JP2016020419A - Bluish black transparent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bluish black color transparent film excellent in absorption property in near infrared part while being added transparent neutral gray clear bluish color.SOLUTION: There is provided a bluish black transparent film having a transparent substrate film and a coloring layer consisting of a coating composition arranged on at least single surface of the substrate film, the coating composition contains a composite oxide black pigment (A) having a property for absorbing visible ray and near infrared ray and consists of main component metal containing copper, manganese and iron, molar ratio of manganese/iron of 3/1 to 30/1 and molar ratio of copper/(manganese+iron) of 1/2 to 1.2.2.SELECTED DRAWING: None

Description

  The present invention relates to a black transparent film having a bluish tint.

  Conventionally, from the viewpoint of protection of the global environment and energy saving, research on materials that can reflect or shield infrared rays (infrared cut materials) has been actively conducted. Application of transparent film using infrared cut material to windows of houses, buildings, vehicles, etc. is being studied, and by suppressing the light in the infrared region of the incident light, the temperature rise in the room and in the car is suppressed. Attempts have been made to try.

  Among infrared cut materials, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO) are known as colorless and transparent materials. These materials are transparent without absorbing light in the visible light region, but absorb light in the infrared region. However, these materials have a problem that the absorptivity in the infrared region is insufficient unless the addition amount, coating amount, or film thickness is increased. There is also a problem that light absorption in the near infrared region is not so strong. Further, since rare metals such as indium (In) and tin (Sn) are used as constituent components, there are resource limitations.

  On the other hand, considering the coloring of the window glass, the window of the vehicle, etc., it is generally colored black from the viewpoint of suppressing the temperature rise, and carbon black is usually used. Carbon black is black in dark color, but when made into a thin film, it becomes yellowish and has a brownish hue. For this reason, in order to adjust this hue, the carbon black is used after being subjected to a blue tint or the like. Organic black pigments include perylene black and azomethine azo black. However, these organic black pigments transmit light in the infrared region without absorbing it. Further, it is known that the light resistance is inferior to that of inorganic pigments.

  Taking advantage of the transparency that is one of the characteristics of the fine particle pigment, a colored transparent film prepared by applying the fine particle pigment directly to the film or attaching an adhesive layer colored with the fine particle pigment to the film can be used to It is known to color building window glass and vehicle windows. Especially for coloring liquid crystal displays (LCDs), plasma display panels (PDPs), and organic EL panels using colored transparent films, clear neutral gray that is different from dark black and blue tints. A bluish tint is preferred.

  However, as described above, the most frequently used carbon black, when made into a thin film, has a yellowish dull color and a brownish hue. For this reason, it cannot be said that the clear neutral gray has a vivid blue hue. Further, since perylene black exhibits a reddish purple hue when it is formed into a thin film, it cannot be said that it exhibits a clear neutral gray clear bluish color. And azomethine azo black has a preferable hue, but does not absorb light in the infrared region. Moreover, even with inorganic pigments, there are currently few materials that have excellent light transmission, a clear neutral gray, vivid blue, and excellent infrared absorption performance.

  The pigment used as described above is required to have light resistance. For this reason, the expectation with respect to the inorganic pigment excellent in light resistance compared with an organic pigment is increasing. For example, a copper (Cu) -manganese (Mn) -iron (Fe) -based composite oxide black pigment having a high tinting strength and a bluish hue, which is prepared by a wet method, is known (Patent Documents 1 to 3). 3). Moreover, the complex oxide which exhibits black and has an absorptivity in the wavelength range from visible region to infrared region is known (patent documents 4 to 6). Furthermore, it is known that carbon black is used for an optical film for display aimed at a neutral gray color tone (Patent Documents 7 and 8).

Japanese Patent No. 3212065 JP 2002-309123 A Japanese Patent No. 3347934 Japanese Patent No. 4348872 JP 2001-99497 A JP 2007-230848 A JP 2004-69931 A JP 2000-265133 A

  However, even the pigments described in Patent Documents 1 to 6 can obtain a clear neutral gray clear blue color suitable for coloring LCDs, PDPs, and organic EL panels. It wasn't. For this reason, colored transparent films using these pigments are not suitable for coloring LCDs and the like. In addition, the optical films and the like described in Patent Documents 7 and 8 have a color tone adjusted to neutral gray using a color pigment other than carbon black together with carbon black. For this reason, the clear, neutral gray and vivid bluish color of the intended use was not obtained.

  The present invention has been made in view of such problems of the prior art, and the problem is that a clear neutral gray clear blue color is added and the near-infrared region is provided. An object of the present invention is to provide a black transparent film having a blue tint with excellent absorption characteristics.

That is, according to this invention, the black transparent film which has the bluish color shown below is provided.
[1] A characteristic of comprising a transparent substrate film and a colored layer comprising a coating composition disposed on at least one surface of the substrate film, wherein the coating composition absorbs visible light and near infrared rays. And has a molar ratio of manganese / iron of 3/1 to 30/1 and a molar ratio of copper / (manganese + iron) of 1 / A black transparent film having a bluish color, containing a composite oxide black pigment (A) of 2 to 1.2 / 2.
[2] The black transparent film having a bluish color according to [1], wherein the coating composition further contains a plastic paint (B).
[3] The black transparent film having a bluish color according to [1], wherein the coating composition further contains a transparent adhesive (C).
[4] The black transparent film having a bluish color according to [1], wherein the coating composition further contains a transparent pressure-sensitive adhesive (D).
[5] The composite oxide black pigment (A) has a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ and has a BET specific surface area of 30 m ² / g or more. The black transparent film which has the bluish color in any one of-[4].
[6] The above [1] to [5], wherein the composite oxide black pigment (A) contains 2 to 10 mol% of divalent metal of at least one of calcium and magnesium in a ratio to the copper. A black transparent film having the bluish color according to any one of the above.
[7] The black transparent film having a bluish color according to any one of [1] to [6], wherein the complex oxide black pigment (A) has a BET specific surface area of 40 m ² / g or more.
[8] In the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8 to 0. A black transparent film having the blueness described.

  The black transparent film having a bluish color of the present invention can obtain a clear neutral gray clear bluish color when used alone, and has a composite oxide black pigment excellent in absorption characteristics in the near infrared region. It was produced using the coating composition containing this. For this reason, the black transparent film having a bluish color of the present invention is given a clear bluish color of transparent neutral gray and has excellent absorption characteristics in the near infrared region.

