TWI414570B - Coating compositions for forming pattern and pattern forming method - Google Patents

Abstract

The invention relates to a coating composition for forming a pattern comprising a resin, a flat powder shaped magnetic component, and a solvent. The viscosity of the coating composition is 1,000-10,000 mPa.s after 15 seconds from being applied to a object to be coated, and is above 50,000 mPa.s after 90 seconds from being applied to a object to be coated. The invention also relates to a pattern forming method including coating a film on an object to be coated, arranging magnets on the surface of the coated film, and adding a magnetic field to the coated film through the magnets, and aligning magnetic components through the magnetic field.

Description

Coating composition for forming a pattern and pattern forming method

The present invention relates to a coating material for forming a pattern which is formed by applying a flat powdery magnetic material to a coating material which is, for example, a non-magnetic material, and a pattern forming method using the coating material.

In the past, it has been proposed to apply a magnetic powder coating to the surface of an object to be coated (the object to be coated), and then magnetically align the magnetic powder by using a magnetic field (magnetization energy) formed by the magnet to form a floating pattern with characters and figures. The method of coating the film. Patent Document 1 discloses a method of forming a liquid coating film containing a powdery magnetic coating on the surface of an object to be coated, and applying a magnetic field to the coating film while maintaining the flow state of the coating film. Patent Document 2 discloses a method and apparatus for forming a coating film having the above-described pattern. Patent Document 3 discloses a paint for pattern formation in which a solid content in a coating film after coating the coating material for one minute is set to 70% by mass or less.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

In a coating film having a pattern in which characters and patterns float, it is required to have a clear feeling, a sense of depth, and a sense of movement in which the pattern moves. However, among the means described in Patent Documents 1 to 3, there is a problem that these requirements cannot be sufficiently satisfied.

An object of the present invention is to provide a paint for pattern formation and a pattern forming method which can form a pattern having excellent sharpness, depth and movement.

In order to solve the above problems, in an embodiment of the present invention, there is provided a paint for forming a pattern comprising a resin, a flat powdery magnetic body, and a solvent. The paint for pattern formation has a viscosity of 1,000 to 10,000 mPa after 15 seconds from the application of the coating. s, and the viscosity after 50,000 seconds from the application of the coated object is 50,000 mPa. s above.

The resin is preferably an acrylic resin, and the paint for pattern formation further preferably contains a rheology control agent. The rheology control agent is at least one selected from the group consisting of a nitrocellulose resin, a cellulose acetate butyrate (CAB) resin, a microgel, and a vinyl acetate resin. It is better. Further, the coating material for pattern formation may further contain a polyisocyanate compound as a curing agent.

The resin is preferably a vinyl acetate resin. Further, it is preferable that the paint for pattern formation further contains at least one of a dye and a nano pigment.

According to another aspect of the present invention, there is provided a pattern forming method comprising the steps of: applying a coating material for forming a pattern to a coating material to form a coating film, and arranging a magnet along a surface of the coating film, and The magnet applies a magnetic field to the coating film and the magnetic field in the coating film is aligned by the magnetic field.

Preferably, the step of forming the coating film and disposing the magnet is a step of arranging a plurality of magnets having a sheet shape adjacent to each other along the surface of the coating film, and is provided with a surface magnetic pole and a back surface of each adjacent magnet The step of arranging the respective magnets is such that the magnetic poles are different from each other and the sides of the magnets are in contact with each other. In this case, the step of aligning the magnetic body includes: applying a magnetic field to the coating film by the plurality of magnets, and causing the magnetic body to be approximately parallel with respect to the surface of the coating film at a contact portion of each of the magnets adjacent to each other in contact with the magnet The step of extending is to form a pattern on the coating film by at least the magnetic body on the contact portion of each magnet. Further, the step of aligning the magnetic body preferably includes a step of applying a magnetic field having a magnetic flux density of 15 to 350 mT to the coating film.

The best aspect of implementing the invention

Hereinafter, the embodiment of the present invention will be described as an embodiment of the paint for pattern formation, which will be described based on the drawings. In the following description, the paint for pattern formation is simply referred to as a paint.

The coating material is used to form a coating film on the object to be coated, which contains a resin as a precursor of the coating film, and a magnetic body and a solvent dispersed in the resin to form a coating film pattern. When the coating film is desired to be colored, the coating may further contain a colorant. The viscosity of the paint after 15 seconds from the application of the coated object is set to 1,000 to 10,000 mPa. s, and the viscosity of the paint after 90 seconds from the application of the coated object is set to 50,000 mPa. s above.

Examples of the resin include an acrylic resin and a vinyl acetate resin. The acrylic resin can be obtained by radical polymerization of a radical polymerizable monomer. The weight average molecular weight of the acrylic resin is preferably 10,000 to 200,000, more preferably 15,000 to 150,000. The weight average molecular weight was measured by GPC (gel permeation chromatography) and calculated using a polystyrene conversion algorithm.

The radically polymerizable monomer which is an acrylic resin component may be, for example, a polymerizable monomer containing a hydroxyl group. Specific examples of the hydroxyl group-containing polymerizable monomer are not particularly limited, and specific examples thereof may be, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid. -2-hydroxybutyl ester and ε-caprolactone ring-opening addition of 2-hydroxyethyl (meth)acrylate. These specific examples may be, for example, the Plaxel FA series and the Plaxel FM series manufactured by Daicel Chemical Industry Co., Ltd.

The radical polymerizable monomer may be, for example, a monomer having a carboxyl group, a monomer having an epoxy group, methyl (meth)acrylate or ethyl (meth)acrylate, in addition to a polymerizable monomer having a hydroxyl group. Isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene, vinyl toluene, and α-methylstyrene. The monomer having a carboxyl group may be, for example, (meth)acrylic acid, maleic acid, and itaconic acid. The epoxy group-containing monomer may be, for example, glycidyl (meth)acrylate. The components of the acrylic resin may be used singly or in combination of two or more. These components can be polymerized by a known method.

When an acrylic resin is used as the resin, the coating may contain a rheology control (RC) agent or a hardener in order to adjust the viscosity of the coating. The RC agent adjusts the viscosity of the coating to the aforementioned range by the inherent viscosity of the RC agent. The RC agent may be, for example, a cellulose acetate butyrate resin, a nitrocellulose resin, or a microgel.

The specific example of the cellulose acetate butyrate-based resin is not particularly limited, and the specific example may be, for example, the CAB series manufactured by Eastman Chemical Co., Ltd. The CAB series may be, for example, CAB-171-15, CAB-321-0.1, CAB-381-0.1, CAB-381-0.5, CAB-381-2, CAB-381-20, CAB-381-20BP, CAB- 500-5, CAB-531-1 and CAB-553-0.4. When a cellulose acetate butyrate-based resin is used as the RC agent, the ratio of the cellulose acetate butyrate-based resin in the coating to the total amount of the resin and the cellulose acetate butyrate-based resin is preferably in terms of solid content. It is 20 to 40% by mass.

The specific example of the nitrocellulose-based resin is not particularly limited, and the specific example may be, for example, HIG 1/16, HIG 1/8, HIG 1/4, HIG 1/2, HIG 1/2A, HIG manufactured by SNPE Japan. 1. HIG 2, HIG 5, HIG 7 and HIG 20. When a nitrocellulose-based resin is used as the RC agent, the ratio of the nitrocellulose-based resin in the coating to the total amount of the resin and the nitrocellulose-based resin is preferably 3 to 13 by mass in terms of solid content. %.

Microgel means microparticles composed of a polymer formed by a polymerizable monomer which is internally crosslinked (that is, hardened into a network). The microgel is one of the RC agents, and the adhesion of the coating is imparted by the addition of the microgel. The method for producing a microgel can be carried out by suspension polymerization or emulsion polymerization of a polymerizable monomer and a crosslinkable monomer having two or more polymerizable groups in water to prepare a microgel aqueous dispersion, and by using a solvent. A method of substituting a microgel dispersion. In addition to such a method, the method for producing a microgel can also be used to polymerize a monomer and crosslinkability in an organic solvent in which a polymerizable monomer cannot dissolve the polymerizable monomer. The monomer is copolymerized to prepare a solution in which the microgel solution is dispersed. The organic solvent may, for example, be an organic solvent having a low solubility parameter, such as an aliphatic hydrocarbon. The microgel dispersion used in the present invention can be produced by any of the above production methods.

The polymerizable monomer may, for example, be a polymerizable monomer which is a specific example of the acrylic resin component. The crosslinkable monomer having two or more polymerizable groups may be, for example, a polymerizable unsaturated monocarboxylic acid ester of a polyhydric alcohol, a polymerizable unsaturated alcohol ester of a polybasic acid, and an aromatic substituted with two or more vinyl groups. Family compound. The crosslinkable monomer may specifically be, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-Butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate Ester, 1,6-hexanediol diacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, and divinylbenzene. The RC agent may be used alone or in combination of two or more.

