JP2009190987A - Cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic that has appearance of high chroma and excellent brightness (high chroma feeling of appearance and brightness of appearance) even without using an interference fiber containing two or more kinds of polymer compounds, provides an application site with a high chroma in application (high chroma feeling of cosmetic film), optically changes texture of application site and provides the application site with transparency and three-dimensional feeling (texture improvement effect of application site). <P>SOLUTION: The cosmetic includes at least any one of a void-containing resin film that is composed of a crystalline polymer and contains voids inside and a void-containing resin fiber that is composed of a crystalline polymer and includes voids inside. The void-containing resin film and/or the void-containing resin fiber contains long voids inside in a state in which their length directions are oriented in one direction and the voids are not formed at a fixed distance from the surface of the void-containing resin film and/or the void-containing resin fiber. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has an appearance with high saturation and excellent luster, and when applied, can also impart high saturation to the application site, and also optically changes the texture of the application site to provide a transparent feel. And an excellent cosmetic that can impart a three-dimensional effect.

  In recent years, in makeup cosmetics such as nail polish and eyeliner, base makeup cosmetics such as foundation and teak, and skin care cosmetics such as lotion and emulsion, There has been a demand for cosmetics that can impart high saturation and can optically change the texture of the application site to impart transparency and stereoscopic effect. Further, in order to increase the commercial value of such a cosmetic, it is desired that the appearance is high in chroma and excellent in glitter.

  From the viewpoint of solving such problems, conventionally, for example, colored cosmetics containing interference fibers containing two or more kinds of polymer compounds having different refractive indexes have been proposed (see Patent Document 1). Yes. However, in this technique, it is necessary to use special interference fibers containing two or more kinds of polymer compounds, and in order to obtain a desired degree of effect, a relatively large amount of interference fibers are contained in the cosmetic. There was a disadvantage that it was necessary to make it.

JP 2005-314393 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention has an appearance with high chroma and excellent glitter without using interference fibers containing two or more kinds of polymer compounds (high chroma of appearance, glitter of appearance) and when applied. Can also give high saturation to the application site (high saturation of the decorative film), and can optically change the texture of the application site to give a sense of transparency and three-dimensionality (of the application site) The object is to provide excellent cosmetics.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, when a polymer molded body (polymer film) made of a crystalline polymer such as PBT (polybutylene terephthalate) is stretched at a high speed under an appropriate temperature condition, a resin film containing a cavity is formed. Resin film) is finely cut and blended into cosmetics, so that it has excellent effects as described above (high chroma of appearance, gloss of appearance, high chroma of cosmetic film, improved texture of application area) This is a finding that an effect can be imparted. Further, when a resin composition made of a crystalline polymer such as PBT (polybutylene terephthalate) is melt-spun and stretched at a high speed under an appropriate temperature condition, it becomes a resin fiber containing a cavity, and this stretched fiber (a cavity-containing resin) (Fiber) is also cut short and blended into cosmetics, so that it has excellent effects as described above (high-saturation appearance, brightness of appearance, high-saturation appearance of cosmetic film, and texture improvement effect on the application site) ).
That is, the void-containing resin film and the void-containing resin fiber have a multilayer structure composed of a resin layer (refractive index of about 1.5 in the case of PBT) and a hollow layer (air layer, refractive index 1). And having a structural light interference (structural coloration) effect between these layers, and therefore, when blended in a cosmetic, it is possible to give the cosmetic an appearance with high chroma and excellent luster. . In addition, when the cosmetic is applied to nails or skin, it is possible to impart high saturation to the application site, and optically change the texture of the application site to give a sense of transparency and stereoscopic effect. It is possible to achieve the effect of being able to.
The void-containing resin film and the void-containing resin fiber can be composed of only one type of crystalline polymer such as PBT. Therefore, as in the past, interference fibers containing two or more types of polymer compounds Even without the use of cosmetics, it is possible to provide a cosmetic with excellent effects as described above. In addition, the void-containing resin film and the void-containing resin fiber can give an excellent effect even if the amount is a small amount with respect to the cosmetic, and from these, the cosmetic of the present invention. Is considered advantageous in terms of cost and manufacturability.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A void-containing resin film comprising a crystalline polymer and containing voids therein and at least one of void-containing resin fibers comprising a crystalline polymer and containing voids therein, the void-containing resin The film and / or the cavity-containing resin fiber contains an elongated cavity in a state where its length direction is oriented in one direction, and in a cross section perpendicular to the orientation direction of the cavity, About 10 cavities having the shortest distance from the center to the surface of the cavity-containing resin film and / or the cavity-containing resin fiber, from each center to the surface of the cavity-containing resin film and / or the cavity-containing resin fiber. The distance h (i) is calculated, and the calculated arithmetic average value h (avg) of each distance h (i) is expressed by the following formula: h (avg)> T / 100 [where T is Represents the arithmetic mean value of the thickness in the cross section of the void-containing resin film and / or the radius in the cross section of the void-containing resin fiber, and the ten voids are any one parallel to the thickness direction of the void-containing resin film. And / or the cavity-containing resin selected from cavities existing in a region sandwiched between another straight line parallel to the one straight line and separated by 20 × T. Is selected from cavities existing in a region obtained by rotating any one line segment indicating the radius of the fiber 360 ° in the circumferential direction].
<2> The cosmetic according to <1>, wherein at least one of the void-containing resin film and the void-containing resin fiber is colored.
<3> The average length of the cavity in the direction perpendicular to the thickness direction of the cavity-containing resin film and / or the length direction of the cavity-containing resin fiber orthogonal to the orientation direction of the cavity is defined as r (μm). The cosmetic according to any one of <1> to <2>, wherein an L / r ratio when the average length of the cavities in the alignment direction of the cavities is L (μm) is 10 or more.
<4> The above <1> to <3, wherein the crystalline polymer in at least one of the void-containing resin film and the void-containing resin fiber is at least one selected from polyolefins, polyesters, and polyamides > Is a cosmetic according to any one of the above.
<5> The cosmetic according to any one of <1> to <4>, wherein the content of at least one of the void-containing resin film and the void-containing resin fiber is 0.1 to 65% by mass. .