  Hereinafter, preferred embodiments will be described as examples, and the details of the black transparent film having a bluish color of the present invention will be described. The blue transparent film having a bluish color of the present invention (hereinafter also simply referred to as “transparent film”) comprises a transparent base film and a coating composition disposed on at least one surface of the base film. A colored layer. And the coating composition which comprises a colored layer contains complex oxide black pigment.

  The composite oxide black pigment contained in the coating composition has a property of absorbing visible light and near infrared light, and is composed of oxides of main component metals including copper, manganese, and iron. In addition, when measuring the transmittance in the wavelength range from visible light to infrared, it is preferable to have a minimum wavelength in the wavelength range of 600 to 800 nm, particularly in the wavelength range of 400 to 1000 nm. Moreover, it is more preferable to have the maximum wavelength in which the transmittance is maximum in the wavelength range of 400 to 1000 nm in the wavelength range of 400 to 500 nm. Since the composite oxide black pigment has such optical characteristics, a clear neutral gray vivid bluish color can be obtained by single use. In addition, the composite oxide black pigment is soft and excellent in dispersibility despite being extremely fine particles. Furthermore, even if it does not contain an element such as chromium (Cr), the desired transparent neutral gray clear blue color can be obtained, which is excellent in safety and has high utility value.

  The transmittance of the composite oxide black pigment in a predetermined wavelength region is measured by, for example, measuring the transmittance in the wavelength region of 300 to 2500 nm using a spectrophotometer (trade name “U-4100”, manufactured by Hitachi, Ltd.). It can be confirmed by doing. Compared with carbon black, which is widely used as a black pigment, the composite oxide black pigment used in the present invention has a low transmittance in the wavelength range of 500 to 1500 nm from visible light to infrared, and has a stronger absorption in this wavelength region. It is shown.

Furthermore, the present inventors have found that a black pigment having a spinel structure composed of oxides of main component metals including copper, manganese, and iron is useful among the composite oxides. In particular, in a Cu—Mn—Fe-based composite oxide black pigment having a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ , the composition of manganese (Mn) / iron (Fe) (molar ratio) It was found that the absorption characteristics in the near infrared region can be remarkably improved by adjusting (). For example, when the composition has a large manganese / iron molar ratio (many manganese and little iron), the absorption in the near infrared region increases. However, a composition having a too large molar ratio of manganese / iron not only does not increase the absorption in the near infrared region, but also tends to decrease the coloring power. For this reason, in order to achieve efficient infrared shielding while maintaining the coloring power, the molar ratio of manganese / iron is set to 3/1 to 30/1, preferably 4/1 to 10/1. . By setting the molar ratio of manganese / iron within the above range, the transmittance in the near infrared region (800 to 1500 nm) can be reduced, and a clearer blue color can be obtained.

  If the molar ratio of manganese / iron is less than 3/1 (the ratio of iron increases), the hue becomes yellowish and shows a transmittance curve that approximates carbon black. For this reason, high absorptivity in the near infrared region cannot be obtained. On the other hand, when the molar ratio of manganese / iron exceeds 30/1 (the ratio of iron decreases), not only the hue of the hue does not become strong, but also the coloring power decreases. If the hue is yellowish, it tends to be difficult to absorb light in the near infrared region. On the other hand, the absorptivity in the near-infrared region tends to increase as the hue bluish increases. That is, the composite oxide black pigment used in the present invention has a double effect that it shows a clear bluish hue and is excellent in light absorption in the near infrared region.

Moreover, the coloring power and particle diameter of the resulting composite oxide black pigment vary depending on the increase or decrease of the copper content. For this reason, it is preferable to appropriately control the copper content. Specifically, the composite oxide black pigment of the present invention preferably has a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ . The molar ratio of copper / (manganese + iron) is 1/2 to 1.2 / 2, preferably 1/2 to 1.1 / 2. When the molar ratio of copper / (manganese + iron) is less than ½ (the ratio of copper decreases), the hue becomes dull and the coloring power decreases. On the other hand, when the molar ratio of copper / (manganese + iron) exceeds 1.2 / 2 (the proportion of copper increases), the pigment particle size tends to increase, so that the pigment has a small BET specific surface area. End up.

  Furthermore, in addition to copper, manganese, and iron, introduction of a divalent metal of at least one of calcium (Ca) and magnesium (Mg) is extremely effective in adjusting the color tone and coloring power. By introducing the divalent metal, a more vivid and neutral gray bluish black pigment can be obtained. However, if the amount of divalent metal introduced is too small, the sharpness tends to be insufficient. On the other hand, if the amount of divalent metal introduced is excessive, there will be no significant change in hue and no further effect will be expected. For this reason, it is preferable to set it as 2-10 mol% in the ratio with respect to copper, and, as for the introduction amount of a bivalent metal, it is more preferable to set it as 4-8 mol%. These divalent metals can be used alone or in combination of two or more.

The BET specific surface area of the composite oxide black pigment is preferably 30 m ² / g or more, and more preferably 40 m ² / g or more. When the BET specific surface area is less than 30 m ² / g, the coloring power tends to decrease, and there is a tendency to obtain a clear bluish color. Moreover, the haze value of a transparent film can be 10% or less that a BET specific surface area is 30 m < ² > / g or more. Furthermore, when the BET specific surface area is 40 / m ² or more, the haze value of the transparent film can be made 3.5% or less, and a transparent film with more excellent transparency can be obtained. The haze value is a physical property value that is a measure of transparency, and is represented by a value of a ratio of diffuse transmittance to total light transmittance. When the transparency is high, the haze value decreases, and as the transparency decreases, the haze value increases. In the case of a black colored film having a bluish color, it can be said that the transparency is sufficiently high if the haze value is 3.5% or less. The BET specific surface area of the composite oxide black pigment was measured by a nitrogen adsorption method in accordance with Japanese Industrial Standard JIS Z8830-1990 using a BET specific surface area measuring device (trade name “NOVA-2000”, manufactured by Quantachrome). can do.

As a method for expressing the color tone, there is a CIE L ^* a ^* b ^* color system (color space) which is expressed by the International Commission on Illumination (CIE) and expresses a visible color as a color space. In this CIE L ^* a ^* b ^* color system, a color is expressed by three coordinates, lightness is “L ^* ”, red (magenta) to green is “a ^* ” (positive is magenta, negative is green) , Yellow to blue correspond to “b ^* ” (positive is yellow, negative is blue), respectively. The neutral gray tone is ideally displayed when both the a and b values are close to zero. When the composite oxide black pigment is used, for example, a transparent film having an a value of −4 to 0, preferably −2 to 0, and a b value of −8 to 0, preferably −8 to −3. Can be manufactured. Since the above complex oxide black pigment can provide a film having the above color tone when used alone, there are many advantages in terms of quality stability, production / material cost, etc., and there is a possibility that it can be used effectively. It is expensive.

