JP2008144068A - Aqueous coating composition, method for forming design coating film, method for coating board for building and body of automobile - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous coating composition forming a uniform coating film which varies hue by watching angle and imparts shading and texture with feeling of profundity and feeling of depth, and to provide applications for the aqueous coating composition. <P>SOLUTION: The aqueous coating composition comprises glitter flakes, an emulsion resin and water, wherein the glitter flakes has a laminated structure at least composed of two resin layers with different refractive index. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous coating composition and use thereof. More specifically, an aqueous coating composition that forms a highly designable coating film that gives a color tone and texture with a sense of depth and depth as well as a hue that changes depending on the viewing angle, a method for forming a design coating film, The present invention relates to a building material board and a method of painting an automobile body.

  In various industrial products such as automobiles, the diversification of appearance designs is progressing. Typical examples of means for enhancing the appearance design include solid color coatings, metallic color coatings, and pearl color coatings.

  Among these coatings, recent pearl color coatings include interference mica pigments that are coated with metal oxides on the surface of mica pigments, changing the hue according to the angle seen by the interference effect of light, and appearance design The sex is greatly enhanced.

  For example, a paint having good glitter and color developability by blending the above-mentioned interference mica pigment into an aqueous paint is disclosed (see Patent Document 1). Usually, in the case of solvent-based paints, the interference mica pigment can be easily dispersed. However, when the interference mica pigment is used in the aqueous paint as described above, the dispersibility is poor due to the aqueous system. For this reason, conventionally, an interference mica pigment is previously dispersed in a solvent or a dispersing resin, and this is dispersed in an aqueous paint. The reason is that since the surface of the interference mica pigment is a metal oxide, water enters this portion, that is, moisture enters the surface and is likely to aggregate. Therefore, it cannot be uniformly dispersed. In addition, even if it is dispersed in appearance, if it becomes a mass that aggregates and settles, it settles, or even if it does not settle, it is dispersed as micro-aggregates. Therefore, if the micro-aggregates are present in the coating after the coating film is formed after coating, the water content in the micro-aggregates may cause whitening of the coating or color unevenness. May occur.

  Recently, a bright material having a multilayer laminated structure of resin has been reported (see Patent Documents 2-6). In Patent Documents 2-6, as one of the application types of the glitter material described in the document, it is contained in a two-component acrylic urethane-based solvent-based paint and coated on a PET base material or ABS base material. The formation of a coating film is described. However, these are examples used for solvent paints, and application to water-based paints is not described. Further, since the solvent-type paint essentially contains a volatile solvent such as toluene and xylene, it is not preferable in terms of environmental pollution and adverse effects on the human body.

As described above, it is difficult to simply convert a solvent-type paint into a water-based paint, and it is necessary to make a resin emulsion. Furthermore, it is necessary to control the film-forming properties and the viscosity at the time of painting, which are unique properties of water-based paints.
JP 2003-231858 A JP 2000-229370 A JP 2000-246829 A JP 2001-347798 A JP 2006-233356 A JP 2006-233356 A

  The present invention has been made in order to solve the above-described conventional problems, and an object of the present invention is an aqueous coating composition, in which the hue changes depending on the viewing angle and has a sense of depth and depth. Another object of the present invention is to provide a water-based coating composition that forms a uniform coating film that gives a good texture. Moreover, it is providing the use of such an aqueous coating composition.

  The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that all the above problems can be solved by using a special glitter material in an aqueous emulsion coating composition containing an emulsion resin and water, and completed the present invention.

  The aqueous coating composition of the present invention is an aqueous coating composition containing a glittering material, an emulsion resin, and water, and the glittering material has a laminated structure portion of at least two types of resin layers having different refractive indexes. Have.

  In a preferred embodiment, the aqueous coating composition of the present invention further contains a film-forming aid.

  In a preferred embodiment, the aqueous coating composition of the present invention further comprises a thickener.

  In a preferred embodiment, the bright material is a coating containing any one of the resins constituting the at least two types of resin layers and / or a resin different from these resins around the laminated structure portion. Has a layer.

  In a preferred embodiment, the glitter material has a substantially flat cross section.

  In a preferred embodiment, the glitter material includes a dye layer containing an achromatic dye and / or a chromatic dye in the laminated structure.

  In a preferred embodiment, the brilliant material has an alternately laminated structure portion of two types of resin layers having different refractive indexes, the solubility parameter value (SP1) of the high refractive index side resin and the solubility parameter of the low refractive index side resin. The ratio (SP ratio) of the values (SP2) is in the range of 0.8 ≦ SP1 / SP2 ≦ 1.1, and a coating layer made of a fiber-forming resin is provided around the alternately laminated structure portion.

  In a preferred embodiment, a chromatic color component is contained in the alternate laminated structure and / or the coating layer.

  In a preferred embodiment, the glitter material has a substantially flat cross section, and the flatness of the cross section is 3.5 or more.

  In preferable embodiment, the thickness of the said alternately laminated structure part is 10 micrometers or less.

  In a preferred embodiment, the high refractive index side resin and the low refractive index side resin are hardly alkali-soluble resins, and the fiber-forming resin is an alkali-soluble resin.

  According to another situation of this invention, the formation method of the designable coating film is provided. In this method of forming a design coating film, the aqueous coating composition of the present invention is applied on a substrate having an uneven shape on the surface.

  In a preferred embodiment, an undercoat paint is applied to the surface of the substrate to form an undercoat layer, then a colored paint is applied to form a colored coating film layer, and then the aqueous paint composition is applied. To do.

  In a preferred embodiment, a clear coating is applied on the design coating film formed by the method for forming a design coating film to form a clear layer.

  In preferable embodiment, the said uneven | corrugated shape is 1 mm or more in uneven | corrugated depth.

  According to another aspect of the present invention, a building material board is provided. This building material board has a coating film formed by the design coating film forming method of the present invention.

  In a preferred embodiment, in the building material board of the present invention, the base material is made of a ceramic material.

  In a preferred embodiment, the aqueous coating composition of the present invention further comprises a curing agent.

  According to another aspect of the present invention, a method for painting an automobile body is provided. This method of painting an automobile body is a method of painting an automobile body in which a first base paint, a second base paint, and a clear paint are applied in this order after an undercoat layer and an intermediate coat layer are formed on the surface of an object to be coated. The second base paint is the aqueous paint composition of the present invention.

  In a preferred embodiment, the first base paint is water-based, and the first base paint, the second base paint, and the clear paint are applied by wet-on-wet and then baked in a three-coat one-bake method.

  According to the present invention, there is provided an aqueous coating composition that forms a uniform coating film that changes in hue depending on the viewing angle and gives a color tone and texture with a sense of depth and depth. Can do. Moreover, the use of such an aqueous coating composition can be provided.

  Such an effect can be achieved by using a special glitter material in an aqueous emulsion coating composition containing an emulsion resin and water. Specifically, a special glittering material having a laminated structure part of at least two types of resin layers having different refractive indexes is used in an aqueous emulsion coating composition containing an emulsion resin and water, whereby the glittering material is coated with paint. It can be uniformly dispersed in the composition, and the obtained coating film can give a color tone and texture with a sense of depth and depth as well as a hue that changes depending on the viewing angle due to the interference of light. Moreover, if it is set as the emulsion coating composition which has the said structure, since the form of an emulsion will not remain in a coating film and a uniform coating film will be obtained, the finishing external appearance of a coating film is excellent. In addition, color unevenness and whitening of the coating film can be prevented. These effects are also due to the fact that the glittering material used in the present invention is formed of a resin, so that it can be easily and uniformly dispersed in an aqueous coating composition.

[1. Water-based paint composition)
The water-based coating composition of the present invention contains a bright material, an emulsion resin, and water. Preferably, a film forming aid is included. Preferably, a thickener is included. The ratio of the total solid content in the aqueous coating composition of the present invention is preferably 5 to 70% by weight, more preferably 5 to 60% by weight, still more preferably 5 to 50% by weight, and particularly preferably 10 to 40% by weight. It is.

(1-1. Bright material)
The glitter material has a laminated structure portion of at least two types of resin layers having different refractive indexes. Arbitrary appropriate thickness can be employ | adopted for the thickness of each resin layer in a laminated structure part. Preferably, it is the range of 0.02-0.5 micrometer. When the thickness is less than 0.02 μm or exceeds 0.5 μm, it may be difficult to obtain a sufficient optical interference effect in a useful wavelength region. The thickness of each resin layer in the laminated structure is more preferably in the range of 0.05 to 0.15 μm.

  When the optical distance in the resin component constituting each resin layer, that is, the product of the layer thickness and the refractive index is equal, a higher optical interference effect can be obtained. In particular, it is preferable that twice the sum of the two optical distances equal to the primary reflection is the maximum interference color when it is equal to the wavelength of the desired color.

