JP2005146023A - Coating film made of chromogenic polymer structure, coating film-forming method and coating material - Google Patents

Coating film made of chromogenic polymer structure, coating film-forming method and coating material Download PDF

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JP2005146023A
JP2005146023A JP2003381747A JP2003381747A JP2005146023A JP 2005146023 A JP2005146023 A JP 2005146023A JP 2003381747 A JP2003381747 A JP 2003381747A JP 2003381747 A JP2003381747 A JP 2003381747A JP 2005146023 A JP2005146023 A JP 2005146023A
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coating film
block copolymer
coating
forming
containing
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JP4581377B2 (en
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Katsunori Funaki
Koji Kondo
Kiyoharu Tsutsumi
聖晴 堤
克典 舩木
晃次 近藤
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Daicel Chem Ind Ltd
Toyota Motor Corp
ダイセル化学工業株式会社
トヨタ自動車株式会社
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Abstract

PROBLEM TO BE SOLVED: To obtain a coating film that self-constructs a coloring structure and exhibits an interference color excellent in design without containing a pigment.
The coating film of the present invention has a microphase-separated structure formed from a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are bonded, and each phase of the microphase-separated structure. The unit cell spacing D (nm) formed by the above is such that the incident angle (θ) of the light with respect to the lattice surface is any angle of 0 ° <θ ≦ 90 °, and N and m are independent from 1 to 10. When it is any integer, it is characterized by comprising a chromophoric polymer structure satisfying the following formula (1).
350 (nm) ≦ N (2nD sin θ) / m ≦ 800 (nm) (1)
(Where n is the average refractive index of the block copolymer)
[Selection figure] None

Description

  The present invention relates to a coating film using color development based on a microphase-separated structure formed by a block copolymer, a method for forming the coating film, and a coating material for forming the coating film. The coating film and paint are useful as a coating film and paint for automobiles and decorations.

  Common pigments used in paints are roughly classified into colored pigments and bright pigments. Coloring pigments include inorganic materials such as petals, yellow lead, bitumen, titanium oxide, and carbon black, and organic pigments such as phthalocyanine, quinacridone, and azo pigments, which use light absorption depending on the molecular structure. It has a developed coloring mechanism. Further, as the bright pigment, there are pigments typified by aluminum flake pigments and various pearl pigments, and these have the effect of imparting a bright feeling to the coating film by utilizing the light reflecting action.

  In recent years, with the diversification of values, the design appearance of the coating film is required to have a novel design (for example, grain feeling) different from the design obtained from conventional colored pigments and bright pigments. became. Since the color development in conventional colored pigments is due to light absorption, there are problems such as lowering the overall lightness due to subtractive color mixing when using several pigments, and this will extend the design of the coating film. Are naturally limited.

  Japanese Patent No. 3233883 discloses a diblock copolymer having a specific molecular weight in which two types of polymer chains that are incompatible with each other and having different refractive indexes are combined, and a homopolymer that is compatible with the block chain of the diblock copolymer. A chromophoric polymer structure comprising a microphase-separated structure formed from the above and having a lattice spacing formed by each layer of the microphase-separated structure in a specific range is disclosed. Although this document describes that the color-forming polymer structure can be used as it is as a decorative plate or a plastic material for decoration without being colored by a pigment or the like, a method for forming the block copolymer into a paint or the paint There is no description about forming a coating film using the.

Japanese Patent No. 3233883

  SUMMARY OF THE INVENTION An object of the present invention is to provide a paint and a coating film that self-constructs a coloring structure and exhibits an interference color excellent in design without containing a pigment, and a method for forming the coating film.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors obtain a chromophoric polymer structure having a micro phase separation structure having a specific characteristic formed from a specific block copolymer by dissolving it in a solvent. It was found that when a paint is applied to the surface of an object to be coated and the solvent is evaporated, a coating film exhibiting an interference color with high chroma and excellent design can be obtained.

That is, the present invention has a microphase-separated structure formed from a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are bonded, and a unit formed by each phase of the microphase-separated structure The grating interval D (nm) is an angle where the incident angle (θ) of the light with respect to the grating surface is 0 ° <θ ≦ 90 °, and N and m are any integers of 1 to 10, which are independent of each other. In some cases, a coating film comprising a color forming polymer structure satisfying the following formula (1) is provided.
350 (nm) ≦ N (2nD sin θ) / m ≦ 800 (nm) (1)
(Where n is the average refractive index of the block copolymer)

In this coating film, the wavelength at the reflected light wavelength from the Nth lattice plane from the coating surface characterized by the lattice spacing D formed by each phase of the microphase separation structure and the average refractive index n of the block copolymer. It is preferable that the reflectance is 30% or more when the light is incident at an angle of 90 ° with respect to the coating film surface. In a preferred coating film, the difference between the solubility parameter of at least one polymer block chain in the block copolymer and the solubility parameter of the material to be coated is 5 (J / cm 3 ) 1/2 or less.

  The present invention is also a method for forming the above-mentioned coating film on the surface of an object to be coated, wherein a solution containing at least a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are combined and a solvent is coated. Provided is a coating film forming method including a step of directly applying to a body surface and a step of evaporating a solvent.