  A coating composition containing a composite oxide black pigment (A) and a resin material such as a transparent paint (B), a transparent adhesive (C), or a transparent adhesive (D) for plastic is prepared. A coating film, an adhesive film, or a pressure-sensitive adhesive film provided with a clear neutral gray clear bluish color if this coating composition is applied onto at least one surface of a transparent base film The transparent film of this invention which has coloring layers, such as these, can be manufactured.

  Transparent paint for plastic is a resin material that has fluidity and can be applied on and attached to at least one surface of a transparent base film, and then dried to form a coating film (film). is there. Transparent paints for plastics include, for example, acrylic paints, polyurethane paints, unsaturated polyester paints, alkyd paints, aminoalkyd paints, vinyl paints, epoxy paints, modified epoxy paints, phthalic acid paints Synthetic resin paints such as paints and chlorinated rubber paints; Oil-based paints such as oil finish paints and oil-based varnishes; Cellulose (fibrous) paints such as nitrocellulose lacquers and acrylic lacquers; Natural materials such as lacquer, shellac varnish, cashew resin paints Resin paints can be mentioned.

  The transparent paint for plastic contains, for example, a resin material having physical properties and pigment dispersibility for protecting or coloring the base film and exhibiting good adhesion to the base film. Specific examples of such resin materials include polyurethane resins, acrylic resins, polyester resins, polyether resins, epoxy resins, silicon resins, fluorine resins, alkyd resins, vinyl chloride-vinyl acetate resins. Copolymer, alkoxysilane resin, phenol resin, phenoxy resin, melamine resin, vinyl alcohol resin, ethylene-vinyl alcohol resin, polyvinyl butyral resin, polyimide resin, polyamide resin, styrene resin, rosin ester resin, and Examples thereof include cellulose resins. These resin materials can be used individually by 1 type or in combination of 2 or more types.

  A transparent adhesive is a substance that can bring two surfaces into a bonded state by a chemical force and / or a physical force. The adhesive includes an organic adhesive and an inorganic adhesive. Specific examples of organic adhesives include starch, dextrin, glue, casein, rosin, natural rubber, asphalt, tar and other natural adhesives; nitrocellulose, cellulose acetate and other semi-synthetic adhesives; polyurethane , Urea, melamine, phenol, epoxy, polyester, polyimide, polybenzimidazole, vinyl acetate, polyvinyl alcohol, vinyl chloride, acrylic, polyvinyl acetal, cyanoacrylate, polyethylene ( PE, EVA), chloroprene, nitrile rubber, butyl rubber, SBR, SBS / SIS, polysulfide, silicon rubber, vinyl / phenol, epoxy / phenol, chloroprene / phenol, nitrile / phenol , Nitrile Epoxy, synthetic adhesive nylon-epoxy, and the like. Specific examples of the inorganic adhesive include a cement adhesive, a sodium silicate adhesive, and a ceramic adhesive.

  A transparent adhesive agent contains the resin material which has the adhesiveness for making a base film adhere | attach an adherend and making it the state integrated, for example. Specific examples of such resin materials include polyurethane resins, acrylic resins, polyester resins, polyether resins, epoxy resins, silicon resins, fluorine resins, alkyd resins, vinyl chloride-vinyl acetate resins. Copolymer, alkoxysilane resin, phenol resin, phenoxy resin, melamine resin, vinyl alcohol resin, ethylene-vinyl alcohol resin, polyvinyl butyral resin, polyimide resin, polyamide resin, styrene resin, rosin ester resin, and Examples thereof include cellulose resins. These resin materials can be used individually by 1 type or in combination of 2 or more types.

  Transparent pressure-sensitive adhesive is a kind of adhesive that can be bonded in a short time at room temperature under extremely weak pressure without activating action such as water, solvent, and heat. It is a substance that can be easily peeled off without contaminating. Examples of the transparent adhesive include acrylic adhesives, rubber adhesives, silicon adhesives, polyurethane adhesives, polyester adhesives, and the like.

  The transparent adhesive contains a resin material having adhesiveness. Specific examples of such resin materials include polyurethane resins, acrylic resins, silicon resins, rosin ester resins, styrene-butadiene resins, polyvinyl ether resins, and synthetic rubbers. These resin materials can be used individually by 1 type or in combination of 2 or more types.

  Resin materials suitably used for the above resin materials include polyurethane resins, acrylic resins, polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, acetal group modified polyvinyl alcohol, butyral group modified polyvinyl alcohol, and silanol. Examples thereof include group-modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer, polyether, and polyester. In addition, a resin obtained by modifying an acrylic resin, a phenoxy resin, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, a butyral group-modified polyvinyl alcohol, or the like with a fluorine-modified silicon group or a long-chain alkyl group can also be used.

  The coating composition may contain a solvent such as water or an organic solvent, or may be prepared without a solvent. Specific examples of the organic solvent include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, cyclohexanone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, and butyl acetate. . In addition, organic solvents such as acetone, cyclohexane, tetrahydrofuran, N-methyl-2-pyrrolidone, dioxane, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, and cellosolve acetate are used. You can also. Although content of solid content in the coating composition prepared using the organic solvent etc. is not specifically limited, It is preferable that it is about 3-95 mass%.

  For example, when using a coating composition containing a transparent plastic paint as a resin material, first, a composite oxide black pigment and a paint such as urethane paint or acrylic paint are placed in a paint shaker and combined. The oxide black pigment is sufficiently dispersed to form a paint. And after apply | coating the obtained coating material (coating composition) on transparent base film, such as PET film, if it dries and forms a colored layer, the black transparent film which has the blueness of this invention will be obtained be able to.

  When a coating composition containing a transparent adhesive as a resin material is used, first, a composite oxide black pigment and an adhesive such as a urethane adhesive are placed in a paint shaker, and the composite oxide black pigment is added. Is sufficiently dispersed to form a paint. And after apply | coating the obtained adhesive coating material (coating composition) on transparent base film, such as PET film, if it dries and forms the colored layer which has adhesiveness, it has the blueness of this invention A black transparent film can be obtained.