The hardener can adjust the viscosity of the coating to the aforementioned range by hardening the acrylic resin. Examples of the curing agent include an amine resin, a polyisocyanate compound, a blocked polyisocyanate compound, an epoxy compound, and a polycarbodiimide. The hardener may be used alone or in combination of two or more. In the above specific examples, a polyisocyanate compound is preferred from the viewpoint of exhibiting excellent curability of the acrylic resin. The specific example of the polyisocyanate compound is not particularly limited as long as it is a compound containing two or more isocyanate groups, and specific examples thereof include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and a fat. A cyclic polyisocyanate compound. Examples of the aromatic polyisocyanate compound include a monomeric body such as toluene diisocyanate, 4,4-diphenylmethane diisocyanate, xylene diisocyanate, and m-xylene diisocyanate. The aliphatic polybasic isocyanate compound may, for example, be a hexamethylene diisocyanate. The polycyclic isocyanate compound of the alicyclic group may, for example, be a polyvalent body such as isophorone diisocyanate. As the type of the plural, for example, a diurate type, a urate type, and an adduct type can be cited. The concept of "multiple bodies" in this specification includes not only general entities but also oligomers.

Examples of the vinyl acetate-based resin include a vinyl acetate-vinyl chloride copolymer resin, an ethylene-vinyl acetate-vinyl chloride graft copolymer resin, and an ethylene-vinyl acetate copolymer resin. The number average molecular weight of the vinyl acetate resin is preferably from 15,000 to 44,000, more preferably from 20,000 to 30,000. Examples of the vinyl acetate-vinyl chloride copolymer resin include VYNS-3, VYHH, VYHD, VMCH, VMCC, VMCA, VERR-40, VAGH, VAGD, VAGF, VAGC, and VROH manufactured by The Dow Chemical Company. When a vinyl acetate-based resin is used as the resin, the ratio of the vinyl acetate-based resin in the coating material to the total amount of the resin is preferably 40 to 100% by mass in terms of solid content. When the vinyl acetate-based resin is used as a resin for the coating film, the vinyl acetate-based resin also functions as a base material for the coating film, and when both the ethyl acetate-based resin and the acrylic resin are used as the resin in the coating material, It has the function of an RC agent as an acrylic resin.

When a coating film is formed, a magnetic field is applied in addition to a magnetic field, and moves along a magnetic field line in the coating material to form a pattern along the magnetic line of force. In order to recognize the pattern from the outside of the coating film, the magnetic body must be able to reflect the light from the outside, and thus form a flat powder. The shape of the magnetic body may be, for example, a snow flake shape, a film shape, a plate shape, or a sheet shape. The magnetic body may be formed of a ferromagnetic material, or may be formed by coating a surface of a flat powdery pigment with a magnetic material (for example, a metal having magnetic properties). The ferromagnetic body may be, for example, iron oxide, nickel, cobalt, and alloys of such metals with other metals. The aforementioned pigment may be, for example, mica, titania-coated mica, aluminum flakes, stainless steel flakes, alumina flakes, and glass flakes. The magnetic metal of the coated pigment may be, for example, nickel, cobalt, and copper.

The long axis length of the flat magnetic body is preferably 1 to 80 μm, and the thickness of the magnetic body is preferably 0.1 to 1 μm. The content of the magnetic substance in the coating material is preferably from 3 to 30% by mass in terms of solid content.

The solvent functions as a solvent or a dispersion medium for each component other than the solvent in the coating. The specific example of the solvent is not particularly limited as long as the components other than the solvent are not aggregated and settled, and specific examples of the solvent may be, for example, an ester solvent, a ketone solvent, an ether solvent, and an aromatic solvent.

Examples of the ester solvent include methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether. Acetate and propylene glycol monomethyl ether acetate. The ketone solvent may be, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone. Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. Examples of the aromatic solvent include toluene and xylene. The solvent may be used alone or in combination of two or more. When the paint contains the following dye as a colorant, an ester solvent and a ketone solvent are preferred from the viewpoint of excellent solubility of the dye, and ethyl acetate, butyl acetate, methyl ethyl ketone is preferred. And cyclohexanone (anone) is more preferred.

The resin used for the coating is not suitable for use as a solvent by using an alcohol solvent and an aliphatic hydrocarbon solvent alone because of its low solubility. However, the alcohol solvent and the aliphatic hydrocarbon solvent can be used by being mixed with the above-described ester solvent, ketone solvent, ether solvent, and aromatic solvent. Further, in order to adjust the ratio of the solid content (nonvolatile matter) of the coating material, for example, the evaporation rate of the solvent may be considered, and a thinner for dilution may be further contained in the coating material.

As a coloring agent, a dye, a pigment, and a nano pigment are mentioned, for example. The coloring agent may be used alone or in combination of two or more. Among them, dyes and nano pigments are preferred from the viewpoint that the coating film exhibits excellent clarity, movement and depth.

The dye is dissolved in, for example, the above solvent to impart a hue to the coating film. The specific example of the dye is not particularly limited, and specific examples thereof may be, for example, a monoazo dye, a disazo dye, a metal st salt azo dye, an anthraquinone dye, an anthraquinone dye, or a phthalocyanine dye. , pyrazolone dye, stilbene dye, thiazole dye, acridine dye, azine dye, quinoline dye, diphenylmethane dye, oxazine A dye, a triphenylmethane dye, a thiazine dye, an indophenol dye, and a perylene dye. The dye may be used singly or in combination of two or more kinds. The colorant is preferably a dye which has excellent solubility to a solvent and has excellent light resistance.

The pigment is a colored or colorless microparticle that is insoluble in water or the aforementioned solvent, and can impart a hue and design to the coating film. Specific examples of the pigment are not particularly limited as long as they are generally used organic pigments and inorganic pigments, and the organic pigments may be, for example, azo lake pigments, insoluble azo pigments, condensed azo pigments, Phthalocyanine pigments, anthraquinone pigments, perylene pigments, perinone pigments, phthalone pigments, oxazine pigments, quinacridone A pigment, an isoindolinone pigment, a benzimidazolone pigment, a diketopyrrolopyrrole pigment, and a metal complex pigment. The inorganic pigment may be, for example, yellow iron oxide, red iron oxide, carbon black, and titanium dioxide. In order to exert a brightness, a pigment having a glittering property can also be used for the coating film. Such a pigment may be, for example, an aluminum flake, a mica pigment, an interference mica pigment, a hologram pigment, a gold-plated glass flake pigment, and a flake pigment formed of a cholesteric liquid crystal polymer. When a pigment is used, if the pigment contains a coating film that is more concealed from the surface of the coating, the light from the outside of the coating film cannot reach the deep layer of the coating film, and the depth of the coating pattern is deep. I am afraid it will not be enough. The pigment may be used singly or in combination of two or more kinds.

The nano pigment means a pigment having a particle diameter of such a general pigment particle size, and similarly to the above-mentioned pigment, it is a colored or colorless fine particle which is not dissolved in water or the solvent, and can impart a hue and design to the coating film. The nanopigment is mixed with a resin, a solvent, and an additive by, for example, a disperser to form a paste. Further, in the production of the pigment, the nanopigment is dispersed by a disperser to make the average particle diameter of the primary particles smaller than the average particle diameter at the time of production of the usual pigment, and has a paste shape. The average particle diameter of the paste in the paste is preferably 50 to 300 nm when measured by a light scattering method using, for example, a N4 light scattering measuring machine manufactured by Coulter. Such a nano pigment may be, for example, NSP-VG series and NSP-CZ series manufactured by Rihong Bics. NSP-VG series and NSP-CZ series can be, for example, NSP-VG050(F)WHITE, NSP-VG105 RED, NSP-VG111(D)MAGENTA, NSP-VG151(D)RED, NSP-VG201(D)ORANGE, NSP -VG306(D)YELLOW, NSP-VG403(D)GREEN, NSP-VG503(D)BROWN, NSP-VG651(C)BLUE, NSP-VG701(C)VIOLET, NSP-VG805(C)BLACK, NSP-CZ051 (D) WHITE, NSP-CZ101 (D) RED, NSP-CZ112 (D) MAGENTA, NSP-CZ115 (D) RED, NSP-CZ201 (D) ORANGE, NSP-CZ306 (D) YELLOW, NAP-CZ401 (D ) GREEN, NSP-CZ503 (D) BROWN, NSP-CZ655 (C) BLUE, NSP-CZ702 (D) VIOLET, NSP-CZ807 (D) BLACK. In the above specific examples, the resin in the paste of the NSP-VG series is a vinyl acetate-vinyl chloride copolymer resin, and the resin in the paste of the NSP-CZ series is a cellulose acetate butyrate resin. The nano pigments may be used alone or in combination of two or more.