  According to the present invention, various problems in the prior art can be solved, and without using an interference fiber containing two or more kinds of polymer compounds, it has an appearance with high chroma and excellent luster (high chroma of the appearance, (Glossiness of appearance), when applied, high saturation can be imparted to the application site (high saturation feeling of the decorative film), and the texture of the application site is optically changed to create transparency and stereoscopic effect Can be provided (effect of improving the texture of the application site).

(Cosmetics)
The cosmetic material of the present invention comprises at least one of a void-containing resin film comprising a crystalline polymer and containing a void therein, and a void-containing resin fiber comprising the crystalline polymer and having a void therein. If necessary, other components are appropriately contained.

<Cavity-containing resin film / Cavity-containing resin fiber>
Hereinafter, the void-containing resin film and the void-containing resin fiber will be described in order. The void-containing resin film and the void-containing resin fiber are both made of a crystalline polymer and contain voids inside. Since the void-containing resin film and the void-containing resin fiber have these characteristics, the cosmetics of the present invention can be applied to a high-saturation appearance, a bright appearance, a high-saturation appearance of the cosmetic film, and the texture of the application site. It can be provided as an excellent improvement effect.

<< Cavity-containing resin film >>
-Crystalline polymer (void-containing resin film)-
In general, polymers are classified into crystalline polymers and amorphous (amorphous) polymers, but even crystalline polymers are not 100% crystalline, and long chain molecules are regularly formed in the molecular structure. It includes aligned crystalline regions and non-regularly arranged amorphous (amorphous) regions.
Therefore, the crystalline polymer only needs to include at least the crystalline region in the molecular structure, and the crystalline region and the amorphous region may be mixed.

  The crystalline polymer in the void-containing resin film is not particularly limited and may be appropriately selected depending on the intended purpose. For example, high-density polyethylene, polyolefins (for example, polypropylene), polyamides (PA) (For example, nylon-6), polyacetals (POM), polyesters (for example, PET, PEN, PTT, PBT, PPT, PHT, PBN, PES, PBS, etc.), syndiotactic polystyrene (SPS), polyphenylene Examples thereof include sulfides (PPS), polyether ether ketones (PEEK), liquid crystal polymers (LCP), and fluororesins. Among these, from the viewpoint of mechanical strength of the void-containing resin film and production, at least one of polyolefins, polyesters, and polyamides is preferable, and polyesters are more preferable. Two or more kinds of these polymers may be blended or copolymerized.

