JP2006233356A - Glitter flake having light interference color-generating function - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glitter flake inhibiting the apparent intensity reduction of interference reflection light by white-reflection light, having a light-emitting function having the light interference-generated color and chromatic color jointly and capable of being developed to a merchandise field requiring an excellent esthetic property. <P>SOLUTION: This glitter flake having the light interference color-generating function is obtained by cutting a conjugate fiber constituted by an alternately laminated body part obtained by alternately laminating polymer layers having different refractive indices from each other and having 0.8≤(SP1/SP2)≤1.1 range of a ratio (SP ratio) of the solubility parameter value (SP1) of a higher refractive index side polymer to the solubility parameter value (SP2) of a lower refractive index, parallel to the long axial direction of a flat cross section, and a covering layer consisting of a fiber-forming polymer for covering the alternatively laminated body part, and the conjugate fiber has a polymer layer containing at least a chromatic component. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a bright material having a light interference color development function which has both a light interference color development function and a chromatic color development function and which has an unprecedented aesthetic property.

  A composite fiber having an optical interference coloring function composed of an alternating laminate of independent polymer layers having different refractive indexes interferes with the wavelength in the visible light region by the reflection / interference action of natural light. Its color has brightness like metallic luster, exhibits a pure and clear color (single color) with a characteristic wavelength, and expresses aesthetics completely different from the color developed by light absorption of dyes and pigments (chromatic color). A typical example of a composite fiber having such a light interference coloring function is disclosed in Patent Document 1.

However, when a fiber having a light interference coloring function disclosed in Patent Document 1 (pamphlet) is cut and used as a bright material to produce a paint or cosmetic, white reflection from the fiber surface Light is emitted from the fiber as reflected light together with interference reflected light of a specific wavelength, and the white reflected light lowers the purity of the interference reflected light, feels whitish to our eyes, and inhibits the clear color of the interference color itself. It was. As a countermeasure against this white reflected light, when making a coated product using the above-mentioned light interference coloring fiber, first use a chromatic color layer with strong absorbency such as black or haze on the base, and cut the light interference coloring fiber on it. There has been proposed a method in which a fiber is contained in a transparent resin for forming a coating film and applied or sprayed to form a brightening agent layer. However, any of these methods is a usage method in which the use of a cut fiber of a light interference coloring fiber is limited, and there is a problem that it is difficult to apply to a white product or a product having a bright color tone.
International Publication No. 98/46815 Pamphlet

  The present invention was made against the background described above, and its purpose is to suppress the apparent decrease in the intensity of interference reflected light caused by white reflected light, and to have a coloring function that combines light interference coloring and chromatic color. An object of the present invention is to provide a glittering material that can be developed into a product field that requires excellent aesthetics.

  According to the study by the present inventors, the visibility of the light interference color development is improved by using a structure having an alternate laminate portion having a light interference color development function and a layer having a chromatic color development function. The present inventors have found that a coloring effect of both interference color and chromatic color can be obtained with a single luster material without requiring a device for suppressing white reflected light in order to exhibit a chromatic effect.

  Thus, according to the present invention, the ratio (SP ratio) of the solubility parameter value (SP1) of the high refractive index side polymer to the solubility parameter value (SP2) of the low refractive index side polymer is 0.8 ≦ SP1 / SP2 ≦ 1. .1 range, polymer layers having different refractive indexes, alternately laminated in parallel to the long axis direction of the flat cross section, and a coating made of a fiber-forming polymer that coats the alternate laminate parts A brilliant material having a light interference coloring function, characterized in that it is a brilliant material obtained by cutting a composite fiber composed of a layer, and the composite fiber has a polymer layer containing at least a chromatic component. Material "is provided.

  The glitter material of the present invention improves the visibility of light interference coloring by combining the light interference coloring effect due to the alternating laminate part composed of two kinds of polymers having different refractive indexes and the chromatic effect due to the chromatic color component-containing layer. At the same time, a unique coloration is realized by combining with chromatic colors, and the coloration is excellent in aesthetics, which has never been seen before.

  The cross-sectional structure perpendicular to the fiber axis of the composite fiber used for the glitter material of the present invention will be described with reference to FIG. (1) to (3) in FIG. 1 schematically show cross-sectional shapes when the conjugate fiber of the present invention is cut at right angles to the length direction, and the two types have different refractive indexes. The alternately laminated body portion composed of polymer layers has a flat cross-sectional shape, and a large number of two types of polymer layers are alternately laminated in parallel with the long axis direction (horizontal direction in the drawing) of the flat cross section. And the coating layer which consists of a fiber-forming polymer surrounds the outer peripheral part, and a chromatic color component is contained in any one of the said alternately laminated body part (including intermediate | middle layer) and a coating layer. That is, in (1), the intermediate layer of the alternating laminate part, (2) in the covering layer covering the alternating laminate part, (3) in the high refractive index side polymer layer and low The refractive index side polymer layer contains a chromatic color component.

  The thickness of each polymer layer in such an alternately laminated body is preferably in the range of 0.02 to 0.5 μm. When the thickness is less than 0.02 μm or exceeds 0.5 μm, it is difficult to obtain the expected optical interference effect in a useful wavelength region. Furthermore, the thickness is preferably in the range of 0.05 to 0.15 μm. Further, when the optical distance between the two polymer components, that is, the product of the layer thickness and the refractive index is equal, a higher optical interference effect can be obtained. In particular, when the sum of the two optical distances equal to the primary reflection is equal to the wavelength of the desired color, the maximum interference color is obtained, which is preferable. In addition, when providing an intermediate | middle layer in an alternate laminated body part, although the thickness of this intermediate | middle layer is arbitrary, the range of 1.0-10 micrometers, especially 2.0-5.0 micrometers is suitable.

  The cross-sectional shape of the alternate laminate perpendicular to the fiber axis direction of the composite fiber is flat as shown in FIG. 1, and has a long axis (horizontal direction in the drawing) and a short axis (vertical direction in the drawing). is doing. Those having a large flatness ratio (major axis / minor axis) of the cross section influence the effective area for light interference, that is, the major axis of the alternately laminated body portion can be made large, which is a preferable fiber cross-sectional form. . When the flatness of the cross section of the fiber is 3.5 or more, preferably 4.5 or more, particularly preferably 7 or more, the flat major axis surfaces of the fibers are easily arranged in parallel with each other during use, and the light interference coloring function Is preferable. However, if the flatness ratio is too high, the yarn forming property is greatly reduced, so it is preferably 15 or less, particularly 12 or less. The flatness ratio is calculated including the covering layer portion when a covering layer made of a fiber-forming polymer described later is formed on the outer peripheral portion of the flat cross section.

  Moreover, in the cross section of the composite fiber, the number of polymer layers that are independent from each other in the alternately laminated body portions of different polymer layers is preferably 10 to 120 layers. When the number of stacked layers is less than 10, the interference effect is reduced. On the other hand, if the number of laminated layers exceeds 120 layers, an increase in the amount of reflected light can no longer be expected, and the die structure for spinning becomes complicated, making it difficult to produce yarn.

