JP2006233357A - Raw material of glitter flake and glitter flake having optical interfering function - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new glitter raw material capable of obtaining a fine or thin glitter flake having an excellent light interference color-generating function by a post-treatment and enabling the development to a merchandise field requiring a further esthetic property, and a glitter flake. <P>SOLUTION: This raw material for the glitter flake having an optical interfering function is obtained by cutting a conjugate fiber obtained by covering an alternately laminated material part having ≤10 μm thickness obtained by laminating a hardly alkali soluble polymer layers having different refractive indices and having 0.8≤(SP1/SP2)≤1.1 range ratio (SP ratio) of the solubility parameter value (SP1) of a high refractive index side polymer to the solubility parameter value (SP2) of the low refractive index side polymer parallel to the long axial direction of a flat cross section, with an easily alkali soluble polymer having ≥2.0 μm thickness. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a glitter material having a light interference coloring function. More specifically, the present invention relates to a bright material material having a novel light interference coloring function, in which a high-quality bright material having a light interference coloring function can be easily obtained by treatment with an alkaline aqueous solution or the like.

  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, the fiber having a light interference color-developing function disclosed in the pamphlet does not peel off the alternate laminate when trying to reduce the fineness, or even if the peeling does not occur, the spinning condition deteriorates due to polymer deterioration during spinning. In addition, spots are generated at the time of stretching and the light interference effect is reduced, so this is cut and used as a glittering material, and further improvement in aesthetics such as painting and cosmetics that require particularly fineness is required. There are limits to the development of applied products.
International Publication No. 98/46815 Pamphlet

  The present invention has been made against the background described above, and its purpose is to develop a fine or thin glitter material having an excellent light interference coloring function by post-processing, and to develop into a product field where further aesthetics are required. An object of the present invention is to provide a new bright material material and a bright material that can be used.

  According to the study of the present inventors, even if the thickness of the alternate laminate body portion is reduced, if the composite fiber structure is formed by covering the periphery with a polymer, peeling of the alternate laminate body portion is less likely to occur. Uniformity at the time of drawing is improved, and if the composite fiber is cut to make a bright material raw material, and the coating polymer is removed from the bright material raw material, a fine or thin bright material excellent in light interference coloring function is stabilized. The present invention has been found.

  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. An alternately laminated body portion having a thickness of 10 μm or less, in which an alkali poorly soluble polymer layer having a refractive index different from each other in the range of 1 is alternately laminated in parallel to the long axis direction of the flat cross section, has a thickness of 2. There is provided a bright material material having an optical interference function obtained by cutting a composite fiber coated with an alkali-soluble polymer of 0 μm or more.

  Since the glitter material of the present invention has a coating layer, the process stability at the time of manufacture is good, and even if the thickness of the alternating laminate portion is thin, a high-quality one having excellent light interference is obtained. It is done. Further, since the coating layer is composed of an alkali-soluble polymer, for example, by treating with an aqueous alkali solution, a fine or thin glittering material having a light interference coloring function can be easily obtained.

  The glitter material raw material of the present invention is a glitter material raw material obtained by cutting a specific composite fiber, and the fiber axis perpendicular cross-sectional structure of the composite fiber will be described with reference to FIG. Each of (1) to (3) in FIG. 1 schematically shows a cross-sectional shape when the above-mentioned composite fiber is cut at right angles to its length direction, and consists of two alkali-insoluble polymer layers. The alternate laminated body portion 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 an alkali-soluble polymer surrounds the outer peripheral part, (2) WHEREIN: The aspect which provided another alkali poorly soluble protective layer in the middle, (3) WHEREIN: A several alternating laminated body part is alkalinized. An embodiment in which a readily soluble polymer is coated simultaneously is shown.

  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 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 distance of the desired color, the maximum interference color is obtained, which is preferable.

  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 protective layer portion when a protective layer made of an alkali poorly soluble polymer described later is formed on the outer peripheral portion of the flat cross section.

  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 small. On the other hand, when the number of laminated layers exceeds 120 layers, the increase in the amount of reflected light can no longer be expected, and the die structure becomes complicated and yarn production becomes difficult. It becomes difficult to satisfy the requirements and it is difficult to achieve the object of the present invention.