  An intermediate layer is provided in the laminated structure as necessary. In this case, any appropriate thickness can be adopted as the thickness of the intermediate layer. Preferably it is the range of 1.0-10 micrometers, More preferably, it is the range of 2.0-5.0 micrometers.

  Arbitrary appropriate content rates can be employ | adopted for the content rate of the said brilliant material in the water-based coating composition of this invention in the range which does not impair the effect of this invention. For example, the weight concentration with respect to the total solid content is preferably 50% by weight or less. If the content ratio of the glittering material exceeds 50% by weight, the fluidity and workability of the paint may be deteriorated, or the adhesion of the coating film may be deteriorated. When the content ratio of the glittering material is relatively high, generally, the obtained coating film has a dark color, and the polychromaticity tends to appear more clearly. When the content ratio of the glittering material is relatively low, the base coating film may become lighter as the base can be seen through, and the polychromaticity tends to appear lighter. Sex can be selected.

  Here, in order to clarify the specificity of the glitter material, a conventional interference mica pigment (sometimes referred to as a pearl mica pigment) will be described. In the interference mica pigment, a translucent or opaque mica is coated with a metal oxide such as titanium dioxide in order to increase its hiding power. There is also a metal layer provided thereon.

  In the case of a translucent interference mica pigment, part of the incident light is absorbed or reflected, and the remaining light is emitted from the interference mica pigment as transmitted light. Therefore, the transmitted light has low intensity and low purity.

  In the case of an opaque interference mica pigment, incident light is absorbed or reflected, and transmitted light is hardly generated, so that it has a high hiding power. However, since the number of laminated mica itself is small, the reflection intensity is not sufficient and the interference color is not sufficient. Note that the hiding power decreases as the amount of light transmitted through the interference mica pigment increases.

  The glittering material used in the present invention does not increase the hiding power as much as possible by coating a metal oxide such as titanium dioxide on a mica substrate made of a translucent or opaque body as in the prior art. It is based on a completely opposite idea. That is, it has a laminated structure part composed of at least two types of transparent resin layers, and develops color by interference reflection of light (interference color) and color by emission light that transmits light other than reflection interference (transmission color of bright material). ) To maximize design and decoration.

  The bright material used in the present invention not only simply expresses interference light and transmitted light but also has a function of controlling the interference light and transmitted light other than the interference light. Here, “control” means that the intensity of interference light or transmitted light (reflection intensity for interference light, transmission intensity for transmitted light), or the peak wavelength in the reflection spectrum and transmission spectrum can be arbitrarily changed. Thus, it exhibits a light intensity conversion function and a light wavelength conversion function. Such a function can be made more prominent by providing a dye layer containing an achromatic dye and / or a chromatic dye in the laminated structure portion of the glittering material, for example.

  The glitter material used in the present invention has a laminated structure portion of at least two types of resin layers having different refractive indexes. Arbitrary appropriate resin can be employ | adopted as resin which comprises this resin layer. For example, simple resins such as polyester, polyacrylonitrile, polystyrene, nylon, polypropylene, polyvinyl alcohol, polycarbonate, polyethylene naphthalate, polyethylene terephthalate, polymethyl methacrylate, polyether ether ketone, polyparaphenylene terephthalamide, polyphenylene sulfide, or the like And copolymer resins and blend resins.

  Any appropriate number of laminated layers can be adopted as the number of laminated resin layers in the glitter material used in the present invention. From the viewpoint of optical functionality (reflection reflection and transmission of light) and production, 5 or more layers are preferable, a range of 10 to 150 layers is more preferable, and a range of 10 to 120 layers is more preferable.

  When the laminated structure portion in the glitter material used in the present invention has two types of resin layers having different refractive indexes, it is preferable that the laminated structure has an alternately laminated structure. Moreover, when it has 3 or more types of resin layers from which a refractive index differs, it is preferable to laminate | stack repeatedly in a predetermined order, without changing the order of these 3 or more types of resin.

  As a method for producing a glittering material having a laminated structure as described above, the laminated structure is obtained by, for example, cutting the laminated structure after forming the laminated structure by any appropriate multilayer thin film forming method. be able to. For example, physical vapor deposition methods such as vacuum vapor deposition, electron beam vapor deposition, ion plating, molecular beam epitaxy, casting and spin coating, plasma polymerization, Langmuir-Blodget (LB) method, melting, wet, dry, etc. Various spinning methods can be used. In particular, a melt spinning method that is excellent in productivity and capable of reducing the price is preferable.

  When the melt spinning method is used, a laminated structure (thread-like) can be continuously obtained by using a melt composite spinning apparatus equipped with a special die for forming the laminated structure, and further subjected to a stretching treatment. Thus, a laminated structure portion having a desired cross-sectional dimension can be manufactured. Then, you may cut | disconnect to the desired length according to various uses.

  As one preferable embodiment of the glitter material used in the present invention, one of the resins constituting the at least two types of resin layers and / or different from these resins is provided around the laminated structure portion. It has a coating layer containing resin. Providing a coating layer is preferable from the viewpoint of improving mechanical strength such as prevention of peeling of the laminated structure and wear resistance, and stability of gloss and reflection strength. Further, the coating layer may be a single single layer, or may be a double or multiple layer. The coating layer may include a dye layer containing an achromatic dye and / or a chromatic dye.

  Arbitrary appropriate shape can be employ | adopted for the cross-sectional shape of the luster material used for this invention. For example, a substantially flat cross section and a substantially rectangular cross section can be mentioned.

  When the cross-sectional shape of the glitter material used in the present invention is a substantially flat cross section, it has a major axis and a minor axis. A bright material having a large cross-sectional flatness (major axis / minor axis) is preferable because a major axis that affects an effective area for light interference can be increased. The flatness of the cross section of the glittering material is preferably 3.5 or more, more preferably 4.5 or more, and further preferably 7 or more. When the flatness is in the above range, the light interference coloring function is improved, which is preferable. The upper limit of the flatness is preferably 15 or less, more preferably 12 or less, in order to prevent the productivity from decreasing. The flatness ratio is calculated including the covering layer portion when the covering layer is formed on the outer peripheral portion of the flat cross section.

  When the cross-sectional shape of the glitter material used in the present invention is a substantially rectangular cross-section, when the length of the side perpendicular to the laminated surface in the cross-section is 1, the length of the side parallel to the laminated surface is 0.8 to 25 The length of the bright material in the direction perpendicular to the cross section is preferably 0.8 to 4000. By adopting a substantially rectangular cross-sectional shape as described above, both of the coloring effect due to the reflection interference action and the coloring effect due to the transmission action can be exhibited without impairing productivity, paintability, moldability and the like.

  In the case of taking a substantially rectangular cross-sectional shape, when the length of the side perpendicular to the laminated surface in the cross section is 1, and the length of the side parallel to the laminated surface is less than 0.8, the color developing surface Is likely to be directed to the incident light side, and the coloring effect due to the reflection interference action may be insufficient. When the length of the side perpendicular to the laminated surface in the cross section is 1, and the length of the side parallel to the laminated surface is greater than 25, a problem occurs during the production of the glitter material (for example, melt compound spinning). There is a possibility that it is impossible to stably obtain a bright material that reflects or interferes with light having a desired wavelength. When the length of the side perpendicular to the laminated surface in the cross section is 1, and the length of the glitter material in the direction perpendicular to the cross section exceeds 4000, the glitter material in the paint is clogged with a spray gun or the like during coating. There is a risk that proper coating cannot be performed.

  Another preferred embodiment of the glitter material used in the present invention has an alternately laminated structure portion of two types of resin layers having different refractive indexes, and has a solubility parameter value (SP1) of the high refractive index side resin and low refractive index. The ratio (SP ratio) of the solubility parameter value (SP2) of the rate side resin is in the range of 0.8 ≦ SP1 / SP2 ≦ 1.1, and a coating layer made of a fiber-forming resin around the alternately laminated structure portion Have The high refractive index side resin and the low refractive index side resin are preferably hardly alkali-soluble resins.

  The ratio (SP ratio) of the solubility parameter (SP1) of the high refractive index side resin and the solubility parameter (SP2) of the low refractive index side resin is more preferably in the range of 0.85 ≦ SP1 / SP2 ≦ 1.05.

  When a combination of resins having the SP ratio as described above is used, for example, when an alternately laminated flow of two types of resins is discharged from the spinneret, the interfacial tension acting on the interface is reduced, so a uniform alternately laminated structure portion is easily obtained. Can get to. On the other hand, when the SP ratio is outside the above range, for example, the discharged resin flow tends to be rounded by the surface tension, and the contraction force works so as to minimize the contact area between the two resin laminate interfaces, Moreover, since the laminated structure portion is multi-layered, the shrinkage force is increased, and therefore, the laminated surface may be rounded while being curved and a good flat shape may not be obtained. Furthermore, if the resin flow is released at the mouthpiece outlet, there is a possibility that the balus effect that tends to swell increases.