  In the present invention, as described above, the cross-sectional shape of the alternately laminated body portion is a flat shape in which a large number of polymer layers having different refractive indexes are alternately laminated. It is very important for the reflection intensity and monochromaticity (clear color development) that the parallelism of the layers, that is, the optical distance of each layer is uniform both in the major axis direction and the minor axis direction of the flat cross section. In order to form a flat laminate structure with a large interfacial area, it is possible to achieve a uniform laminate thickness by controlling the laminate formation process in the complicated die channel, the balus after discharge, the interfacial tension, etc. For this purpose, it is important to specify the ratio of solubility parameters (SP values) between polymer layers having different refractive indexes. That is, the ratio (SP ratio) of the solubility parameter (SP1) of the high refractive index side polymer to the solubility parameter (SP2) of the low refractive index side polymer is in the range of 0.8 ≦ SP1 / SP2 ≦ 1.1, particularly 0.85. ≦ SP1 / SP2 ≦ 1.05 is necessary. When such a combination of polymers is used, a uniform alternating laminate structure can be easily obtained because the interfacial tension acting on the interface is reduced when an alternating laminated flow of two kinds of polymers is discharged from the spinneret. On the other hand, when the SP ratio is out of the above range, the discharged polymer flow tends to be rounded by the surface tension, and the contraction force works to minimize the contact area of both polymer lamination interfaces. Since the structure has a multi-layer structure, the shrinkage force is increased, and therefore, the laminated surface is curved and rounded, and a favorable flat shape cannot be obtained. In addition, the polymer stream also has a large basal effect that tends to swell when released at the die outlet.

  As a preferable combination that satisfies the above requirements, for example, polyethylene terephthalate in which 0.3 to 10 mol% of a dibasic acid component having a sulfonic acid metal base is copolymerized with respect to all dibasic acid components forming a polyester And a polybasic methacrylate having an acid value of 3 or more, and a 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 the polyester. A combination of polyethylene naphthalate and aliphatic polyamide, a copolymerized aromatic polyester copolymerized with 5-30 mol% of a dibasic acid or glycol component having an alkyl group in the side chain per total repeating unit, and polymethyl methacrylate 9,9-bis (parahydroxyethoxyphenyl) fluorene per repeating unit Polyethylene terephthalate copolymerized with 0 to 80 mol% or a combination of polyethylene naphthalate and polymethyl methacrylate, and 20 to 80 mol% of 9,9-bis (parahydroxyethoxyphenyl) fluorene with respect to all repeating units and metal sulfonate A combination of polyethylene terephthalate or polyethylene naphthalate and aliphatic polyamide copolymerized with 0.3 to 10 mol% of the dibasic acid component having a salt per total dibasic acid component forming the polyester, 2, 2 -A combination of polycarbonate and polymethyl methacrylate containing bis (parahydroxyphenyl) propane as a dihydric phenol component, 9,9-bis (parahydroxyethoxyphenyl) fluorene and 2,2-bis (parahydroxyphenyl) propane (mol) Ratio is 2 / 80 to 80/20) and the and the like can be exemplified a combination of polycarbonate and polymethyl methacrylate click relay to dihydric phenol component.

  In the present invention, the thickness of the alternately laminated body portion need not be particularly limited, and may be appropriately set according to the fineness required for the composite fiber according to the application. In particular, when a composite fiber having an optical interference function with a fineness is required, the thickness of the alternately laminated body portion is set to 10 μm or less, preferably 2 to 7 μm, and the fiber forming property for forming a coating layer to be described later If the polymer is, for example, a readily alkali-soluble polymer, it is preferable to obtain a composite fiber having a light interference color-developing function with fineness by treating with an alkali. 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 that covers the alternating laminate portion may be formed of any fiber-forming polymer, for example, may be formed of any of the polymers forming the alternating laminate portion, or two types You may coat | cover more than double with the above fiber-forming polymer. Especially, it is preferable that the coating layer of the outermost layer is formed of a polymer that is easily soluble in alkali rather than the polymer that forms the alternately laminated body portion. 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 obtained more easily.

  In addition, an alkali easily soluble polymer here means that there exists a difference of 10 times or more compared with the alkali weight loss rate of the polymer which forms the alternately laminated body part. Specifically, when treated with an aqueous alkali solution, the alkali-soluble polymer of the coating layer is dissolved at a rate 10 times or more faster than the alkali-poorly soluble polymer constituting the alternately laminated body portion. 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. As a result, the light interference coloring function is deteriorated.

  Examples of the alkali-soluble polymer preferably used include polylactic acid, polyethylene terephthalate copolymerized with polyethylene glycol and polybutylene terephthalate, polyethylene terephthalate blended with polyethylene glycol and / or alkali metal salt of alkylsulfonic acid, and polyethylene glycol and / or Examples thereof include polyethylene terephthalate and polybutylene terephthalate copolymerized with a dibasic acid component having a sulfonic acid metal base.

  Here, polylactic acid generally contains L-lactic acid as a main component, but may contain other copolymerization components such as D-lactic acid within a range not exceeding 40% by weight. . The polyethylene terephthalate or polybutylene terephthalate copolymerized with polyethylene glycol is preferably such that the copolymerization ratio of polyethylene glycol is 30% by weight or more, whereby the alkali dissolution rate is remarkably improved. Further, polyethylene terephthalate and polybutylene terephthalate blended with alkali metal alkyl sulfonate and / or polyethylene glycol is 0.5 to 3.0% by weight in the former and 1.0 to 4.0% by weight in the latter. The range is preferred, and the average molecular weight of the latter polyethylene glycol is suitably in the range of 600 to 4000. Further, polyethylene terephthalate and polybutylene terephthalate copolymerized with polyethylene glycol and / or dibasic acid component having a sulfonic acid metal base, the former is in the range of 0.5 to 10.0% by weight, the latter is the dibasic acid component. A range of 1.5 to 10 mol% is appropriate for all dibasic acid components forming the polyester.

  The thickness of the coating layer is 2.0 μm or more, preferably 2.0 to 10 μm, particularly preferably 3.0 to 5.0 μm. In this way, by providing a coating layer made of a fiber-forming polymer around the alternating laminate part, the polymer flow distribution between the vicinity of the wall surface and inside received in the final discharge hole during melt spinning can be relaxed, The shear stress distribution received by the laminated body portion is reduced, and an alternate laminated body in which the thickness of each layer across the inner and outer layers is more uniform can be obtained. In addition, when the coating layer is formed of two or more kinds of polymers, the total thickness may be 2.0 μm or more. For example, even if the thickness of the inner coating layer is less than 2.0 μm, If the total thickness of the coating layers is 2.0 μm or more, the above effect can be exhibited. Therefore, if the outer coating layer is formed of an alkali-soluble polymer, only the outer coating layer is removed by alkali treatment, and thus a uniform thickness coated with a coating layer having a thickness of less than 2.0 μm is obtained. It becomes possible to easily obtain a composite fiber having an optical interference coloring function having an alternating laminate portion.