The melt viscosity of the crystalline polymer in the void-containing resin film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 700 Pa · s, more preferably 70 to 500 Pa · s. 80 to 300 Pa · s is more preferable. When the melt viscosity is 50 to 700 Pa · s, it is preferable in that the shape of the melt film discharged from the die head during melt film formation is stable and uniform film formation is facilitated. In addition, when the melt viscosity is 50 to 700 Pa · s, the viscosity at the time of melt film formation becomes appropriate and the extrusion becomes easy, or the melt film at the time of film formation is leveled to reduce unevenness. preferable.
Here, the melt viscosity can be measured by a plate type rheometer or a capillary rheometer.

The intrinsic viscosity (IV) of the crystalline polymer in the void-containing resin film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.4 to 1.2, 0.6 -1.0 is more preferable, and 0.7-0.9 is still more preferable. When the IV is 0.4 to 1.2, the strength of the formed film is increased, and this is preferable in that the film can be efficiently stretched.
Here, the IV can be measured by an Ubbelohde viscometer.

There is no restriction | limiting in particular as melting | fusing point (Tm) of the said crystalline polymer in the said void containing resin film, Although it can select suitably according to the objective, 40-350 degreeC is preferable and 100-300 degreeC is more preferable. 100 to 260 ° C. is more preferable. The melting point of 40 to 350 ° C. is preferable in that the shape can be easily maintained in a temperature range expected for normal use, and even if a special technique required for processing at a high temperature is not particularly used. It is preferable at the point which can form a stable film.
Here, the melting point can be measured by a differential thermal analyzer (DSC).

There is no restriction | limiting in particular as a weight average molecular weight of the said crystalline polymer in the said void containing resin film, Although it can select suitably according to the objective, 5,000-1,000,000 are preferable and 10,000. -800,000 are more preferable, and 15,000-70,000 are still more preferable. If the weight average molecular weight is less than 5,000, mechanical strength as a film may be insufficient or breakage may occur during production. If it exceeds 1,000,000, it is difficult to melt and is not suitable for production. On the other hand, when the weight average molecular weight is within the more preferable range, it is advantageous in terms of mechanical properties and production suitability.
Here, the weight average molecular weight can be measured by a gel permeation chromatography (GPC Gel Permeation Chromatography) method.

--- Polyester resin--
Here, among the crystalline polymers, polyester resins that are particularly preferably used from the viewpoint of mechanical strength and production will be described.
The polyesters (hereinafter referred to as “polyester resins”) mean a general term for polymer compounds having an ester bond as a main bond chain. Accordingly, examples of the polyester resin suitable as the crystalline polymer include the exemplified PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate), PPT ( Polycondensation of polypentamethylene terephthalate), PHT (polyhexamethylene terephthalate), PBN (polybutylene naphthalate), PES (polyethylene succinate), PBS (polybutylene succinate), dicarboxylic acid component and diol component All polymer compounds obtained by the reaction are included.

  The dicarboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, oxycarboxylic acids, and polyfunctional acids. Can be mentioned.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, naphthalenedicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodium sulfoisophthalic acid. Acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid are preferable, and terephthalic acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid are more preferable.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, eicoic acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, maleic acid, and fumaric acid. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid. Examples of the oxycarboxylic acid include p-oxybenzoic acid. Examples of the polyfunctional acid include trimellitic acid and pyromellitic acid. Among the aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, succinic acid, adipic acid, and cyclohexanedicarboxylic acid are preferable, and succinic acid and adipic acid are more preferable.

  The diol component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diols, alicyclic diols, aromatic diols, diethylene glycol, and polyalkylene glycols. Group diols are preferred.