  This coating film forming method further includes (a) a step of incorporating a homopolymer compatible with the block chain of the block copolymer before completion of the coating film formation, and (b) crosslinking of the block copolymer before completion of the coating film formation. A step of incorporating an agent into the system, and a step of crosslinking the block copolymer with the crosslinking agent, and (c) a polymerizable monomer that can be polymerized by itself and is compatible with the block copolymer before the film formation is completed. And a step of polymerizing the polymerizable monomer, or (d) a step of using a block copolymer containing a basic nitrogen atom-containing group as a block copolymer and adding a halogen compound to the system before the completion of the formation of the color-forming thin film. And a quaternization reaction of the nitrogen atom in the block copolymer containing the basic nitrogen atom-containing group with the halogen compound The emissions hydride ion may include the step of liberating.

  The present invention also provides a paint capable of forming the above-mentioned coating film, which comprises at least a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are bonded, and a solvent.

  The paint may further comprise (i) a homopolymer compatible with the block chain of the block copolymer, (ii) a crosslinking agent of the block copolymer, or (iii) a polymerizable monomer compatible with the block copolymer. In addition, (iv) a block copolymer containing a basic nitrogen atom-containing group may be contained, and a halogen compound may be further contained.

  According to the coating film of the present invention, even if it does not contain a pigment, it builds a color developing structure itself and expresses an interference color with excellent design. Therefore, a new design property can be created and the design property can be expanded. Moreover, the coating film of the present invention does not cause a decrease in lightness while ensuring high saturation and high reflection color. According to the coating film forming method and the coating material of the present invention, a coating film having the above excellent characteristics can be easily formed.

  A block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are chemically bonded at each end forms an ordered microphase-separated structure in which the sizes and intervals of the polymer phases are uniform. The chromophoric polymer structure constituting the coating film of the present invention has such a microphase separation structure and a unit cell interval formed by each phase of the microphase separation structure (repetition period length of the microphase separation structure). D (nm) is an incident angle (θ) of light with respect to the lattice plane being any angle of 0 ° <θ ≦ 90 °, and N and m are any one of independent integers 1 to 10 In the above, the above formula (1) is satisfied. Here, the color development by this grating is derived from the fact that light having a wavelength that is enhanced by the interference between the reflected light from the outermost surface (first grating surface) and the reflected light from the Nth grating surface from this surface can be seen. In addition, the reflected light from the same surface is strengthened with light having a wavelength of 1 / m of the fundamental wavelength (2nDsin θ).

When light is irradiated onto the diffraction grating, the light is reflected by the grating surface and interferes with each other, and the intensity of only the diffraction line in the direction satisfying the condition of the following expression (2) increases.
N (2Dsinθ) = mλ / n (2)
(Where D is the unit lattice spacing (surface spacing), N is the number of lattices in the depth direction from the surface, θ is the angle between the incident light and the lattice plane, λ is the wavelength of light, and m is an integer from 1 to 10. , N represents the refractive index of the material constituting the diffraction grating)
The formula (1) defines the condition (range visible to the human eye) in which the λ is the wavelength of visible light (350 to 800 nm) in the formula (2). That is, the color forming polymer structure constituting the coating film of the present invention has a lattice interval that can diffract visible light.

  Formula (1) indicates that any angle in which θ is 0 ° <θ ≦ 90 ° (for example, 30 °, 45 °, 60 °, 90 °, etc.), and N and m are each independently 1 to 10 However, in particular, θ is 90 ° (that is, when light is incident perpendicularly to the coating surface) and N is an integer of 1 to 3 (particularly 1) (that is, the coating surface). In the case where light is reflected by the first to third lattice planes), it is preferable to satisfy the expression (1). N in Formula (1) shows the average refractive index of a block copolymer. The average refractive index means an arithmetic average value of refractive indexes of each block. n is usually about 1.4 to 1.7.

  The unit cell interval D is usually 80 nm or more, and more preferably about 100 to 1000 nm. The unit cell spacing D can be confirmed by observing with a transmission electron microscope.

  The block copolymer includes a diblock copolymer in which two polymer chains are bonded at each end, a triblock copolymer in which three polymer chains are bonded at each end, and the like. preferable.

  When the molecular weight of the block copolymer (the molecular weight of the block copolymer refers to the sum of the molecular weights of the blocks constituting the block copolymer) is large (for example, 5 million or more), the above formula ( The unit cell spacing D satisfying 1) can be obtained. However, when the molecular weight of the block copolymer is small, the lattice space is narrow by itself, and it is difficult to obtain a desired cell space. However, even if it is a block copolymer whose molecular weight is not so high, if a homopolymer that is compatible with one of these block chains (polymer chains) is mixed, the lattice spacing is expanded, so the above formula (1) is satisfied. The unit cell interval D to be obtained can be obtained. In this case, a homopolymer compatible with one block chain and a homopolymer compatible with another block chain may be used in combination. Also, the desired unit cell spacing D can be obtained by expanding the lattice spacing by crosslinking the block copolymer with a crosslinking agent capable of crosslinking the block copolymer during or after the formation of the coloring structure (color-forming coating film). Furthermore, a desired unit cell spacing can be obtained by polymerizing a polymerizable monomer that is capable of polymerizing itself at the time of or after the formation of the color developing structure (color forming coating film) and is compatible with the block copolymer. D can also be obtained.

