JP2006077377A - Glitter material having optical interference property and coating and cosmetic comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a glitter material that develops excellent optical interference properties, exhibits a nonconventional clear hue and is especially suitable for a cosmetic and a coating. <P>SOLUTION: The glitter material is obtained by cutting optical interference fibers which has a flat cross section and with which at least two kinds of polymers having different refractive indexes are laminated in parallel with the major axis direction of the flat cross section. The luminescent material has ≥8.5 chroma C* by L*C*h* color system. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a glittering material comprising a flat optical coherent fiber in which at least two polymers having different refractive indexes are laminated in parallel with the major axis direction of a flat cross section.

Conventionally, various bright materials for use in paints and cosmetics have been proposed, and Patent Documents 1 to 3 disclose a fiber obtained by cutting light-interfering fibers into a powder form.
However, in the field of cosmetics and paints, other colorants and fillers are often mixed and used. In addition, in cosmetics such as foundations and manicures, after applying a base cosmetic, a cosmetic containing a glitter material is applied, or conversely, a cosmetic containing a glitter material is applied, and then the top cosmetic composition is applied. Giving is generally done. Further, the paint may be overcoated or undercoated.
Therefore, in order to deal with the various cases as described above and to make the color effect due to light interference stand out, there is a demand for a glittering material exhibiting a more vivid hue.

Japanese Patent Laid-Open No. 11-124748 JP-T-2004-519429 JP-T-2004-523487

  The present invention has been made in view of the above-described background art, and an object thereof is to provide a glittering material that expresses excellent light coherence and exhibits an unprecedented bright hue and is particularly suitable for cosmetics and paints. is there.

  As a result of the inventor's repeated studies to achieve the above object, when a polymer polymerized using a specific catalyst is used for a light interference fiber, the saturation of the light interference fiber is remarkably improved. The present inventors have found that when such fibers are used in cosmetics and paints, they exhibit an extremely bright hue and exhibit an excellent light interference effect that has never been achieved.

  Thus, according to the present invention, at least two kinds of polymers having a flat cross section and different refractive indexes are obtained by cutting the optical coherent fiber laminated in parallel with the major axis direction of the flat cross section. A glittering material having a light interference function is provided, wherein the glittering material has a saturation C * of 8.5 or more according to the L * C * h * color system.

  According to the glittering material of the present invention, it exhibits excellent light coherence, has an unprecedented vivid hue, and can exhibit excellent color effects when used in cosmetics and paints. For this reason, even if other colorants and fillers are contained in cosmetics and paints, and when used in cosmetics, they can be used in combination with base and top cosmetic compositions to provide excellent color effects. The effect that it can maintain is produced.

The glitter material of the present invention is a glitter formed by cutting a light-interfering fiber having a flat cross section and at least two polymers having different refractive indexes laminated in parallel with the major axis direction of the flat cross section. It is a material.
The cutting length of the glitter material is preferably 0.01 to 1000 mm, more preferably 0.01 to 100 mm.

  1 and 2 are diagrams schematically showing a cross-sectional form of the optical coherent fiber. As is clear from the figure, the cross section of the optical coherent fiber has a flat cross section, and two kinds of polymers are laminated in parallel with the major axis direction of the flat cross section, thereby A large area that is effective for interference is formed.

In the present invention, polymers having different refractive indexes are laminated, and the polymers are preferably combined as follows. In general, the refractive index of the polymer is in the range of 1.30 to 1.82, of which the general-purpose polymer is in the range of 1.35 to 1.75. Among these, when the refractive index of the polymer component on the high refractive index side is n ₁ and the refractive index of the polymer component on the low refractive index side is represented by n ₂ , the ratio of the refractive indexes of both polymers n ₁ / n _What is necessary is just to select what becomes ₂ in the range of 1.02-1.40.

  In the present invention, it is important that the saturation C * in the L * C * h * color system of the glitter material is 8.5 or more. Not bright colors and light interference effect can be expressed.

  In order to obtain such a bright material having high chroma, at least one of the above polymers is obtained by polycondensing an aromatic dicarboxylate ester in the presence of a catalyst containing a titanium compound component and a phosphorus compound. A titanium alkoxide represented by the following general formula (I), a titanium alkoxide represented by the following general formula (I) and an aromatic polyvalent represented by the following general formula (II): It is a component containing at least one selected from the group consisting of products obtained by reacting carboxylic acids or anhydrides thereof, and can be achieved by making the phosphorus compound a compound represented by the following general formula (III) .