As described above, the coating viscosity after application of the coated object for 15 seconds is set to 1,000 to 10,000 mPa. s, and the coating viscosity after coating the coated object for 90 seconds is set to 50,000 mPa. s above. When the coating film is formed, the magnetic body is stabilized based on magnetic lines of force extending approximately parallel to the surface of the object to be coated, shrinkage of the coating material accompanying evaporation of the solvent, and shape of the magnetic body (ie, a flat powder shape), thereby being The surface of the applicator is aligned in a manner that extends approximately parallel. The coating viscosity after application of the coated object for 15 seconds is less than 1,000 mPa. In the case of s, for example, the magnetic body is sedimented, and the magnetic body cannot be uniformly dispersed in the coating film. If the coating is applied to the coated object for 15 seconds, the viscosity of the coating exceeds 10,000 mPa. s, since the viscosity of the coating material is too high, the magnetic body cannot be moved, and it is not possible to align in a manner to extend approximately parallel with respect to the surface of the object to be coated. If the coating is applied to the coated object for 90 seconds, the viscosity of the coating is less than 50,000 mPa. s, because the viscosity of the coating is too low, the magnetic body is easy to move, resulting in disorder of the alignment of the magnetic body. The coating material can be prepared by mixing the aforementioned components by a known method.

Next, a pattern forming method using the aforementioned coating material will be described. The pattern of the present embodiment is a step of applying a coating material onto a substrate to form a coating film by using a pattern forming device, a step of arranging a magnet along the surface of the coating film, and applying a magnetic field to the coating film by a magnet, and It is formed by the step of aligning the magnetic body in the coating film by the magnetic field.

As shown in the second diagram and the third (d) diagram, the pattern forming apparatus includes a plurality of magnets having a sheet shape, and in the present embodiment, a pair of magnets. The third (d) is a cross-sectional view of the 3d-3d line of the second figure. Among the pair of sheet magnets, a sheet magnet 11 has a quadrangular (square) shape as viewed from above the sheet magnet 11, and has a circular hole at the center portion, and the hole can be embedded in another sheet having a disk shape. Magnet 12. The sheet magnet 11 has various thicknesses, and the sheet shape of the present application includes a shape called a film shape or a plate shape in addition to a shape generally called a sheet shape. The shape of the sheet magnet 11 is not limited to a square shape, and may be a polygonal shape such as a triangle or a hexagon, or a circular shape or an elliptical shape. Since the shape of the pattern can be determined by the shape of the sheet magnet 12, the sheet magnet 12 may have a shape that exhibits a shape other than a circle, and may have a shape that presents characters such as N and A.

The sheet magnet 12 has an N pole on its surface (above the sheet magnet 12 of the third (d) diagram), and has an S pole on its back surface (below the sheet magnet 12 of the third (d) diagram). The sheet magnet 11 located around the sheet magnet 12 has an S pole on its surface and an N pole on its back surface. In other words, the surface magnetic poles and the back magnetic poles of the adjacent sheet magnets 12 and the sheet magnets 11 are configured such that the adjacent sheet magnets 11 and 12 are different from each other. The outer peripheral surface 13 (side surface) of the sheet magnet 12 and the inner peripheral surface 14 (side surface) of the sheet magnet 11 are in contact with each other. The material of the sheet magnets 11, 12 may be, for example, a mixture of any of an alloy, a ferrite, a rare earth, and the like, and a rubber or a plastic. Specific examples of the sheet magnets 11 and 12 are not particularly limited, and may be, for example, an AlNiCo magnet, a KS steel, an MK steel, an oxidized magnet magnet, a samarium cobalt magnet, and a neodymium.

Each of the magnets 11 and 12 is produced in the following manner. That is, as shown in the third (a) diagram, the chip magnet 11 having a quadrangular shape is formed from a magnet sheet, and is magnetized such that the surface has an S pole and the back surface has an N pole. The magnetic sheet is formed by a general material such as plastic or rubber. Then, as shown in the third (b) diagram, in order to form a pattern having a circular shape, the sheet-shaped magnet 12 having a circular shape penetrates from the central portion of the sheet-shaped magnet 11. At this time, the separation hole 15 which is the separation trace of the sheet magnet 12 is formed in the sheet magnet 11. Then, as shown in the third (c) diagram, the surface and the back surface of the sheet magnet 12 are reversed. Finally, as shown in the third (d) diagram, the inverted sheet magnet 12 is embedded in the separation hole 15 of the sheet magnet 11. In this way, a pattern forming device having one of the magnetic poles 11 and 12 in which the magnetic poles of the adjacent sheet magnets 11 and 12 are reversed can be obtained. When the pattern forming apparatus is used to form a pattern on the coating film, a pattern having a circular shape is formed on the surface and the back surface of the coating film so as to be symmetrical with each other.

Each of the magnets 11, 12 can also be produced by the following method. That is, an unmagnetic magnetic sheet constituting a sheet-shaped magnet having a quadrangular shape is prepared, and a central portion of the magnetic sheet is formed into a circular shape in order to form a circular pattern. Thereby, the separator having a circular shape is separated from the magnet piece. At this time, a separation hole as a separation trace of the separation piece is formed in the magnetic sheet. Furthermore, the magnetic piece and the separation piece are respectively magnetized. At this time, the magnetic piece and the separation piece are magnetized so as to have magnetic lines of force extending in mutually different directions. Then, the magnetic separator is inserted into the separation hole of the magnetic sheet. In this manner, it is also possible to obtain a pattern forming device having one of the magnetic poles 11 and 12 in which the magnetic poles of the adjacent sheet magnets 11 and 12 are reversed.

In the present embodiment, in the step of forming the coating film while arranging the magnet, the coating material is first prepared, applied to the object to be coated, and the object to be coated is attached to the pattern forming apparatus. That is, in the present embodiment, the step of forming the coating film while arranging the magnets is a step of arranging a plurality of magnets 11 and 12 having a sheet shape adjacent to each other along the surface of the coating film by using the pattern forming device. It is a step of arranging the magnets such that the surface magnetic poles and the back magnetic poles of the adjacent magnets 11 and 12 are different from each other, and the magnets 11 and 12 are adjacent to each other, and the side faces of the magnets 11 and 12 are in contact with each other. Specifically, after the coating material is prepared, as shown in the first figure, the coating material is applied onto the plate-like coated object 16 formed of a non-magnetic material to form a liquid coating film 17, and the coated object 16 is simultaneously coated. The pattern forming apparatus is attached to the sheet-like magnets 11 and 12 along the surface of the coating film 17. The sheet magnets 11, 12 may be attached to the back surface of the object 16 by an adhesive tape as shown in the first figure, or may be disposed above the coating film 17 at a predetermined distance.

In the present embodiment, the step of aligning the magnetic body may be performed by using the pattern forming device, wherein the step includes: applying a magnetic field to the coating film 17 by the plurality of magnets 11, 12, adjacent to the magnets 11, 12 The contact portions of the magnets 11 and 12 that are in contact with each other are arranged such that the magnetic body extends approximately parallel to the surface of the coating film 17, and at least the magnetic body on the contact portion of each of the magnets 11, 12 is formed on the coating film 17. The steps of the drawing. That is, in the step of aligning the magnetic body in the present embodiment, the magnetic field generated by the sheet magnets 11, 12 acts on the magnetic body in the coating film 17. The magnetic flux density of the magnetic field applied to the coating film 17 by the sheet magnets 11 and 12 depends on the magnetic flux density of the magnetic field of the magnets 11, 12 itself, the distance between the magnets 11, 12 and the coating film 17, and the object 16 to be coated. Material and thickness. The magnetic field applied to the coating film 17 by the sheet magnets 11, 12 has a magnetic flux density of 10 to 350 mT (tesla), preferably 15 to 350 mT. By setting the magnetic flux density of the magnetic field to 15 to 350 mT, the pattern of the coating film 17 can exhibit an excellent sense of clarity, depth, and movement as compared with the case where the magnetic flux density is outside the above range. As the solvent evaporates and the hardener acts as a hardener, the resin hardens and the liquid coating film solidifies. Then, after applying a magnetic field to the coating film for a set period of time, the object to be coated is taken out from the pattern forming device. Thereby, a coating film having a pattern is formed on the surface of the object to be coated, and a coated article having the object to be coated is obtained. The dried film thickness of the coating film is, for example, 5 to 50 μm.