  As a combination of resins having the SP ratio as described above, for example, a dibasic acid component having a sulfonic acid metal base is copolymerized in an amount of 0.3 to 10 mol% with respect to all dibasic acid components forming the polyester. Of polyethylene terephthalate and polymethyl methacrylate having an acid value of 3 or more, and dibasic acid component having a sulfonic acid metal salt is copolymerized in an amount of 0.3 to 5 mol% per total dibasic acid component forming polyester Polyethylene naphthalate and aliphatic polyamide in combination, a copolymerized aromatic polyester having a copolymer of 5 to 30 mol% of a dibasic acid component or glycol component having an alkyl group in the side chain per total repeating unit Combination with methyl methacrylate, 9,9-bis (parahydroxyethoxyphenyl) fluorene as all repeating units 20 to 80 mol% of copolymerized polyethylene terephthalate or a combination of polyethylene naphthalate and polymethyl methacrylate, 9,9-bis (parahydroxyethoxyphenyl) fluorene and 20 to 80 mol% of all repeating units and sulfonic acid A combination of polyethylene terephthalate or polyethylene naphthalate and an aliphatic polyamide copolymerized with 0.3 to 10 mol% of the dibasic acid component having a metal salt per total dibasic acid component forming the polyester; 2, A combination of polycarbonate and polymethylmethacrylate containing 2-bis (parahydroxyphenyl) propane as a dihydric phenol component, 9,9-bis (parahydroxyethoxyphenyl) fluorene and 2,2-bis (parahydroxyphenyl) propane ( this Molar ratio of as combinations of polycarbonate and polymethyl methacrylate to 20/80 to 80/20) a dihydric phenol component.

  Arbitrary appropriate thickness can be employ | adopted for the thickness of the alternate laminated structure part of two types of resin layers from which said refractive index differs. The thickness is preferably 10 μm or less, more preferably 2 to 7 μm.

  The fiber-forming resin forming the coating layer is preferably an alkali-soluble resin. If the alkali-soluble resin is used, a composite fiber having a fine-light interference color-developing function can be obtained by alkali treatment. In addition, when removing all the coating layers by this alkali treatment, it cannot be overemphasized that it is necessary to contain the chromatic component mentioned later in layers other than a coating layer.

  The coating layer may be formed of any fiber-forming resin, may be formed of any of the resins forming the alternately laminated structure portion, or two or more types of fiber-forming resins. It may be covered with two or more layers. In particular, it is preferable that the outermost coating layer is formed of a resin that is more easily soluble in alkali than the resin that forms the alternately laminated structure. By subjecting such a composite fiber to an alkali treatment, at least a part of the coating layer can be removed, and a composite fiber having an optical interference function with a fineness can be easily obtained.

  In addition, the alkali-soluble resin here means that there is a difference of 10 times or more compared with the alkali weight loss rate of the resin forming the alternately laminated structure portion. Specifically, when treated with an aqueous alkali solution, the alkali-soluble resin of the coating layer is dissolved at a rate 10 times or more faster than the alkali-insoluble resin constituting the alternately laminated structure. When the difference in dissolution rate is less than 10 times, when carrying out the alkaline aqueous solution treatment to remove the coating layer, the alternate laminated body part is also subjected to erosion action, resulting in lamination thickness unevenness due to disorder of the laminated structure or swelling. There is a possibility that the light interference coloring function is lowered.

  Examples of the alkali-soluble resin include polylactic acid, polyethylene terephthalate copolymerized with polyethylene glycol and polybutylene terephthalate, polyethylene terephthalate blended with polyethylene glycol and / or alkali metal alkyl sulfonate, and polyethylene glycol and / or sulfone. Examples thereof include polyethylene terephthalate and polybutylene terephthalate obtained by copolymerizing a dibasic acid component having an acid metal base.

  The polylactic acid is generally composed mainly of L-lactic acid, but may contain other copolymer components such as D-lactic acid within a range not exceeding 40% by weight.

  In the polyethylene terephthalate or polybutylene terephthalate copolymerized with polyethylene glycol, the copolymerization ratio of polyethylene glycol is preferably 30% by weight or more, and this can significantly improve the alkali dissolution rate.

  In polyethylene terephthalate and polybutylene terephthalate blended with alkali metal alkyl sulfonate and / or polyethylene glycol, the blend ratio of alkyl metal sulfonate alkali metal salt is preferably in the range of 0.5 to 3.0 wt%. The blending ratio is preferably in the range of 1.0 to 4.0% by weight. The average molecular weight of polyethylene glycol is preferably in the range of 600 to 4000.

  In polyethylene terephthalate and polybutylene terephthalate copolymerized with polyethylene glycol and / or a dibasic acid component having a sulfonic acid metal base, the content of polyethylene glycol is preferably in the range of 0.5 to 10.0% by weight. The content ratio of the dibasic acid component having a metal base is preferably in the range of 1.5 to 10 mol% with respect to all the dibasic acid components forming the polyester.

  Arbitrary appropriate thickness can be employ | adopted for the thickness of the coating layer which consists of said fiber-forming resin. Preferably it is 2.0 micrometers or more, More preferably, it is 2.0-10 micrometers, More preferably, it is 3.0-5.0 micrometers. In this way, by providing a coating layer made of a fiber-forming resin around the alternately laminated structure portion, the resin flow distribution between the vicinity of the wall surface and inside received in the final discharge hole during melt spinning can be relaxed, and alternately The distribution of shear stress received by the laminated structure portion is reduced, and an alternate laminated structure portion in which the thickness of each layer across the inner and outer layers is more uniform can be obtained. When the coating layer is formed of two or more kinds of resins, the total thickness is preferably 2.0 μm or more. For example, even if the thickness of the inner coating layer is less than 2.0 μm, If the thickness of the outer coating layer combined is 2.0 μm or more, the above effect can be exhibited. Therefore, if the outer coating layer is formed of a readily alkali-soluble resin, only the outer coating layer is removed by alkali treatment, so that a uniform thickness coated with a coating layer having a thickness of less than 2.0 μm is obtained. A composite fiber having an optical interference coloring function having an alternately laminated structure portion can be easily obtained.

  If the coating layer made of the above fiber-forming resin is too thin, for example, less than 2.0 μm, the fiber single yarn fineness becomes small and the cross section is flat. Problems are likely to occur in handling in the processing process. In addition, the fiber-forming resin to be coated in contact with the alternately laminated structure portion is a solubility parameter of a resin (high refractive index side resin or low refractive index side resin) constituting both sides in the major axis direction of the alternately laminated structure portion. It is preferable that the solubility parameter value (SP3) is about the same as the value. Specifically, it is preferable that 0.8 ≦ SP1 / SP3 ≦ 1.2 and / or 0.8 ≦ SP2 / SP3 ≦ 1.2.

It is preferable that a chromatic component is contained in any of the resin layers of the alternately laminated structure portion and the coating layer made of the fiber-forming resin. The chromatic color here means any appropriate chromatic color. For example, it includes not only various colors in the visible light region of 380 nm to 780 nm but also colors having substantially no saturation such as black and gray. As chromatic color components preferably used, CaS (colorless), MgF ₂ (red), CeF ₃ (colorless), ZnS (colorless), ZnSe (yellow), Si, SiO ₂ (colorless), Ge, Te, Fe ₂ O ₃ (reddish brown), Pt, Va, Al ₂ O ₃ (colorless), MgO (colorless), Y ₂ O ₃ (colorless), S ₂ O ₃ (yellowish green), SiO (colorless), HfO ₂ (colorless) , ZrO ₂ (colorless), CeO ₂ (yellowish green), Nb ₂ O ₅ (colorless), Ta ₂ O ₅ (colorless), TiO ₂ (colorless), Ag, Al, Au, Cu, Rb, Ti, Ta, Examples thereof include pigments such as W, Zn, MoS ₂ (black), Bi, and carbon black. These may be used alone or in combination of two or more. Further, anthraquinone yellow pigment (CI.P.Y.147), iron oxide yellow pigment (CI.P.Y.119), perolene red dye (CI.SR.135), polyazo red pigment (CI.P.R.214), quinacdrine red pigment (CI.P.R.122), azomethine-based purple dye (CI.S.V.49), phthalocyanine blue pigment (CI.P.B.15. .3), ultramarine blue pigment (CI.P.Bl.29), phthalocyanine green pigment (CI.P.G.7), iron oxide brown pigment (CI.P.R.101), etc. are used. be able to.