  In addition, as described above, the cross-sectional shape of the alternately laminated body portion of the conjugate fiber has 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 the monochromaticity (clear color development) that the parallelism of the alternating layers, that is, the optical distance of each layer is uniform in both 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 polymethylmethacrylate containing 2-bis (parahydroxyphenyl) propane as a dihydric phenol component, 9,9-bis (parahydroxyethoxyphenyl) fluorene and 2,2-bis (parahydroxyphenyl) propane (mol) The ratio is 20 / Examples thereof include a combination of polycarbonate and polymethyl methacrylate having 80 to 80/20) as a dihydric phenol component.

  In the present invention, it is important that the thickness of the alternately laminated body portion is 10 μm or less, preferably 2 to 7 μm. When this thickness exceeds 10 μm, it is not possible to obtain a glittering material having a fine or thin optical interference coloring function even by alkali treatment, and the object of the present invention cannot be achieved.

  In addition, you may provide the protective layer which consists of an alkali poorly soluble polymer with a thickness of 0.1-3 micrometers, Preferably 0.3-1.0 micrometer in the said alternating laminated body part as needed. When the thickness is less than 0.1 μm, the effect of providing the protective layer is reduced. On the other hand, when the thickness exceeds 3 μm, it is difficult to obtain a fine or thin glitter material even when treated with an alkaline aqueous solution. Become.

  The polymer for forming the protective layer is not particularly limited as long as it is hardly soluble in alkali, but the solubility of the polymer (high refractive index side polymer or low refractive index side polymer) constituting both sides in the major axis direction of the alternating laminate portion. It is preferable that the solubility parameter value (SP3) is the same as the parameter value, specifically 0.8 ≦ SP1 / SP3 ≦ 1.2 and / or 0.8 ≦ SP2 / SP3 ≦ 1.2. Is preferred. Among them, when the high melting point side polymer among the alternately laminated polymers is used, the protective layer portion is first formed with the high melting point side polymer having a high cooling and solidifying rate during melt spinning, so that a flat cross-sectional shape due to the interfacial energy and the balas effect is formed. Deformation can be suppressed, the parallelism of the laminated structure is maintained, and the aesthetics are improved.

  Next, the above-mentioned composite fiber has a flat cross-sectional shape, and an alternate laminated body portion in which a large number of independent polymer layers having different refractive indexes are alternately laminated in parallel to the major axis direction of the flat cross-section ( (If necessary, it has a protective layer) must be coated with an alkali-soluble polymer having a thickness of 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 an alkali-soluble polymer around the alternating laminate part, the polymer flow distribution between the vicinity of the wall surface and inside received by the inside of the final discharge hole during melt spinning can be relaxed. Even if the thickness of the laminated body portion is 10 μm or less, the shear stress distribution received by the laminated portion is reduced to obtain an alternating laminated body in which the thickness of each layer across the inner and outer layers is more uniform, and the resulting composite fiber is subjected to an alkali treatment If the coating layer is removed, a fine or thin glittering material having an excellent light interference coloring function can be easily obtained.

  Here, when the thickness of the coating layer is too thin and less than 2.0 μm, the fiber single yarn fineness becomes small and the cross section is flat. There is a problem. In the case of providing a coating layer made of a readily alkali-soluble polymer directly around the alternating laminate part, the long axis direction of the alternating laminate part is the same as in the case of forming the protective layer made of the alkali poorly soluble polymer. It is preferable that the solubility parameter value (SP4) is approximately the same as the solubility parameter value of the polymer (the high refractive index side polymer or the low refractive index side polymer) constituting both sides. Specifically, it is preferable that 0.8 ≦ SP1 / SP4 ≦ 1.2 and / or 0.8 ≦ SP2 / SP4 ≦ 1.2.

  In addition, the alkali poorly soluble and easily soluble polymer referred to in the present invention means that there is a difference of 10 times or more between the alkali weight loss rates. 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 the erosion action, resulting in lamination thickness unevenness due to disorder or swelling of the laminated part. As a result, the light interference coloring function is deteriorated.

  Examples of the alkali-soluble polymer preferably used include polylactic acid, polyethylene terephthalate or polybutylene terephthalate copolymerized with polyethylene glycol, polyethylene terephthalate blended with polyethylene glycol and / or alkali metal salt of alkylsulfonic acid, or polyethylene glycol and Examples thereof include polyethylene terephthalate or 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 or polybutylene terephthalate blended with alkali metal alkyl sulfonate and / or polyethylene glycol has a former range of 0.5 to 3.0% by weight and the latter 1.0 to 4.0% by weight. The range is preferred, and the average molecular weight of the latter polyethylene glycol is suitably in the range of 600 to 4000. The polyethylene terephthalate or polybutylene terephthalate copolymerized with polyethylene glycol and / or a dibasic acid component having a sulfonic acid metal base has the former in the range of 0.5 to 10.0% by weight, and the latter forms a polyester. A range of 1.5 to 10 mol% per total dibasic acid component is suitable.