In the first figure, magnetic lines of force (magnetic fields) 18 extending from the N pole of the sheet magnet 12 toward the S pole of the sheet magnet 11 are indicated by arrows. As indicated by the arrow, the magnetic lines of force 18 are aligned approximately parallel to the surface of the coating film 17 at the contact portion 19 of the two sheet magnets 11, 12. In other words, the extreme value (maximum value) of the magnetic lines 18 enclosed between the magnetic poles of the adjacent chip magnets 11 and 12 is located at the contact portion 19 of the adjacent sheet magnets 11, 12. Therefore, the magnetic body dispersed in the coating film 17 on the object 16 is aligned in the direction in which the magnetic lines 18 extend in accordance with the magnetic field generated by the adjacent sheet magnets 11, 12. Therefore, at the contact portion 19 of the two sheet magnets 11, 12, the magnetic body is aligned so as to extend approximately parallel to the surface of the coating film 17. As a result, the light from above the coating film 17 is most easily reflected by the magnetic body in the coating film 17 at the contact portion 19 of the two sheet magnets 11, 12, and the surface of the coating film 17 can be clearly recognized.

By using the pattern forming apparatus of the present embodiment, the pattern of the coating film 17 can exhibit excellent clarity, depth, and movement, and will be described based on the fourth and fifth figures. When the coating film 17 is viewed from directly above it, as indicated by the solid line in the fifth drawing, the annular pattern 21 which becomes clear can be recognized. When the eye is inclined to the right of the fifth figure, the annular pattern 21 is moved to the right (the second point chain line of the fifth figure). The distance L in which the pattern 21 moves is the moving distance.

As shown in the fourth figure, when the coating film 17 is viewed from the front side thereof by the eye 22, the magnetic body 23 in the coating film 17 is aligned when the incident light 24a is irradiated to extend approximately parallel with respect to the surface of the coating film 17. The magnetic body 23 is reflected, and the reflected light 24b extends directly above the eye 22. At this time, the respective magnetic bodies 23 aligned so as to extend approximately in parallel with respect to the surface of the coating film 17 are aligned in the alignment direction thereof. Therefore, the contrast between the bright portion generated by the strong reflected light 24b and the dark portion of the unreflected light 24 becomes large, and the boundary portion of the pattern 21 becomes conspicuous. Therefore, the aforementioned annular pattern 21 can be clearly seen. Further, the magnetic body 23 deep inside the coating film 17 (the lower portion of the fourth drawing) is also aligned so as to extend approximately in parallel with respect to the surface of the coating film 17, due to reflection from the magnetic body 23. The light 24b also enters the eye, giving the pattern 21 a sense of depth.

Then, if the eye 22 is inclined to the right by about 45 degrees from the upper side in the fourth figure, the incident light 24a of the magnetic body 23 which is inclined to the right side of the magnetic body 23 by about 22.5 degrees is reflected, and is visible from the eye 22. See reflected light 24b. At this time, since the magnetic body 23 inclined to the right aligns the angles thereof, the reflected light 24b from the magnetic body 23 is enhanced, and the pattern 21 can be clearly seen. Therefore, the pattern 21 will appear to move only at a distance L.

On the other hand, as shown in the sixth figure, the adjacent sheet magnets 11 and 12 are not in contact with each other, and when the inner peripheral surface 14 of the sheet magnet 11 and the outer peripheral surface 13 of the sheet magnet 12 are provided with a gap 20, two sheets are provided. The arc radius (curvature radius) depicted by the magnetic lines of force 18 enclosed by the magnets 11 and 12 becomes large. Further, the direction of the magnetic lines of force 18 is aligned with respect to the surface of the coating film 17 so as to extend approximately parallel, and is an approximately central portion of the outline of the pattern, that is, the inner peripheral surface 14 of the sheet-shaped magnet 11 and the sheet shape. Approximately the central portion of the outer peripheral surface 13 of the magnet 12. Therefore, the pattern in which the magnetic body 23 is used as the alignment reference has a wide width, and may become blurred. Further, the magnetic body 23 existing deep inside the coating film 17 is aligned in the same manner as the magnetic body 23 on the surface of the coating film 17, and the depth of the pattern cannot be obtained, and the feeling of movement cannot be obtained.

In this regard, it will be explained in accordance with the seventh figure. In the case shown in the seventh figure, although a certain degree of directivity of the magnetic body 23 can be observed, since the magnetic body 23 is not aligned neatly, the coating film 17 is observed from the upper side with the eye 22 and the eye 22 is used. When the coating film 17 is obliquely observed to the right, the reflected light 24b is not aligned, and the pattern 21 may not be clearly recognized. Therefore, even if it is assumed that the eye 22 is moved to have a portion in which the pattern 21 can be clearly seen, it is local, and its position is undetermined, and it is feared that the sense of movement is substantially not obtained.

The present embodiment described above has the advantages described below.

In the coating and in the initial stage of applying the coating to the object 16 to be coated, the magnetic body 23 in the coating is aligned in an irregular direction. As shown in the first figure, if the magnetic field of the magnets 11, 12 acts on the coating, the magnetic field lines 18 extend perpendicularly to the surface of the object 16 at a position where the magnetic lines of force 18 extend perpendicularly with respect to the surfaces of the magnets 11, 12. . Therefore, in the paint, where the magnetic lines of force 18 extend perpendicularly to the surface of the object 16 to be coated, the magnetic body 23 is aligned perpendicularly to the surface of the object 16 to be coated. Further, at a position where the magnetic lines of force 18 extend approximately parallel with respect to the surfaces of the magnets 11, 12, the magnetic lines of force 18 extend approximately parallel to the surface of the object 16 to be coated. Therefore, in the coating material, the magnetic lines 18 extend approximately parallel with respect to the surface of the object 16 to be coated, and the magnetic body 23 is aligned approximately in parallel with respect to the surface of the object 16 to be coated. By the alignment of the magnetic body, a pattern can be formed on the coating film on the object to be coated.

Therefore, the viscosity of the coating applied to the initial stage of the object 16 must be set within a range in which the magnetic body 23 can move in the coating. On the other hand, the viscosity of the coating applied to the subsequent stage of the coated object 16 must be set to "when the coated object 16 is taken out from the pattern forming device, that is, when the magnetic field does not act on the coating film 17, no paint flows. Or the alignment of the magnetic body 23 in the coating becomes disordered, and the range of the alignment of the magnetic body 23 in the coating is maintained.

In the coating of the present embodiment, the paint viscosity after setting 15 seconds from the application of the coated object 16 is set to 1,000 to 10,000 mPa. s, the viscosity of the coating is relatively low in the initial stage of coating application. Therefore, even in a narrow area in the coating film 17, the magnetic body 23 is rapidly moved and aligned in the paint in a state in which the magnetic bodies 23 are aligned in the direction along the magnetic lines of force 18 by the magnetic field. Moreover, since the viscosity of the paint after 90 seconds from the application of the object to be coated is set to 50,000 mPa. Above s, the viscosity of the coating is relatively high in the late stage of coating of the coating, and the coating film is solidified in a state in which the alignment of the magnetic body 23 is fixed. Therefore, the pattern of the coating film formed by the magnetic body 23 can exhibit excellent clarity, depth, and movement.

In the pattern forming method of the present embodiment, by using the paint described above, the pattern of the coating film can exhibit excellent clarity, depth, and movement. Further, in the pattern forming method of the present embodiment, the surface magnetic poles and the rear magnetic poles of the adjacent pairs of the magnets 11 and 12 are different from each other in that the adjacent magnets 11 and 12 are different from each other and the sides of the magnets 11 and 12 are in contact with each other. The magnets 11 and 12 are arranged. Further, by applying the magnetic field to the coating film 17 by the magnets 11, 12, the magnetic body 23 is approximately parallel to the surface of the coating film 17 at the contact portion of the magnets 11, 12 adjacent to the magnets 11, 12, which are in contact with each other. In the manner of the ground extension, at least the magnetic body 23 on the contact portion of each of the magnets 11, 12 forms a pattern on the coating film 17. Therefore, the pattern of the coating film can exhibit an excellent sense of clarity, depth, and movement as compared with the case where a gap is formed between the adjacent magnets 11 and 12.

The above embodiment can also be modified, for example, in the following manner.

The coating material may contain an RC agent when a vinyl acetate resin is used as the resin.

In the step of forming the coating film while disposing the magnet, the coating material may be applied to the object to be coated after the object to be coated is attached to the pattern forming device, or the coating material may be applied to the object to be coated, and then the object to be coated may be applied. Installed on the pattern forming device.

The magnetic body 23 may be used in combination of a plurality of magnetic bodies 23 having different materials, or a plurality of magnetic bodies 23 having different sizes may be used in combination. In such cases, the coating film 17 can have a new pattern.