  The amount of the chromatic color component added is preferably 0.05 to 3.0% by weight as the weight concentration with respect to the total solid content of the resin layer. If it is less than 0.05% by weight, the accuracy of addition tends to be insufficient, and color spots are likely to occur. If it exceeds 3.0% by weight, the added amount is too large and the fiber structure forming property is likely to be hindered. In general, it may be set as appropriate according to the type of chromatic color component to be used while checking the degree of color development. In addition, the resin layer containing a chromatic color component in contact with the alternately laminated structure portion is also the same as the solubility parameter value of the resin (high refractive index side resin or low refractive index side resin) in contact with the alternate laminated structure portion. The solubility parameter value (SP4) is preferred. Specifically, it is preferable that 0.8 ≦ SP1 / SP4 ≦ 1.2 and / or 0.8 ≦ SP2 / SP4 ≦ 1.2.

  Arbitrary appropriate methods can be employ | adopted for the method of adding the said chromatic color component. For example, a method of adding and dispersing a master chip containing the chromatic color component at a high concentration in the resin forming the layer to be added is preferable in terms of simple and uniform dispersion.

  The glitter material of the second preferred embodiment, that is, having an alternately laminated structure part of two types of resin layers having different refractive indexes, the solubility parameter value (SP1) of the high refractive index side resin and the low refractive index side resin The ratio (SP ratio) of the solubility parameter value (SP2) is in the range of 0.8 ≦ SP1 / SP2 ≦ 1.1, and a glitter having a coating layer made of a fiber-forming resin around the alternately laminated structure portion The elongation of the material is preferably in the range of 10 to 60%, and more preferably in the range of 20 to 40%. When the elongation is too large, for example, in the step of finally cutting the glittering material, the fibers are easily deformed by the tension applied to the glittering material, so that the process passability may be reduced. On the other hand, when the elongation is too small, it becomes difficult to absorb the tension applied to the glittering material, so that there is a tendency for fluff and yarn breakage to increase. Even if the elongation is within this range, depending on the type of resin used, birefringence (Δn) can be further increased by stretching the composite fiber that has been spun and cooled and solidified, and two types of resins can be obtained. The difference in refractive index between them is defined as “the difference in refractive index of the resin plus the difference in birefringence of the fiber”. As a result, the difference in refractive index can be increased as a whole, so that the light interference coloring function is enhanced.

  The glitter material of the second preferred embodiment can take any suitable form. For example, false twisted crimped yarn, composite mixed yarn, and thick yarn can be mentioned. Preferably, the heat shrinkage at 130 ° C. to 150 ° C. is 3% or less. When the thermal shrinkage rate exceeds the above range, for example, when the glitter material is cut, deformation such as shrinkage of the fiber occurs and the light interference coloring function tends to be lowered. For example, when it is used for a paint, since it is dried and heat-set at the same temperature in the painting process and the printing process, it preferably has the same heat resistance in terms of quality.

  The bright material that can be used in the present invention described above may be manufactured by further adding any appropriate process. Bright materials that can be used in the present invention include, for example, JP 2000-229370, JP 2000-246829, JP 2001-347798, JP 2006-233356, and JP 2006-233356. The luster material described in the publication can be used.

(1-2. Emulsion resin)
As said emulsion resin, arbitrary appropriate emulsion resin can be employ | adopted in the range which does not impair the effect of this invention. For example, acrylic emulsion, silicon-modified acrylic emulsion, fluorine emulsion, urethane emulsion, and epoxy emulsion can be mentioned. An acrylic emulsion is particularly preferable. As the content ratio of the emulsion resin in the aqueous coating composition of the present invention, any appropriate content ratio can be adopted as long as the solid content concentration of the emulsion resin is considered and the effects of the present invention are not impaired.

  The acrylic emulsion is obtained by emulsion polymerization of an unsaturated monomer composition mainly composed of an acrylic monomer as a raw material using an emulsifier. Arbitrary appropriate monomers can be employ | adopted as a preferable unsaturated monomer used as a raw material for manufacturing an acrylic emulsion. Examples thereof include a hydroxyl group-containing unsaturated monomer, an acid group-containing unsaturated monomer, an acrylic ester monomer, and other unsaturated monomers.

  Examples of the hydroxyl group-containing unsaturated monomer include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, Plaxel FM-1 (ε-caprolactone-modified hydroxyethyl methacrylate manufactured by Daicel Chemical Industries), polyethylene glycol Mention may be made of alcohols such as monoacrylate or monomethacrylate, polypropylene glycol monoacrylate or monomethacrylate.

  Examples of the acidic group-containing unsaturated monomer include carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid and maleic acid.

  Examples of the acrylic ester monomers include esters of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, butyl, hexyl, ethylhexyl, and lauryl.

  Examples of the other unsaturated monomers include unsaturated hydrocarbons such as styrene, α-methylstyrene, vinylnaphthalene, butadiene, and isoprene; nitriles such as acrylonitrile and methacrylonitrile; acrylamide, methacrylamide, and N-methylolacrylamide. Amides such as N, N-dimethylacrylamide and diacetone acrylamide; polyoxyalkylene derivatives such as polyethylene glycol methyl ether acrylate and methacrylate;

  Arbitrary appropriate emulsifiers and initiators can be used as the emulsifier and initiator used in emulsion polymerization of unsaturated monomers.

  The acrylic emulsion may be used in combination with a curing agent, or may be a non-curing type used without using a curing agent.

  Arbitrary appropriate particle diameters can be employ | adopted for the particle diameter of the acrylic resin particle in the said acrylic emulsion in the range which does not impair the effect of this invention. Preferably it is 0.01-100 micrometers, More preferably, it is 0.1-10 micrometers.

  Arbitrary appropriate number average molecular weights can be employ | adopted for the number average molecular weight of the acrylic resin particle in the said acrylic emulsion in the range which does not impair the effect of this invention. Preferably it is 1000-1 million, More preferably, it is 5000-100000.

  A commercially available resin can also be used as the emulsion resin. Examples of commercially available emulsion resins include acrylic emulsions such as “Boncoat” (trade name) manufactured by Dainippon Ink, “Yodosol” (trade name) manufactured by NSC Japan, and “Cybinol” (trade name) manufactured by Seiden Chemical. ), “Acry Reset” (trade name) manufactured by Nippon Shokubai Co., Ltd. can be mentioned. The emulsion particles of such an emulsion resin are usually non-crosslinked particles.

  The emulsion resin may be a core / shell type emulsion. The core-shell type emulsion can be produced by any suitable method such as two-stage emulsion polymerization using the unsaturated monomer composition and the emulsifier. The core part may be cross-linked or non-cross-linked, but the shell part is preferably non-cross-linked.

(1-3. Water)
The aqueous coating composition of the present invention is an aqueous coating composition and essentially contains water. The water may be water contained in the above emulsion resin, may be water blended separately from the emulsion resin, or a combination thereof.

  Any appropriate amount of water can be adopted as the amount of water in the aqueous coating composition of the present invention as long as the effects of the present invention are not impaired.

(1-4. Film-forming aid)
In the aqueous coating composition of the present invention, a film-forming aid may be blended as necessary. By blending the film-forming aid, when the emulsion resin particles are fused to form a film by evaporating water, the flow of the film is improved. As a result, the appearance of the coating film is improved.

  Any appropriate film-forming aid may be employed as the film-forming aid. Examples of commercially available film-forming aids include texanol (trade name, manufactured by Eastman Chemical Japan), butyl cellosolve (manufactured by Kyowa Hakko), and C5-12 (trade name, manufactured by Kyowa Hakko). Can do. The film-forming aid is preferably 2 to 15% by weight based on 100 resin solids. If it is less than 2% by weight, the film forming property may be inferior, and the design property may be slightly inferior. If it exceeds 15% by weight, the water resistance of the resulting coating film may deteriorate, which is not preferable.

(1-5. Thickener)
You may mix | blend a thickener with the water-based coating composition of this invention as needed. Any appropriate thickener can be adopted as the thickener. The thickener is preferably 0.5 to 3% by weight based on 100 resin solids. If it is less than 0.5% by weight, sufficient thixotropy may not be obtained, and the design may be slightly inferior, which is not preferable. If it exceeds 3% by weight, the water resistance of the resulting coating film may deteriorate, which is not preferable.

(1-5. Other components)
The water-based coating composition of the present invention may contain any appropriate other component. For example, curing agents, crosslinked resin particles, viscosity modifiers, antifoaming agents, UV absorbers, antioxidants, surface conditioners, surfactants, flow conditioners, pH adjusters, plasticizers, dyes, wax emulsions, fungi Agents, preservatives, coupling agents, hindered amines, and hindered phenols.