  The molecular weight of the block copolymer is usually 200,000 or more, preferably 300,000 or more, more preferably 400,000 or more, and particularly preferably 500,000 or more. When the molecular weight of the block copolymer is less than 200,000, the amount of homopolymer to be mixed increases, so that the regularity of the formed microphase separation structure tends to be disturbed. The upper limit of the molecular weight of the block copolymer is not particularly limited, but is preferably 1 million or less from the viewpoint of ease of synthesis.

  As the block copolymer, a wide variety of block copolymers may be used as long as the plurality of block chains constituting the block copolymer are incompatible with each other and have different refractive indexes. In order to develop a strong color with a small thickness, the refractive index difference is preferably as large as possible. For example, the refractive index difference (Δn) is 0.05 or more, more preferably 0.07 or more. The upper limit of the refractive index difference is not particularly limited, but is generally about 0.4. The block copolymer can be produced by a known method such as radical polymerization, living polymerization (living anion polymerization, etc.), but a commercially available product may be used.

  As typical examples of the block copolymer suitable for obtaining the chromogenic polymer structure in the present invention, diblock copolymer (PS-b-PMMA) composed of polystyrene (PS) and polymethyl methacrylate (PMMA), PS and polybutadiene (PB) diblock copolymer (PS-b-PB), poly2-vinylpyridine (P2VP) and PMMA diblock copolymer (P2VP-b-PMMA), PS and polyisoprene (PI) diblock Copolymer (PS-b-PI), diblock copolymer composed of P2VP and PI (P2VP-b-PI), diblock copolymer composed of PMMA and PI (PMMA-b-PI), diblock copolymer composed of PMMA and PB ( PMMA-b-PB), poly-2-vinyl naphth Diblock copolymer (P2VN-b-PMMA) composed of Len (P2VN) and PMMA, diblock copolymer (P2VN-b-PBA) composed of P2VN and polybutyl acrylate (PBA), poly-4-vinylpyridine (P4VP) and PMMA Diblock copolymer (P4VP-b-PMMA), diblock copolymer (P2VP-b-PBA) composed of P2VP and PBA, diblock copolymer (PVC) composed of polyvinylcarbazole (PVC) and poly t-butyl methacrylate (PtBMA) -B-PtBMA), diblock copolymer of PS and polypentafluoropropyl acrylate (PPPFA) (PS-b-PPPFA), P2VN and polytrifluoroisopropyl methacrylate (PTFIPMA) Diblock copolymer (PS-b-PTFIPMA) but the like made, these are examples, not intended to be limited thereto.

  Suitable block copolymers include, as block chains, polymers of aromatic vinyl compounds (polystyrene, polyvinyl naphthalene, polyvinyl pyridine, polyvinyl carbazole, etc.), polymers of (meth) acrylic acid esters (polymethacrylate, polyacrylate), and Block copolymer having a block chain made of a polymer selected from polymers of conjugated dienes (polybutadiene, polyisoprene, etc.), for example, a diblock of a polymer of an aromatic vinyl compound and a polymer of a (meth) acrylic acid ester Copolymers, diblock copolymers of a polymer of an aromatic vinyl compound and a polymer of a conjugated diene, a diblock copolymer of a polymer of a (meth) acrylic ester and a polymer of a conjugated diene are included.

  In the coating film of the present invention, in order to obtain high chroma color development, the unit lattice spacing D formed by each phase of the microphase separation structure, the number N of lattices in the depth direction from the coating surface, the average refraction of the block copolymer In the reflected light wavelength characterized by the rate n, the reflectance when light of that wavelength is incident on the surface of the coating film at an angle of 90 ° is 30% or more, particularly 60% or more (especially 80% or more). Is preferred. The reflectance can be obtained by computer simulation using commercially available refractive index calculation software.

  The coating film of the present invention may be composed of only one kind of the above-mentioned chromophoric polymer structure, but it is composed of a mixture of two or more chromophoric polymer structures having different hues (different color development wavelengths). It may be. When a mixture of two or more kinds of color-forming polymer structures is used, various kinds of high-design colors (eg, iridescence and pearly luster) can be obtained depending on the combination and mixing ratio.

In the coating film of the present invention, the difference between the solubility parameter of at least one polymer block chain in the block copolymer and the solubility parameter of the material to be coated (surface material) is 5 (J / cm 3 ) 1/2 or less, In particular, it is preferably 4 (J / cm 3 ) 1/2 or less. Such a coating film is excellent in adhesion to the surface of the object to be coated. As the solubility parameter, the value of the solubility parameter according to the method of Fedors [see Polym. Eng. Sci., 14, 147 (1974)] can be adopted. The solubility parameter of the polymer (polymer block chain) and the material to be coated can be determined by a known method, for example, a method described in documents such as “Polymer Handbook”, 4th edition. For such a coating film, first, the solubility parameter of the material to be coated is obtained, and within this range, within ± 5 (J / cm 3 ) 1/2 [particularly within ± 4 (J / cm 3 ) 1/2 ] Can be formed by selecting and using a block copolymer comprising a polymer block chain having a solubility parameter of

  Although the thickness of a coating film can be suitably selected in the range which does not impair the designability etc., it is 1-200 micrometers normally, Preferably it is about 5-50 micrometers. On the coating film of the present invention, another coating film (for example, a coating film using a clear paint) can be provided.