  Moreover, it is preferable that said composite fiber has the elongation in the range of 10 to 60%, particularly in the range of 20 to 40%. When this elongation is too large, the fiber is likely to be deformed by the tension applied to the composite fiber in the step of cutting 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, it is preferable that said composite fiber has a thermal shrinkage rate of 130% to 150 ° C. of 3% or less. When the thermal shrinkage rate exceeds this range, when the composite fiber is cut into a luster material, deformation such as shrinkage of the fiber occurs and the light interference coloring function is likely 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 bright material raw 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, first, an alkali hardly soluble polymer having a different refractive index is obtained from 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 ratio (SP ratio) is 0.8 ≦ SP1 / SP2 ≦ 1.1 in the case of melting and discharging into an alternating laminate structure, it is more soluble in alkali than both the high refractive index side polymer and the low refractive index side polymer. An unstretched fiber having a structure in which the alternate laminate portion is covered with a protective layer is obtained by coating the alternate laminate structure with a high-speed alkali-soluble polymer. The single fiber fineness of the undrawn fiber varies depending on the draw ratio, but is arbitrary as long as the fineness of the glitter material obtained after the alkaline aqueous solution treatment is 4.0 dtex or less, preferably 0.2 to 3.0 dtex. . The thickness of the coating layer is arbitrary as long as the thickness of the coating layer after stretching is 2.0 μm or more.

  Although it may be drawn as necessary, the conditions are not particularly limited, and conventionally known 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.

  If necessary, the composite fiber that has been subjected to drawing and heat treatment can be cut into the bright material raw material of the present invention. At this time, it may be cut to a length according to the application, but when used in the field of application of paper, paint, ink, cosmetics, the fiber from the point of handling at the time of use and the aesthetics of the final product obtained. It is preferable to cut so that the axial fiber length is longer than the minor axis length of the fiber cross section excluding the alkali-soluble polymer part. 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 the present invention, the above-mentioned glitter material can be treated with an alkaline aqueous solution before use, for example, to remove the alkali-soluble polymer, thereby obtaining a glitter material having a fine or thin optical interference function.

  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 paint, resin composition, ink composition, artificial marble molded product, coated paper, cosmetic composition, etc. 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 / cm and 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 1-8 and Comparative Examples 1-2]
A structure in which the high refractive index polymer (Polymer 1) and the low refractive index polymer (Polymer 2) shown in Table 1 are composed of 21 layers of alternating laminate portions and the periphery is covered with a highly alkali-soluble polymer 3 Then, the melt spinning was carried out and wound up at the speed shown in Table 1. The obtained unstretched fibers were stretched at the magnifications shown in Table 1 to obtain a composite fiber having a cross-sectional optical interference coloring function as shown in (1) of FIG. The evaluation results are shown in Table 2.

In the table, polymer abbreviations are as follows.
PET: Polyethylene terephthalate copolymer PET1: 5-sodium sulfoisophthalic acid component 0.8 mol% copolymer polyethylene terephthalate copolymer PET 2: 9,9-bis (parahydroxyethoxyphenyl) fluorene (BPEF) 70 mol% copolymer polyethylene terephthalate Copolymerization PET3: 9,9-bis (parahydroxyethoxyphenyl) fluorene (BPEF) 70 mol% and 5-sodium sulfoisophthalic acid component 0.8 mol% copolymerization polyethylene terephthalate PEN: polyethylene-2,6-naphthalate copolymerization PEN1: 5-sodium sulfoisophthalic acid component 1.5 mol% copolymerized polyethylene-2,6-naphthalate copolymer PEN2: BPEF 70 mol% copolymerized polyethylene-2,6-naphthalate PC: poly Boneto copolymer PC: 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene (BCF) 70 mol% copolymerized polycarbonate PMMA: polymethyl methacrylate PS: Polystyrene Ny6: Nylon-6
PEGPBT: Polyethylene glycol having an average molecular weight of 4000 50% by weight (5.2 mol%) copolymerized polybutylene terephthalate PEGPET: 10% by weight of polyethylene glycol having an average molecular weight of 4000 Copolymerized polyethylene terephthalate copolymer PET: 3 weight of polyethylene glycol having an average molecular weight of 4000 % And 5-sodium sulfoisophthalic acid component 6 mol% copolymerized polyethylene terephthalate