  The titanium compound component used as a catalyst for the polycondensation reaction used in the present invention needs to be a titanium compound that is soluble in the polymer from the viewpoint of reducing foreign matters resulting from the catalyst of the final product, The titanium compound component includes a compound represented by the following general formula (I), a compound represented by the general formula (II) and an aromatic polyvalent carboxylic acid represented by the following general formula (II) or anhydrous The product needs to be reacted with the product.

  Here, the titanium alkoxide represented by the general formula (I) specifically includes tetraisopropoxy titanium, tetrapropoxy titanium, tetra-n-butoxy titanium, tetraethoxy titanium, tetraphenoxy titanium, octaalkyl trititanate, And hexaalkyl dititanate are preferably used.

  The aromatic polyvalent carboxylic acid represented by the general formula (II) to be reacted with the titanium alkoxide of the present invention or an anhydride thereof includes phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, and these Anhydrides are preferably used.

  When the titanium alkoxide is reacted with an aromatic polyvalent carboxylic acid or an anhydride thereof, a part or all of the aromatic polyvalent carboxylic acid or an anhydride thereof is dissolved in a solvent, and the titanium alkoxide is added to the mixed solution. It is carried out by dripping and heating at a temperature of 0-200 ° C. for at least 30 minutes, preferably at a temperature of 30-150 ° C. for 40-90 minutes. There is no restriction | limiting in particular about the reaction pressure in this case, A normal pressure is enough. As the solvent for dissolving the aromatic polyvalent carboxylic acid or its anhydride, any of ethanol, ethylene glycol, trimethylene glycol, tetramethylene glycol, benzene, xylene and the like can be used as desired.

  Here, the reaction molar ratio between the titanium alkoxide and the aromatic polyvalent carboxylic acid or its anhydride is not particularly limited, but if the proportion of the titanium alkoxide is too high, the color tone of the resulting polyester deteriorates or the softening point. In contrast, if the proportion of titanium alkoxide is too low, the polycondensation reaction may not proceed easily. For this reason, it is preferable that the reaction molar ratio of the titanium alkoxide and the aromatic polyvalent carboxylic acid or its anhydride is in the range of 2/1 to 2/5.

  The catalyst system for polycondensation used in the present invention comprises the above titanium compound component and a phosphorus compound represented by the following general formula (III), and consists essentially of an unreacted mixture of both. It is.

  Examples of the phosphorus compound (phosphonate compound) of the general formula (III) include carbomethoxymethanephosphonic acid, carboethoxymethanephosphonic acid, carbopropoxymethanephosphonic acid, carbobutoxymethanephosphonic acid, carbomethoxyphenylmethanephosphonic acid, carboethoxyphenyl. It is preferably selected from dimethyl esters, diethyl esters, dipropyl esters, dibutyl esters and the like of phosphonic acid derivatives such as methanephosphonic acid, carboprotoxyphenyl methanephosphonic acid, carbobutoxyphenyl methanephosphonic acid and the like.

  The above phosphonate compound has a relatively slow reaction time with the titanium compound compared to the phosphorus compound that is usually used as a stabilizer, so the duration of the catalytic activity of the titanium compound during the reaction is long. The amount of the titanium compound added to the polyester can be reduced. Further, even when a large amount of stabilizer is added to the catalyst system containing the phosphorus compound of the general formula (III), the thermal stability of the resulting polyester is not lowered and the color tone is not deteriorated.

In the present invention, the catalyst containing the titanium compound component and the phosphorus compound needs to satisfy the following mathematical expressions (1) and (2) at the same time.

  Here, (P / Ti) is 1 or more and 15 or less, preferably 2 or more and 15 or less, and more preferably 10 or less. When this (P / Ti) is less than 1, the hue of the polyester is yellowish, which is not preferable. On the other hand, if (P / Ti) exceeds 15, the polycondensation reactivity of the polyester is greatly lowered, making it difficult to obtain the target polyester. The proper range of (P / Ti) is characterized by being narrower than that of a normal metal catalyst system. However, when it is within the proper range, an unprecedented effect as in the present invention can be obtained.

  On the other hand, (Ti + P) is from 10 to 100, more preferably from 20 to 70. When (Ti + P) is less than 10, the productivity in the spinning process is greatly reduced, and satisfactory performance cannot be obtained. Further, when (Ti + P) exceeds 100, a small amount of foreign matter due to the catalyst is generated, which is not preferable. In the above formula, a suitable amount of Ti is about 2 to 15 mmol%.