  Here, when the coating layer is too thin and less than 2.0 μm, the single fiber fineness becomes small and the cross section is flat. Prone to problems. In addition, the fiber-forming polymer that contacts and coats the alternating laminate part is a solubility parameter of a polymer (high refractive index side polymer or low refractive index side polymer) that constitutes both sides in the major axis direction of the alternating laminate part. 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.

In the present invention, in addition to the above-mentioned requirements, it is important that a chromatic color component is contained in at least one of the alternating laminate portion and the coating layer. The chromatic color here 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, and is not particularly limited. 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 of the pigment include W, Zn, MoS ₂ (black), Bi, and carbon black, and 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), quinacudrine-based red pigment (CI.P.R.122), azomethine-based purple dye (CI.S.V.49), phthalocyanine-based 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 addition amount of these pigments is suitably in the range of 0.05 to 3.0% by weight. When the amount is less than 0.05% by weight, the accuracy of addition tends to be insufficient and color spots tend to occur. On the other hand, when it exceeds 3.0% by weight, the added amount is too much and the fiber structure forming property is easily inhibited. In general, it may be appropriately set according to the type of pigment used while confirming the degree of color development. In addition, the polymer layer containing a chromatic pigment in contact with the alternating laminate part is also approximately the same as the solubility parameter value of the polymer (high refractive index side polymer or low refractive index side polymer) in contact with the alternating laminate part. 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.

  The method of adding these pigments is arbitrary, but a method of adding and dispersing a master chip containing the pigment in a high concentration to the polymer forming the layer to be added is desirable in terms of simple and uniform dispersion of the pigment.

  The composite fiber preferably has an elongation of 10 to 60%, particularly 20 to 40%. If this elongation is too large, in the process of cutting the composite fiber to make a glittering material, the fiber tends to be deformed by the tension applied to the composite fiber, so that the process passability tends to be lowered. . On the other hand, when the elongation is too small, it becomes difficult to absorb the tension applied to the composite fiber, 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 polymer used, birefringence (Δn) can be further increased by stretching the composite fiber that has been spun and cooled and solidified, and two types of polymers can be obtained. The difference in refractive index between them is defined as “the difference in refractive index of the polymer plus the difference in birefringence of the fiber”. As a result, the difference in refractive index as a whole can be increased, so that the light interference coloring function is enhanced.

  Furthermore, the composite fiber can take any form such as false twisted crimped yarn, composite blended yarn, thick yarn, etc., and its heat shrinkage at 130 ° C. to 150 ° C. is 3% or less. preferable. When the thermal shrinkage rate exceeds this range, when this is cut into a bright material, deformation such as fiber shrinkage occurs and the light interference coloring function tends to deteriorate. 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 composite fiber used for the glitter material of the present invention described above can be produced by, for example, the following method. That is, according to the method described in International Publication No. 98/46815 pamphlet, first, polymers having different refractive indexes are converted into a ratio of the solubility parameter (SP1) of the high refractive index side polymer and the solubility parameter (SP2) of the low refractive index side polymer ( When the SP ratio is melt-discharged into an alternate laminate structure in a combination in the range of 0.8 ≦ SP1 / SP2 ≦ 1.1, the alternate laminate structure is covered by covering the alternate laminate structure with a fiber-forming polymer. An unstretched fiber having a structure in which a body part is covered with a covering layer is obtained.

  Drawing and various composite heat treatments may be performed as necessary, but the conditions are not particularly limited, and conventionally known combined drawing conditions for undrawn fibers may be adopted. For example, the polymer can be stretched at any temperature as long as the polymer molecular chain is oriented at a temperature in the vicinity of the glass transition temperature (Tg ± 15 ° C.) of the polymer having the highest glass transition temperature. The temperature here is the temperature of a heating medium such as a hot plate or a heating roller. The draw ratio may be appropriately set according to how much strength and heat shrinkage properties are imparted to the finally obtained drawn fiber, but usually 0.70 to 0.95 times the maximum draw ratio. It may be stretched at. In addition, in order to improve heat resistance, such as a heat shrink characteristic, you may heat-process subsequent to extending | stretching.

  The glitter material of the present invention can be produced by cutting the composite fiber. At this time, it may be cut to a length according to the application, but when used in application fields such as paper, paint, ink, cosmetics, from the viewpoint of handling at the time of use and aesthetics of the final product obtained. It is preferable to cut so that the fiber length in the fiber axis direction is longer than the short axis length of the fiber cross section. The upper limit of the length is usually about 50 mm, but it is preferably 1 mm or less particularly for applications such as cosmetics and paints that are desired to be finely dispersed. Preferably, the length is longer than the major axis length of the laminated portion, and is preferably several tens to several hundreds μm. In addition, in the case of the fiber cross section which has the coating layer by an alkali-soluble polymer, it is preferable to cut | disconnect so that cut length may become longer than the short-axis length of the fiber cross section except this coating part.

The glittering material of the present invention can be made into a finer or thinner glittering material by, for example, treating with an alkaline aqueous solution before use to remove the alkali-soluble polymer.
The glittering material of the present invention is blended in an appropriate amount in a solution or resin, and used in combination with other color pigments, such as paints, resin compositions, ink compositions, artificial marble molded products, coated papers, and cosmetic compositions. It can be used for various applications as a product or a composition thereof.

  For example, when blended in paint, acrylic resin, polyester resin, epoxy resin, phenol resin, urea resin, fluororesin, polyester-urethane curing resin, epoxy-polyester curing resin as the thermosetting resin in the base material resin , Acrylic-polyester resin, acrylic-urethane curable resin, acrylic-melamine curable resin or polyester-melamine curable resin, etc., as a thermoplastic resin, polyethylene resin, polypropylene resin, petroleum resin, thermoplastic polyester resin or thermoplastic resin It is preferable to use a fluororesin or the like and use polyisocyanate, amine, polyamide, polybasic acid, acid anhydride, polysulfide, boron trifluoride, acid dihydrazide, imidazole, or the like as the curing agent. The content of the glittering material in the coating is preferably adjusted to be 0.1 to 30% by weight in the coating film after drying and curing. A more preferable content is 1 to 20% by weight. When the content of the glitter material is less than 0.1% by weight, the coating film does not have sufficient glitter, while when it is more than 30% by weight, the improvement of the glitter is small for the content, On the contrary, the color tone of the substrate may be impaired. Since this glittering material does not impair the color tone of the substrate, it can be used for paints of all colors. For example, in addition to primary colors such as red, blue, green, and black, it can be used for pastel colors that are difficult to adjust.

  When mix | blending in a resin composition, said various thermosetting resin or thermoplastic resin can be utilized for base material resin. Further, if a thermoplastic resin having a melting point or a softening point lower than the melting point of the polymer constituting the glittering material of the present invention is used, injection molding becomes possible, so that a molded product having a complicated shape can be obtained.

  When mix | blending with an ink composition, it is preferable to use that whose fiber length is 500 micrometers or less. If the fiber length is too long, the glitter material appears to jump out on the appearance of the handwriting, and the smoothness tends to be impaired.