  Furthermore, when using a coating composition containing a transparent adhesive as a resin material, first put a composite oxide black pigment and an adhesive such as an acrylic adhesive or a urethane adhesive in a paint shaker, The composite oxide black pigment is sufficiently dispersed to form a paint. And after apply | coating the obtained adhesive coating material (coating composition) on transparent base film, such as PET film, if it dries and forms the colored layer which has adhesiveness, it has the blueness of this invention A black transparent film can be obtained. In addition, what is necessary is just to apply | coat a coating composition on a base film according to a conventionally well-known method. For example, a coater such as a gravure coater, a comma coater, a roll coater, or a Meyer bar coater can be used.

  As the polyurethane resin contained in the urethane-based paint, adhesive, and pressure-sensitive adhesive, a conventionally known polyurethane resin produced from a polyol and a polyisocyanate can be used. As the polyol, it is possible to use short-chain diols, polyhydric alcohol compounds, polymer polyols, and the like that are conventionally used in the production of polyurethane resins. Moreover, as polyisocyanate, the diisocyanate conventionally used for manufacture of a polyurethane-type resin, the polyurethane prepolymer which has an isocyanate group at the terminal, etc. can be used. Moreover, you may make polyisocyanate and polyamine react as needed. As the polyamine, a short-chain diamine conventionally used in the production of polyurethane resins can be used. In the present specification, “polyurethane” is a general term for polyurethane, polyurea, and polyurethane-polyurea. A polyurethane-type resin can be used individually by 1 type or in combination of 2 or more types.

  Short chain diols include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, and alkylenes thereof. Oxide low molar adducts (number average molecular weight less than 500); 1,4-bishydroxymethylcyclohexane, alicyclic glycols such as 2-methyl-1,1-cyclohexanedimethanol and alkylene oxide low molar adducts thereof ( Number average molecular weight less than 500); aromatic glycols such as xylylene glycol and their alkylene oxide low molar adducts (number average molecular weight less than 500); bisphenols such as bisphenol A, thiobisphenol, sulfone bisphenol and their alkyles Oxide low mol adduct (number average molecular weight of less than 500); and the like alkyl dialkanolamines, such as alkyl diethanolamine having 1 to 18 carbon atoms. These short chain diols can be used singly or in combination of two or more.

  Examples of polyhydric alcohol compounds include glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate, 1,1,1-trimethylol ethane, and 1,1,1-trimethyl. And methylolpropane. These polyhydric alcohol compounds can be used singly or in combination of two or more.

  Examples of the polymer polyol include (1) Polyether glycol such as polyethylene glycol, polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol, polyhexamethylene glycol; (2) polyethylene adipate diol Polyester polyols such as polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, polyneopentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol (3) polycaprolactone diol, polycaprolactone triol, poly- A polylactone polyol such as methyl valerolactone diol; (4) a polycarbonate diol such as polyhexamethylene carbonate diol; (5) a polyolefin polyol such as polybutadiene glycol, polyisopropylene glycol, and hydrides thereof; (6) α, Mention may be made of polymethacrylate diols such as ω-polymethyl methacrylate diol, α, ω-polybutyl methacrylate diol. The number average molecular weight of these polymer polyols is preferably about 500 to 2,000. These polymer polyols can be used singly or in combination of two or more.

  (1) Examples of polyether polyols include those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.).

  (2) Polyester polyols include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, aceline acid, etc.) and / or aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, etc.) and low molecular weight Glycols (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, etc.) Is obtained by condensation polymerization.

  Polyisocyanates include toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy- 1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), jurylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, Aromatic diisocyanates such as benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl; methylene diisocyanate, 1,4- Aliphatic diisocyanates such as tramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene Alicyclic diisocyanates such as diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI; mention may be made of polyurethane prepolymers obtained by reacting these diisocyanates with low molecular weight polyols or polyamines so that the ends are isocyanates. Can do.

  Examples of polyamines include aliphatic diamine compounds such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and octamethylenediamine; phenylenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-methylenebis (phenyl) Amine), 4,4′-diaminodiphenyl ether, aromatic diamine compounds such as 4,4′-diaminodiphenylsulfone; cyclopentanediamine, cyclohexyldiamine, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, isophorone Examples include alicyclic diamine compounds such as diamines; hydrazines such as hydrazine, carbohydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide. These polyamines can be used singly or in combination of two or more.

The method for producing the polyurethane resin is not particularly limited, and a polyurethane resin produced according to a conventionally known polyurethane production method can be used. The polyurethane resin may be synthesized without a solvent or may be synthesized using an organic solvent. As an organic solvent used at the time of synthesis, methyl ethyl ketone, methyl-n-propyl ketone, methyl isozutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, and cyclohexanone are preferable. Also, acetone, cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchlorethylene, trichloroethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, and N-methyl-2 -Pyrrolidone etc. can also be used.

  As the polyurethane resin, polyester-urethane resin, polycarbonate-urethane resin, and polyether-urethane resin are preferable. The polystyrene-reduced weight average molecular weight of the polyurethane-based resin measured by gel permeation chromatography (GPC) is preferably 5,000 to 1,000,000.

  Urethane-based paints include solvent-type polyurethane paints, water-based polyurethane paints, thermoplastic polyurethane paints, two-part polyurethane paints, one-part polyurethane paints, UV-curable polyurethane paints, moisture-curable polyurethane paints, and curing agent-curable types. Examples thereof include polyurethane paints and polyurethane emulsion paints. Among them, a thermoplastic polyurethane paint in which a polyurethane resin having no free isocyanate group is dissolved in a solvent; a two-component polyurethane paint in which a prepolymer having a free isocyanate group is reacted with a polyol; evaporation of the solvent, moisture in the air, Alternatively, a one-component polyurethane paint that is cured by heating or the like is preferable, and a one-component solvent-type polyurethane paint is more preferable.

Urethane adhesives include solvent-based polyurethane adhesives, water-based polyurethane adhesives, reactive polyurethane adhesives, hot-melt polyurethane adhesives, isocyanate single-component polyurethane adhesives, and isocyanate-mixed raw-material polyurethane adhesives (rubbers) Rubber-urethane adhesives produced by mixing isocyanates with isocyanates; vinyl urethane adhesives produced by mixing isocyanates with PVA aqueous solutions), thermoplastic polyurethane adhesives, two-part polyurethane adhesives, one-part Examples thereof include an adhesive polyurethane adhesive, an ultraviolet curable polyurethane adhesive, a moisture curable polyurethane adhesive, a curing agent curable polyurethane adhesive, and a polyurethane emulsion adhesive.
Among them, a thermoplastic polyurethane adhesive in which a polyurethane resin having no free isocyanate group is dissolved in a solvent; a two-component polyurethane adhesive in which a prepolymer having a free isocyanate group and a polyol are reacted; evaporation of the solvent, in the air A one-component polyurethane adhesive that cures by moisture or heating is preferable, and a two-component polyurethane adhesive is more preferable.