  The polyester polymer used in the present invention is a polymer obtained by polycondensation of an aromatic dicarboxylate ester in the presence of a catalyst containing the above titanium compound component and a phosphorus compound. The aromatic dicarboxylate ester is preferably a diester composed of an aromatic dicarboxylic acid and an aliphatic glycol.

  Here, the aromatic dicarboxylic acid is preferably terephthalic acid. More specifically, terephthalic acid preferably accounts for 70 mol% or more based on the total aromatic dicarboxylic acid, and the terephthalic acid accounts for 80 mol% or more based on the total aromatic dicarboxylic acid. Preferably it is. Examples of preferable aromatic dicarboxylic acids other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, and the like.

  The other aliphatic glycol is preferably alkylene glycol, and for example, ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexanemethylene glycol, and dodecamethylene glycol can be used. In particular, ethylene glycol is preferable.

  In the present invention, the polyester is particularly preferably polyethylene terephthalate. Here, the polyester is preferably a polyester having ethylene terephthalate composed of terephthalic acid and ethylene glycol as the main repeating unit. Here, “main” means that the ethylene terephthalate repeating unit accounts for 70 mol% or more based on all repeating units in the polyester.

  The polyester used in the present invention may be a copolyester obtained by copolymerizing a component constituting the polyester as an acid component or a diol component in addition to the main repeating unit composed of an aromatic dicarboxylic acid and an aliphatic glycol.

  As a component to be copolymerized, as an acid component, as well as the above aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. These difunctional carboxylic acid components or ester-forming derivatives thereof can be used as raw materials. The diol component to be copolymerized is not only the above aliphatic diol but also an alicyclic glycol such as cyclohexanedimethanol, fragrance such as bisphenol, hydroquinone, and 2,2-bis (4-β-hydroxyethoxyphenyl) propane. Group diols can be used as raw materials.

Furthermore, polyfunctional compounds such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol can be copolymerized and used as raw materials.
These may be used alone or in combination of two or more.

  In the present invention, an aromatic dicarboxylate ester composed of an aromatic dicarboxylic acid and an aliphatic glycol as described above is used. This aromatic dicarboxylate ester is a diester of an aromatic dicarboxylic acid and an aliphatic glycol. It can also be obtained by a conversion reaction, or can be obtained by a transesterification reaction between a dialkyl ester of an aromatic dicarboxylic acid and an aliphatic glycol. However, the method using a dialkyl ester of an aromatic dicarboxylic acid as a raw material and via a transesterification reaction is added as a stabilizer during the polycondensation reaction compared to the method of performing a diesterification reaction using an aromatic dicarboxylic acid as a raw material. There is an advantage that there is little scattering of the phosphorus compound.

  Furthermore, it is preferable to add a part and / or the whole amount of the titanium compound before the start of the transesterification reaction, and to serve as two catalysts of the transesterification reaction catalyst and the polycondensation reaction catalyst. By doing in this way, content of the titanium compound in polyester can be reduced finally. An example of polyethylene terephthalate, more specifically, a transesterification reaction between a dialkyl ester of an aromatic dicarboxylic acid mainly composed of terephthalic acid and ethylene glycol, a titanium alkoxide represented by the following general formula (I), and At least one selected from the group consisting of a product obtained by reacting a titanium alkoxide represented by the following general formula (I) with an aromatic polycarboxylic acid represented by the following general formula (II) or an anhydride thereof A phosphorus compound represented by the following general formula (III) is added to a reaction mixture containing a diester of an aromatic dicarboxylic acid and ethylene glycol, which is obtained in the presence of a titanium compound component containing Is preferably added and polycondensed in the presence of these.

  The transesterification reaction is usually carried out under normal pressure. However, when the transesterification reaction is carried out under a pressure of 0.05 to 0.20 MPa, the reaction by the catalytic action of the titanium compound component is further promoted, and the secondary reaction is carried out. Since biological diethylene glycol is not generated in large quantities, properties such as thermal stability are further improved. As temperature, 160-260 degreeC is preferable.

  In the present invention, when the aromatic dicarboxylic acid is terephthalic acid, terephthalic acid and dimethyl terephthalate are used as starting materials for the polyester. In this case, the aromatic dicarboxylic acid is obtained by depolymerizing polyalkylene terephthalate. The recovered dimethyl terephthalate or the recovered terephthalic acid obtained by hydrolyzing the dimethyl terephthalate can be used in an amount of 70% by weight or more based on the total acid components constituting the polyester. In this case, the polyalkylene terephthalate is preferably polyethylene terephthalate. In particular, the recovered PET bottle, the recovered fiber product, the recovered polyester film product, and the polymer waste generated in the manufacturing process of these products are used. It is preferable from the viewpoint of effective utilization of resources to use a recycled polyester using a raw material source for polyester production.