  Ink compositions include inks for writing instruments such as various ballpoint pens and sign pens, and printing inks such as gravure inks and offset inks, and can be used in any ink composition. Examples of inks for writing instruments include acrylic resins, styrene-acrylic copolymers, polyvinyl alcohol, polyacrylic acid salts, vinyl acrylate copolymers, water-soluble plants such as microbial polysaccharides such as xanthan gum or guar gum And the like, and those composed of water, alcohol, hydrocarbon, ester and the like as a solvent.

  Examples of gravure ink vehicles include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin shell, maleic resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate, ethyl cellulose, chlorinated rubber, cyclized rubber, ethylene-acetic acid Resin mixture such as vinyl copolymer resin, urethane resin, polyester resin, alkyd resin, gilsonite, dammar or shellac, mixture of the above resin, water-soluble resin or aqueous emulsion resin obtained by water-solubilizing the above resin, and hydrocarbon, alcohol, ether And those composed of a solvent such as ester or water.

Examples of vehicles for offset ink include rosin-modified phenolic resins, petroleum resins, alkyd resins, or resins such as these dry-modified resins, vegetable oils such as linseed oil, tung oil or soybean oil, and n-paraffin, isoparaffin, aromatech. , Naphthene, α-olefin, or a solvent such as water.
It should be noted that conventional additives such as dyes, pigments, various surfactants, lubricants, antifoaming agents, and leveling agents may be appropriately selected and blended with the various vehicle components.

  When using bright materials for artificial marble moldings, the outermost layer is a transparent gel coat layer, an intermediate layer containing bright materials inside, and a three-layer structure of artificial marble layers containing colored aggregate below the intermediate layer It is preferable to make it. With this configuration, since the outermost layer is a transparent gel coat layer, the strong reflected light emitted from the intermediate layer and the pattern of the artificial marble layer are combined to form a marble-like appearance having a glittering and high glitter.

  The thickness of the transparent gel coat layer is preferably 0.3 to 0.7 mm in consideration of a sense of depth and a reduction in visible light transmittance. The component of the transparent gel coat layer is not particularly limited, but a thermosetting resin is preferable from the viewpoint of ease of handling and high processability. Specifically, unsaturated polyester resin, vinyl ester resin, epoxy resin, urethane resin, phenol resin, or a mixture or modified product thereof (for example, modified product in which the terminal group of unsaturated polyester resin is changed to acrylic), etc. Is mentioned. In particular, unsaturated polyester resins are preferable because they are highly transparent, inexpensive and easily available.

  The intermediate layer is for giving a high gloss to the marble-like appearance, and should not cover the pattern of the artificial marble layer. Therefore, it is necessary to provide at least visible light transparency. However, it is not necessary to use the same main component as the outermost transparent gel coat. As long as the appearance is not impaired, a layer other than the intermediate layer may be further provided between the transparent gel coat layer and the artificial marble layer. Specifically, the color tone of the artificial marble molded product can be easily adjusted by arranging a colored film having high visible light permeability.

  The intermediate layer preferably has a thickness in the range of 0.05 to 1 mm, and a thermosetting resin having high visible light permeability is suitable as its constituent component. Further, in addition to the glittering material, a curing agent or an accelerator may be contained, and a thickener, a thixotropic agent, an antifoaming agent, or a property improver may be blended as necessary. Furthermore, one or more selected from colored pigments, other metal pigments (such as aluminum pigments and iron oxide pigments), and interference color pigments (such as mica coated with metal oxides) do not significantly impair the color tone of the substrate. You may mix | blend in the range.

  The artificial marble layer preferably has a thickness of 3 to 25 mm, the main component thereof is a thermosetting resin, and contains aggregates, accelerators, curing agents, and colorants as other components. As the thermosetting resin, the thermosetting resin of the transparent gel coat layer can be used. For example, unsaturated polyester resin. As the aggregate, an inorganic material such as glass frit, cryolite, aluminum hydroxide, calcium carbonate or silica powder, or an organic material such as thermoplastic polyester resin can be used. Furthermore, you may contain glass fiber as a reinforcing material as needed.

  When the blending ratio of the glittering material in the intermediate layer is excessively low, it is difficult to obtain the glitter and the sense of depth. On the other hand, when it is excessively high, there are problems in terms of cost and physical properties. Therefore, the blending ratio of the glittering material in the intermediate layer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin.

  When strength is required for the artificial marble molded product, an FRP layer may be provided on the back surface of the artificial marble layer. In this case, since the FRP layer is disposed on the back surface of the artificial marble layer, the glossiness of the artificial marble molded product is not impaired. The FRP layer is obtained, for example, by impregnating a chopped strand glass mat with a thermosetting resin such as an unsaturated polyester resin, a vinyl ester resin, or an epoxy resin, followed by heat curing. Further, if a colorant is added to the FRP layer, it is possible to color the artificial marble molded product or to shield light rays from the back surface.

  The method for producing the artificial marble molded product is not particularly limited, and a conventional method can be used as it is. For example, when manufacturing the thing of complicated shape like a bathtub, methods, such as a casting method and a press molding method, can be utilized. Moreover, when manufacturing the bathtub provided with the FRP layer, after forming an artificial marble layer, the method of spraying the thermosetting resin containing chopped strand glass on the surface of the artificial marble layer with a spray gun (spray-up method) Alternatively, a chopped strand glass mat impregnated with a thermosetting resin may be attached to the surface of the artificial marble layer by a hand lay-up method and then cured at 50 ° C. for 1 hour. Alternatively, before forming the artificial marble layer, the FRP layer may be formed in advance on the surface of the back mold material of the bathtub by the spray-up method or the hand lay-up method.

  The length of the glitter material used for the artificial marble molded product is preferably 0.01 to 2 mm. If the length exceeds 2 mm, cracks are likely to occur during the molding process of the intermediate layer. On the other hand, if the length is less than 0.01 mm, the reduction in glitter tends to be significant.

  In the case of adding a glittering material to the coated paper, an adhesive made of stearic acid, alkali salt of lauric acid, copolymer latex or starch, a solvent such as surfactant and water, if necessary, an antioxidant, Solutions obtained by blending ultraviolet absorbers, water-resistant agents, antiseptic / antifungal agents, bactericides, antifoaming agents, fragrances and / or dyes, blade coaters, air knife coaters, roll coaters, curtain coaters, bar coaters, gravure By applying a single layer or two or more layers on one side or both sides of a base paper with a coating device such as a coater or a size press coater, a coated paper with high glitter can be obtained.

  Further, the glitter material of the present invention is used in cosmetics, in particular, cosmetics for the skin and lips of the face and human body, and surface growth parts such as nails, eyelashes or hair (hereinafter sometimes referred to as cosmetic compositions). It can be used by containing.

  In the cosmetic composition, the glittering material is 0.01 to 50% by weight, preferably 0.1 to 30% by weight, more preferably 0.3 to 20% by weight, based on the total amount of the composition. It can be included.

