 50 g was loaded with a Hoover Muller at a load of 150 lb (= 667N) and kneading and dispersing three times under the conditions of a rotation speed of 100 rpm, to obtain a resin composition (b-4) for forming a second layer.

(Resin composition (b-5))
Carbon nanotube (Nanosil Co., NC-7000) 1.08 g, acrylic polyol resin (DIC Corporation Acridic A-801-P) 24.0 g as resin, toluene: butyl acetate mass ratio 7: 3 mixing 88.4 g of solvent and 1 g of a resin-type dispersant (BYK111, manufactured by BYK Chemie) as a dispersant are weighed into a 225 cm3 glass bottle, and dispersed for 1 hour using a paint shaker using zirconia beads as a medium to obtain a dispersion. In addition, 100 parts by mass of the dispersion, 78.1 parts by mass of the acrylic polyol resin (DICRIC A-801-P manufactured by DIC), and 29.6 parts by mass of the isocyanate resin (Bernock DN-950 manufactured by DIC) were mixed with a high-speed stirrer. The mixture was stirred to obtain a resin composition for forming a second layer (b-5).

(Resin composition (b-6))
Carbon nanotubes (manufactured by CNano, Flotube 9000, MWCNT, fiber length 10 μm, fiber diameter 12.5 nm, carbon purity 96.5%) 1.08 g, 120 g of acrylic resin (DIC Corporation, Acrydic 44-179) as resin 30 g of melamine resin (manufactured by DIC, Super Becamine L-117-60), 10 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene, ethyl acetate 10 g was charged into a 225 cm 3 glass bottle and dispersed for 1 hour using a paint shaker using zirconia beads as a medium to obtain a second layer forming resin composition (b-6).

(Resin composition (b-7))
Carbon nanotube (manufactured by Southwest NanoTechnologies, SMW210, MWCNT, fiber length 5 μm, fiber diameter 10 nm, carbon purity 75%) 1.08 g, resin as acrylic resin (DIC Corporation, Acrydic 44-179) 120 g, melamine resin ( DIC, Super Becamine L-117-60) 30 g, Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, ektapro EEP (manufactured by Eastman Kodak) 5 g, toluene 15 g, xylene 10 g, ethyl acetate 10 g 225 cm 3 Was dispersed for 1 hour using a paint shaker using zirconia beads as a medium to obtain a resin composition (b-7) for forming a second layer.

(Resin composition (b-8))
4.05 g of carbon nanotubes (Nanosil, NC-7000), 120 g of acrylic resin (DIC, Acridic 44-179) as resin, 30 g of melamine resin (Superbeccamin L-117-60, manufactured by DIC) , 10 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene and 10 g of ethyl acetate are charged into a 225 cm 3 glass bottle, and a zirconia bead is used as a medium with a paint shaker Then, dispersion was performed for 1 hour to obtain a resin composition for forming a second layer (b-8).

(Resin composition (b-9))
1.08 g of carbon nanotubes (manufactured by Nanosil, NC-7000), 61.5 g of tripropylene glycol diacrylate (manufactured by Toagosei Co., Ltd., Aronix M-220), 28.5 g of polyester acrylate (manufactured by Daicel Ornex, Ebecryl 812), Cyclohexanenon 12.5 g, photopolymerization initiator (BASF Japan, Irgacure 907) was kneaded 3 times with a Hoover Marler under a load of 150 lb (= 667 N) and a rotation speed of 100 rpm, and the resin composition for forming the second layer (b -9) was obtained.

(Resin composition (bc-1))
1.08 g of carbon black (manufactured by Degussa, COLOR Black FW-200), 120 g of acrylic resin (manufactured by DIC, Acrydic 44-179) as a resin, melamine resin (manufactured by DIC, Super Becamine L-117-60) ) 30 g, 10 g of Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene and 10 g of ethyl acetate are charged into a 225 cm 3 glass bottle, and paint shaker using zirconia beads as media Was used for 1 hour to obtain a resin composition for forming a second layer (bc-1).

(Resin composition (bc-2))
Carbon black (Mitsubishi Carbon Co., MA-100) 1.08 g, resin as acrylic resin (DIC Co., Acridic 44-179) 120 g, melamine resin (DIC Co., Super Becamine L-117-60) 30 g, Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene and 10 g of ethyl acetate are charged into a 225 cm 3 glass bottle, and a paint shaker is used with zirconia beads as a medium. The resulting mixture was dispersed for 1 hour to obtain a resin composition for forming a second layer (bc-2).