[2. Use of water-based paint composition (1): Water-based paint composition for building materials and method for forming design coating film]
When the aqueous coating composition of the present invention is used for building materials, the glittering material preferably contains 0.1 to 50% by weight, more preferably 5 to 40% by weight in the total solid content in the coating.

(2-1. Method for forming a design coating film)
In using the aqueous coating composition of the present invention for building materials, the design coating film forming method of the present invention applies the aqueous coating composition of the present invention onto a substrate having an uneven shape on the surface. The term “on the substrate” as used herein means not only the case where it is applied directly to the substrate, but also the case where it is applied after another layer is provided on the substrate.

  Arbitrary appropriate uneven | corrugated shape can be employ | adopted as said uneven | corrugated shape. For example, various shapes in which spots, stripes, bricks, mosaics, etc. may be distributed are mentioned. As described above, it is only necessary to have at least a bent portion and exhibit a multicolored feeling according to the angle of the surface at that portion.

  The concavo-convex shape preferably has a concavo-convex depth of 1 mm or more. When the unevenness depth is less than 1 mm, there is a possibility that a multicolor feeling that can be visually recognized cannot be sufficiently obtained. Further, it is difficult to stably coat the convex portions by roll coating. The uneven depth refers to the width between the upper end of the uneven portion of the uneven surface and the lower end of the recessed portion. The uneven depth is more preferably 1 to 30 mm, further preferably 1 to 20 mm or more, and particularly preferably 3 to 10 mm.

  The concavo-convex shape has a smooth surface with almost no smooth surface on the entire surface to be coated, and is entirely composed of a concave portion and a convex portion, and has a smooth surface as a reference surface, and is partially concave and / or convex with respect to the smooth surface. Any of the parts may be present. Moreover, the diagram may be drawn by a concave part and / or a convex part. Furthermore, the uneven | corrugated shape for providing material feelings, such as a stone material tone and a brick tone, may be sufficient.

  Any appropriate method can be adopted as the application method. For example, atomization coating and roll coating can be mentioned. Examples of the atomizing coating include spray coating, airless spray coating, air spray coating, and rotary atomization coating.

  When the coating film is formed by the atomization coating, it is preferable to use a thixotropic coating composition in order to perform efficient atomization and prevent sagging or unevenness after the coating. The thixotropic coating composition is easily atomized by a relatively low viscosity when subjected to a high shear force during atomization, and has viscosity after adhering to the surface to be coated. The arrangement of the light-interfering flake pigment due to sagging or unevenness is not disturbed, which is preferable.

  The roll coating is a coating method widely used when a designable coating film is formed only on the convex portion of the substrate. When performing the coating by the roll coating, the thixotropic property required in the atomization is not necessary, but the thickness unevenness of the coating film surface easily occurs due to the unevenness existing on the roll surface instead. That is, the roll used for roll coating has unevenness on the surface based on the substrate characteristics. For this reason, the coating film may have irregularities reflecting the irregularities of the roll, which may cause disorder in the orientation of the light interference flake pigment. Therefore, it is preferable that the coating film is smoothed to some extent during the period from application to drying of the coating film. When such an action is required, it is preferable to use a Newtonian coating composition.

  Here, thixotropic property and Newtonian property can be evaluated by a thixo index which is a ratio of torque at low shear force and torque at high shear force.

  The relationship between the shearing force and the torque is measured by a B-type viscometer DV-I + VISCOMETER manufactured by BROOKFIELD. The torque at the low shear force is a torque when measured using the above apparatus at a spindle rotational speed of 6 rpm, and the torque at the above high shear force is a torque measured using the above apparatus at a spindle rotational speed of 60 rpm. is there.

  When the thixo index [(torque of low shear force) / (torque of high shear force)] is 3-6, it can be used as the thixotropic paint. It can be used as a tonian paint.

  The thixo index can be adjusted by selecting the type of thickener added to the paint. Any appropriate thickener can be adopted as the thixotropic thickener. For example, the salt of a polycarboxylic acid compound can be mentioned. Any appropriate thickener can be adopted as the Newtonian thickener. For example, urethane modified polyether can be mentioned. The thickener is preferably added at a ratio of 0.1 to 5% by mass with respect to the paint.

  In building material applications, the film thickness of the coating film formed from the aqueous coating composition of the present invention is preferably 10 to 40 μm.

  You may dry after apply | coating the water-based coating composition of this invention. Any appropriate method can be adopted as the drying method. For example, a method of preheating the object to be coated and applying it after heating, a method of heating and drying without preheating, or a method of drying at ambient temperature is used. For example, when pre-heating the object to be coated, it is preferable to carry out at a substrate temperature of about 30 to 80 ° C., a heating and drying temperature of 40 to 150 ° C., and an atmospheric temperature of 5 to 40 ° C. However, it suffices if the emulsion is fused and a coating film can be formed.

When the water-based coating composition of the present invention is applied to the ceramic material, the undercoating layer may be formed on the surface of the substrate to form the undercoating layer, and then the coating film may be formed. Furthermore, after applying a colored paint to form a colored coating layer and coloring the substrate in a desired color tone, a coating film made of the aqueous coating composition of the present invention may be formed on the colored coating layer. Arbitrary appropriate things can be adopted as the above-mentioned undercoat paint and the above-mentioned colored paint.
Although it does not restrict | limit especially as an undercoat coating material, A water-based coating material is preferable and an acrylic emulsion is mentioned, for example.
Although it does not restrict | limit especially as a coloring paint, For example, a coloring pigment is included and an aqueous emulsion is preferable.

You may apply a clear coating material on the coating film formed with the aqueous coating material composition of this invention. This is preferable in that the surface protection function by the coating film is excellent. Any appropriate paint can be adopted as the clear paint. The coating thickness of the clear coating can be any appropriate thickness. For example, it can be set to 10 to 30 μm.
Although it does not restrict | limit especially as a clear coating material, For example, an acrylic resin, an acrylic urethane resin, etc. are mentioned, Preferably, it is an aqueous type, For example, an acrylic emulsion resin and a silicone modified acrylic emulsion resin are mentioned.

(2-2. Board for building materials)
The building material board of the present invention has a coating film formed by the design coating film forming method of the present invention.

  The coating film formed by the water-based coating composition of the present invention containing a special glitter material has a property that the color tone changes depending on the viewing angle because the glitter material causes light interference. When such a coating film is formed on the surface of a substrate having a concavo-convex shape on the surface, the color appears to change according to the concavo-convex shape of the surface, that is, a very special appearance design (ie, multicolored feeling) Can be expressed. In other words, because the reflection of a color different from that of the flat portion is exhibited along the uneven shape, the uneven shape is visually recognized with not only a three-dimensional feeling but also a change in color tone due to the unevenness. Can be expressed. Since the surface of the base material has an uneven shape, for example, the plane is bent at the convex portion, and if the glittering material is present at the bent portion, a multicolor feeling that the color varies depending on the angle is obtained. Will be presented. Such a very special appearance design cannot be obtained on a smooth coated surface such as a metal plate or a press-molded automobile body. In particular, building board is a field that requires special design, including the feel of stone and brick, and in such fields, various uneven shapes are formed on the surface. ing. Therefore, when a coating film as described above is formed on a material in such a field, an appearance design completely different from that of an automobile body or the like can be expressed.

  Any appropriate base material can be adopted as the base material of the building material board. For example, an inorganic material, an organic material, and a composite thereof can be given. Specifically, for example, ceramic-based substrates such as slate, cement, calcium silicate plate, wood piece cement plate, ceramics, glass, plastic, wood, stone, concrete, fiber, fabric, paper, a plurality of these The thing which consists of a base material, these laminated bodies, an elastic waterproofing membrane, the coating body which coated sealing etc. can be mentioned. Especially, it is preferable that it is a board for construction materials which consists of ceramic materials, such as a calcium-silicate board and a wood chip cement board, for durability and workability. The said base material is manufactured by arbitrary appropriate manufacturing methods, and formation of uneven | corrugated shape, control, etc. can also be performed according to arbitrary appropriate methods.

  Any appropriate color tone can be used for the surface to be coated. For example, when coating is performed on a dark-colored surface to be coated, the effect of the design of the present invention can be expressed more clearly. Therefore, the coated surface preferably has an L value of 50 or less, more preferably 40 or less, by color measurement before painting. The L value is a numerical value corresponding to L * in the L * a * b * color system and represents lightness. The larger the L value, the whiter, and the smaller the L value, the blacker.

  When the glittering material is present in the coating film, the glittering material gradually changes according to the change in the angle of incident light or the viewing angle, and is observed to exhibit a multicolored feeling. Therefore, in the coating film containing the said brilliant material, since interference of the light by a brilliant material occurs, it has a multicolor feeling according to the uneven | corrugated shape. Therefore, when viewed from the highlight position, interference colors such as silver, yellow, red, blue, and green are observed depending on the film thickness of the coating film. However, when viewed from the shade position, these interferences are observed. A complementary color of the color or a color in which the transmitted color is reflected and absorbed according to the base color can be seen.