  Urethane adhesives include solvent-based polyurethane adhesives, water-based polyurethane adhesives, two-component polyurethane adhesives, one-component polyurethane adhesives, UV-curable polyurethane adhesives, moisture-curable polyurethane adhesives, and curing agents. Examples thereof include a curable polyurethane pressure-sensitive adhesive and a polyurethane emulsion-type pressure-sensitive adhesive. Among these, a two-component polyurethane pressure-sensitive adhesive that reacts a prepolymer having a free isocyanate group with a polyol; a one-component polyurethane pressure-sensitive adhesive that cures by evaporation of solvent, moisture in the air, or heating is preferable. More preferred is a solvent-soluble polyurethane adhesive.

  The acrylic resin contained in acrylic paints, adhesives, and pressure-sensitive adhesives can be obtained by synthesizing acrylic or methacrylic monomers by conventional polymerization methods such as radical polymerization, cationic polymerization, and anionic polymerization. A conventionally known acrylic resin can be used. Hereinafter, “acryl” and “methacryl” are also referred to as “(meth) acryl”.

  Specific examples of the (meth) acrylic monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth). Acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) Acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl (meth) acrylate, EO-modified (meth) acrylate, PO-modified (meth) acrylate, dicyclopentenyl (meth) acrylate , Tetramethylpiperidyl (meth) acrylate, pentamethylpiperidyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- ( (Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-1,2 , 2,6,6-pentamethylpiperidine, etc. . These (meth) acrylic monomers can be used singly or in combination of two or more. In addition to the above monomers, styrene monomers and acrylonitrile monomers can also be used.

  The acrylic resin can be obtained by polymerizing an acrylic or methacrylic monomer by a conventionally known polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.

  The kind of solvent used in the solution polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction. Specific examples of the solvent include water; methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, n-pentyl alcohol, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ethylene Alcohol solvents such as glycol, propylene glycol and diethylene glycol; aliphatic hydrocarbon solvents such as petroleum ether, hexane and heptane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; diethyl ether, dibutyl ether and tetrahydrofuran (THF), ether solvents such as dioxane; methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, 2-octa Ketone solvents such as ethyl, cyclohexanone, cyclopentanone and methyl isobutyl ketone; ester solvents such as ethyl acetate, propyl acetate and butyl acetate; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N- Examples include amide solvents such as methylpyrrolidone (NMP). The amount of solvent used is appropriately determined depending on the conditions of the polymerization reaction. Usually, it is about 0.1 to 100 times, preferably about 0.2 to 20 times by mass ratio to the polymerization component. In addition, these solvents can be used individually by 1 type or in combination of 2 or more types.

  Conventional polymerization initiators can be used. Specific examples of the polymerization initiator include peroxides such as benzoyl peroxide, dibutyl peroxide and cumene hydroperoxide; azo polymerization such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). Mention may be made of initiators. These polymerization initiators can be used singly or in combination of two or more. Although the usage-amount of a polymerization initiator is not specifically limited, Usually, it is about 0.1-10 mass% with respect to a polymerization component.

  The temperature of the polymerization reaction is appropriately set depending on the reaction conditions. Usually, the temperature may be any temperature from room temperature (25 ° C.) to the boiling point of the solvent used. In order to adjust the polymerization degree of the acrylic resin, a chain transfer agent such as mercaptans or a polymerization inhibitor such as hydroquinone may be added to the polymerization reaction system.

  The polystyrene-reduced weight average molecular weight of the acrylic resin measured by gel permeation chromatography (GPC) is preferably 1,000 to 1,500,000, and is 5,000 to 1,000,000. More preferably.

  Acrylic paints can have various coating strengths by combining hard monomers (methacrylic acid and esters thereof) and soft monomers (acrylic acid and esters thereof). Acrylic paints include solvent-type thermoplastic acrylic resin paints (acrylic lacquer paints), solvent-type curable acrylic resin paints (two-component reactive paints, baking dry paints, etc.), water-soluble acrylic resin paints, and emulsion-type acrylics. Examples thereof include resin paints and acrylic-modified alkyd resin paints. Among these, a fast-drying acrylic lacquer coating mainly composed of a hard monomer and the solvent in the coating evaporates to form a dry coating film, and a two-component reaction type acrylic resin coating of an acrylic resin and a crosslinking agent (isocyanate, etc.) are preferable. A solvent-type thermoplastic acrylic resin paint is more preferable.

  Examples of the acrylic pressure-sensitive adhesive include a solvent type (solution type), an emulsion type, a hot melt type, and an oligomer syrup type. Of these, solvent-type and emulsion-type pressure-sensitive adhesives are preferable.

  As the solvent-type pressure-sensitive adhesive, three types of monomers, a main monomer that exhibits adhesiveness, a comonomer that exhibits cohesiveness, and a functional group-containing monomer that contributes to the improvement of adhesive force and serves as a crosslinking base point, are used in a solvent. A copolymer obtained by radical polymerization using an initiator is preferred. As the main monomer, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or the like can be used. As the comonomer, vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate and the like can be used. As functional group-containing monomers, acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate Diethylaminoethyl methacrylate, acrylamide, methylol acrylamide, glycidyl methacrylate, maleic anhydride and the like can be used. As the emulsion-type pressure-sensitive adhesive, a base polymer containing an aqueous medium, which is obtained by polymerizing a surfactant added to a monomer, is used. A solvent-type acrylic pressure-sensitive adhesive or the like is particularly preferably used.

  As the transparent substrate film constituting the transparent film of the present invention, those having excellent transparency, mechanical strength, thermal stability, moisture shielding property, isotropy and the like are preferable. Materials constituting the base film include glass; polyester polymers such as polyethylene terephthalate and polyethylene naphthalate; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; acrylic polymers such as polymethyl methacrylate; polystyrene, acrylonitrile and styrene. Examples thereof include styrene polymers such as copolymers (AS resins); polycarbonate polymers and the like.