When the surface of the object 16 is curved, each of the sheet magnets 11 and 12 may be arranged curved along the surface of the coating film 17.

The degree of alignment of the magnetic body 23 (degree of pattern representation) may be measured in advance based on, for example, the magnetic field strength of the sheet magnets 11, 12, the thickness of the object to be coated, the thickness of the coating film, and the content of the magnetic body 23 in the coating. , get the data, and then use the data to form the desired pattern.

Each of the sheet magnets 11 and 12 may be disposed to have a gap therebetween. Further, it is also possible to use only one magnet instead of the pair of sheet magnets 11, 12, or to use three or more sheet magnets, and to arrange the magnets so that the magnetic poles of the adjacent sheet magnets are different from each other.

Example

Next, the above embodiments will be more specifically described by way of examples and comparative examples.

(Test on viscosity of paint) In this test, the viscosity of the paint is investigated when the magnetic material in the paint is aligned by the action of the magnetic field, and the viscosity of the paint is maintained when the magnetic field is not applied to the magnetic body forming the desired pattern. .

Specifically, a plurality of sample liquids having a set viscosity are first prepared. The prepared sample solution has a viscosity of 2,000 mPa. s, 3,000mPa. s, 7,000mPa. s, 9,000mPa. s, 14,000mPa. s and viscosity 52,000mPa. There are six kinds of s. The viscosity of each sample solution was adjusted to the above values under the conditions of a temperature of 20 ° C and a relative humidity of 65%.

Then, 1% by mass of a magnetic pigment containing iron oxide (Tarox AM-200, manufactured by Titanium Industries Co., Ltd.) was added to each sample solution, and the mixture was uniformly stirred to prepare a test solution. Each test liquid was applied to an ABS resin substrate having a thickness of 1 mm, and coated with a thickness of about 200 μm by an applicator, and a magnet (magnetic flux density of 30 mT on the substrate) was loaded from the back surface of the substrate. Take the time of the loading as 0 seconds, and take pictures of the magnetic pigment on the surface of the substrate from the time of 5 seconds, 10 seconds, 30 seconds, 60 seconds, 120 seconds, and 180 seconds after the loading, and visually confirm whether or not along the edge. The magnetic field forms a pattern. The results are shown in Table 1. In Table 1, "○○" indicates that the pattern can be clearly recognized, "○" indicates that the pattern can be confirmed, and "×" indicates that the pattern cannot be confirmed.

As shown in Table 1, it can be seen that the magnetic material in the coating has a coating of 2,000 mPa in order to form a pattern. The viscosity of s takes 10 seconds and the paint has 9,000 mPa. The viscosity of s takes 60 seconds. In the actual coating operation, the coating material cannot be applied to the object to be coated instantaneously. In order to achieve the set thickness, the coating material may be repeatedly applied, and the coating must be carried out for a certain period of time (about 45 seconds). Therefore, it can be seen that in order to form the magnetic body along the magnetic field, the coating is used as the starting point, and the viscosity of the coating must be 1,000 to 10,000 mPa after 15 seconds from the end of the coating. s. If the coating is 15 seconds from the end of the coating, the viscosity of the coating exceeds 10,000 mPa. s, the magnetic body in the paint cannot form a clear pattern.

Further, for each of the sample liquids, the magnet was taken out 180 seconds after the magnet was loaded. When the magnet is taken out, a clear pattern is formed in each sample liquid. Then, the time at which the magnet was taken out was taken as 0 seconds, and at 60 o'clock and 180 seconds from the time when the magnet was taken out, a photograph of the pattern on the substrate was taken, and it was visually confirmed whether or not the shape of the pattern was maintained. The results are shown in Table 2. In Table 2, "○○" indicates that the pattern can be clearly recognized, "○" indicates that the pattern can be confirmed, and "×" indicates that the pattern cannot be confirmed.

As shown in Table 2, it is known that in order to maintain the pattern of the coating film, that is, to maintain the alignment state of the magnetic body, the coating must have 50,000 mPa. Visibility above s. The viscosity of the coating is less than 50,000 mPa. When s, it is impossible to maintain a clear pattern.

(Synthesis Example 1) In Synthesis Example 1, an acrylic resin was prepared in the following order. In the following description, "parts" means "parts by mass". Further, the solid fraction was measured in accordance with JIS-K5601-1-2 (ISO 3251 which is an international standard) which is an industrial standard of Japan, and the acid value was measured in accordance with JIS-K5601-2-1 (ISO3682). 36 parts of toluene and 22 parts of methyl isobutyl ketone were placed in a reaction vessel equipped with a thermometer, a stirring blade, a dropping device, a cooling tube, a nitrogen introduction tube, and a temperature control device, and stirred in a nitrogen gas stream while the reaction container was placed. The temperature was raised to 110 ° C. Then, a polymerization catalyst solution containing 12 parts of toluene, 5 parts of methyl isobutyl ketone (MIBK) and 4 parts of tributyl hexyl peroxy hexanoate, and 35 parts of methyl methacrylate and methacrylic acid are contained. A mixed solution of a polymerizable monomer composed of 53 parts of n-butyl ester, 10 parts of 2-hydroxyethyl methacrylate and 1 part of methacrylic acid was dropped into a reaction vessel over 3 hours using a different dropping funnel. During the dropwise addition, the solution in the reaction vessel was continuously stirred. After 10 minutes from the start of the dropwise addition, the inside of the reaction vessel was heated to 120 ° C while maintaining the same temperature. After the completion of the dropwise addition, an additional polymerization catalyst solution containing 4 parts of toluene, 2 parts of MIBK, and 0.5 part of t-butyl peroxyhexanoate was dropped into the reaction container over 1 hour using a dropping funnel. During the dropwise addition, the solution in the reaction vessel was continuously stirred. After the dropwise addition, the temperature in the reaction vessel was maintained at 120 ° C for 2 hours to be matured, and the inside of the reaction vessel was cooled to obtain an acrylic resin. In the following description, the acrylic resin obtained in accordance with the procedure of Synthesis Example 1 is referred to as "acrylic resin A". The solid content of the acrylic resin A was 55 mass%, and the weight average molecular weight of GPC in terms of polystyrene was 16,000.

(Synthesis Example 2) In Synthesis Example 2, an acrylic resin was prepared in the following order. In the same reaction vessel as the reaction vessel used in Synthesis Example 1, 67 parts of toluene and 36 parts of MIBK were charged, and the mixture was stirred in a nitrogen gas stream while raising the temperature in the reaction vessel to 110 °C. Then, a mixed solution of a polymerizable monomer composed of 37 parts of methyl methacrylate, 38 parts of n-butyl methacrylate, 23 parts of butyl methacrylate and 2 parts of styrene, and 8 parts of toluene, MIBK A polymerization catalyst solution composed of 4 parts and 1 part of perbutyl peroxyhexanoate was separately dropped into the reaction vessel over 3 hours using a different dropping funnel. During the dropwise addition, the solution in the reaction vessel was continuously stirred in a nitrogen gas stream while maintaining the temperature in the reaction vessel at 110 °C. After the completion of the dropwise addition, an additional polymerization catalyst solution of 5 parts of toluene, 2 parts of MIBK, and 0.5 part of t-butyl peroxyhexanoate was dropped into the reaction container over 1 hour using a dropping funnel. During the dropwise addition, the solution in the reaction vessel was continuously stirred while maintaining the temperature in the reaction vessel at 110 °C. After the dropwise addition, the temperature in the reaction vessel was raised to 120 ° C, and the mixture was allowed to stand at the same temperature for 2 hours to be matured, and the inside of the reaction vessel was cooled to obtain an acrylic resin. In the following description, the acrylic resin obtained in accordance with the procedure of Synthesis Example 2 is referred to as "acrylic resin B". The solid content of the acrylic resin B was 45 mass%, and the weight average molecular weight of GPC in terms of polystyrene was 138,000.

(Synthesis Example 3) In Synthesis Example 3, a vinyl acetate-based resin was prepared. In other words, vinyl acetate was prepared by stirring and mixing 20 parts of a vinyl acetate-vinyl chloride copolymer (trade name: VMCH, manufactured by The Dow Chemical Co., Ltd.), 60 parts of MIBK, and 20 parts of methyl ethyl ketone (MEK). Resin. The solid content of the vinyl acetate resin was 20% by mass.

(Synthesis Example 4) In Synthesis Example 4, a nitrocellulose-based resin was prepared. In other words, nitrocellulose-based resin was prepared by stirring and mixing 21.43 parts of nitrocellulose (trade name: HIG2, manufactured by Bergerac), 62.86 parts of isobutyl acetate, and 15.71 parts of toluene. In the following description, the nitrocellulose-based resin obtained by the procedure of Synthesis Example 4 is referred to as "nitrocellulose-based resin A". The solid content of the nitrocellulose-based resin A was 15% by mass.