  More specifically, skin products (foundation), makeup products for cheeks or eye shadows, lip products, concealers, blusher, mascara, eyeliner, makeup products for eyebrows, lip or eye pencils Nail products, body make-up products, hair make-up products (hair mascara or hair spray) and the like. These cosmetic compositions can be used to apply to keratin materials or used to modify makeup, for example, over makeup already deposited on keratin materials (The composition is applied as a top product, commonly referred to as a top coat).

The cosmetic composition should be applied over makeup accessories (supports) such as artificial nails, false eyelashes, artificial hair, wigs, pastels or patches attached to the skin or lips. You can also.
At this time, the glittering material of the present invention can be contained in a hydrophilic medium or a lipophilic medium to form a cosmetic composition.

The cosmetic composition, or the base (base) composition and / or the top composition includes 2 or 5 water or a hydrophilic organic solvent such as water and alcohol, particularly ethanol, isopropanol or n-propanol. And a mixture with a polyol such as a linear or branched lower monoalcohol having 5 carbon atoms, glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol, polyethylene glycol and the like. The hydrophilic phase may also contain C ₂ ethers and C ₂ -C ₄ aldehydes that are hydrophilic. Water or a mixture of water and a hydrophilic organic solvent is present in the composition according to the invention or at least one of the base and / or top composition in an amount of 0 to 90% by weight (especially with respect to the total weight of the composition). 0.1 to 90% by weight), preferably 0 to 60% by weight (particularly 0.1 to 60% by weight).

  Either the cosmetic composition or the base and / or top composition includes, in particular, fatty substances that are liquid at room temperature (usually 25 ° C.) and / or fatty substances that are solid at room temperature, such as waxes, pasty fatty substances It may contain a fatty phase composed of rubber and a mixture thereof. Furthermore, the fatty phase may contain a lipophilic organic solvent.

  Fatty substances that are liquids at room temperature, generally called oils, that can be used in the above cosmetics, are 4-10, such as animal-derived hydrocarbon oils such as perhydrosqualene, heptanoic acid or octanoic acid triglycerides, etc. Liquid triglycerides or sunflower oils, corn oil, soybean oil, grape seed oil, sesame oil, apricot oil, macadamia oil, castor oil and avocado oil, caprylic / capric acid triglycerides, jojoba oil, shea butter Linear or branched hydrocarbons derived from minerals or synthetics such as vegetable hydrocarbon oils, paraffin oils and derivatives thereof, hydrogenated polyisobutenes such as petroleum jelly, polydecene, parleam, eg Purcellin oil (Purcellin) oil), Myristi Synthetic esters and ethers of fatty acids such as isopropyl acid, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, isostearyl lactate, octyl hydroxystearate, hydroxystearic acid Polyol esters such as octyldodecyl acid, diisostearyl malate, triisocetyl citrate, heptanoic acid ester of aliphatic alcohol, octanoic acid ester, decanoic acid ester, propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate, and Pentaerythritol ester, octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpenta Aliphatic alcohols having 12 to 26 carbon atoms such as decanol, oleyl alcohol, partially hydrocarbon- and / or silicone-based fluorinated oils, phenyltrimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenylmethyldimethyltrisiloxane , Diphenyldimethicone, phenyldimethicone, polymethylphenylsiloxane, and the like, optionally volatile, such as cyclomethicone having a phenyl group, dimethicone, etc., or linear or cyclic, liquid or pasty at room temperature Mention may be made of silicone oils such as methylsiloxane (PDMS) and mixtures thereof.

These oils may be contained in the range of 0.01 to 90% by weight, preferably 0.1 to 85% by weight, based on the total weight of the composition.
Either the cosmetic composition or the base and / or top composition may contain one or more cosmetically acceptable organic solvents (acceptable tolerance, toxicity and feel). These solvents may be contained in the range of 0 to 90% by weight, preferably 0 to 60% by weight, more preferably 0.1 to 30% by weight, based on the total weight of the composition.

  Solvents that can be used in the compositions of the present invention include acetates such as methyl acetate, ethyl, butyl, amyl, 2-methoxyethyl or isopropyl, ketones such as methyl ethyl ketone, methyl isobutyl ketone; toluene, xylene, hexane, Mention may be made of hydrocarbons such as heptane, aldehydes having 5 to 10 carbon atoms, ethers having at least 3 carbon atoms, and mixtures thereof.

  Furthermore, either the composition of the present invention or the base and / or top composition may comprise a fatty material that is solid or pasty at room temperature, such as rubber or wax. The wax may be hydrocarbon based, fluoride based and / or silicone based and may be of plant, mineral, animal or synthetic origin. In particular, the wax preferably has a melting point higher than 25 ° C, more preferably higher than 45 ° C.

  The “wax” that can be used in the present invention includes beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline wax, ceresin wax or ozokerite, polyethylene or Fischer-Tropsch wax, alkyl or alkoxy dimethyl having 16 to 45 carbon atoms. There may be mentioned synthetic waxes such as silicone waxes such as corn.

  The rubber is usually a high molecular weight polydimethylsiloxane (PDMS) or cellulose rubber or polysaccharide, and the pasty material is usually a hydrocarbon compound such as lanolin and its derivatives or PDMS.

  The nature and quality of the solid material depends on the desired mechanical properties and feel. These may contain 0 to 50% by weight of wax, preferably 1 to 30% by weight, based on the total weight of the cosmetic composition.

  Furthermore, either the cosmetic composition or the base and / or top composition may contain a film-forming polymer. In the present invention, the “film-forming polymer” refers to a polymer that forms a film on a support, particularly a keratin material, alone or in the presence of a film-forming aid.

  The film-forming polymer can be selected from vinyl polymers, polycondensates or polymers or natural sources. Examples of the film-forming polymer include acrylic polymer, polyurethane, polyester, polyamide, polyurea, and cellulose polymer. The film-forming polymer can be dissolved or dispersed in the form of solid particles in the physiologically acceptable medium of the composition.

  The film-forming polymer is present in either the composition according to the invention or the base and / or top composition in an amount of 0.01 to 60% by weight, preferably 0.5 to 40% by weight, based on the total weight of the composition, More preferably, it may be contained in the range of 1 to 30% by weight.

  The film-forming polymer can be combined with a film-forming aid. Such a film-forming agent can be selected from known compounds, and in particular, can be selected from a plasticizer and a fusion aid.

One of the cosmetic compositions or the base and / or top composition is in particular a suspension, dispersion, solution, gel, in particular an oil-in-water (O / W) or water-in-oil (W / O) emulsion. Or in the form of multiple (W / O / W or polyol / O / W or O / W / O) emulsions, creams, pastes, foams, especially dispersions of vesicles in ionic or nonionic lipids, biphasic or Multiphase lotions, sprays, powders, pastes, especially soft pastes (especially after 10 minutes of measurement in cone / planar geometry, at a shear rate of 200 s ⁻¹ and moving at 25 ° C. on the order of 0.1 to 40 Pa · s. It may be in the form of a paste having a specific viscosity. The composition may comprise an organic, especially anhydrous continuous phase.