  Examples of the aliphatic diol include ethylene glycol, propane diol, butane diol, pentane diol, hexane diol, neopentyl glycol, and triethylene glycol. Among them, propane diol, butane diol, pentane diol, and hexane diol are exemplified. Particularly preferred. Examples of the alicyclic diol include cyclohexanedimethanol. Examples of the aromatic diol include bisphenol A and bisphenol S.

  There is no restriction | limiting in particular as melt viscosity of the said polyester resin, Although it can select suitably according to the objective, 50-700 Pa.s is preferable, 70-500 Pa.s is more preferable, 80-300 Pa.s is further preferable. When the melt viscosity is higher, voids (cavities) are more likely to be exhibited during stretching. However, when the melt viscosity is 50 to 700 Pa · s, extrusion is easier during film formation, and the resin flow is stably retained. It is preferable in that it is difficult to occur and the quality is stabilized. Further, the melt viscosity of 50 to 700 Pa · s is preferable in that the stretching tension is appropriately maintained at the time of stretching, and the film is easily stretched uniformly and is not easily broken. In addition, when the melt viscosity is 50 to 700 Pa · s or more, the shape of the melt film discharged from the die head at the time of film formation is easily maintained, so that stable molding can be performed and the product is not easily damaged. It is preferable in terms of improving physical properties.

  There is no restriction | limiting in particular as intrinsic viscosity (IV) of the said polyester resin, Although it can select suitably according to the objective, 0.4-1.2 are preferable, 0.6-1.0 are more preferable, More preferred is 0.7 to 0.9. When the IV is larger, voids are more likely to be generated during stretching. However, when the IV is 0.4 to 1.2, extrusion is easier during film formation, and the resin flow is stable and retention is less likely to occur. It is preferable in that the quality is stabilized. Furthermore, when the IV is 0.4 to 1.2, the stretching tension is appropriately maintained at the time of stretching, and therefore, it is easy to stretch uniformly and it is preferable in that a load is not easily applied to the apparatus. In addition, when the IV is 0.4 to 1.2, it is preferable in that the product is hardly damaged and the physical properties are increased.

  There is no restriction | limiting in particular as melting | fusing point of the said polyester resin, Although it can select suitably according to the objective, From viewpoints, such as heat resistance and film forming property, 150-300 degreeC is preferable and 180-270 degreeC is more preferable. .

  In addition, as said polyester resin, the said dicarboxylic acid component and the said diol component may respectively superpose | polymerize with 1 type, and may form the polymer, and the said dicarboxylic acid component and / or the said diol component are 2 or more types. A polymer may be formed by copolymerization. Further, as the polyester resin, two or more kinds of polymers may be blended and used.

  In the blend of two or more polymers, the polymer added to the main polymer has a melt viscosity and an intrinsic viscosity that are close to those of the main polymer, and the addition amount is smaller when the film is formed or melted. It is preferable in that the physical properties are enhanced during extrusion and the extrusion becomes easy.

  In addition, for the purpose of improving the flow characteristics of the polyester resin, controlling light transmittance, and improving the adhesion with the coating solution, a resin other than polyester may be added to the polyester resin.

Thus, the void-containing resin film is made of a crystalline polymer as described above. The void-containing resin film is preferably composed of at least one kind of crystalline polymer, and more preferably composed of only one kind of crystalline polymer.
The void-containing resin film can be obtained from only a crystalline polymer without adding a void-forming agent such as inorganic fine particles added to form voids (cavities) in the prior art or incompatible resins. A cavity can be formed by a simple process. Furthermore, no special equipment for dissolving the inert gas in the resin in advance is required.

  Here, as long as the said void containing resin film is a component which does not contribute to expression of a cavity, other components other than the said crystalline polymer may be included as needed. Examples of the other components include fillers, heat stabilizers, antioxidants, ultraviolet absorbers, organic lubricants, nucleating agents, dyes, pigments, flame retardants, mold release agents, dispersants, coupling agents, and fluorescent whitening. Agents and the like. Whether or not the other component contributes to the development of the cavity can be determined by whether or not a component other than the crystalline polymer (for example, each component described later) is detected in the cavity or at the interface portion of the cavity.