(Resin composition (bc-3))
2.7 g of carbon black (manufactured by Mitsubishi Carbon Co., MA-100), 120 g of acrylic resin (manufactured by DIC, Acridic 44-179) as resin, melamine resin (manufactured by DIC, Super Becamine L-117-60) 30 g, Solvesso 150 (manufactured by TonenGeneral Sekiyu KK) as a solvent, 5 g of Ektapro EEP (manufactured by Eastman Kodak), 15 g of toluene, 10 g of xylene and 10 g of ethyl acetate are charged into a 225 cm 3 glass bottle, and a paint shaker is used with zirconia beads as a medium. Dispersion was performed for 1 hour to obtain a resin composition for forming a second layer (bc-3).

[Example 1]
Using a PET film (manufactured by Toray Industries, Lumirror 100, T60) as a base material, the resin composition (a-1) is coated on one side using a bar coater so that the film thickness after drying is 50 μm, and then an electric oven It was dried at 150 ± 5 ° C. for 60 minutes to produce a first layer [A layer] on the substrate. At this time, the lightness (L ^* ) defined by JIS Z8729 was 2.6 using a color difference meter (manufactured by NIPONDENSHOKU, SpectroColorMeterSE2000) from the surface direction in which the first layer [A layer] was laminated.
Subsequently, the resin composition (b-1) was applied onto the first layer [A layer] using an air spray so that the film thickness after drying was 20 μm, and the obtained coating film surface was in an electric oven. Was dried at 150 ± 5 ° C. for 20 minutes to form a second layer [B layer] on the first layer [A layer], and a laminate 1 was obtained.

[Examples 2-14, Comparative Examples 1-5]
As shown in Table 3, except for the combination of the resin composition for forming the first layer and the resin composition for forming the second layer, and the film thickness, by the same method as the laminate 1 of Example 1, Laminated bodies 2 to 14 and 19 to 23) were obtained, respectively.

[Example 15]
A bar coater is attached to the release-treated surface of a release film that has been subjected to a release treatment on one side of a 100 μm-thick PET (polyethylene terephthalate) film so that the film thickness after drying the resin composition (a-7) is 50 μm. After coating, the coating was dried in an electric oven at 150 ± 5 ° C. for 60 minutes, and irradiated with ultraviolet rays using a conveyor type ultraviolet irradiator to be cured to produce a first layer [A layer].
Subsequently, the resin composition (b-1) was applied onto the first layer [A layer] using an air spray so that the film thickness after drying was 20 μm, and the obtained coating film surface was heated in an electric oven. It dried at 150 +/- 5 degreeC for 20 minutes, and formed 2nd layer [B layer] on 1st layer [A layer]. After that, the laminate 15 was obtained by peeling the release film.

[Example 16]
Using a PET film (manufactured by Toray Industries, Lumirror 100, T60) as a base material, the resin composition (a-1) is coated on one side using a bar coater so that the film thickness after drying is 50 μm, and then an electric oven It was dried at 150 ± 5 ° C. for 60 minutes to produce a first layer [A layer] on the substrate.
Subsequently, on the first layer [A layer], the resin composition (b-9) was applied using an air spray so that the film thickness after drying was 20 μm, and at 150 ± 5 ° C. in an electric oven. The laminate was dried for 60 minutes, irradiated with ultraviolet rays using a conveyor type ultraviolet irradiator, and cured to form a second layer on the first layer [A layer].

[Example 17]
The resin composition (a-8) for forming the first layer is put into an injection molding machine (M-50A2-DM, manufactured by Meiki Seisakusho Co., Ltd.) having a cylinder set temperature of 220 ° C. and a mold temperature of 40 ° C. to be molded. The 1st layer [A layer] of the board | plate material (110 mm long x 90 mm wide x 80 micrometers in thickness) whose surface is a mirror surface was produced.
Subsequently, the resin composition (b-1) was applied onto the first layer [A layer] using an air spray so that the film thickness after drying was 20 μm, and the obtained coating film surface was in an electric oven. Was dried at 150 ± 5 ° C. for 20 minutes to form a second layer [B layer] on the first layer [A layer], and a laminate 17 was obtained.

[Example 18]
A laminate 18 was obtained in the same manner as the laminate 17 of Example 17 except that the thickness of the first layer [A layer] was 150 μm.