  The coating film of the present invention comprises a step of directly applying a solution containing at least a block copolymer having a plurality of polymer chains incompatible with each other and having different refractive indexes bonded to each terminal, and a solvent, to the surface of the object to be coated; and And a step of evaporating the solvent. A solution containing at least a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are bonded at each end exhibits a disordered mixed state. In this method, by increasing the molecular weight of the block copolymer, the control range of the hue of the coating film can be expanded. The solution containing at least a block copolymer in which a plurality of polymer chains having different refractive indexes and incompatible with each other are bonded at each end and a solvent is the coating material of the present invention.

  The solvent can be appropriately selected according to the type of block copolymer, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane and octane; and alicyclic groups such as cyclohexane and methylcyclohexane. Hydrocarbons; alcohols such as methanol, ethanol, isopropyl alcohol and butanol; esters such as ethyl acetate and butyl acetate; organic acids such as acetic acid; ketones such as acetone and methyl ethyl ketone; diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane Linear or cyclic ethers such as: nitriles such as acetonitrile and benzonitrile; aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide; triethylamine and tributy Nitrogen-containing aromatic compounds such as pyridine; amine such as an amine methylene chloride, halogenated hydrocarbons such as chloroform; water; and mixed solvents thereof.

  The material of the object to be coated is not particularly limited, and may be any of plastic (including a resin coating layer), glass, ceramics, concrete, metal, paper, and wood. The concentration of the block copolymer in the coating can be appropriately selected in consideration of viscosity, coating workability, solubility, etc., but generally 0.5 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 About 15% by weight. The coating material may contain components other than the block polymer and the solvent. Such components include homopolymers that are compatible with the block chain of the block copolymer described below, cross-linking agents for the block copolymer, polymerizable monomers that are compatible with the block copolymer, halogen compounds, other polymers, oils, Examples thereof include pigments, dyes, additives (plasticizers, desiccants, dispersants, etc.).

  The method for applying the paint to the surface of the object to be coated is not particularly limited, and a conventional method such as a coating method, a spray method, a dipping method, or the like can be employed. Further, drying of the coated film after application (evaporation of the solvent) is not particularly limited, and can be performed by a conventional method, for example, natural drying, heat drying, reduced pressure drying or the like.

  The method for forming the coating film further comprises: (a) a step of incorporating a homopolymer compatible with the block chain of the block copolymer into the system before the formation of the color forming coating film; A step of incorporating a block copolymer cross-linking agent (cross-linking monomer) into the system before completion of the formation and a step of cross-linking the block copolymer with the cross-linking agent; The method may include a step of containing a polymerizable monomer that is polymerizable and compatible with the block copolymer, and a step of polymerizing the polymerizable monomer. When these steps are provided, the unit cell spacing D is expanded while maintaining the coloring structure by inserting the homopolymer between the lattices, crosslinking the block copolymer, or inserting the polymerizable monomer between the lattices of the polymer. . Since the lattice spacing D can be controlled by adjusting the type and amount of the homopolymer, crosslinking agent, and polymerizable monomer to be added, the color of the coating film can be changed using the same block copolymer.

  In (a), examples of the homopolymer compatible with the block chain of the block copolymer include a homopolymer composed of the same monomer as the block chain. Such a homopolymer may be contained, for example, in a solution (paint) containing a block copolymer before coating, or may be contained in a solution containing a block copolymer after coating.

  In (b), the cross-linking agent for the block copolymer is not particularly limited as long as it can cross-link the block copolymer during or after the formation of the color developing structure. For example, the block copolymer is a basic nitrogen atom-containing group. (For example, a nitrogen-containing heterocyclic skeleton such as a pyridine skeleton or a quinoline skeleton, an N, N-disubstituted amino group or the like), the block copolymer is converted into a quaternary reaction of a nitrogen atom. A compound that can be crosslinked can be used. Representative examples of such compounds include dihalogen compounds such as diiodobutane (dihalogenated alkyls such as diiodoalkane and dibromoalkane). In the quaternization reaction using a dihalogen compound, halide ions are liberated as in the case of (d) described later, and this increases the refractive index of the phase of the block copolymer having quaternary ammonium ions. Further, there is an advantage that the reflectance at the lattice interface is increased and the color development becomes bright. The liberated halide ions can be exchanged with other anions (for example, hypohalite ions such as hypochlorite ions). For example, the crosslinking agent may be contained in a solution (paint) containing a block copolymer before coating, or may be contained in a solution containing a block copolymer after coating, or a coating film formed after coating (primary (Coating film) may be contained. Crosslinking is usually performed after the coating film (primary coating film) is formed (after solvent evaporation), and a final color-forming coating film is obtained by this crosslinking.