-Cavity (Cavity-containing resin film)-
The void-containing resin film contains voids and is characterized by the void content of the voids and the aspect ratio of the voids.
The “cavity” means a vacuum domain or a gas phase domain existing inside the void-containing resin film.

The void content means the total volume of the contained cavities relative to the sum of the total volume of the solid phase portion of the void-containing resin film and the total volume of the contained cavities.
The void content is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, preferably 3% by volume or more and 50% by volume or less, and 5 to 40% by volume. More preferred is 10 to 30% by volume.
Here, the void content can be calculated based on the specific gravity by measuring the specific gravity.
Specifically, the void content can be obtained by the following equation (1).
Cavity content (%) = {1- (Density of cavity-containing resin film after stretching) / (Density of polymer molded body before stretching)} (1)

The aspect ratio of the cavity is defined as the average length of the cavity in the thickness direction orthogonal to the orientation direction of the cavity, r (μm), and the average length of the cavity in the orientation direction of the cavity, L (μm). It means the L / r ratio.
The aspect ratio of the cavities is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more.

  2A to 2C are diagrams for specifically explaining the cavity aspect ratio of the void-containing resin film, in which FIG. 2A is a perspective view of the void-containing resin film, and FIG. 2B is a void in FIG. 2A. It is AA 'sectional drawing of a containing resin film, FIG. 2C is BB' sectional drawing of the cavity containing resin film in FIG. 2A.

  In the manufacturing process of the void-containing resin film, the void is usually oriented along the first stretching direction. Therefore, the “average length of the cavity (r (μm)) in the thickness direction orthogonal to the orientation direction of the cavity” is perpendicular to the surface 1a of the cavity-containing resin film 1 and perpendicular to the first stretching direction. This corresponds to the average thickness r (see FIG. 2B) of the cavity 100 in a simple cross section (cross section AA ′ in FIG. 2A). The “average length (L (μm)) of the cavities in the orientation direction of the cavities” is a cross section perpendicular to the surface 1a of the cavity-containing resin film 1 and parallel to the first stretching direction (FIG. This corresponds to the average length L (see FIG. 2C) of the cavity 100 in the section BB ′ in 2A.

In addition, said 1st extending | stretching direction shows the extending direction of 1 axis | shaft, when extending | stretching is only 1 axis | shaft. Usually, since longitudinal stretching is performed along the direction in which the molded body flows during production, this longitudinal stretching direction corresponds to the first stretching direction.
Moreover, when extending | stretching is biaxial or more, at least 1 direction is shown among the extending directions aiming at cavity formation. Usually, even in stretching with two or more axes, longitudinal stretching is performed along the flow direction of the molded body during production, and a cavity can be formed by this longitudinal stretching. It corresponds to the first stretching direction.

  Here, the average length (r (μm)) of the cavities in the thickness direction orthogonal to the orientation direction of the cavities can be measured by an image of an optical microscope or an electron microscope. Similarly, the average length (L (μm)) of the cavities in the alignment direction of the cavities can be measured by an image of an optical microscope or an electron microscope.

  The void-containing resin film includes an average number P of the cavities in a thickness direction perpendicular to the orientation direction of the cavities, a refractive index difference ΔN between the crystalline polymer layer and the cavity layer, and the ΔN and the P The product has characteristics.

In the manufacturing process of the void-containing resin film, the void is usually oriented along the first stretching direction. Therefore, the “number of the cavities in the thickness direction orthogonal to the orientation direction of the cavities” is a cross section perpendicular to the surface 1a of the cavity-containing resin film 1 and perpendicular to the first stretching direction (A- in FIG. 2A). In the A ′ cross section), this corresponds to the number of cavities 100 included in the film thickness direction.
The average number P of the cavities in the thickness direction perpendicular to the orientation direction of the cavities is not particularly limited and can be appropriately selected according to the purpose, preferably 5 or more, more preferably 10 or more, 15 or more are more preferable.
Here, the average number P of the cavities in the thickness direction orthogonal to the orientation direction of the cavities can be measured by an image of an optical microscope or an electron microscope.