[3. Application of water-based paint composition (2): Water-based paint composition for automobile and method of painting automobile body]

(3-1. Water-based paint composition for automobiles)
When the aqueous coating composition of the present invention is used for automobile applications, the aqueous coating composition of the present invention preferably further contains a curing agent.

  Any appropriate curing agent can be adopted as the curing agent. Preferably, a melamine resin and a blocked polyisocyanate compound are used. The melamine resin is, in particular, a methylolated melamine resin having an average of 3 or more methylol groups per triazine nucleus, or a melamine resin in which a part of the methoxy group is replaced with an alkoxy group having 2 or more carbon atoms. Furthermore, hydrophilic melamine having an imino group and having an average degree of condensation of about 2 or less and a mononuclear ratio of about 50% by weight or more is preferable. Use blocked polyisocyanate compounds in which isocyanate groups of polyisocyanate compounds having at least two isocyanate groups in one molecule are blocked with a blocking agent such as oxime, phenol, alcohol, lactam, mercaptan, etc. Can do.

  Preferably the said hardening | curing agent mix | blends 20-100 weight part with respect to the solid content total 100 weight part in the water-based coating composition of this invention.

  When the aqueous coating composition of the present invention is used for automobile applications, the blending amount of the glittering material is preferably 0.1 to 50% by weight as the concentration in the total solid content in the aqueous coating composition of the present invention. 0.5 to 40% by weight is more preferable.

  When the aqueous coating composition of the present invention is used for automobile applications, any appropriate addition such as the above-mentioned film-forming aid, thickener, surface conditioner, antioxidant, ultraviolet absorber, antifoaming agent, etc. An agent may be blended.

(3-2. Car body painting method)
A coating film for automobiles is usually formed by performing an undercoating of an electrodeposition coating, followed by an intermediate coating, and an overcoating thereon. The automobile body coating method of the present invention is a method for coating an automobile body in which a first base paint, a second base paint, and a clear paint are applied in this order after an undercoat layer and an intermediate coat layer are formed on the surface of an object to be coated. Then, the second base paint is the above-mentioned aqueous paint composition for automobiles.

  The first base paint may be either water-based or solvent-based, but is preferably water-based.

  When the first base paint is solvent-based, examples of the binder include film forming resins such as acrylic resins, polyester resins, alkyd resins, and fluorine resins, and curing agents such as amino resins and / or block polyisocyanate compounds. Is used. The preferable solid content in the paint is in the range of 30 to 70% by weight during production and 10 to 50% by weight during application. The dry film thickness of the coating film formed is preferably 10 to 30 μm. When the first base paint is water-based, any appropriate water-based paint composition can be adopted. For example, components other than the glittering material in the present invention may be the same as the water-based coating composition.

  The first base paint may contain a color pigment. Examples of the color pigment include organic azo lake pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, and isoindolinone. Examples of inorganic pigments include inorganic pigments, metal complex pigments, inorganic yellow lead, yellow iron oxide, bengara, carbon black, titanium dioxide, and extender pigments such as calcium carbonate, barium sulfate, clay, and talc.

  The color pigment that can be used in the first base paint is for forming a color base layer from a layer formed by the first base paint. In the present invention, when a transparent material that does not contain a pigment is used as the bright material, it is preferable to use black or a color similar thereto, for example, a dark color base layer, in order to further enhance the coloring effect. . When a harmonious color tone is desired, a color other than black or a color similar to it may be preferable. When the layer structure of the glittering material includes a dye layer or a color component, it is preferable to employ a color base layer that is in harmony with the color.

  The binder of the clear coating is not particularly limited, but comprises a coating forming resin such as an acrylic resin, a polyester resin, an alkyd resin, or a fluorine resin, and a curing agent such as an amino resin and / or a block polyisocyanate compound. A resin composition, an acid-epoxy acrylic paint composed of an acrylic resin having an acid group and an epoxy compound can be used. The preferable solid content in the paint is in the range of 30 to 70% by weight during production and 10 to 50% by weight during application. The dry film thickness of the coating film formed is preferably about 30 to 60 μm.

  In the method of painting an automobile body according to the present invention, the first base paint is water-based, and the first base paint, the second base paint, and the clear paint are applied by wet-on-wet and then baked. It is preferable to perform the baking method. That is, for example, the first base paint is applied, and after setting for 2 to 3 minutes, preheating (50 to 80 ° C., 5 to 10 minutes) is performed, and then the second base paint is applied and applied for 2 to 3 minutes. After setting, preheat (50 to 80 ° C., 5 to 10 minutes), apply clear paint, set for 3 to 5 minutes, and then baked at once with each coating layer uncured (for example, , 120-160 ° C. for 10-40 minutes). The above preheating may or may not be performed, but it is preferable to perform preheating.

  In addition, the application | coating process of a 1st base coating material may be abbreviate | omitted, a 2nd base coating material may be applied on intermediate coating, and a clear coating material may be applied then.

[4. Other uses of water-based paint composition]
The water-based coating composition of the present invention can be applied to any other appropriate use other than the above uses. For example, building materials such as doors and shoji paper; fashion accessories such as sun visors, parasols, beach umbrellas; display parts such as show windows and vending machines equipped with backlights; electrical signs; various lighting tools; It can be applied to other uses.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on weight.

[Manufacture of bright materials]
[Production Example 1]: Production of glittering material (1) Polyethylene naphthalate (PEN) having a refractive index of 1.63 is used as a first polymer, and nylon 6 having a refractive index of 1.53 is used as a second polymer. By alternately laminating 30 layers and covering the periphery with a coating layer made of polyethylene naphthalate, the thickness of the first polymer da = 0.072 μm and the thickness of the second polymer db = 0.077 μm A bright material (1) was obtained. The dimension ratio of the glitter material (1) is such that when the length A of the side perpendicular to the laminate surface of both polymers is 1, the length B of the side parallel to the laminate surface is 4 to 5, and the length of the glitter material L was set in the range of 15-20.

[Production Example 2]: Production of glittering material (2) SP1 = 19.1 copolymerized PEN1 as a high refractive index side resin (5-sodium sulfoisophthalic acid component 1.5 mol% copolymerized polyethylene-2,6-naphthalate ), Nylon 6 with SP2 = 22.5 as the low refractive index side resin, and copolymer PEN2 with SP4 = 19.1 as the intermediate layer (located in the center of the laminate) (blue pigment (phthalocyanine made by Dainippon Seika) Pigments: 5-sodium sulfoisophthalic acid component 1.5 mol% copolymer polyethylene-2,6-naphthalate containing 0.9% by weight of CI P.B1.15.3)) at 290 ° C. and 270 ° C., respectively. After being melted at 290 ° C. and weighed, it was introduced into a spinning pack together with copolymer PEN1 to be a coating layer and spun at 1200 m / min. The obtained undrawn yarn was drawn 2.0 times at a preheating temperature of 90 ° C., heat-set at 180 ° C. and wound to obtain a glittering material (2) having an alternating laminate portion with 41 layers. It was.

[Related to building material use]: Examples (1-1) to (1-35)

[Example (1-1)]: Production of water-based coating composition (1-1) To 100.0 parts of Yodosol AD57 (acrylic emulsion resin, NV 50%, manufactured by NSC Japan), texanol (film-forming aid, 8 parts (manufactured by Eastman Chemical Japan) was dropped while stirring with a disper, and then 0.4 parts of SN deformer 154 (antifoaming agent, San Nopco) was added dropwise, followed by stirring for 5 minutes.
Thereafter, 2.7 parts of glittering material (1) was added while stirring was continued, and then 64.5 parts of tap water was added and stirred for 10 minutes.
Thereafter, SN thickener 615 (polycarboxylic acid type, thixotropic thickener, manufactured by San Nopco) was added to adjust the viscosity to 40 ± 3 seconds with Iwata NK # 2 cup. A composition (1-1) was obtained.
Table 1 shows the blending components, viscosity, heating residue, PWC, and viscosity evaluation of the aqueous coating composition (1-1) obtained above.
In Table 1, the heating residue is the total solid content concentration in the paint. Moreover, PWC shows a pigment density | concentration and says the weight density | concentration (%) of the luster material contained in the total solid content in a coating material here. Furthermore, “chi” in the viscosity evaluation means that the thixo index (TI) is 3 or more and means thixotropy, and “d” means that the thixo index (TI) is less than 3. Means Newtonian.