One of the above cosmetic compositions, or base and / or top compositions, further comprises vitamins, thickeners (especially clays that are optionally modified), trace elements, emollients, sequestering agents, perfumes. In addition, it may contain components commonly used in cosmetics such as alkalizing or acidifying agents, preservatives, UV blockers or mixtures thereof.
Cosmetic compositions, in particular base and top compositions, can be obtained by preparation methods usually used in the cosmetic or dermatological field.

  A colorant may be contained in the cosmetic composition or in the base and / or top composition. The additional colorant can be selected from pigments, nacres, colorants and mixtures thereof. Here, the pigment refers to particles of some form that are white or colored, inorganic or organic, insoluble in physiological saline, and intended to color the composition. Also, pearl foil refers to some form of iridescent particles that are produced in the shell or synthesized by a particular mollusk.

  The pigment is present in the cosmetic composition, in particular in the base and / or top composition, from 0 to 15% by weight, in particular from 0.01% to 15% by weight, preferably 0%, based on the weight of the composition. It is preferable to make it contain in 0.01 to 10 weight%, More preferably, it is 0.02 to 5 weight%.

  The pigments are white or colored and can be inorganic and / or organic. Among inorganic pigments, titanium dioxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide (black, yellow or red), chromium oxide, manganese violet, ultramarine blue, chromium hydrate, iron, which are optionally surface-treated Mention may be made of metal powders such as blue, aluminum powder and copper powder.

  Among the organic pigments, mention may be made of lacquers based on carbon black, D & C type pigments and carmine, barium, strontium, calcium, aluminum.

  The pearl foil is present in the composition, in particular in the base and / or top composition, in an amount of 0 to 25% (in particular 0.01 to 25%), preferably 0, based on the total weight of the composition. It may be contained in the range of 0.01 to 15% by weight, more preferably 0.02 to 5% by weight.

  Pearl foil pigments are pearl foil pigments such as mica coated with titanium or bismuth oxychloride, mica-titanium coated with iron oxide, especially mica-titanium coated with iron blue or chromium oxide, organic of the above type Pigment coated mica-titanium pigments such as titanium and pearl foil pigments based on bismuth oxychloride.

  The colorant may be a colorant selected from water-soluble or fat-soluble colorants or colored polymers. The coloring material is present in the composition, in particular in the base and / or top composition, from 0 to 6% by weight (in particular from 0.01 to 6% by weight), preferably from 0. You may make it contain in the range of 01 to 3 weight%.

  Examples of fat-soluble colorants are soybean oil, Sudan brown, DC Yellow 11, DC orange 5, quinoline yellow, Sudan red III (CTFA name, D & C red 17), lutein, quinizarin green (CTFA name, DC green 6) , Alizurolpurple SS (CTFA name, DC violet No. 2), lycopene, beta carotene, bixin, capsantein and other carotenoid derivatives and / or mixtures thereof.

  Among water-soluble colorants, for example, Aleurites Moluccana Willd, Alkanna Tinctoria Tausch, Areca Catechu L., Arrabidaea Chica E. and B., Bixa Orellana L (annatto), Buta Monosperma Lam, Caesalpina Echinata Lam, Caesalpina Sappan L. Calophyllum Inophyllum L., Carthamus Tinctorius L., Cassia Alata L., Chrozophora Tinctoria L., Crocus Sativus L., Curcuma Longa L., Diospyros Gilletii de Wild, Eclipta Prostrata L., Gardenia Erubescens Stapf. And Hutch., Gardenia Terni Schum. And Thhonn., Genipa Americana L., Genipa Brasiliensis L., Guibourtia Demeusei (Harms) J. Leon, Haematoxylon Campechianum L., Helianthus annuus, Humilia Balsamifera (Aubl.) St-Hi1., Isatis Tinctoria L., Merit perenis, Monascus purpureus, Monascus ruber, Monascus pilosus, Morus Nigra L., Picramnia Spruceana, Pterocarpus Erinaceus Poir., Pterocarpus Soyauxii Taub., Rocella Tinctoria L., Rothmannia Whitfieldii (Lindl.) Dand., Schlegb. ., Simira Ti Contains extracts of colorant plants such as nctoria Aublet, Stereospermum Kunthianum Cham., Symphonia Globulifera L., Terminalia Catappa L., Sorgho, Aronia melanocarpa, and Lawson from Lawsonia Inermis L. also known as Impatiens Balsamina Mono- or polycarbonyl derivatives such as naphthoquinone, red wood extract, beet liquid, fuchsin disodium salt, red fruit extract, anthocyanin, dihydroxyacetone, isatin, alloxan, ninhydrin, glyceraldehyde, mesotartaric aldehyde 4,5-pyrazolinedione derivatives and mixtures thereof, and these skin colorants may be combined with direct colorants or indole derivatives and / or mixtures thereof.

  The colorant may be a colored polymer, i.e. a polymer comprising at least one organic coloring group. Colored polymers usually contain less than 10% by weight of colored material relative to the total weight of the polymer.

  The colored polymer may have any chemical nature, in particular a naturally derived polymer such as polyester, polyamide, polyurethane, polyacrylic acid, polymethacrylic acid, polycarbonate, cellulose or chitosan polymer or mixtures thereof. Yes, preferably a polyester or polyurethane polymer.

The colored polymer may have a colored group, and in particular may be grafted on the polymer chain by a covalent bond.
In particular, the colored polymer may be a copolymer based on at least two different monomers, at least one of which is an organic colored monomer.

  The monomers of the colored polymer are anthraquinone, methine, bismethine, azamethine, arylidene, 3H-dibenzo [7, ij] isoquinoline, 2,5-diarylaminoterephthalic acid and its esters, phthaloylphenothiazine, phthaloylphenoxazine, Phthaloylacridone, anthrapyrimidine, anthrapyrazole, phthalocyanine, quinophthalone, indophenol, perinone, nitroarylamine, benzodifuran, 2H-1-benzopyran-2-one, quinophthalone, perylene, quinacridone, triphenodioxazine, fluoridine ), 4-amino-1,8-naphthalimide, thioxanthrone, benzoanthrone, indanthrone, indigo, thioindigo, xanthene, acridine, azine, oxazine Can.

  The colored polymer is present in the composition according to the invention, in particular in the base and / or top composition, from 0 to 50% by weight, in particular from 0.01 to 50% by weight, relative to the total weight of the composition, Preferably, it may be contained in the range of 0.5 to 25% by weight, more preferably 0.2 to 20% by weight.

  Advantageously, the interfering particles and the additional colorant are 2 or more (especially in the range of 2 to 500), more preferably 5 or more (especially 5 or more) in the cosmetic composition or in the top composition. Present in a weight ratio of interfering particles / additional colorant actives in the range of 500).

  In addition to the additional colorant, the composition according to the invention may further contain a filler. The expression filler should be understood to mean any form of particles that are colorless or white, inorganic or synthetic and are insoluble in the medium of the composition regardless of the temperature at which the composition is produced. These fillers also serve to modify the rheology or feel of the composition.