  Example 1 is a polyethylene-2,6-naphthalate copolymerized with 1.5 mol% of a 5-sodium sulfoisophthalic acid component and nylon-6, and a polyethylene copolymer of 2.5 mol% of polyethylene glycol having an average molecular weight of 4000. Butylene terephthalate was melted at 290 ° C., 270 ° C., and 230 ° C., respectively, introduced into a spinning pack after measurement, and spun at 1200 m / min. The obtained undrawn yarn was drawn twice at a preheating temperature of 60 ° C., and was heat-set at 150 ° C. and wound up. Even if the obtained composite fiber was treated with alkali, there was no damage to the alternately laminated body portion, and the interference reflected light of the obtained composite fiber exhibited a clear green color.

  In Examples 2 and 3, polyethylene terephthalate (PET) or polyethylene-2,6-naphthalate (PEN) copolymerized with 70 mol% of 9,9-bis (parahydroxyethoxyphenyl) fluorene (BPEF) and polymethyl methacrylate (PMMA) and polylactic acid were melt-metered at 300 ° C., 255 ° C., and 230 ° C., respectively, and then introduced into a spinning pack and wound up at 2000 m / min.

  Example 4 is the same as Example 2 except that polycarbonate obtained by copolymerizing 70 mol% of 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene (BCF) was used, and the melting temperature was 300 ° C. Spinning in the same manner. The obtained conjugate fiber had a clear color and strong reflection intensity. Moreover, there was no damage of the alternately laminated body part in the alkaline aqueous solution treatment step.

  Example 5 shows PET and nylon-6 copolymerized with 0.8 mol% of 5-sodium sulfoisophthalic acid, and PET copolymerized with PEG and 5-sodium sulfoisophthalic acid component to impart alkali solubility. Using, spinning was performed at melting temperatures of 290 ° C., 270 ° C., and 290 ° C., respectively, 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. The reflection intensity was slightly smaller due to the smaller difference in refractive index compared with other combinations, but a composite fiber excellent in heat resistance and strength could be obtained.

  In Example 6, PET and nylon-6 copolymerized with 70 mol% of 9,9-bis (parahydroxyethoxyphenyl) fluorene (BPEF) and 0.8 mol% of 5-sodium sulfoisophthalic acid component, In order to impart solubility, PET copolymerized with PEG and a 5-sodium sulfoisophthalic acid component was used and spun at melting temperatures of 290 ° C., 270 ° C., and 290 ° C., respectively, and wound at a speed of 2000 m / min. The obtained undrawn yarn was preheated at 80 ° C., drawn 2.0 times, and heat-set at 180 ° C. A composite fiber excellent in reflection strength, heat resistance, and solvent resistance could be obtained.

  In Example 7, polycarbonate (PC) and PMMA were melted at 290 ° C. and 255 ° C., and polylactic acid was melted at 230 ° C., weighed and introduced into a spin pack, and spun at 3000 m / min. The obtained composite fiber had a large flatness and a strong vivid color.

  In Example 8, a cross section ((2) in FIG. 1) in which an intermediate protective layer of PC was provided around the laminated portion of PMMA and PC was formed. Excellent in heat resistance.

  On the other hand, in Comparative Example 1, the PET obtained by copolymerizing 10% by weight of PEG with PEN and PET, which are expected to be close in SP value and excellent in the ability to form a uniform laminate, was melted at 310 ° C., 300 ° C., and 290 ° C., respectively. And introduced into a spinning pack and wound up at 1000 m / min. The spun yarn was stretched 3 times by preheating at 80 ° C. and heat-set at 180 ° C. Since the dissolution rate of the coating layer in the alkaline aqueous solution is 3 times (10 times or less) of the polymer constituting the alternating laminate part, the smaller one is observed, alkali erosion is observed in the treated alternating laminate part, and the reflection strength Decreased significantly.

  In Comparative Example 2, nylon-6, polystyrene, and polylactic acid were melted at 270 ° C., 270 ° C., and 230 ° C., introduced into a spinning pack, and wound up at 2000 m / min. Since the polymer SP ratio of the alternate laminate portion is out of the scope of the present invention, the layer thickness of the alternate laminate portion is increased, the light interference coloring function is insufficient, the reflection intensity is small, and the object of the present invention is The clear color to be obtained was not obtained.