Here, there is no particular limitation on the method of depolymerizing the recovered polyalkylene terephthalate to obtain dimethyl terephthalate, and any conventionally known method can be employed. Further, the method for recovering terephthalic acid from the recovered dimethyl terephthalate is not particularly limited, and any conventional method may be used. Regarding impurities contained in terephthalic acid, the total content of 4-carboxybenzaldehyde, p-toluic acid, benzoic acid and dimethyl hydroxyterephthalate is preferably 1 ppm or less. The monomethyl terephthalate content is preferably in the range of 1 to 5000 ppm. The recovered terephthalic acid and alkylene glycol can be directly esterified, and the resulting ester can be polycondensed to produce a polyester.
In the present invention, the polyester is more preferably a recycled polyester as described above.

  The intrinsic viscosity of the polyester used in the present invention is preferably in the range of 0.40 to 0.80, more preferably in the range of 0.45 to 0.75, and particularly preferably in the range of 0.50 to 0.70. An intrinsic viscosity of less than 0.40 is not preferable because the strength of the fiber is insufficient. On the other hand, if the intrinsic viscosity exceeds 0.80, it is necessary to excessively increase the intrinsic viscosity of the raw material polymer, which is uneconomical.

  The polyester used in the present invention contains a small amount of additives as necessary, such as lubricants, pigments, dyes, antioxidants, solid phase polymerization accelerators, fluorescent brighteners, antistatic agents, antibacterial agents, ultraviolet absorbers, light Stabilizers, heat stabilizers, light-shielding agents, matting agents, etc. may be included, and in particular, titanium oxide is preferably added as a matting agent, and an antioxidant as a stabilizer is preferably added. It is preferable to add 0.01 to 2 μm of titanium oxide so that 0.01 to 10% by weight is contained in the finally obtained polyester composition.

  Moreover, as an antioxidant, although a hindered phenolic antioxidant is preferable, it is preferable that the addition amount of a hindered phenolic antioxidant is 1 weight% or less. If it exceeds 1% by weight, it may cause scum at the time of yarn production, and even if added over 1% by weight, the effect of improving the melt stability is saturated, which is not preferable. The amount of hindered phenol antioxidant added is more preferably in the range of 0.005 to 0.5% by weight. It is also preferable to use these hindered phenol antioxidants and thioether secondary antioxidants in combination. The method for adding the antioxidant to the polyester is not particularly limited, but preferably includes a method of adding at any stage after the completion of the ester exchange reaction or the esterification reaction until the polymerization reaction is completed.

  Furthermore, in the polymer constituting the fiber, examples of the polymer other than the above-described polyester, that is, a polymer that exhibits optical interference in combination with the above-described polyester include polyamide and polyolefin. Of these, polyamide is preferred.

  In the present invention, the flatness of the fiber is preferably in the range of 2.0 to 15.0, more preferably 2.5 or more, and more preferably 3.0 or more. Here, the flatness ratio is a value represented by a ratio W / T between the long axis length W and the short axis length T of the flat cross section. In addition, as shown in FIG. 2, when a non-stacked region is formed in the outer layer portion of the flat cross section, the flatness ratio is calculated including the outer layer portion. As for the upper limit of the flatness ratio, if the value exceeds 15.0, the shape becomes excessively thin, and it becomes difficult to maintain a flat cross section, and there is a concern that a part of the cross section is bent. In this respect, the flatness ratio that is easy to handle is 15 at most, and 10.0 or less is particularly preferable.

  According to the optical interference theory, when the thickness of all layers is equal to the reference thickness, the number of polymer layers in the fiber reaches a saturation state when there are at most 10 layers, and the number of layers is more than that. Increasing the number only complicates the fiber forming process. However, if the aspect ratio is 2.0 or more, the thickness of each lamination unit tends to fluctuate. If the number of laminations is not 15 or more, the amount of interference light may be insufficient. Therefore, the number of stacked layers is preferably 15 or more. Furthermore, the larger the flatness ratio is, the larger the number of layers is, the more preferable the number of layers is, and the more preferable are 20 layers or more and 25 layers or more. A larger number of layers can compensate for the thickness fluctuation and increase interference, but it is easier to handle due to the difficulty of its manufacturing technology, especially the complexity of the spinneret and the control of the molten polymer flow. Is up to 50 layers. Beyond that, since the fluctuation width of the thickness of the laminate increases and it becomes difficult to obtain the effect of simply increasing the number of layers, it is practically preferable to use 80 layers or less.