(Synthesis Example 5) In Synthesis Example 5, a nitrocellulose-based resin was prepared. In other words, nitrocellulose-based resin was prepared by stirring and mixing 21.43 parts of nitrocellulose (trade name: HIG7, manufactured by Bergerac), 62.86 parts of isobutyl acetate, and 15.71 parts of toluene. In the following description, the nitrocellulose-based resin obtained by the procedure of Synthesis Example 5 is referred to as "nitrocellulose-based resin B". The solid content of the nitrocellulose-based resin B was 15% by mass.

(Synthesis Example 6) In Synthesis Example 6, a cellulose acetate butyrate-based resin was prepared. In other words, 20 parts of cellulose acetate butyrate (trade name CAB531-1, manufactured by Eastman Chemical Co., Ltd.) and 80 parts of butyl acetate were stirred and mixed to obtain a cellulose acetate butyrate-based resin. The solid content of the cellulose acetate butyrate-based resin was 20% by mass.

(Synthesis Example 7) In Synthesis Example 7, the microgel dispersion solution was prepared in the following order. That is, 100 parts of bishydroxy ethyl taurine, 97 parts of neopentyl glycol, and ruthenium were placed in a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a temperature control device, a condenser, and a cooling tube. 176 parts of acid, 139 parts of phthalic anhydride and 20 parts of xylene were heated in a reaction vessel under a nitrogen gas stream, and the solution in the reaction vessel was refluxed, and the water formed by the reaction was azeotropically removed with xylene. After the start of the reflux, the temperature in the reaction vessel was adjusted to 190 ° C in about 2 hours, and stirring and dehydration were continued until the acid value of the carboxylic acid was 145. Then, the temperature in the reaction vessel was lowered to 140 ° C or lower and maintained at the same temperature, and 234 parts of glycidyl tert-carbonate (trade name Cardura E10, manufactured by Shell Co., Ltd.) was added dropwise over 30 minutes. After the dropwise addition, the solution in the reaction vessel was further stirred for 2 hours, and the reaction was terminated to obtain a polyester resin. The polyester resin had an acid value of 60, and the number average molecular weight of GPC in terms of polystyrene was 1,100.

Then, 200 parts of deionized water was placed in a reaction vessel equipped with a stirrer, a cooler, a temperature control device, a nitrogen gas introduction tube, and a dropping device, and the mixture was stirred under a nitrogen gas stream and the temperature inside the reaction vessel was raised to 80 °C. Then, 8.6 parts of the polyester resin obtained in the above step and 0.65 parts of dimethylethanolamine were put into a reaction container to be dissolved. Then, a solution of 3.9 parts of azocyanashitic acid dissolved in 39 parts of deionized water and 3.71 parts of dimethylethanolamine was added to the reaction vessel. Then, a mixed solution of 122 parts of methyl methacrylate, 81 parts of n-butyl methacrylate, 26 parts of 2-hydroxyethyl methacrylate and 4 parts of ethylene glycol dimethacrylate was used for 60 minutes. Drop into the reaction vessel. After the completion of the dropwise addition, the temperature inside the reaction vessel was raised to 80 ° C, and a solution of 1.3 parts of azocyanatocaric acid dissolved in 12 parts of deionized water and 1.21 parts of dimethylethanolamine was added to the reaction vessel. Then, the temperature in the reaction vessel was maintained at 80 ° C, and the solution in the reaction vessel was stirred for 60 minutes to obtain a microgel emulsion.

The emulsion of the microgel was placed in a reaction vessel, and the microgel emulsion was stirred while maintaining the temperature in the reaction vessel at 80 to 90 ° C while adding xylol (xylol) to the reaction vessel. Further, by using azeotropy of mixed xylene and water, the emulsion of the microgel was replaced with a mixed xylene solution of the microgel at 8 hours to obtain a dispersion solution of the microgel. The particle diameter of the microgel measured by the light scattering method was 0.2 μm, and the microgel content in the microgel dispersion solution was 25% by mass.

Next, the modulation of the paint in each example will be described. The coatings in the following examples were prepared by combining the components in an atmosphere of 25 ° C, stirring the components of the respective components other than the magnetic pigment for 5 minutes, and stirring for 15 minutes while the magnetic pigments were combined.

(Example 1) In Example 1, the coating material was prepared in the following order. In other words, the acrylic resin A as a resin is placed in a stainless steel container, and the acrylated resin A is added, and the nitrocellulose-based resin A as an RC agent is added, followed by addition of isobutyl acetate as a solvent. Resin solution. In addition, a metal salt-missing azo dye (trade name: VALIFAST RED 3306, manufactured by Orient Chemical Industries, Ltd., 100% solid content) as a coloring agent was dissolved in MEK to prepare a coloring liquid having a concentration of 20% by mass. In addition, the resin solution was stirred, and the coloring liquid was added thereto, and then an iron oxide-based magnetic pigment (TAROX AM-200, manufactured by Titanium Industries, Inc.) as a magnetic material was added to prepare a coating material. The addition ratio of each component is shown in Table 3, for example.

(Examples 2 to 4) In the examples 2 to 4, the coating materials were prepared in the same manner as in Example 1 except that the types and addition ratios of the respective components were changed to those shown in Table 3.

(Example 5) In Example 5, the coating material was prepared in the following order. In other words, the acrylic resin A was placed in a stainless steel container, and the acrylic resin A was stirred, and the cellulose acetate butyrate-based resin obtained in accordance with Synthesis Example 6 was added as an RC agent, and butyl acetate was further added to prepare a resin. Solution. Further, the ethyl acetate was stirred, and the microgel dispersion solution obtained in accordance with Synthesis Example 7 was slowly added to prepare a microgel diluent. Further, a dye (trade name: VALIFAST RED 3306, manufactured by Orient Chemical Industries, Ltd., 100% solid content) was dissolved in MEK to prepare a coloring solution having a concentration of 20% by mass. In addition, the above-mentioned resin solution was stirred, and the microgel dilution liquid and the coloring liquid were sequentially added, and then a magnetic pigment (product name TAROX AM-200 manufactured by Titanium Industries Co., Ltd.) was added to prepare a coating material. The addition ratio of each component is shown in Table 3, for example.

(Example 6) In Example 6, the coating was prepared in the following order. In other words, the vinyl acetate resin obtained in accordance with Synthesis Example 3 was placed in a stainless steel container, and the vinyl acetate resin was stirred while the acrylic resin A was added to prepare a resin solution. Further, a dye (trade name: VALIFAST RED 3306, manufactured by Orient Chemical Industries, Inc., 100% solid content) was dissolved in MEK to prepare a coloring solution having a concentration of 20% by mass. Further, the resin solution was stirred and a coloring liquid was added thereto, and then a magnetic pigment (product name TAROX AM-200 manufactured by Titanium Industries, Ltd.) was added to prepare a coating material. The addition ratio of each component is shown in Table 3, for example.

(Example 7) In Example 7, the coating material was prepared in the same manner as in Example 1 except that the types and addition ratios of the respective components were changed to those shown in Table 3.

(Example 8) In Example 8, the coating was prepared in the following order. In other words, a vinyl acetate-based resin obtained in accordance with Synthesis Example 3 was placed in a stainless steel container, and the vinyl acetate-based resin was stirred while sequentially adding ethyl acetate, butyl acetate, MEK, and a solvent as a solvent. Butanol, a resin solution was prepared. Further, an anthraquinone dye (trade name: PLAST BLUE 8550, manufactured by Kiba Chemical Industry Co., Ltd., 100% solid content) was dissolved in xylene to prepare a coloring solution having a concentration of 20% by mass. Further, the resin solution was stirred and a coloring liquid was added thereto, and then a magnetic pigment (product name TAROX AM-200 manufactured by Titanium Industries, Ltd.) was added to prepare a coating material. The addition ratio of each component is shown in Table 3, for example.

(Example 9) In Example 9, the coating was prepared in the following order. In other words, the vinyl acetate resin obtained in accordance with Synthesis Example 3 was placed in a stainless steel container, and the vinyl acetate resin was stirred while sequentially adding ethyl acetate, butyl acetate, MEK, n-butanol, xylene, A phthalocyanine-based nano pigment (trade name NSP-VG663 (D) BLUE manufactured by Rihong BICS Co., Ltd., 20% solid content) and magnetic pigment (product name TAROX AM-200 manufactured by Titanium Industries Co., Ltd.) were used to prepare a coating. The addition ratio of each component is shown in Table 4, for example. The product name NSP-VG663(D)BLUE manufactured by Nippon BICS Co., Ltd. consists of 10 parts of PIGMENT BLUE 15, 10 parts of vinyl acetate-vinyl chloride copolymer and 80 parts of MIBK.