  The composite fibers obtained in the above Examples and Comparative Examples were bundled, the oil agent adhering to the surface was removed, and cut into a length of 150 μm perpendicular to the yarn length direction to obtain a bright material. The glitter materials composed of the composite fibers of Examples 1 to 8 all had the same excellent light interference coloring function as the composite fiber before cutting, but the glitter materials composed of the composite fibers of Comparative Examples 1 and 2 were light. The interference coloring function was insufficient.

[Example 9]
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. Further, since the glitter material is fine, the skin surface of the face to which the powder is applied was very smooth.

[Example 10]
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)
Amount of 100 g of total water When this foundation was applied to the face, it was excellent in aesthetics and had a novel makeup effect due to light interference. Moreover, since the luster material was fine, the skin surface of the face to which the foundation was attached was very smooth.

[Example 11]
A mascara having the following composition was prepared.
15 g of carboxymethylcellulose,
Laponite 0.2g,
10 g of the glitter material obtained in Example 3,
0.05 g of disodium salt of fuchsin,
Amount of 100 g of total water When this mascara was applied to the eyelashes, an excellent color effect with aesthetics, which has never been seen before, was obtained. Moreover, since the luster material is fine, the surface (side surface) of the eyelashes with the mascara was very smooth.

[Example 12]
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 4,
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. Further, since the glitter material is fine, the surface of the nail to which the nail polish solution is applied was very smooth.

[Comparative Example 3]
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. .

[Example 13]
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 unprecedented color effect due to highly aesthetic interference. Moreover, since the luster material was fine, the painted surface was very smooth.

[Example 14]
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 highly aesthetic light interference. Further, since the glittering material is fine, the glittering material can be uniformly dispersed when the intermediate layer is applied, and a smooth coated surface is obtained, so that the workability is good.

[Example 15]
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 exhibited an excellent color effect due to highly aesthetic light interference. Further, since the glittering material is fine, the printed surface is very smooth.

  Since the glitter material having the light interference coloring function of the present invention has good process stability at the time of yarn production, it has an excellent light interference coloring function even if the thickness of the alternately laminated structure portion is small. If the coating layer is removed, a material having a fine optical interference function can be easily obtained. In particular, not only the dispersibility when used in paints, inks, artificial marble, coated paper, cosmetics, coatings, etc. is improved, but also the surface smoothness of the resulting product is improved and the light interference coloring function is also good. Aesthetics are also good.

(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 Alternating layered body portions having a thickness of 10 μm or less, which are formed by alternately laminating alkali hardly soluble polymer layers having different rates in parallel to the long axis direction of the flat cross section, are made of an alkali-soluble polymer having a thickness of 2.0 μm or more. A luster material raw material having an optical interference function obtained by cutting a coated composite fiber.   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 Alternating layered body portions having a thickness of 10 μm or less, which are formed by alternately laminating alkali-insoluble polymer layers having different rates in parallel to the long axis direction of the flat cross section, have a thickness of 0.1 to 3.0 μm. A luster material raw material having an optical interference function obtained by cutting a composite fiber covered with a protective layer made of a soluble polymer and further coated with an alkali-soluble polymer having a thickness of 2.0 μm or more.   The bright material material having an optical interference function according to claim 1, wherein the number of layers of the alternately laminated body portion is 10 or more and the flatness of the flat cross section is 3.5 or more.   The alkali-soluble polymer has poly (lactic acid), polyethylene terephthalate copolymerized with polyethylene glycol or polybutylene terephthalate, polyethylene terephthalate blended with polyethylene glycol and / or an alkali metal salt of alkyl sulfonic acid, or polyethylene glycol and sulfonic acid metal base. The bright material material having an optical interference function according to any one of claims 1 to 3, which is polyethylene terephthalate or polybutylene terephthalate copolymerized with a dibasic acid component.   The luster material raw material which has an optical interference function in any one of Claims 1-4 whose fiber length of a fiber axial direction is longer than the short-axis length of the fiber cross section except an alkali-soluble polymer part.   A bright material having a light interference coloring function obtained by treating the bright material raw material according to claim 5 with an alkaline aqueous solution.   A product containing the glittering material having a light interference coloring function according to claim 6 or a composition thereof.   A paint containing the bright material having a light interference coloring function according to claim 6.   A resin composition comprising the bright material having an optical interference function according to claim 6.   An ink composition containing the bright material having an optical interference function according to claim 6.   An artificial marble molded article containing the glitter material having an optical interference function according to claim 6.   Coated paper containing the bright material having an optical interference function according to claim 6.   A cosmetic composition containing the bright material having an optical interference function according to claim 6.

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