  In (c), the polymerizable monomer that can be polymerized by itself and is compatible with the block copolymer may be any monomer that can be polymerized by heat or the like at the time of forming a colored structure (including after formation). Either a functional monomer or a polyfunctional monomer may be used. Representative examples of such monomers include, for example, aromatic vinyl compounds (styrene, vinyl naphthalene, vinyl pyridine, vinyl carbazole, divinyl benzene, etc.), (meth) acrylic acid esters (bifunctional methacryl-modified products of bisphenol, etc.) Poly (meth) acrylic acid ester of a polyhydroxy compound), conjugated dienes and the like. Among these, polyfunctional monomers (for example, polyfunctional (meth) acrylic acid esters) are preferable in that the lattice spacing can be increased with a three-dimensional network structure and can be reliably expanded. The monomer is preferably a compound that does not volatilize, for example, a monomer having a boiling point of 150 ° C. or higher. When the polymerizable monomer is used, a polymerization initiator is usually used. Conventional polymerization initiators can be used. The polymerizable monomer may be contained, for example, in a solution (paint) containing a block copolymer before coating, or may be contained in a solution containing a block copolymer after coating. (Primary coating film) may be contained. Polymerization of the polymerizable monomer is usually carried out after the formation of the coating film (primary coating film) (after evaporation of the solvent) by heating, irradiation with light, etc., and a final color-forming coating film is obtained by this crosslinking. It is done. In addition, when performing both the process of said (b) and the process of (c), regardless of the order of bridge | crosslinking by a crosslinking agent and superposition | polymerization of a polymerizable monomer, you may perform bridge | crosslinking by a crosslinking agent first, and polymerizability. The polymerization of the monomer may be performed first.

  The use amount of each component of the homopolymer in (a), the cross-linking agent in (b), and the polymerizable monomer in (c) is not particularly limited, taking into account its type, color developability, operability, cost, etc. Generally, it is about 0 to 500 parts by weight (for example, 10 to 500 parts by weight), preferably 0 to 300 parts by weight (for example, 30 to 300 parts by weight) with respect to 100 parts by weight of the block copolymer. Part), more preferably about 0 to 200 parts by weight (for example, 50 to 200 parts by weight).

  The method for forming the coating film includes (d) a step of using a block copolymer containing a basic nitrogen atom-containing group as a block copolymer, and adding a halogen compound to the system before the completion of the formation of the color-forming coating film, and A step of liberating halide ions by quaternization reaction of nitrogen atoms in the block copolymer containing the basic nitrogen atom-containing group by the halogenated compound may be included. When this step is included, the liberated halide ions increase the refractive index of the phase of the block copolymer having quaternary ammonium ions, so that the reflectance at the lattice interface increases and the color development becomes clearer.

  Examples of the block copolymer containing a basic nitrogen atom-containing group include block polymers having a nitrogen-containing heterocyclic skeleton such as a pyridine skeleton and a quinoline skeleton, and an N, N-disubstituted amino group. The halogen compound may be any halogen compound that can cause a quaternization reaction of a nitrogen atom. For example, alkyl iodide such as methyl iodide, ethyl iodide, propyl iodide, butyl iodide; methyl bromide, odor And halogenated hydrocarbons such as alkyl bromide such as ethyl bromide, propyl bromide and butyl bromide. The halogen compound includes the dihalogen compounds exemplified as the crosslinking agent. Of these, iodinated hydrocarbons and brominated hydrocarbons are preferred as the halogen compounds. The halogen compound may be contained, for example, in a solution (paint) containing a block copolymer before coating, or may be contained in a solution containing a block copolymer after coating, or a coating film (first film) formed after coating. (Subsequent coating film) may be contained. The quaternization reaction is usually carried out under heating as necessary after the formation of the coating film (primary coating film) (after solvent evaporation), and liberation of halide ions by this quaternization reaction. As a result, a final color-developing coating film is obtained. The liberated halide ions can be exchanged with other anions (for example, hypohalite ions such as hypochlorite ions).

  The amount of the halogen compound used in the above (d) is not particularly limited and can be appropriately set in consideration of the type, color developability, operability, cost, etc. Generally, with respect to 100 parts by weight of the block copolymer, It is about 0-500 weight part (for example, 10-500 weight part), Preferably it is about 0-300 weight part (for example, 30-300 weight part), More preferably, it is about 0-200 weight part (for example, 50-200 weight part). It is.

  The color-forming microphase separation structure (color-forming structure) formed in this way is based on the volume fraction of each block chain phase (including the phases formed in the steps (a) to (d)). Although it can take forms (structures) such as lamellae and co-continuity, any form may be used from the viewpoint of color development.

  The coating film and coating material of the present invention are useful as, for example, coating films and coating materials for automobiles and decorations.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples.