[Examples (1-2) to (1-3)]: Production of water-based coating compositions (1-2) to (1-3) Implementation was performed except that the composition of each component was changed as shown in Table 1. In the same manner as in Example (1-1), aqueous coating compositions (1-2) to (1-3) were obtained.
It shows in Table 1 about the compounding component of the aqueous coating composition (1-2)-(1-3) obtained above, a viscosity, a heating residue, PWC, and viscosity evaluation.

[Examples (1-4) to (1-6)]: Production of water-based coating compositions (1-4) to (1-6) SN thickener 615 as SN thickener 601 (associative thickener) as a thickener , Newtonian, manufactured by San Nopco), except that the composition of each component is shown in Table 1, in the same manner as in Example 1-1, the aqueous coating composition (1-4) to (1-6) was obtained.
It shows in Table 1 about the compounding component, viscosity, heating residue, PWC, and viscosity evaluation of the aqueous coating composition (1-4)-(1-6) obtained above.

[Examples (1-7) to (1-9)]: Production of aqueous coating compositions (1-7) to (1-9) Aqueous coating compositions (1-3) and (1) obtained above -6) was blended as shown in Table 2 to prepare aqueous coating compositions (1-7) to (1-9).

[Examples (1-10) to (1-15)]
(Base material)
As an object to be coated in the following coating, a “UB board 12” tile tone (manufactured by Ube board) was used. On this surface, there are approximately 100 irregularities having a depth of 2 mm per 1 m 2. Apply "Ultra Sealer III White" (trade name) manufactured by Nippon Paint Co., Ltd. as an undercoat to the above-mentioned object, and further apply "Odetite 339" (trade name, manufactured by Nippon Paint Co., Ltd.) as a colored paint. A painted plate was obtained. When the color value of the surface of the coated plate on which the base coating film was formed was measured by “CR-300” (trade name, manufactured by Konica Minolta Sensing), L = 30, a = 0.9, b = −1. It was 9.

(Spray painting)
Using the aqueous coating compositions (1-1) to (1-3) obtained above, an air spray gun “W-100” (trade name, Anest Iwata) with a substrate surface temperature of 60 ± 5 ° C. The coated plate on which the base coating film was formed was painted by the company). The above coating was performed by spray coating so as to have a film thickness of 20 μm over the entire surface of the object to be coated. After drying at 100 ° C. for 10 minutes, “Audite 200 Clear” (manufactured by Nippon Paint Co., Ltd.) is applied as a clear coating to a thickness of 20 μm and dried at 100 ° C. for 10 minutes to obtain a test coating plate. It was.

(Roll coating)
Using the aqueous coating compositions (1-4) to (1-6) obtained above, the “roll coater” (trade name, manufactured by Sanwa Seiki Co., Ltd.) at a substrate surface temperature of 60 ± 5 ° C. Thus, the coated plate on which the base coating film was formed was painted. The said coating was performed so that it might become a film thickness of 10 micrometers with respect to a convex-part coating surface by roll coating. After drying at 100 ° C. for 10 minutes, “Audite 200 Clear” (manufactured by Nippon Paint Co., Ltd.) is applied as a clear coating to a thickness of 20 μm and dried at 100 ° C. for 10 minutes to obtain a test coating plate. It was.

(Evaluation)
The multicolor feeling and secondary adhesion of the test coating plate obtained above were evaluated by the following methods. The results are shown in Table 3.
<Multicolor>
The external appearance of the obtained test coated plate was visually evaluated according to the following criteria.
○: The color appears to change clearly according to the unevenness of the base material and coating.
(Triangle | delta): A color changes a little according to the unevenness | corrugation of a base material, and coating.
X: The unevenness | corrugation of a base material and the color change according to coating different are not recognized, or the uneven | corrugated feeling of a base material is impaired.
<Secondary adhesion>
A waterproof seal is applied to the surface and the end of the test coating plate with urethane paint ("Rusole 190 Sealer", trade name, manufactured by Nippon Paint Co., Ltd.), left at room temperature for 24 hours, and then immersed in warm water at 60 ° C for 3 days. . Then, the test coating plate was taken out and dried at room temperature for 24 hours, and a grid pattern (2 mm square, 25 squares) was created with a cutter knife.
An adhesive tape ("Nichiban TM", trade name, manufactured by Nichiban Co., Ltd.) was applied on the grid, and the number of cells peeled off when peeled off was evaluated according to the following criteria.
○: Number of peeling mass 2/25 or less Δ: Number of peeling mass 3/25 to 10/25
X: Number of peeling mass 11/25 or more

[Examples (1-16) to (1-20)]
Except having used the coating board shown in Table 4, a water-based coating composition, and the coating method, the coating board for a test was obtained like Example (1-1), and those external appearances and multicolor feeling were evaluated. Evaluation of multicolor feeling was performed by the same method as described above. The results are shown in Table 4.

[Examples (1-21) to (1-22)]
The water-based paint composition (1-3) obtained above was applied to the “UB board 12” tile-like (above) and “UB board 12 flat groove-free (evening)” with no irregularities on the surface (flat-tone, Ube board Except that the coated plate having the same base color L value was spray-coated, test coated plates were prepared in the same manner as in Example (1-1), and their appearance and multicolor feeling were evaluated. The evaluation method of multicolor feeling was performed in the same manner as described above. The results are shown in Table 5.

[Automobile applications]: Production examples 3 to 7, Examples (2-1) to (2-10), Comparative examples (C2-1) to (C2-2)

[Production Example 3]: Production of acrylic emulsion resin (A) 126.5 parts of ion-exchanged water was added to a reaction vessel, and the mixture was heated to 80 ° C while being mixed and stirred in a nitrogen stream. Next, as the first stage α, β-ethylenically unsaturated monomer mixture, 45.21 parts of methyl acrylate, 27.37 parts of ethyl acrylate, 7.42 parts of 2-hydroxyethyl methacrylate, Aqualon HS-10 (Polyoxyethylene alkylpropenyl phenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part, Adekalya soap NE-20 (α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl]) -Ω-hydroxyoxyethylene, manufactured by Asahi Denka Co., Ltd., 80% aqueous solution), a monomer emulsion consisting of 0.5 parts, and ion-exchanged water 80 parts, ammonium persulfate 0.24 parts, and ion-exchanged water 10 parts The agent solution was dropped into the reaction vessel in parallel over 2 hours. After completion of the dropping, aging was performed at the same temperature for 1 hour.
Furthermore, as the α, β-ethylenically unsaturated monomer mixture in the second stage at 80 ° C., 15.07 parts of ethyl acrylate, 1.86 parts of 2-hydroxyethyl methacrylate, 3.07 parts of methacrylic acid, Aqualon HS A monomer emulsion consisting of 0.2 parts of -10 and 10 parts of ion-exchanged water and an initiator solution consisting of 0.06 parts of ammonium persulfate and 10 parts of ion-exchanged water were reacted in parallel over 0.5 hours. It was dripped at the container. After completion of the dropping, aging was performed at the same temperature for 2 hours.
Next, after cooling to 40 ° C. and filtering with a 400 mesh filter, 67.1 parts of ion exchange water and 0.32 part of dimethylaminoethanol were added to adjust the pH to 6.5, an average particle diameter of 150 nm, a non-volatile content of 20%, An acrylic emulsion resin (A) having a solid content acid value of 20 and a hydroxyl value of 40 was obtained.

[Production Example 4]: Production of water-soluble acrylic resin (B) Add 23.89 parts of dipropylene glycol methyl ether and 16.11 parts of propylene glycol methyl ether to a reaction vessel, and mix and stir in a nitrogen stream at 105 ° C. The temperature rose. Next, 13.1 parts of methyl methacrylate, 68.4 parts of ethyl acrylate, 11.6 parts of 2-hydroxyethyl methacrylate, 6.9 parts of methacrylic acid, 10.0 parts of dipropylene glycol methyl ether and t-butyl An initiator solution consisting of 1 part of peroxy 2-ethylhexanoate was dropped into the reaction vessel in parallel over 3 hours. After completion of the dropping, aging was performed at the same temperature for 0.5 hours. Further, an initiator solution consisting of 5.0 parts of dipropylene glycol methyl ether and 0.3 part of t-butylperoxy 2-ethylhexanoate was dropped into the reaction vessel over 0.5 hours. After completion of the dropping, aging was performed at the same temperature for 2 hours.
After removing 11.11 parts of the solvent at 110 ° C. under reduced pressure (70 torr) using a solvent removal apparatus, 204 parts of ion-exchanged water and 7.14 parts of dimethylaminoethanol were added to obtain a water-soluble acrylic resin (B). . The obtained water-soluble acrylic resin (B) had a nonvolatile content of 30.0%, an acid value of 40, a hydroxyl value of 50, and a viscosity of 140 poise (E-type viscometer 1 rpm / 25 ° C.).