[Comparative Example 6]
By changing the resin composition (b-1), which is the resin composition for forming the second layer, to the resin composition (bc-1), a laminate 24 was obtained in the same manner as the laminate 17 of Example 17. Got.

<Evaluation of laminate>
About each obtained laminated body, L ^* , a *, b ^* , gloss value (gloss), jetness, and a feeling of depth were each evaluated by the following method. The results are shown in Table 3.

[L ^* a ^* b ^{* of} laminate]
About the obtained laminated body, the lightness (L ^* ) and chromaticity (a ^* ) prescribed | regulated by JISZ8729 from the surface direction where the 2nd layer [B layer] side was laminated | stacked using the color difference meter (The product made by NIPONDENSHOKU, SpectroColorMeterSE2000). ^* , B ^* ) were measured.

[Gloss value (gloss)]
About the obtained laminated body, 60 degree gloss was measured by gloss meter GM-26D (made by Murakami Color Research Laboratory). The higher the gloss value, the better the gloss.

[Blackness]
The jetness of the laminate was evaluated by L ^* a ^* b ^* . The evaluation criteria are as follows.

A: L * 2.0 or less and b * -2 or more and 0.5 or less (excellent)
○: Over L * 2.0 and 2.5 or less and b * -2 or more and 0.5 or less (good)
X: Exceeding L * 2.5 or exceeding b * -2 and exceeding 0.5 (defect)

[Deep feeling]
As the appearance evaluation of the laminate, the sense of depth was evaluated visually. The evaluation criteria are as follows.

◎: Appearance with excellent depth ○: Appearance slightly inferior but with depth ×: Inferior depth

Table 3 shows the production conditions and evaluation results of the laminates produced in Examples 1 to 18 and Comparative Examples 1 to 6. The L ^{* of} the first layer and the average transmittance of the second layer measured by the above-described method are also shown.

From the above results, a first layer [A layer] having a film thickness of 30 μm or more and 150 μm or less and L ^* of 10 or less, and a carbon nanotube-containing resin composition containing carbon nanotubes and a resin are formed by wet coating. It was confirmed that the laminate in which the second layer [B layer] is laminated has a jet blackness higher than that of the laminate used in the comparative example, and a laminate having a deeper appearance can be obtained. .

Claims (6)

A first layer [A layer] having a film thickness of 30 μm or more and 150 μm or less and L ^* of 10 or less, and a second layer formed by layering a carbon nanotube-containing resin composition containing carbon nanotubes and a resin by a wet coating method [ B layer] (however, it is a laminate having at least two layers of the first layer and the second layer, and the L * of the first layer is 10 or less, on the first layer) L * of the laminate measured from the plane direction on which the second layer is laminated is 2.5 or less, a * is -2.0 or more and 2.0 or less, and b * is -2.0 or more and 0.5 or less. Yes, the second layer is formed by wet coating, and a laminate containing 0.1% by mass to 1% by mass of carbon nanotubes in the material constituting the second layer is excluded. L ^{* of} the laminate measured from the second layer [B layer] side is 2.5 or less, a ^* is −2.0 or more and 2.0 or less, and b ^* is −2.0 or more and 0.5 or less. The laminate according to claim 1.   The laminate according to claim 1 or 2, wherein the average transmittance of the second layer [B layer] at a wavelength of 380 to 780 nm is 5% or more and 80% or less.   The layered product according to any one of claims 1 to 3, wherein the film thickness of the second layer [B layer] is 0.5 µm or more and 50 µm or less.   The laminate according to any one of claims 1 to 4, wherein the carbon nanotube content in the second layer [B layer] is 1 to 20% by mass. A method for producing a laminate having at least two layers of a first layer [A layer] and a second layer [B layer],
The first layer [A layer] has a film thickness of 30 μm or more and 150 μm or less, and L ^* is 10 or less,
The second layer [B layer] is a method for producing a laminate comprising forming a carbon nanotube-containing resin composition containing carbon nanotubes and a resin by a wet coating method (however, at least the first layer and the second layer) A method for producing a laminate having two layers, wherein the L * of the first layer is 10 or less, and the L * of the laminate measured from the plane direction in which the second layer is laminated on the first layer Is 2.5 or less, a * is −2.0 or more and 2.0 or less, and b * is −2.0 or more and 0.5 or less, and the second layer is formed by wet coating, and constitutes the second layer (Excluding the method for producing a laminate containing 0.1% by mass to 1% by mass of carbon nanotubes in the material to be processed).