Example 1
(Paint preparation)
Diblock copolymer (PS-b-PMMA) composed of polystyrene (PS) and polymethyl methacrylate (PMMA) (number average molecular weight: Mn = 235,000-b-220,000, manufactured by Polymer Source Inc.) 10 g, polystyrene ( PS) (Mn = 50,000, manufactured by Polymer Source Inc.) 7.5 g and polymethyl methacrylate (PMMA) (Mn = 44,100, manufactured by Polymer Source Inc.) 7.5 g, bifunctional methacrylic modified bisphenol (Trade name “EB600”, manufactured by Daicel UCB) 10 g and a polymerization initiator (trade name “V60”, manufactured by Wako Pure Chemical Industries, Ltd.) mixed solvent (toluene 40 wt%, xylene 30 wt%, ethyl acetate 20 (Weight%, butyl acetate 10 weight%) in 200 g to obtain a paint.
(Coating formation)
Polyester melamine-based black intermediate coating is applied to a steel plate that has been applied with an intermediate coating thickness of about 30 μm and baked at about 140 ° C. for 30 minutes. The above coating is applied as a base coating, and the solvent is slowly evaporated to give a green color. A wet color film was formed. Thereafter, the added monomer (bisphenol bifunctional methacrylic modified product) is polymerized by heating at 80 ° C. for 5 hours in an oil bath, and the added monomer is three-dimensionally contained in the structure while maintaining the colored structure. A polymerized network structure was formed and the coating film was fixed. The thickness of this coating film was about 20 μm. Next, an acrylic melamine-based clear paint was applied on the coating film to a thickness of about 40 μm and baked at about 140 ° C. for 30 minutes. The difference between the solubility parameter of the polystyrene block chain in the diblock copolymer and the solubility parameter of the surface material of the intermediate coated steel sheet was 4 (J / cm 3 ) 1/2 .
(Design evaluation)
The coated plate produced by the above method showed a bright color tone with a high reflectance and no dullness compared to a coated plate using a conventional interference mica pigment or the like.

Example 2
(Paint preparation)
Diblock copolymer (PS-b-PMMA) composed of polystyrene and polymethylmethacrylate (number average molecular weight: Mn = 215,000-b-201,000, manufactured by Polymer Source Inc.) 10 g, polystyrene (PS) (Mn = 44) , 100, manufactured by Polymer Source Inc.), 5 g of polymethyl methacrylate (PMMA) (Mn = 44,100, manufactured by Polymer Source Inc.), bifunctional methacrylic modified bisphenol (trade name “EB600”, Daicel UCB) 10 g of a polymerization initiator (trade name “V60”, manufactured by Wako Pure Chemical Industries, Ltd.) 200 g of a mixed solvent (40% by weight of toluene, 30% by weight of xylene, 20% by weight of ethyl acetate, 10% by weight of butyl acetate) Dissolved in a coating material.
(Coating formation)
Polyester melamine-based black intermediate paint with a thickness of about 30μm and applied on a steel plate that has been baked at about 140 ° C for 30 minutes. A wet color film was formed. Thereafter, the added monomer (bisphenol bifunctional methacrylic modified product) is polymerized by heating at 80 ° C. for 5 hours in an oil bath, and the added monomer is three-dimensionally contained in the structure while maintaining the colored structure. A polymerized network structure was formed and the coating film was fixed. The thickness of this coating film was about 20 μm. Next, an acrylic melamine-based clear paint was applied on the coating film to a thickness of about 40 μm and baked at about 140 ° C. for 30 minutes. The difference between the solubility parameter of the polystyrene block chain in the diblock copolymer and the solubility parameter of the surface material of the intermediate coated steel sheet was 4 (J / cm 3 ) 1/2 .
(Design evaluation)
The coated plate produced by the above method showed a bright color tone with a high reflectance and no dullness compared to a coated plate using a conventional interference mica pigment or the like.

Example 3
(Paint preparation)
Diblock copolymer (PS-b-PB) composed of polystyrene and polybutadiene (PB) (number average molecular weight: Mn = 155,700-b-142,000, manufactured by Polymer Source Inc.) 10 g, polystyrene (PS) (Mn = 770, manufactured by Polymer Source Inc.) 4 g, polystyrene (PS) (number average molecular weight: Mn = 50,000, manufactured by Polymer Source Inc.) 5 g, polybutadiene (PB) (Mn = 7,300, manufactured by Polymer Source Inc.) 5 g, polybutadiene (PB) (Mn = 9,600, manufactured by Polymer Source Inc.) 5 g, bisphenol bifunctional methacrylic modified product (trade name “EB600”, manufactured by Daicel UCB), and polymerization initiator (trade name “ V60 ", manufactured by Wako Pure Chemical Industries, Ltd.) mixed solvent (toluene 40 wt%, xylene 30 wt%, ethyl acetate 20 wt%, butyl acetate 10fold) %) Was dissolved in 300g, was the paint.
(Coating formation)
Polyester melamine-based black intermediate coating is applied with a thickness of about 30μm and baked at about 140 ° C for 30 minutes. The above coating is applied as a base coating, and the solvent is slowly evaporated to give a blue-green color. A Wet film that develops color was formed. Thereafter, the added monomer (bisphenol bifunctional methacrylic modified product) is polymerized by heating at 80 ° C. for 5 hours in an oil bath, and the added monomer is three-dimensionally contained in the structure while maintaining the colored structure. A polymerized network structure was formed and the coating film was fixed. The thickness of this coating film was about 20 μm. Next, an acrylic melamine-based clear paint was applied on the coating film to a thickness of about 40 μm and baked at about 140 ° C. for 30 minutes. The difference between the solubility parameter of the polystyrene block chain in the diblock copolymer and the solubility parameter of the surface material of the intermediate coated steel sheet was 4 (J / cm 3 ) 1/2 .
(Design evaluation)
The coated plate produced by the above method showed a bright color tone with a high reflectance and no dullness compared to a coated plate using a conventional interference mica pigment or the like.