[Production Example 5]: Production of colored paste (C) 50 g of the water-soluble acrylic resin (B) obtained in Production Example 4 in solid content, 50 g of carbon black (product brand: # 2700B, manufactured by Mitsubishi Chemical Corporation), A pigment dispersant efka-4550 manufactured by Efka Corporation was added in a solid content of 10 g to a stainless beaker. After adding 18.3 g of deionized water, the mixture was stirred well with a desktop disper and the mixture was transferred to an SG mill. To this was added 300 g of zircon beads and stirred for 5 hours in an SG mill to remove the zircon beads and obtain a colored paste (C). The pigment concentration PWC = 50% and the solid content concentration = 43%.

[Production Example 6]: Production of first base paint Primer PX-1000 (bifunctional polyether polyol manufactured by Sanyo Kasei Co., Ltd., number average molecular weight 400, hydroxyl value 278, primary / secondary hydroxyl value ratio = 63/37, water tolerance infinity) 10 g was added, and 10 g of the water-soluble acrylic resin (B) obtained in Production Example 4 was added thereto. Furthermore, 40 g of the acrylic emulsion resin (A) obtained in Production Example 3 was added as a solid content. While stirring this with a desktop disper, 30 g of melamine resin Cymel 204 (Mitsui Chemicals methylated melamine resin) was added in solid content. While continuing stirring, 50 g of the colored paste (C) obtained in Production Example 5 was added. Further, 1 g of SN thickener 615 was added. While continuing stirring, N, N-dimethylethanolamine diluted 10-fold so that the pH of the paint was 8.5 was added to obtain a first base paint.

[Examples (2-1) to (2-5), Comparative Example (C2-1)]: Production of second base paint (water-based paint compositions (2-1) to (2-5), (C2- 1) Production)
Water-based paint compositions (2-1) to (2-5) and (C2-1) were prepared with the formulation shown in Table 6.
In addition, each compounding material in Table 6 means the following material.
Emulsion: acrylic emulsion resin (A) obtained in Production Example 3
Water-soluble resin: water-soluble acrylic resin (B) obtained in Production Example 4
Curing agent: imino group-type methylated melamine resin having a number average molecular weight of 420 and a solid content of 100% by mass (My Coat 723, manufactured by Nippon Cytec Co., Ltd.)
Bright material (1): Bright material (1) obtained in Production Example 1
Bright material (2): Bright material (2) obtained in Production Example 2
Mica: Pearl Grace SME-90-9 (Nippon Koken Co., Ltd.)
Thickener (1): SN thickener 615 (thixotropic thickener, manufactured by San Nopco)
Thickener (2): SN thickener 601 (Newtonian thickener, manufactured by San Nopco)
Film-forming aid (1): Texanol (manufactured by Eastman Chemical Japan)
Film-forming aid (2): Primepole PX-1000 (manufactured by Sanyo Chemical Co., Ltd.)

[Examples (2-6) to (2-10), Comparative Example (C2-2)]
Zinc phosphate-treated dull steel plate with a thickness of 0.8 mm and 10 cm × 50 cm is coated with a cationic electrodeposition paint (trade name “Power Top U-50”, manufactured by Nippon Paint Co., Ltd.) so that the dry film thickness is about 25 μm. The film was electrodeposited and baked at 160 ° C. for 30 minutes. Next, an intermediate coating (trade name “Orga P-2”, manufactured by Nippon Paint Co., Ltd.) is spray-coated on the obtained electrodeposition coating film so that the dry film thickness is about 40 μm, and 140 ° C., 30 Baked for a minute.
After cooling, the white color base paint (first base paint) obtained in Production Example 6 was applied to the intermediate coating film obtained in No. 6 as follows. Using a 4 Ford cup, dilute to 20 seconds at 20 ° C, adjust the viscosity, spray coat in 2 stages so that the dry film thickness is about 30 µm, set it for about 2 seconds, and set the first base A paint layer was formed.
Next, as the second base paint, the aqueous paint compositions (2-1) to (2-5) obtained in Examples (2-1) to (2-5) and Comparative Example (C2-1) and Each of (C2-1) was subjected to No. using deionized water. Using a 4 Ford cup, dilute to 20 seconds at 20 ° C., and wet-on-wet paint on the uncured first base paint layer so that the dry film thickness is about 30 μm. Painted and set for about 7 minutes.
Further, a clear paint (trade name: Macflow O-1810, manufactured by Nippon Paint Co., Ltd.) was applied on the uncured second base coating film so that the dry film thickness was 35 μm. After setting for 5 minutes, it was baked at 140 ° C. for 30 minutes to prepare an evaluation coating plate, and the appearance of the coating film was evaluated. The appearance of the coating film was evaluated based on the following criteria by observing the color unevenness of the coating film.
A: There is no color unevenness and the appearance is very good.
○: No color unevenness and good appearance.
X: There is uneven color.
Table 7 shows the evaluation results.

  Looking at the above examples and comparative examples, the aqueous coating composition of the present invention can form a uniform coating film that changes the hue depending on the viewing angle and gives a color tone and texture with a sense of depth and depth, It can be seen that it is useful for the formation of multilayer coatings on automobile bodies and for the coating of building materials such as uneven building material boards.

  The water-based paint composition of the present invention includes, for example, automobile bodies, sunroofs, side visors, windows, etc .; building materials such as boards for building materials; building materials such as doors and shoji paper; fashion accessories such as sun visors, parasols, beach umbrellas, etc. It can be applied to various uses such as a display unit such as a show window or a vending machine equipped with a backlight, an electric signboard, various lighting tools, and the like.

Claims (20)

A water-based paint composition comprising a glittering material, an emulsion resin, and water,
The glitter material has a laminated structure portion of at least two types of resin layers having different refractive indexes.
Water-based paint composition.   The aqueous coating composition according to claim 1, further comprising a film-forming aid.   The aqueous coating composition according to claim 1, further comprising a thickener.   The bright material has a coating layer including any one of resins constituting the at least two types of resin layers and / or a resin different from these resins, around the laminated structure portion. The aqueous coating composition according to any one of 1 to 3.   The water-based paint composition according to any one of claims 1 to 4, wherein the glitter material has a substantially flat cross section.   The water-based paint composition according to any one of claims 1 to 5, wherein the glittering material includes a pigment layer containing an achromatic pigment and / or a chromatic pigment in the laminated structure portion.   The glittering material has an alternately laminated structure part of two types of resin layers having different refractive indexes, and the ratio between the solubility parameter value (SP1) of the high refractive index side resin and the solubility parameter value (SP2) of the low refractive index side resin. (SP ratio) is in a range of 0.8 ≦ SP1 / SP2 ≦ 1.1, and has a coating layer made of a fiber-forming resin around the alternately laminated structure portion. The water-based paint composition described in 1.   The water-based paint composition according to claim 7, wherein a chromatic color component is contained in the alternately laminated structure portion and / or the coating layer.   The water-based paint composition according to claim 7 or 8, wherein the glitter material has a substantially flat cross section, and a flatness ratio of the cross section is 3.5 or more.   The water-based paint composition according to any one of claims 7 to 9, wherein the thickness of the alternately laminated structure portion is 10 µm or less.   The water-based coating composition according to any one of claims 7 to 10, wherein the high refractive index side resin and the low refractive index side resin are hardly alkali-soluble resins, and the fiber-forming resin is an alkali-soluble resin. .   The formation method of the designable coating film which apply | coats the water-based coating composition in any one of Claim 1 to 3 on the base material which has an uneven | corrugated shape on the surface.   The surface of the base material is coated with an undercoat paint to form an undercoat layer, then a colored paint is applied to form a colored coating film layer, and then the aqueous paint composition is applied. The formation method of the designable coating film of description.   The formation method of the designable coating film of Claim 12 which apply | coats a clear coating material and forms a clear layer on the designability coating film formed with the formation method of the said designability coating film.   The said uneven | corrugated shape is a formation method of the designable coating film in any one of Claim 12-14 whose uneven | corrugated depth is 1 mm or more.   The board for building materials which has the coating film formed by the formation method of the designable coating film in any one of Claim 12-15.   The building material board according to claim 16, wherein the base material is made of a ceramic material.   The aqueous coating composition according to any one of claims 1 to 3, further comprising a curing agent. A method for coating an automobile body, wherein a first base paint, a second base paint, and a clear paint are applied in this order after forming an undercoat layer and an intermediate coat layer on the surface of an object to be coated,
The second base paint is the water-based paint composition according to claim 18.
How to paint car bodies.   The first base paint is water-based, and is performed by a three-coat one-bake method in which the first base paint, the second base paint, and the clear paint are applied by wet-on-wet and then baked. How to paint car bodies.