The refractive index difference ΔN between the crystalline polymer layer and the cavity layer is specifically the difference between N1 and N2 when the refractive index of the crystalline polymer layer is N1 and the refractive index of the cavity layer is N2. It means the value of ΔN (= N1−N2). More specifically, the refractive index N1 of the crystalline polymer layer is made of a resin film that is made of the same type of crystalline polymer as the cavity-containing resin film, which is separately extruded and does not contain a cavity, or The void-containing resin film itself can be measured with an Abbe refractometer. Note that the refractive index of the cavity portion in the cavity-containing resin film was determined to be air as a result of analyzing bubbles generated when the film forming the cavity was cut in water. Refractive index of air = N2 refractive index = 1. By calculating these differences, ΔN (= N1−N2) can be obtained. The refractive indexes N1 and N2 are preferably measured for light having a wavelength of 589 nm.
The product of ΔN and P is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 or more, more preferably 5 or more, and still more preferably 7 or more.

Furthermore, since the void-containing resin film contains the voids but has been added in the past, inorganic fine particles for expressing the voids, incompatible resin, inert gas, etc. are not added, Excellent surface smoothness.
The surface smoothness of the void-containing resin film is not particularly limited and may be appropriately selected according to the purpose. However, Ra = 0.3 μm or less is preferable, Ra = 0.25 μm or less is more preferable, and Ra = More preferably, it is 0.1 μm or less.

Furthermore, the cavity-containing resin film is characterized in that no cavity is formed not only on the film surface but also at a predetermined distance from the film surface.
That is, for the 10 cavities having the shortest distance from the center of the cavity to the surface of the cavity-containing resin film in the cross section perpendicular to the orientation direction of the cavity in the cavity-containing resin film, The distance h (i) to the surface of the containing resin film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) is expressed by the following formula: h (avg)> T / 100 Meet.
However, T represents the arithmetic mean value of the thickness in the cross section, and the ten cavities are separated from any one straight line parallel to the thickness direction by 20 × T parallel to the one straight line. Are selected from cavities existing in a region sandwiched by other straight lines positioned at the same time.

The “center of the cavity” means the center when the cross-sectional shape of the cavity in the cross section is a perfect circle, and is arbitrarily set by, for example, the maximum square center method in the case of other shapes. The center of the circle that minimizes the sum of squares of the deviation from the reference circle is determined, and this is set as the center of the cavity.
The “surface of the void-containing resin film” means the outermost surface of the void-containing resin film in the thickness direction. Usually, it means the upper surface when the void-containing resin film is placed.

Specifically, a section perpendicular to the surface of the void-containing resin film and perpendicular to the longitudinal stretching direction (see FIG. 2D) is examined using a scanning electron microscope at an appropriate magnification of 300 to 3000 times. Take a cross-sectional picture. In the cross-sectional photograph, an arithmetic average value T of the thickness is calculated. As the arithmetic average value T of the thickness, a thickness measured using a long range contact displacement meter or the like may be used.
Next, an arbitrary straight line parallel to the thickness direction is drawn in the cross-sectional photograph, and another straight line that is parallel to the single straight line and separated by 20 × T is drawn.
Then, in each cavity in the cross-sectional photograph, the center of a circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method is determined, and this is set as the center of the cavity.
Then, ten cavities having the shortest distance from the center of the cavity to the surface of the cavity-containing resin film are selected in a region sandwiched between the one straight line and the other straight line. The “distance from the center of the cavity to the surface of the cavity-containing resin film” refers to increasing the radius of the circle to be drawn in order when drawing a circle centered on the “center of the cavity”. The radius of the circle when contacting the surface of the void-containing resin molded product.
Then, for the 10 selected cavities, the distance h (i) from each center to the surface of the cavity-containing resin film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) is calculated. It calculates with the following (1) formula.
h (avg) = (Σh (i)) / 10 (1)
The “distance h (i) from each center to the surface of the void-containing resin film” cannot be measured accurately if the void-containing resin film is curved or stressed. For this reason, it is preferable to measure in a state where it is placed on a flat surface during measurement.
2D is a diagram for specifically explaining the distance h (i) from each center of the cavity to the surface of the cavity-containing resin film, and is a cross-sectional view taken along the line AA ′ of the cavity-containing resin film in FIG. 2A. It is.
As described above, the void-containing resin film has excellent surface smoothness since the void is not formed near the surface of the void-containing resin film while containing the void.