Example 4
(Paint preparation)
Diblock copolymer (P2VN-b-PMMA) composed of poly-2-vinylnaphthalene (P2VN) and polymethyl methacrylate (PMMA) (number average molecular weight: Mn = 225,000-b-270,000, manufactured by Polymer Source Inc.) 10 g, poly-2-vinylnaphthalene (P2VN) (Mn = 54,000, manufactured by Polymer Source Inc.) 7.5 g, polymethyl methacrylate (PMMA) (number average molecular weight: Mn = 44,100, manufactured by Polymer Source Inc.) 7.5 g, 10 g of a bifunctional methacrylic modified bisphenol (trade name “EB600”, manufactured by Daicel UCB) and a polymerization initiator (trade name “V60”, manufactured by Wako Pure Chemical Industries, Ltd.) are mixed solvent (toluene 40 (Wt%, xylene 30 wt%, ethyl acetate 20 wt%, butyl acetate 10 wt%).
(Coating formation)
Polyester melamine-based black intermediate paint with a thickness of about 30μm and applied on a steel plate that has been baked at about 140 ° C for 30 minutes. A wet color film was formed. Thereafter, the added monomer (bisphenol bifunctional methacrylic modified product) is polymerized by heating at 80 ° C. for 5 hours in an oil bath, and the added monomer is three-dimensionally contained in the structure while maintaining the colored structure. A polymerized network structure was formed and the coating film was fixed. The thickness of this coating film was about 20 μm. Next, an acrylic melamine-based clear paint was applied on the coating film to a thickness of about 40 μm and baked at about 140 ° C. for 30 minutes. The difference between the solubility parameter of the polyvinyl naphthalene block chain in the diblock copolymer and the solubility parameter of the surface material of the intermediate coated steel sheet was 2 (J / cm 3 ) 1/2 .
(Design evaluation)
The coated plate produced by the above method showed a bright color tone with a high reflectance and no dullness compared to a coated plate using a conventional interference mica pigment or the like.

Example 5
(Paint preparation)
Diblock copolymer (P2VP-b-PMMA) composed of poly 2-vinylpyridine (P2VP) and polymethyl methacrylate (PMMA) (number average molecular weight: Mn = 235,000-b-220,000, manufactured by Polymer Source Inc.) 10 g, poly 2-vinylpyridine (P2VP) (Mn = 50,000, manufactured by Polymer Source Inc.) 7.5 g, polymethyl methacrylate (PMMA) (number average molecular weight: Mn = 44,100, manufactured by Polymer Source Inc.) 7.5 g, 10 g of bisphenol bifunctional methacrylic modified product (trade name “EB600”, manufactured by Daicel UCB) and a polymerization initiator (trade name “V60”, manufactured by Wako Pure Chemical Industries, Ltd.) mixed solvent (toluene 40 (Wt%, xylene 30 wt%, ethyl acetate 20 wt%, butyl acetate 10 wt%).
(Coating formation)
Polyester melamine-based black intermediate coating is applied to a steel plate that has been applied with an intermediate coating thickness of about 30 μm and baked at about 140 ° C. for 30 minutes. The above coating is applied as a base coating, and the solvent is slowly evaporated to give a green color. A wet color film was formed. Thereafter, the added monomer (bisphenol bifunctional methacrylic modified product) is polymerized by heating at 80 ° C. for 5 hours in an oil bath, and the added monomer is three-dimensionally contained in the structure while maintaining the colored structure. A polymerized network structure was formed and the coating film was fixed. The thickness of this coating film was about 20 μm. Next, an acrylic melamine-based clear paint was applied on the coating film to a thickness of about 40 μm and baked at about 140 ° C. for 30 minutes. The difference between the solubility parameter of the poly-2-vinylpyridine block chain in the diblock copolymer and the solubility parameter of the surface material of the intermediate coated steel sheet was 0.6 (J / cm 3 ) 1/2. It was.
(Design evaluation)
The coated plate produced by the above method showed a bright color tone with a high reflectance and no dullness compared to a coated plate using a conventional interference mica pigment or the like.

Claims (13)