  The filler can be inorganic or organic and can be in any form of platelets, spheres or ovals, regardless of crystal form (eg, sheet, cubic, hexagonal, orthorhombic, etc.). Talc, mica, silica, kaolin, polyamide powder, poly-β-alanine powder and polyethylene powder, tetrafluoroethylene polymer powder, lauroyl lysine, starch, boron nitride, polyvinylidene chloride / acrylonitrile-based polymer hollow microspheres, Acrylic acid copolymer and silicone resin microbeads, elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocarbons, hydroxyapatite, silica hollow microspheres, glass or ceramic microcapsules, 8-22 carbon atoms, Metal soaps preferably derived from organic carboxylic acids having 12 to 18 carbon atoms, such as zinc stearate, magnesium or lithium, zinc laurate, milli Mention may be made of magnesium stannate.

  The filler ranges from 0 to 90% by weight, preferably from 0.01 to 50% by weight, more preferably from 0.02 to 30% by weight, based on the total weight of the composition, in particular the base and / or top composition. You may make it contain.

  The cosmetic composition or base and / or top composition may comprise a particulate phase comprising pigments and / or nacres and / or fillers as described above, which are based on the total weight of the composition The content may be 0 to 98% by weight (particularly 0.01 to 98% by weight), preferably 0.01 to 30% by weight, and more preferably 0.02 to 20% by weight.

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, the solubility parameter value (SP value) of the polymer and each dimension in the fiber cross section were measured by the following methods.
(1) SP value and SP ratio The SP value is a value represented by the square root of the cohesive energy density (Ec). The Ec of the polymer can be obtained by immersing the polymer in various solvents and setting the Ec of the solvent at which the swelling pressure is maximized as the Ec of the polymer. The SP value of each polymer thus determined is described in “PROPERITES OF POLYMERS”, 3rd edition (ELSEVIER), page 792. In the case of a polymer whose Ec is unknown, it can be calculated from the chemical structure of the polymer. That is, it can be determined as the sum of Ec of each substituent constituting the polymer. Ec of each substituent is described in the above-mentioned literature, page 192. Then, for example, the SP ratio of the alternate laminated body portion is calculated from the following equation.
SP ratio = SP value of high refractive index polymer (SP1) / SP value of low refractive index polymer (SP2)

(2) Fiber cross-section measurement Sample fibers are fixed to a flat silicon plate and a beam capsule, and embedded in epoxy resin for 5 days. Next, using a microtome ULTRACUT-S, the sample is cut in a direction perpendicular to the fiber axis, and an ultra-thin sample having a thickness of 50 to 100 nm is prepared and placed on a grid. After vapor treatment with 2% osmium tetroxide at a temperature of 60 ° C. for 2 hours, a photograph is taken (magnification 20000 times) at an acceleration voltage of 100 kV using a transmission electron microscope LEM-2000. From the obtained photograph, the average thickness of each layer of the laminated structure portion and the thickness of the coating layer were measured.

(3) Light interference color development wavelength and intensity A sample fiber (multifilament yarn) is wound around a black plate at a winding density of 40/1 cm with a winding tension of 0.265 cN / dtex (0.3 g / de). A spectrophotometer color eye 3100 (CE-3100) is used for color measurement with a D65 light source. The measurement wavelength was 25 mmφ for the large window, the surface wavelength was included, and the peak wavelength and the reflection intensity were measured under the condition that the light source contained ultraviolet rays. With respect to the reflection intensity, the difference in reflection intensity between the baseline and the peak wavelength was defined as the net reflection intensity.

[Examples 1 to 4 and Comparative Example 1]
The alternating layered body portion having 41 layers composed of a high refractive index polymer (Polymer 1) and a low refractive index polymer (Polymer 2), an intermediate layer (only Examples 1 and 4) and a coating layer described in Table 1 Was melt-spun so as to have a fiber cross-sectional structure composed of The obtained unstretched fiber was stretched at a magnification shown in Table 1 to obtain a composite fiber having a light interference coloring function. The evaluation results are shown in Table 2.

In the table, polymer abbreviations are as follows.
Copolymerized PEN1: Copolymerized polyethylene-2,6-naphthalate copolymerized with 1.5 mol% 5-sodium sulfoisophthalic acid component PET 1: Copolymerized polyethylene terephthalate copolymer PET2 with 9 mol% sodium sulfoisophthalic acid component PET2: 9 , 9-bis (parahydroxyethoxyphenyl) fluorene (BPEF) 70 mol% copolymerized polyethylene terephthalate PC: Polycarbonate PMMA: Polymethyl methacrylate NY6: Nylon-6
PLA: Polylactic acid

  In Example 1, a 1.5 mol% copolymerized polyethylene-2,6-naphthalate and nylon-6 of 5-sodium sulfoisophthalic acid component, and a blue pigment (phthalocyanine pigment CI P. Bl. 15.3 made by Dainichi Seika) ) 0.9 mol% 5-sodium sulfoisophthalic acid component 1.5 mol% copolymer polyethylene-2,6-naphthalate is melted at 290 ° C., 270 ° C. and 290 ° C. And spun at 1200 m / min. The obtained undrawn yarn was drawn 2.0 times at a preheating temperature of 90 ° C., and was heat-set at 180 ° C. and wound up. The interference reflection light of the obtained composite fiber exhibited a clear green color, and further, a blue-green color with gloss and depth was obtained by combination with blue color using a chromatic pigment.

  In Example 2, polyethylene terephthalate (PET) copolymerized with 70 mol% of 9,9-bis (parahydroxyethoxyphenyl) fluorene (BPEF) and polymethyl methacrylate (PMMA), and a green pigment (phthalocyanine type) manufactured by Dainichi Seika Co., Ltd. PMMA containing 1.2% by weight of CI P.G.7) was melt-measured at 300 ° C., 255 ° C., and 255 ° C., and then introduced into a spinning pack, wound up at 2000 m / min, and wound up as it was. A casket having about 2.2 million dtex was prepared from the wound yarn and cut into a length of 25 μm to obtain a glittering material. The resulting glittering material had a deep red color due to the red interference color and the chromatic green color.

  In Example 3, PET and nylon-6 copolymerized with 0.8 mol% of 5-sodium sulfoisophthalic acid containing 0.75% by weight of a violet dye (azomethine CI S.V.49) manufactured by Dainichi Seika Co., Ltd. The nylon 6 was melted at a melting temperature of 290 ° C. and 270 ° C., respectively, and the nylon 6 was distributed and spun into a laminated part and a coating layer in a die, and wound at a speed of 2000 m / min. The obtained undrawn yarn was preheated at 80 ° C., drawn 1.5 times, and heat-set at 180 ° C. A transparent purple with a unique blue luster was obtained, and a composite fiber excellent in heat resistance and strength could be obtained.