  The glitter material of the present invention is contained 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). Can be used.

  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 oil, 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), myristin 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 canol, 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.

  Said 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.

  On the other hand, a conventionally known method can be used as a method for adding a glittering material to the coating. Moreover, the glitter material of this invention can immerse a support body in a coating material, or can spray a support body with a spray by adjusting length.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, each item in an Example was measured with the following method.
(1) Intrinsic viscosity The intrinsic viscosity of the polyester polymer was determined from the viscosity value measured at 35 ° C in a 35 ° C orthochlorophenol solution according to a conventional method.
(2) Titanium and phosphorus content in polyester After the sample was heated and melted on an aluminum plate, it was formed into a molded body having a flat surface with a compression press machine, and a fluorescent X-ray measurement apparatus (Model 3270, manufactured by Rigaku Corporation) And subjected to quantitative analysis.
(3) Amount of diethylene glycol (DEG) The polymer was decomposed using hydrazine hydrate, and measured according to a conventional method using gas chromatography (“263-70” manufactured by Hitachi, Ltd.).
(4) Color measurement Using a color measuring device CM-3610d manufactured by Minolta Co., Ltd., color measurement was performed on an object obtained by attaching a glittering material to a blackboard.
(5) Flatness ratio The length in the major axis direction / the length in the minor axis direction (ratio) was determined with a microscope.
(6) Number of layers The number of layers was determined by directly observing each layer with a microscope.

[Example 1]
To a mixture of 99.1 parts dimethyl terephthalate, 1.3 parts dimethyl 5-sodium sulfoisophthalate, 0.07 parts sodium acetate trihydrate and 60 parts ethylene glycol, 0.009 parts tetra-n-butyl titanate Charge into a SUS container capable of pressure reaction, pressurize to 0.07 MPa and conduct a transesterification reaction while raising the temperature from 140 ° C. to 240 ° C., then add 0.028 part of triethylphosphonoacetate, The exchange reaction was terminated.

  Thereafter, the reaction product is transferred to a polymerization vessel, heated to 290 ° C., subjected to a polycondensation reaction at a high vacuum of 65 Pa or less, and a polyethylene terephthalate system copolymerized with 0.9 mol% of 5-sodium sulfoisophthalic acid. Polyester was obtained and chipped according to a conventional method. This polyester had an intrinsic viscosity of 0.55 and an amount of diethylene glycol of 3.5 mol% (or 1.8 wt%). Further, Ti in this polyester was 5 mmol%, P was 20 mmol%, P / Ti was 4, and P + Ti was 25 mmol%.

  Using this polyester and nylon 6 having an intrinsic viscosity of 1.20, spinning was performed at a base temperature of 280 ° C. and a take-up speed of 1000 m / min using a composite spinneret disclosed in JP-A-11-124748, and a draw ratio of 3 The film was drawn and wound at a stretching temperature (surface temperature of the supply roller) of 110 ° C. and a set temperature of 180 ° C. (surface temperature of the draw roller). At that time, the cross-sectional form was a flat cross section, the number of alternate laminations was 30 layers, and a non-laminated region of copolymerized polyethylene terephthalate was provided on the outer periphery of the flat cross section.

This fiber was bundled, the oil agent adhering to the surface was removed, and cut to a length of 150 μm perpendicular to the yarn length direction to obtain a glittering material.
In this example, as shown in Table 1, the chroma C * was 9.0, and it was vivid and had excellent optical coherence.

[Examples 2 to 4]
The same procedure as in Example 1 was conducted except that the shape of the discharge hole of the composite spinneret was changed and the flatness of the fiber cross section was changed as shown in Table 1.
In any of the examples, stable spinning was possible in the same manner as in Example 1, and a high-quality composite fiber with less fuzz was obtained, and the weaving property was good. In addition, these composite fibers had good color tone and excellent optical coherence as in Example 1.

[Comparative Example 1]
Stainless steel container capable of pressure reaction of 0.064 parts by weight of calcium acetate monohydrate to a mixture of 97.5 parts of dimethyl terephthalate, 1.3 parts of dimethyl 5-sodium sulfoisophthalate and 60 parts of ethylene glycol The mixture was subjected to a transesterification while increasing the pressure from 140 ° C. to 240 ° C. under a pressure of 0.07 MPa, and then 0.044 parts by weight of a 56 wt% phosphoric acid aqueous solution was added to complete the transesterification reaction. I let you.