  1. A unit cell spacing D (nm) having a microphase separation structure formed from a block copolymer in which a plurality of polymer chains having different refractive indexes and incompatible with each other are bonded, and formed by each phase of the microphase separation structure Where the incident angle (θ) of the light with respect to the lattice plane is any angle of 0 ° <θ ≦ 90 °, and N and m are independent integers of 1 to 10, respectively, A coating film comprising a color-forming polymer structure satisfying (1).
    350 (nm) ≦ N (2nD sin θ) / m ≦ 800 (nm) (1)
    (Where n is the average refractive index of the block copolymer)
  2. In the reflected light wavelength from the Nth lattice plane from the coating surface characterized by the lattice spacing D formed by each phase of the microphase separation structure and the average refractive index n of the block copolymer, the light of that wavelength is the coating film The coating film according to claim 1, which has a reflectance of 30% or more when incident at an angle of 90 ° with respect to the surface.
  3. The coating film according to claim 1 or 2, wherein the difference between the solubility parameter of at least one polymer block chain in the block copolymer and the solubility parameter of the material to be coated is 5 (J / cm 3 ) 1/2 or less.
  4. A method for forming a coating film according to any one of claims 1 to 3 on a surface of an object to be coated, comprising: a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are bonded to each other; A coating film forming method comprising a step of directly applying a solution containing at least a surface of an object to be coated, and a step of evaporating a solvent.
  5. 5. The method of forming a coating film according to claim 4, further comprising a step of incorporating a homopolymer compatible with the block chain of the block copolymer into the system before completion of the coating film formation.
  6. 5. The method of forming a coating film according to claim 4, further comprising a step of incorporating a block copolymer crosslinking agent into the system before completion of coating film formation and a step of crosslinking the block copolymer with the crosslinking agent.
  7. 5. The method of forming a coating film according to claim 4, further comprising the steps of: incorporating a polymerizable monomer that can be polymerized itself before completion of coating film formation and being compatible with the block copolymer; and polymerizing the polymerizable monomer. .
  8. A block copolymer containing a basic nitrogen atom-containing group is used as the block copolymer, a step of containing a halogen compound in the system before the completion of the formation of the color-forming thin film, and the basic nitrogen atom-containing group by the halogen compound are included The method of forming a coating film according to claim 4, further comprising the step of liberating halide ions by quaternization reaction of nitrogen atoms in the block copolymer.
  9. A paint capable of forming a coating film according to any one of claims 1 to 3, comprising at least a block copolymer in which a plurality of polymer chains incompatible with each other and having different refractive indexes are bonded to each other and a solvent.
  10. Furthermore, the coating material of Claim 9 containing the homopolymer compatible with the block chain of a block copolymer.
  11. Furthermore, the coating material of Claim 9 containing the crosslinking agent of a block copolymer.
  12. Furthermore, the coating material of Claim 9 containing the polymerizable monomer compatible with a block copolymer.
  13. 10. The paint according to claim 9, which contains a block copolymer containing a basic nitrogen atom-containing group and further contains a halogen compound.
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JP2012228207A (en) * 2011-04-26 2012-11-22 Hamamatsu Univ School Of Medicine Organism mimic
JP2013083766A (en) * 2011-10-07 2013-05-09 Hamamatsu Photonics Kk Method for manufacturing microphase separated structure film
WO2016133115A1 (en) * 2015-02-20 2016-08-25 Jsr株式会社 Self-organized-film forming method, pattern forming method, and self-organized-film forming composition

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GB201804010D0 (en) * 2018-03-13 2018-04-25 Univ Kyoto Structured nanoporous materials, manufacture of structured nanoporous materials and applications of structured nanoporous materials

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JPH0386724A (en) * 1989-08-30 1991-04-11 Toyo Ink Mfg Co Ltd Color-developing composition
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JPH1180379A (en) * 1997-08-29 1999-03-26 Katsunori Funaki Color-developing polymer structure and its production
JP2000072951A (en) * 1998-09-01 2000-03-07 Daicel Chem Ind Ltd Metal/organic polymer composite structure and preparation thereof
JP2003128978A (en) * 2001-10-24 2003-05-08 Nippon Yushi Basf Coatings Kk Primer coating for vehicle, coating film for vehicle and method for coating polyolefin-based substrate for vehicle
JP2004029169A (en) * 2002-06-21 2004-01-29 Seiko Epson Corp Manufacturing method of optical member, optical member, electro-optical device, and electronic equipment
JP2004043605A (en) * 2002-07-10 2004-02-12 Daicel Chem Ind Ltd Pigment comprising color-forming polymer structure, manufacturing method therefor, and coating material

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JPS58129011A (en) * 1982-01-28 1983-08-01 Nippon Telegr & Teleph Corp <Ntt> Coloring polymer composition
JPH0386724A (en) * 1989-08-30 1991-04-11 Toyo Ink Mfg Co Ltd Color-developing composition
JPH1160891A (en) * 1997-08-22 1999-03-05 Katsunori Funaki Metal/organic polymer composite structure and porous body, and preparation thereof
JPH1180379A (en) * 1997-08-29 1999-03-26 Katsunori Funaki Color-developing polymer structure and its production
JP2000072951A (en) * 1998-09-01 2000-03-07 Daicel Chem Ind Ltd Metal/organic polymer composite structure and preparation thereof
JP2003128978A (en) * 2001-10-24 2003-05-08 Nippon Yushi Basf Coatings Kk Primer coating for vehicle, coating film for vehicle and method for coating polyolefin-based substrate for vehicle
JP2004029169A (en) * 2002-06-21 2004-01-29 Seiko Epson Corp Manufacturing method of optical member, optical member, electro-optical device, and electronic equipment
JP2004043605A (en) * 2002-07-10 2004-02-12 Daicel Chem Ind Ltd Pigment comprising color-forming polymer structure, manufacturing method therefor, and coating material

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JP2012228207A (en) * 2011-04-26 2012-11-22 Hamamatsu Univ School Of Medicine Organism mimic
JP2013083766A (en) * 2011-10-07 2013-05-09 Hamamatsu Photonics Kk Method for manufacturing microphase separated structure film
WO2016133115A1 (en) * 2015-02-20 2016-08-25 Jsr株式会社 Self-organized-film forming method, pattern forming method, and self-organized-film forming composition

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