(Example 10) In Example 10, the coating material was prepared in the following order. In other words, the vinyl acetate resin obtained in accordance with Synthesis Example 3 was placed in a stainless steel container, and the vinyl acetate resin was stirred, and ethyl acetate, butyl acetate, MEK, and n-butanol were sequentially added to prepare a resin solution. . In addition, 15 parts of a phthalocyanine pigment (manufactured by Toyo Ink Co., Ltd., Cyanine Blue MR-3), 40 parts of acrylic resin A, 23 parts of MIBK, and 22 parts of butyl acetate were mixed to prepare a coloring liquid. In addition, the resin solution was stirred, and the coloring liquid was added in a ratio of the respective components, for example, as shown in Table 4, and then a magnetic pigment (product name TAROX AM-200, manufactured by Titanium Industries, Ltd.) was added to prepare a coating material.

(Examples 11 to 16) In Examples 11 to 16, the coating materials were prepared in the same manner as in Example 1 except that the types and addition ratios of the respective components were changed to those shown in Table 4.

(Comparative Examples 1 and 2) In Comparative Examples 1 and 2, the coating materials were prepared in the same manner as in Example 1 except that the types and addition ratios of the respective components were changed to those shown in Table 3.

(Comparative Examples 3 and 4) In Comparative Examples 3 and 4, the coating materials were prepared in the same manner as in Example 8 except that the types and addition ratios of the respective components were changed to those shown in Table 4.

(Comparative Example 5) In Comparative Example 5, the coating materials were prepared in the same manner as in Example 1 except that the types and addition ratios of the respective components were changed to those shown in Table 4.

Further, it is an isocyanate-based curing agent (Duranate 24A-90PX, manufactured by Asahi Kasei Chemical Co., Ltd., 90% by mass of solid content), 77.8 parts, 8.2 parts of toluene, 6 parts of xylene, 6 parts of butyl acetate, and propylene glycol monomethyl ether. The acetate was mixed in 2 portions to prepare a hardener solution. Further, as shown in Tables 3 and 4, in the coating materials relating to any of the examples and the comparative examples, the addition ratio of the hardener was added to the above coating material in a ratio shown in Tables 3 and 4. . Further, the solvent for dilution was prepared in the respective components and addition ratios shown in Tables 3 and 4. Further, the solvent for the dilution was added to the paint of each example without stirring, and then the mixture was stirred for 1 minute using a spatula to prepare a diluted paint.

The following evaluations were carried out using the diluted paints of the respective examples. That is, three sheets of a commercially available ABS resin sheet (black, length 20 cm, width 15 cm, thickness 0.1 cm) were prepared as a coated object, and the coated surface was wiped with isopropyl alcohol. On one surface of one of the resin sheets, one surface (N pole) of a disc-shaped magnet having a diameter of 40 mm and a thickness of 2 mm was bonded with an adhesive tape to prepare a test piece for pattern formation. Further, using the remaining resin sheet, a test piece for viscosity measurement for measuring the viscosity of the diluted paint after 15 seconds or 90 seconds after the application of the diluted paint was prepared. The magnetic flux density of the magnetic field on the surface of the resin plate caused by the disk magnet is shown in Table 5 and Table 6. The magnetic flux density of each magnetic field was measured using TESLA METER TM-601 manufactured by KANETEC Corporation.

Furthermore, after coating the diluted coatings of each example, immediately using a spray gun (Wider-100 manufactured by ANEST Iwata Co., Ltd.) at a temperature of 20 ° C and a relative humidity of 65%, each case was used. The diluted coating material was spray-coated on the surface of the three ABS resins described above so that the dried film thickness was about 10 μm. The test piece for pattern formation was placed under the aforementioned atmosphere for 10 minutes. On the other hand, after the two test pieces for the viscosity test are spray-coated for 15 seconds or 90 seconds after the above-mentioned atmosphere, the coating film 17 is scraped off immediately, and the RR type viscometer and the RL type viscometer are used in a sealed state. (All manufactured by Toki Sangyo Co., Ltd., trade name VISCOMETER CONTROLLER RC-500), the viscosity of the coating was measured. The measurement method was "spring relaxation measurement", and the viscosity of the coating was measured at 20 °C. The viscosity at a shear rate of 0.1 (1/sec) is shown in Tables 5 and 6. Because the viscosity of the coating is 500,000mPa. When s or more, the measurement accuracy is deteriorated, so the measured value is 500,000 mPa. When s or more, the viscosity of the coating is recorded as 500,000 mPa in Tables 5 and 6. s above.

With respect to the test piece for forming the pattern described above, the clear coating material placed for 10 minutes was applied so as to have a dry film thickness of 30 μm, left for 10 minutes, placed in a drying oven, and dried at 80 ° C for 30 minutes. The magnet attached to the back of the ABS resin sheet is removed before the application of the clear coating. For the above-mentioned transparent coating, 100 parts of a main component (manufactured by BEE Chemical Co., Ltd., trade name: R240 CI), a curing agent (manufactured by Nippon BEE Chemical Co., Ltd., trade name: R255), and a diluent solvent (Japan BEE Chemical Co., Ltd.) were used. Co., Ltd., product name R240 with diluted thinner) 30 parts mixed and stirred.

In the coating film obtained in this manner, the sharpness, the depth, and the feeling of movement are determined by averaging the visual standards of 10 persons such as the paint designer and the designer, and are determined according to the following criteria. The results are shown in Tables 5 and 6. In Tables 5 and 6, the "15 seconds after" column and the "90 seconds later" column in the "Mr. (mPa.s)" column indicate the value of the paint viscosity after 15 seconds and 90 seconds after the spray coating. . "NCA" means nitrocellulose-based resin A, "NCB" means nitrocellulose-based resin B, "CBA" means cellulose acetate butyrate-based resin, and "MG" means a microgel-dispersed solution. "ACA" means acrylic resin A, "ACB" means acrylic resin B, and "VMCH" means vinyl acetate resin. The "addition amount (% by mass)" in the "RC agent" column indicates the ratio of the RC agent to the total amount of the resin and the RC agent in the coating material when converted by the solid content.

(Clear feeling) ○: The boundary part of the pattern looks very clear △: The boundary part of the pattern looks clear ×: The boundary of the pattern is partially blurred

(depth sense) ○: The difference in light and dark in the pattern is large, and it is very deep. △: There are differences in light and dark in the pattern, and there is a sense of depth. ×: There is a lack of brightness and darkness in the pattern, and there is no sense of depth.

(Moving feeling) ○: If the position of the eye is moved, the boundary portion of the pattern also moves largely, and the pattern is rich in change. △: If the position of the eye is moved, the boundary portion of the pattern also moves to identify the pattern change. ×: If the position of the eye is moved, the movement of the boundary portion of the pattern cannot be recognized, and the pattern is lacking in change.

As shown in Tables 5 and 6, in each of the examples, excellent evaluations were obtained for each item. Therefore, it can be seen that the pattern of the coating film formed by the coating materials of the respective examples can exhibit excellent clarity, depth, and movement. Further, from the evaluation of each of the examples, it was found that by using a dye or a nano pigment as a coloring agent, the pattern of the coating film can exhibit an excellent feeling of clarity, depth, and movement as compared with the case of using a pigment. Further, from the evaluation of Examples 11 to 16, it is understood that since the magnetic field acting on the coating film has a magnetic flux density of 15 to 350 mT, the pattern of the coating film can be excellently sharp compared with the case where the magnetic flux density is outside this range. Feeling, depth and movement.

On the other hand, in Comparative Example 1, the viscosity of the coating was less than 50,000 mPa after 90 seconds from the application. s, the evaluation of the sense of movement and the sense of depth is particularly bad. In Comparative Example 2, the viscosity of the coating after 15 seconds from the coating exceeded 10,000 mPa. s, the evaluation of the sense of clarity and depth is exceptional. In Comparative Example 3, the viscosity of the coating was less than 1,000 mPa after 15 seconds from the application. s, at the same time, the coating viscosity after coating for 90 seconds is less than 50,000 mPa. s, the evaluation of the sense of clarity is particularly bad. Further, in Comparative Example 3, the coating material dripped from the ABS resin sheet during coating, and formation of the coating film was difficult. In Comparative Example 4, the coating viscosity exceeded 10,000 mPa after 15 seconds from the application. s, the evaluation of the sense of clarity and depth is exceptional. In Comparative Example 5, the viscosity of the coating was less than 50,000 mPa after 90 seconds from the application. s, the evaluation of the sense of movement and the sense of depth is particularly bad.