Thereafter, the reaction product is transferred to a polymerization vessel, and diantimony trioxide is added so that the ratio of the number of moles of antimony element in the polyester to the total number of moles of the total aromatic dicarboxylic acid component is 31 mmol%. The temperature was raised to 290 ° C. and a polycondensation reaction was performed at a high vacuum of 65 Pa or less to obtain a polyester having an intrinsic viscosity of 0.55 and 0.9 mol% of 5-sodiumsulfoisophthalic acid copolymerized. Was pelletized according to a conventional method.
Example 1 was repeated except that this polyester pellet was used. In this example, the brilliant material has a lower saturation than the brilliant material of the example and has a duller color tone.

[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 a bright color tone 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 had a vivid color tone and had a new makeup effect by light interference.

[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 to make 100 g of water When this mascara was put on the eyelashes, it showed a vivid color tone and an unprecedented color effect 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 had a vivid color tone and a new color effect due to light interference was obtained.

[Example 9]
The nail polish solution of Example 8 was applied on top of the nail polish solution having the following composition.
19g of nitrocellulose,
6 g of N-ethyl-o, p-toluenesulfonamide,
6 g of tributylacetyl citrate,
Midnight blue pigment 1g,
Hectorite 1.2g,
8 g of isopropyl alcohol,
Ethyl acetate, butyl acetate appropriate amount 100g
By applying nail polish in two layers in this way, the nails show a color effect on the midnight blue base. In addition, the glittering material of the present invention has remarkably improved sharpness as compared with the conventional one, and thus it is extremely excellent without losing it even if it is applied on a nail polish solution having other pigments. The color effect was demonstrated.

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

[Example 10]
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 has an unprecedented vivid color tone and an excellent color effect due to light interference.

  According to the glittering material of the present invention, it exhibits excellent light coherence, has an unprecedented vivid hue, and can exhibit excellent color effects when used in cosmetics and paints. Furthermore, even if other colorants and fillers are contained in cosmetics and paints, and when used in cosmetics, even if used in combination with a base or top cosmetic composition, the excellent color effect is obtained. Can be maintained. For this reason, it gives an unprecedented high-class feeling, and at the same time is extremely excellent in practicality, and thus has an extremely high industrial utility value.

The schematic diagram which shows an example of the cross section of a light interference filament. The schematic diagram which shows an example of the cross section of the optical coherent filament which has a non-lamination part.

Explanation of symbols

A Polymer B Polymer with a refractive index different from A

Claims (7)

  A bright material obtained by cutting a light-interfering fiber in which at least two polymers having a flat cross section and different refractive indexes are laminated in parallel with the major axis direction of the flat cross section, A brilliant material having a light interference function, wherein a saturation C * by an L * C * h * color system is 8.5 or more. At least one of the polymers constituting the glittering material is a polyester obtained by polycondensation of an aromatic dicarboxylate ester in the presence of a catalyst containing a titanium compound component and a phosphorus compound, and the titanium compound component is A titanium alkoxide represented by the following general formula (I) and a titanium alkoxide represented by the following general formula (I) are reacted with an aromatic polycarboxylic acid represented by the following general formula (II) or an anhydride thereof. The phosphorus compound is a compound represented by the following general formula (III), and the content concentrations of titanium and phosphorus are the following formulas (1) and ( The bright material having an optical interference function according to claim 1, which simultaneously satisfies 2).

The aromatic dicarboxylate ester is a diester obtained by a transesterification reaction between a dialkyl ester of an aromatic dicarboxylic acid and an aliphatic glycol in the presence of a catalyst containing a titanium compound component. Formation of titanium alkoxide represented by formula (I) and titanium alkoxide represented by the following general formula (I) and aromatic polycarboxylic acid represented by the following general formula (II) or an anhydride thereof The glittering material having an optical interference function according to claim 1, wherein the glittering material has at least one selected from the group consisting of materials.

  The bright material having an optical interference function according to any one of claims 1 to 3, wherein in the polymer constituting the fiber, at least one of polymers other than polyester is nylon. The bright material having an optical interference function according to any one of claims 1 to 4, which simultaneously satisfies the following requirements (a) to (c).
(A) Fiber flatness: 2.0 to 15.0
(B) Number of polymer layers in fiber: 15 to 80 layers   A paint containing the glitter material according to claim 1.   A cosmetic containing the glitter material according to claim 1.

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