  In Example 4, a chromatic layer of PC containing 0.5% by weight of a pink pigment manufactured by Dainichi Seika (quinacridone CI.P.R.122) is provided at the center of the laminated portion of PMMA and PC, A composite cross section coated with polylactic acid was formed. Melting temperatures were 255 ° C., 290 ° C., 290 ° C., and 235 ° C., respectively, and spinning was performed at 3000 m / min and wound up as it was. A casket of about 2.2 million dtex was prepared from the wound yarn and cut into a length of 25 μm. The cut fiber was immersed in a 4% by weight sodium hydroxide aqueous solution heated to 90 ° C., taken out after 1 minute, and dried. In the obtained cut fiber, only the polylactic acid of the coating layer was dissolved to obtain a fine glittering material. As for the color, the color change was recognized by the angle to see from pink to purple by pink chromatic color and blue interference color.

  Comparative Example 1 was the same as Example 3 except that no pigment was added. The blue color of the interference color of the obtained composite fiber is excellent in aesthetics as in the examples, but there are problems that it becomes whitish due to the overlap of yarns, and the visibility of the interference color decreases depending on the viewing angle.

[Example 5]
Loose face powder having the following composition was prepared.
30g nylon-12 powder,
10 g of the glitter material obtained in Example 1,
3.5 g of iron oxide,
3g of silicone binder,
Amount of 100 g of talc When this powder was applied to the face, it had excellent aesthetics and had a makeup effect that looked like a morpho butterfly due to light interference.

[Example 6]
A foundation having the following composition was prepared.
0.5 g of cetyl dimethicone copolyol / 4-polyglyceryl isostearate / hexyl laurate mixture (Abil WE 09 from Goldschmidt),
10 g of the glitter material obtained in Example 2,
Iron oxide 0.5g,
15 g of volatile silicone (DC245 Fluid from Dow Corning)
The amount which makes the whole water 100g This foundation was excellent in aesthetics, and had the novel makeup effect by interference of light.

[Example 7]
A mascara having the following composition was prepared.
15 g of carboxymethylcellulose,
Laponite 0.2g,
10 g of the glitter material obtained in Example 1,
0.05 g of disodium salt of fuchsin,
Amount of 100 g of total water When this mascara was applied to the eyelashes, it was excellent in aesthetics and a new color effect due to light interference was obtained.

[Example 8]
A nail polish solution having the following composition was prepared.
17.1 g of nitrocellulose,
5.4 g of N-ethyl-o, p-toluenesulfonamide,
5.4 g of tributylacetyl citrate,
10 g of the glitter material obtained in Example 1,
DC Red 34 0.025g,
Hectorite 1.0g,
7.2 g of isopropyl alcohol,
Amount of ethyl acetate and butyl acetate totaling 100 g This nail polish was applied directly to the nails, but it was excellent in aesthetics and a new color effect due to light interference was obtained.

[Comparative Example 2]
Except for using the glitter material of Comparative Example 1 instead of the glitter material of Example 1, the nail polish was adjusted and applied to the nails in the same manner as in Example 8, but the color effect due to the light interference effect was not sufficient. It was.

[Example 9]
A paint obtained by blending the glitter material of Example 1 with a two-component acrylic urethane base paint (product name “R-241 base” manufactured by Nippon Bee Chemical Co., Ltd.) so as to be 10% by weight with respect to the whole paint was obtained. The paint thus formulated is further diluted with an acrylic urethane thinner (product name “T-801 Base” manufactured by Nippon Bee Chemical Co., Ltd.) to a viscosity of about 11 to 12 seconds with Ford Cup # 4, and then the surface is coated. As a color base washed with isopropyl alcohol, coating was performed on a flat plate made of black ABS so as to have a film thickness of 15 to 20 μm, and baking was performed at 80 ° C. for 20 minutes to form a coating layer. The painted surface had an excellent color effect due to aesthetic light interference.

[Example 10]
A transparent unsaturated polyester gel containing 10% by weight of the glitter material of Example 1 was applied to an artificial marble layer made of unsaturated polyester having a thickness of 15 mm containing colored aggregates, and an intermediate thickness of 0.5 mm. A layer was formed, and a transparent unsaturated polyester gel coat layer same as the intermediate layer was formed as the outermost layer to produce an artificial marble molded product. The resulting artificial marble exhibited an excellent color effect due to aesthetic light interference.

[Example 11]
A gravure ink containing 10% by weight of the glitter material of Example 1 in an aqueous emulsion resin using lime rosin as a vehicle was prepared and printed on paper. The printed surface had a vivid color tone and an excellent color effect due to light interference.

  According to the glittering material of the present invention, in addition to the light interference coloring effect due to the alternating laminate portion, the chromatic color effect due to the layer containing the chromatic color component is expressed, so that the visibility of the light interference coloring is improved, By combining light interference coloring and chromatic color, a unique coloring is realized, and it is possible to provide a fiber product exhibiting coloring that is extremely superior in aesthetics. In addition, since a black fiber or base for absorbing white reflected light is not required, bright color expression can be realized and used in a wide range of fields.

(1)-(3) is a cross-sectional schematic diagram in the plane orthogonal to the fiber-axis direction of the brilliant material of this invention, respectively.

Claims (13)

  The ratio (SP ratio) of the solubility parameter value (SP1) of the high refractive index side polymer and the solubility parameter value (SP2) of the low refractive index side polymer is in the range of 0.8 ≦ SP1 / SP2 ≦ 1.1 A composite fiber composed of an alternating laminate portion in which polymer layers having different rates are alternately laminated in parallel to the long axis direction of the flat cross section, and a coating layer made of a fiber-forming polymer that covers the alternating laminate portion. A brilliant material having a light interference coloring function, wherein the brilliant material is obtained by cutting, and the composite fiber has a polymer layer containing at least a chromatic component.   The bright material having a light interference coloring function according to claim 1, wherein an intermediate layer is present in the alternating laminate portion, and the intermediate layer contains a chromatic color component.   The bright material having a light interference color development function according to claim 1 or 2, wherein the number of layers of the alternately laminated body portions is 10 or more and the flatness of the flat cross section is 3.5 or more.   The bright material having a light interference coloring function according to any one of claims 1 to 3, wherein the thickness of the alternately laminated body portion is 10 µm or less.   The bright material having a light interference coloring function according to any one of claims 1 to 4, wherein the coating layer has a thickness of 2.0 µm or more.   The high refractive index side polymer layer and the low refractive index side polymer layer are hardly alkali-soluble polymers, the fiber-forming polymer is alkali-soluble polymer, and at least any of the high refractive index side polymer layer and the low refractive index side polymer layer The glitter material having a light interference coloring function according to any one of claims 1 to 5, wherein a chromatic color component is contained in the layer and the thickness of the alternately laminated body portion is 10 µm or less.   A product containing the glitter material having a light interference coloring function according to any one of claims 1 to 6, or a composition thereof.   The coating material containing the brilliant material which has a light interference color development function of any one of Claims 1-6.   The resin composition containing the brilliant material which has an optical interference function of any one of Claims 1-6.   An ink composition comprising the glitter material having an optical interference function according to any one of claims 1 to 6.   An artificial marble molded article containing the glitter material having an optical interference function according to any one of claims 1 to 6.   Coated paper containing the glitter material having an optical interference function according to any one of claims 1 to 6.   A cosmetic composition containing the glitter material having an optical interference function according to any one of claims 1 to 6.

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