From the evaluation of each comparative example, it is known that the viscosity of the coating from the point of 90 seconds after coating must be 50,000 mPa. s above. The viscosity of the coating rises from the passage of time after coating due to, for example, evaporation of the solvent. When the viscosity is increased, the magnetic body in a region where the magnetic lines of force extend approximately parallel to the surface of the object to be coated is subjected to an increase in the viscosity of the coating material, and is aligned so as to extend parallel to the surface of the object to be coated. For this alignment, the viscosity of the coating from the point of application of 90 seconds must be 50,000 mPa. s above. The viscosity of the coating from the point of coating for 90 seconds is less than 50,000 mPa. In the case of s, the alignment of the magnetic body may be disturbed by convection in the coating accompanying, for example, evaporation of the solvent. Therefore, below 90 seconds, even if the viscosity of the paint reaches 50,000 mPa. S, due to the disorder of the magnetic body, it is impossible to form the desired pattern.

In Example 8 and Comparative Example 5, in order to determine the feeling of clarity and the sense of movement, the L value (L ^* value) of the color difference of the coating film measured by the measurement of minute lightness was measured. That is, the luminance (L ^* value) is measured in accordance with the L ^* a ^* b ^* color system defined in JIS Z8729. Specifically, a small light-sensing measuring device (GMBS-1 manufactured by Murakami Color Technology Research Co., Ltd.) is used, and a region R surrounded by a broken line in the fifth figure (specifically, a region of 9.2 mm in length and 9.2 mm in width) Among them, the light was irradiated under the conditions shown below, and moved at an equal distance within a range of 9.2 mm from the left to the right of the fifth figure, while receiving light at 50 directly above the coating film, and measuring the L ^* value.

(Measurement conditions) Whiteboard correction: -45 degrees of light irradiation and 0 degree of light reception, and the exposure time was 100 msec.

Measurement: Light irradiation at 10 degrees or 25 degrees and light reception at 0 degrees, exposure time was 100 msec.

Furthermore, the relationship between the moving distance (mm) and the L ^* value when the light irradiation angle is 10 degrees is as shown in the eighth (a) and eighth (b) images; when the light irradiation angle is 25 degrees The relationship between the moving distance (mm) and the L ^* value is as shown in the ninth (a) and ninth (b) figures. The eighth (a) and ninth (a) graphs show the results of Example 8, and the eighth (b) and ninth (b) graphs show the results of Comparative Example 5.

As shown in the eighth (a) to ninth (b), in any of the cases where the light irradiation angle is 10 degrees and 25 degrees, a distinct peak, that is, a sharp peak, can be seen in the embodiment 8, while The L ^* value becomes a high value. On the other hand, in Comparative Example 5, there was no significant peak, and the L ^* value was small. In this case, the coating film pattern of Example 8 was shown to exhibit an excellent feeling of clarity as compared with the coating film pattern of Comparative Example 5. Comparing the eighth (a) and the ninth (a), the moving distance of the peak P ₁ when the light irradiation angle is 1 degree is about 4.3 mm, and the movement of the peak P ₂ when the light irradiation angle is 25 degrees The distance is approximately 5.4 mm. That is, the peak P ₂ when the light irradiation angle is 25 degrees shifts to the right of the graph when the peak P _{1 of the} light irradiation angle is 10 degrees. In this case, it means that the bright portion of the pattern moves, that is, the pattern of the eighth embodiment exhibits an excellent sense of movement.

In the same manner as described above, the measurement of the viscosity of the paint, and the evaluation of the feeling of clarity, the sense of depth, and the feeling of movement were carried out in the same manner as described above except that the arrangement of the magnets was changed to the following. That is, as shown in the first figure and the second figure, the center of the chip-shaped magnet 11 having a quadrangular shape having different magnetic poles on the back surface is cut into a circular shape to obtain a sheet-shaped magnet 12. Further, the sheet magnet 12 is inverted at 180 degrees, and is inserted into the separation hole 15 of the sheet magnet 11. At this time, the magnetic poles of the adjacent sheet magnets 11 and 12 are reversed, and the side faces of the magnets 11 and 12 are in contact with each other. The results are shown in Tables 7 and 8.

As shown in Tables 7 and 8, the results similar to the above Tables 5 and 6 were obtained for each of the examples in the test. Therefore, it can be seen that in the test, the pattern of the coating film formed by the coating materials of the respective examples can exhibit excellent clarity, depth, and movement.

11. . . Chip magnet

12. . . Chip magnet

13. . . Peripheral surface

14. . . Inner circumference

15. . . Separation hole

16. . . Painted object

17. . . Coating film

18. . . Magnetic line of force

19. . . Contact area

20. . . gap

twenty one. . . pattern

twenty two. . . eye

twenty three. . . Magnetic body

24a. . . Incident light

24b. . . reflected light

The first figure is a diagram showing magnetic lines of force when a coating film is formed on the surface of the object to be coated and a sheet magnet is placed on the back surface of the object to be coated.

The second drawing is a plan view showing a state in which the inner peripheral surface of the circular hole of the sheet-shaped magnet having a circular hole is in contact with the outer peripheral surface of the sheet-shaped magnet having a circular shape.

The third (a) to third (d) drawings are diagrams showing the manufacturing steps of the sheet magnet.

The fourth figure is a schematic diagram illustrating the clarity, depth and movement of the pattern produced by the coating film.

The fifth figure is a diagram illustrating the pattern of the coating film and the movement feeling of the film.

Fig. 6 is a view showing a magnetic line of force when a coating film is formed on the surface of the object to be coated, and each of the sheet magnets is placed on the back surface of the object to be coated with a space therebetween.

Fig. 7 is a schematic view showing the state of reflection of light on the magnetic material in the coating film when the respective sheet magnets are arranged so as to be spaced apart from each other.

The eighth (a) diagram is a diagram showing the relationship between the moving distance (mm) and the L ^* value in the eighth embodiment when the irradiation angle of light is 10 degrees.

The eighth (b) diagram is a graph showing the relationship between the moving distance (mm) and the L ^* value in Comparative Example 5 when the irradiation angle of light is 10 degrees.

The ninth (a) diagram is a diagram showing the relationship between the moving distance (mm) and the L ^* value in the eighth embodiment when the irradiation angle of light is 25 degrees.

The ninth (b) diagram is a diagram showing the relationship between the moving distance (mm) and the L ^* value in Comparative Example 5 when the irradiation angle of light is 25 degrees.

11. . . Chip magnet

12. . . Chip magnet

13. . . Peripheral surface

14. . . Inner circumference

15. . . Separation hole

16. . . Painted object

17. . . Coating film

18. . . Magnetic line of force

19. . . Contact area

Claims (5)

A pattern forming method, comprising: providing a pattern forming coating material comprising a resin, a flat powdery magnetic substance and a solvent; and a viscosity after 15 seconds from application to the object to be coated It is 1,000~10,000mPa. s, and the viscosity after 50,000 seconds from the application of the coated object is 50,000 mPa. And s or more; and the method comprising: applying the coating for forming a pattern to the object to be coated to form a coating film, and arranging the magnet along the surface of the coating film; and applying a magnetic field to the coating film by the magnet And a step of aligning the magnetic body in the coating film by the magnetic field, wherein the step of aligning the magnetic body comprises the step of applying a magnetic field having a magnetic flux density of 15 to 350 mT to the coating film; and wherein the resin is The acrylic resin, the pattern forming coating material further contains a rheology control agent, which is a group consisting of a nitrocellulose resin, a cellulose acetate butyrate resin, a microgel, and a vinyl acetate resin. At least one of the selected ones. The pattern forming method of claim 1, wherein the pattern forming coating further contains a polyisocyanate compound as a hardener. A pattern forming method according to the first aspect of the invention, wherein the resin is a vinyl acetate resin. The pattern forming method of claim 1, wherein the pattern forming coating further contains at least one of a dye and a nano pigment. The method for forming a pattern according to claim 1, wherein the step of forming a coating film and arranging the magnet comprises: a step of arranging a plurality of magnets having a sheet shape adjacent to each other along a surface of the coating film, comprising: a surface magnetic pole and a rear magnetic pole of the adjacent magnets are adjacent magnets different from each other and the side surfaces of the magnets are in contact with each other The step of arranging the respective magnets; the step of aligning the magnetic bodies comprises: applying a magnetic field to the coating film by the plurality of magnets, and causing the magnetic bodies to be coated relative to each other at the contact points of the magnets in contact with each other by the adjacent magnets The film surface is aligned in a manner to extend approximately parallel, and the step of forming a pattern on the coating film by at least the magnetic body on each of the magnet contact portions.