  Polyethylene, polypropylene, polyolefin having a ring structure or norbornene structure, polyolefin polymers such as ethylene / propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfite polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, fluorine Polymers, silicon-based polymers, blends of these polymers, and the like can also be cited as materials (polymers) constituting the base film.

  Suitable examples of transparent substrate films include glass, acrylic, polyester, polyethylene terephthalate, polyvinyl butyral, polyurethane, polyethylene, polypropylene, polycarbonate, polystyrene, polyimide, polyamide, vinyl chloride, polyethersulfone, polyetheretherketone, polyphenylene. Examples thereof include films made of sulfide, cellulose, acrylic silicon, fluororesin, and the like. Among these, a biaxially stretched polyethylene terephthalate film is preferable because it can ensure the strength necessary for various applications.

  The thickness of the base film is preferably 20 to 100 μm, and more preferably 25 to 40 μm. These substrate films may be subjected to corona treatment, antistatic treatment, easy adhesion treatment, and the like as necessary.

  Furthermore, it is also preferable to use a conventionally known transparent material and a composite oxide black pigment in combination within a range not impairing the effects of the present invention. For example, as a transparent infrared cut material, it is preferable to mix and use a composite oxide black pigment in order to compensate for effects that cannot be obtained with colorless and transparent ITO (tin-doped indium oxide) or ATO (antimony-doped tin oxide).

  Further, for the purpose of imparting slipperiness and water resistance, for example, silicone oil and / or modified silicone oil (for example, polydimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, alkyl-modified polydimethylsiloxane), Various waxes, acrylic polymers, long-chain alkyl-modified polymers, fluorine-modified polymers, siloxane-modified polymers, and the like can be added to the coating composition.

  In addition, conventional additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, and a filler are added to the coating composition as long as the effects of the present invention are not impaired. It can aim, or can give functionality or design nature.

  Hereinafter, the present invention will be described more specifically based on examples. In the following text, “parts” and “%” are based on mass unless otherwise specified.

(Production of complex oxide black pigment)
[Production Example 1]
Water was added and completely dissolved in 120 parts of copper sulfate, 130 parts of manganese sulfate, and 53.4 parts of iron sulfate to prepare 1000 parts of a mixed salt aqueous solution. In addition, water was added to 120 parts of caustic soda and completely dissolved to prepare 1000 parts of an aqueous caustic soda solution. The prepared mixed salt aqueous solution and caustic soda aqueous solution were simultaneously added dropwise to 1600 parts of water as a precipitation medium to complete the precipitation reaction over 1 hour. The pH of the reaction solution was adjusted to a range of 12.0 to 13.0. Further, after the dropwise addition of the mixed salt aqueous solution was completed, the excess caustic soda aqueous solution was dropped as it was. After completion of the dropwise addition, a solution obtained by diluting 60 parts of hydrogen peroxide (hydrogen peroxide concentration: 35%) into 120 parts of water was added dropwise to oxidize.

After completion of the oxidation treatment, the liquid temperature was raised to 80 ° C. and aging was performed for 1 hour. After thoroughly washing with water to wash away residual salts, the product obtained by filtration was dried at 100 to 140 ° C. to obtain a dried product. The obtained dried product was baked at 580 ° C. for 1 hour to obtain a baked product. The obtained fired product was pulverized to obtain a composite oxide black pigment 1 having a BET specific surface area of 51.2 m ² / g. The obtained composite oxide black pigment 1 was subjected to powder X-ray diffraction analysis and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 1.

[Production Example 2]
Except that 120 parts of copper sulfate, 130 parts of manganese sulfate, and 53.4 parts of iron sulfate were used, and 3.6 parts of calcium chloride were dissolved in the precipitation medium (water), the same as in Production Example 1 described above. As a result, a composite oxide black pigment 2 having a BET specific surface area of 54.8 m ² / g was obtained. The obtained composite oxide black pigment 2 was subjected to powder X-ray diffraction analysis and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 2.

[Production Example 3]
A composite oxide black having a BET specific surface area of 47.5 m ² / g, in the same manner as in Production Example 2 except that 120 parts of copper sulfate, 144.4 parts of manganese sulfate and 29.7 parts of iron sulfate were used. Pigment 3 was obtained. The obtained composite oxide black pigment 3 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 3.

[Production Example 4]
A composite oxide black having a BET specific surface area of 43.3 m ² / g in the same manner as in Production Example 2 except that 120 parts of copper sulfate, 152.1 parts of manganese sulfate, and 16.7 parts of iron sulfate were used. Pigment 4 was obtained. The obtained composite oxide black pigment 4 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 4.

[Production Example 5]
Except for using 120 parts of copper sulfate, 144.4 parts of manganese sulfate, and 29.7 parts of iron sulfate, and dissolving 5.0 parts of magnesium chloride together with calcium chloride in the precipitation medium (water). In the same manner as in Example 2, composite oxide black pigment 5 having a BET specific surface area of 49.2 m ² / g was obtained. The obtained composite oxide black pigment 5 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 5.

[Production Example 6]
A composite oxide black pigment 6 having a BET specific surface area of 40.6 m ² / g was prepared in the same manner as in Production Example 2 except that 120 parts of copper sulfate, 157 parts of manganese sulfate and 8.6 parts of iron sulfate were used. Got. The obtained composite oxide black pigment 6 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 6.

[Production Example 7]
A composite oxide black having a BET specific surface area of 50.6 m ² / g, as in Production Example 2 except that 132 parts of copper sulfate, 144.4 parts of manganese sulfate and 29.7 parts of iron sulfate were used. Pigment 7 was obtained. The obtained composite oxide black pigment 7 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 7.

[Production Example 8]
Except that 120 parts of copper sulfate, 130 parts of manganese sulfate, and 53.4 parts of iron sulfate were used, and that 1.4 parts of calcium chloride was dissolved in the precipitation medium (water), the same as in Production Example 2 described above. As a result, a composite oxide black pigment 8 having a BET specific surface area of 52.6 m ² / g was obtained. The obtained composite oxide black pigment 8 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 8.

[Production Example 9]
Except that 120 parts of copper sulfate, 130 parts of manganese sulfate, and 53.4 parts of iron sulfate were used, and 7.2 parts of calcium chloride were dissolved in the precipitation medium (water), the same as in Production Example 2 described above. As a result, a composite oxide black pigment 9 having a BET specific surface area of 56.7 m ² / g was obtained. The obtained composite oxide black pigment 9 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 9.

[Production Example 10]
A composite oxide black having a BET specific surface area of 47.3 m ² / g in the same manner as in Production Example 2 except that 120 parts of copper sulfate, 121.7 parts of manganese sulfate and 66.7 parts of iron sulfate were used. Pigment 10 was obtained. The obtained composite oxide black pigment 10 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 10.

[Production Example 11]
A composite oxide black having a BET specific surface area of 49.5 m ² / g in the same manner as in Production Example 2 except that 108 parts of copper sulfate, 144.4 parts of manganese sulfate and 29.7 parts of iron sulfate were used. Pigment 11 was obtained. The obtained composite oxide black pigment 11 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 11.

[Production Example 12]
A composite oxide black having a BET specific surface area of 36.5 m ² / g, as in Production Example 2, except that 120 parts of copper sulfate, 157.6 parts of manganese sulfate and 7.4 parts of iron sulfate were used. Pigment 12 was obtained. The obtained composite oxide black pigment 12 was subjected to powder X-ray diffraction analysis and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 12.

[Production Example 13]
A composite oxide black having a BET specific surface area of 29.4 m ² / g, as in Production Example 2, except that 156 parts of copper sulfate, 144.4 parts of manganese sulfate and 29.7 parts of iron sulfate were used. Pigment 13 was obtained. The obtained composite oxide black pigment 13 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. In addition, Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 13.

(Film production)
[Example 1]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100 g of polyester polyol (condensate of adipic acid and 1,4-butanediol, OHv = 112 mgKOH / g, Av = 0.1 mgKOH / g), and 57.2 g of toluene. Prepared. After heating and stirring was started and the inside of the system became uniform, 33.5 g of hexamethylene diisocyanate (HDI) was added at 50 ° C. (NCO group was twice equivalent to OH group), and the temperature was raised to 80 ° C. For 3 hours to obtain a urethane prepolymer solution. After adding 93.3 g of DMF to the obtained urethane prepolymer solution and cooling to 40 ° C., 17 g of isophoronediamine (IPDA) was added dropwise to react with the NCO group of the urethane prepolymer. Stirring until 2,270 cm ⁻¹ absorption due to free isocyanate groups, as measured by infrared absorption spectrum analysis, disappeared to obtain a polyurethane resin PU1 solution having a weight average molecular weight of 71,000 (solid content 50%). .

  A solution of the composite oxide black pigment 1 and the polyurethane resin PU1 is put in a paint shaker (manufactured by Red Devil) with a pigment content of 1 PHR (PHR = (pigment (g) / resin (g)) × 100). Pigment 1 was sufficiently dispersed to form a paint to obtain a paint. The obtained paint was applied onto a PET film with a # 6 bar coater and then dried to obtain a sample film E1. The film thickness of the coating film formed on the obtained sample film E1 was 3 to 4 μm. Using a haze meter (trade name “HGM-2DP”, manufactured by Suga Test Instruments Co., Ltd.), the haze value (haze value (%) = (diffuse transmittance / total light transmittance) of the obtained sample film E1 by the C light source ) × 100). The haze value of the sample film E1 was 2.7%, and it was confirmed that the sample film E1 was excellent in transparency (Table 2).

[Example 2]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 100 g of methyl methacrylate and 42.9 g of toluene were charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. After reacting for 8 hours, 57.1 g of toluene was added to obtain a solution of acrylic resin AC1 having a weight average molecular weight of 53,000 (solid content concentration 50%).

  The composite oxide black pigment 1 and the acrylic resin AC1 are put in a paint shaker (manufactured by Red Devil) with a pigment content of 1 PHR (PHR = (pigment (g) / resin (g)) × 100), and the composite oxide black pigment 1 Was sufficiently dispersed to form a paint to obtain a paint. The obtained paint was applied on a PET film with a # 6 bar coater and then dried to obtain a sample film E2. The film thickness of the coating film formed on the obtained sample film E2 was 3 to 4 μm. The haze value of the sample film E2 was 2.8%, and it was confirmed that the sample film E2 was excellent in transparency (Table 2).

[Example 3]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100 g of polyester polyol (condensate of adipic acid and 1,3-butanediol, OHv = 112 mgKOH / g, Av = 0.1 mgKOH / g), and 53.6 g of toluene. Prepared. After heating and stirring was started and the inside of the system became uniform, 25.0 g of 4,4′-methylenebis (phenylene isocyanate) (MDI) was added at 50 ° C., and the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until 2,270 cm ⁻¹ absorption due to free isocyanate groups disappeared, as measured by infrared absorption spectrum analysis, and then 71.4 g of toluene was added to give a polyurethane resin having a weight average molecular weight of 65,000. A solution of PU2 (solid content 50%) was obtained.

  Composite oxide black pigment 1, a resin in which polyurethane resin PU2 solution and a crosslinking agent (trade name “Coronate HX”, manufactured by Nippon Polyurethane Co., Ltd., NV = 100%, NCO = 11%) are blended at 100/5, The pigment content is 1 PHR (PHR = (pigment (g) / resin (g)) × 100) is put in a paint shaker (manufactured by Red Devil), and the composite oxide black pigment 1 is sufficiently dispersed to form a paint. Got. The obtained adhesive paint was applied onto a PET film with a # 6 bar coater and then dried to obtain a sample film E3. The film thickness of the coating film formed on the obtained sample film E3 was 3 to 4 μm. The haze value of the sample film E3 was 3.1%, and it was confirmed that the sample film E3 was excellent in transparency (Table 2).

[Example 4]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with nitrogen gas, 100 g of polyester polyol (polypropylene glycol, OHv = 112 mgKOH / g) and 53.6 g of MEK were charged. After heating and stirring was started and the inside of the system became uniform, 25.0 g of MDI was added at 50 ° C., and the temperature was raised to 80 ° C. for reaction. The reaction was allowed to proceed until 2,270 cm ⁻¹ absorption due to free isocyanate groups disappeared, as measured by infrared absorption spectrum analysis. Then, 71.4 g of MEK was added, and polyurethane resin PU3 having a weight average molecular weight of 62,000. Solution (solid content 50%) was obtained.

  A solution of the composite oxide black pigment 1 and the polyurethane resin PU3 is put in a paint shaker (manufactured by Red Devil) with a pigment content of 1 PHR (PHR = (pigment (g) / resin (g)) × 100). Pigment 1 was sufficiently dispersed to form a paint, and an adhesive paint was obtained. The obtained pressure-sensitive adhesive paint was applied onto a PET film with a # 6 bar coater and then dried to obtain a sample film E4. The film thickness of the coating film formed on the obtained sample film E2 was 3 to 4 μm. The haze value of the sample film E4 was 3.1%, and it was confirmed that the sample film E4 was excellent in transparency (Table 2).

[Example 5]
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 100 g of butyl acrylate and 66.7 g of toluene were charged. After heating to 80 ° C. in a nitrogen atmosphere, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. After reacting for 8 hours, 33.3 g of toluene was added to obtain a solution of acrylic resin AC2 having a weight average molecular weight of 136,000 (solid content concentration 50%).

  A solution of the composite oxide black pigment 1 and the acrylic resin AC2 is put in a paint shaker (manufactured by Red Devil) with a pigment content of 1 PHR (PHR = (pigment (g) / resin (g)) × 100). Pigment 1 was sufficiently dispersed to form a paint, and an adhesive paint was obtained. The obtained pressure-sensitive adhesive paint was applied onto a PET film with a # 6 bar coater and then dried to obtain a sample film E5. The film thickness of the coating film formed on the obtained sample film E5 was 3 to 4 μm. The haze value of the sample film E5 was 3.0%, and it was confirmed that the sample film E5 was excellent in transparency (Table 2).

[Example 6]
A coating film was prepared and a sample film E6 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 2 was used. The haze value of the sample film E6 was 3.4%, and it was confirmed that the sample film E6 was excellent in transparency (Table 2).

[Example 7]
A paint was prepared and a sample film E7 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 3 was used. The haze value of the sample film E7 was 2.6%, and it was confirmed that the sample film E7 was excellent in transparency (Table 2). The sample film E7 had particularly good sharpness and was more bluish than the sample film E6.

[Example 8]
A paint was prepared and a sample film E8 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 4 was used. The haze value of the sample film E8 was 3.2%, and it was confirmed that the sample film E8 was excellent in transparency (Table 2). The sample film E8 had particularly good sharpness and was more bluish than the sample film E6.

[Example 9]
A paint was prepared and a sample film E9 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 5 was used. The haze value of the sample film E9 was 2.8%, and it was confirmed that the sample film E9 was excellent in transparency (Table 2). The sample film E9 had particularly good sharpness and was more bluish than the sample film E6.

[Example 10]
A coating film was prepared and a sample film E10 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 6 was used. The haze value of the sample film E10 was 2.6%, and it was confirmed that the sample film E10 was excellent in transparency (Table 2). The hue of the sample film E10 was the same as that of the sample film E6, but was slightly dull and the coloring power was slightly lowered.

[Example 11]
A paint was prepared and a sample film E11 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 7 was used. The haze value of the sample film E11 was 3.0%, and it was confirmed that the sample film E11 was excellent in transparency (Table 2). The sample film E11 had particularly good sharpness and strong bluishness. The hue of the sample film E11 was the same as that of the sample film E7.

[Example 12]
A paint film was prepared and a sample film E12 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 8 was used. The haze value of the sample film E12 was 3.2%, and it was confirmed that the sample film E12 was excellent in transparency (Table 2).

[Example 13]
A paint was prepared and a sample film E13 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 9 was used. The haze value of the sample film E13 was 3.5%, and it was confirmed that the sample film E13 was excellent in transparency (Table 2).

[Comparative Example 1]
A coating film was prepared and a sample film C1 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 10 was used. The haze value of the sample film C1 was 3.0%. Moreover, this sample film C1 was inferior in sharpness, and the hue was yellowish (yellowish dullness).

[Comparative Example 2]
A coating film was prepared and a sample film C2 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 11 was used. The haze value of the sample film C2 was 3.8%. In addition, the hue of the sample film C2 was higher than that of the sample film of Example 1, was not bluish, and was inferior in coloring power.

[Comparative Example 3]
A coating film was prepared and a sample film C3 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 12 was used. The haze value of the sample film C3 was 4.2%. In addition, the hue of the sample film C3 was much better than that of the sample film of Example 1, was not bluish, and was inferior in coloring power.

[Comparative Example 4]
A coating film was prepared and a sample film C4 was prepared in the same manner as in Example 1 except that the composite oxide black pigment 13 was used. The haze value of the sample film C4 was 5.6%. In addition, the hue of the sample film C4 was much higher than that of the sample film of Example 1, and was whitish black and unclear.

[Comparative Example 5]
A coating film was prepared and a sample film C5 was produced in the same manner as in Example 1 except that carbon black (CB) was used. The haze value of the sample film C5 was 6.5%. This sample film C5 was inferior in sharpness, and the hue was yellowish and dull (yellowish).

About the sample films E7, C1, and C5, L value, a value, and b value in the CIE LAB (L ^* a ^* b ^* ) color system were measured. Table 3 shows the measurement results. As shown in Table 3, both the a value (a ^* ) and the b value (b ^* ) are negative values only in the sample film E7, and only the sample film E7 expresses a neutral gray color tone. I understand that.

  As shown in Tables 1 and 2, it can be seen that the hue of the sample film C1 (Comparative Example 1) produced using the composite oxide black pigment 10 containing a large amount of iron in the composition is yellowish.

Claims (8)

A transparent base film, and a colored layer made of a coating composition disposed on at least one surface of the base film,
The coating composition has a characteristic of absorbing visible light and near infrared light, and is composed of oxides of main component metals including copper, manganese, and iron, and a molar ratio of manganese / iron is 3/1 to 30/1. A black transparent film having a bluish color, containing a composite oxide black pigment (A) having a copper / (manganese + iron) molar ratio of 1/2 to 1.2 / 2.   The black transparent film having bluish color according to claim 1, wherein the coating composition further contains a plastic paint (B).   The black transparent film having bluish color according to claim 1, wherein the coating composition further contains a transparent adhesive (C).   The black transparent film having a bluish color according to claim 1, wherein the coating composition further contains a transparent pressure-sensitive adhesive (D). The composite oxide black pigment (A) has a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ and has a BET specific surface area of 30 m ² / g or more. A black transparent film having the bluish color according to claim 1.   6. The composite oxide black pigment (A) according to claim 1, wherein at least one of divalent metals of calcium and magnesium is introduced at a ratio of 2 to 10 mol% with respect to the copper. A black transparent film having the blueness described. The black transparent film having a bluish color according to any one of claims 1 to 6, wherein the composite oxide black pigment (A) has a BET specific surface area of 40 m ² / g or more. In the CIE LAB (L ^* a ^* b ^* ) color system, the a value is -4 to 0 and the b value is -8 to 0. The bluishness according to any one of claims 1 to 7. A black transparent film having