  When the h (avg) satisfies the relationship of h (avg)> T / 100, the cosmetic of the present invention containing the void-containing resin film is advantageous in that it exhibits excellent glitter.

  The thickness of the void-containing resin film is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20 to 150 μm, more preferably 20 to 100 μm, and still more preferably 20 to 50 μm. When the thickness is less than 20 μm, the number of cavities may decrease and the glitter may be deteriorated. When the thickness exceeds 150 μm, rigidity (stiffness) increases, and it is difficult to prepare cosmetics. The ratio of width may be reduced and the cosmetic effect may be reduced. On the other hand, when the thickness is within the further preferable range, it is advantageous in terms of formulation and cosmetic properties.

-Properties (Cavity-containing resin film)-
The void-containing resin film has various excellent characteristics in, for example, glossiness due to having the void inside. In other words, characteristics such as glossiness can be adjusted by changing the mode of the void-containing resin film (for example, the mode and the thickness of the void).

The glossiness as an index of glossiness conforms to the definition described in JIS standard Z8741.
There is no restriction | limiting in particular as glossiness of the said void containing resin film, According to the objective, it can select suitably, When an incident angle is 60 degrees or less and it measures by injecting light with a wavelength of 400-800 nm, it is 60. It is preferably at least 70, more preferably at least 70, and even more preferably at least 80. However, the angle of incidence of the incident angle perpendicular to the surface of the void-containing resin film is 0 °. Here, the glossiness can be measured by a variable glossmeter.

-Manufacturing method (cavity-containing resin film)-
The void-containing resin film can be produced, for example, by stretching a polymer molded body made of a crystalline polymer as described above.

In addition, the said polymer molded object shows the thing which consists of said crystalline polymer, and does not contain a cavity especially, for example, a polymer film, a polymer sheet, etc. are mentioned.
There is no restriction | limiting in particular as a method of manufacturing the said polymer molded object, According to the objective, it can select suitably, For example, when a crystalline polymer is a polyester resin, it manufactures suitably with a melt film forming method. be able to. Moreover, the production of the polymer molded body may be performed independently of the stretching of the polymer molded body, or may be performed continuously.

  In the stretching of the polymer molded body, the polymer molded body is stretched at least uniaxially. And by the said extending | stretching, while a polymer molded object is extended | stretched and the cavity oriented along the 1st extending | stretching direction is formed in the inside, a cavity containing resin film is obtained.

The reason why the cavities are formed by stretching is that the at least one crystalline polymer constituting the polymer molded body is composed of a plurality of types of crystal states and includes a crystal containing crystals that are difficult to stretch during stretching. It is considered that when the resin is peeled and stretched in such a manner that the resin is torn, this serves as a cavity forming source to form a cavity.
Note that such void formation by stretching is possible not only when there is only one kind of crystalline polymer but also when two or more kinds of crystalline polymers are blended or copolymerized.

  The stretching method is not particularly limited and includes, for example, uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching. In any stretching method, the longitudinal direction along the flowing direction of the formed body during production is used. Stretching is preferably performed.

In general, in the longitudinal stretching, the number of longitudinal stretching stages and the stretching speed can be adjusted by the combination of rolls and the speed difference between the rolls.
The number of stages of the longitudinal stretching is not particularly limited as long as it is one or more, but it can be stretched more than two stages in terms of more stable and high-speed stretching and production yield and machine restrictions. It is preferable to do. Further, longitudinal stretching in two or more stages is advantageous in that a cavity can be formed by stretching in the second stage after confirming the occurrence of necking in the first stage.
Here, the necking means a constriction-like deformation that occurs when the polymer molded body is stretched (Polymer Engineering Lecture 6 Edited by Plastics Society of Japan, published by Jigoku Shoin, first published on April 25, 1966) Issue reference). In addition, the phenomenon that the polymer formed body deforms while constricted at the time of stretching and the cross section rapidly decreases at the constricted portion is defined as “the necking is expressed”.

  There is no restriction | limiting in particular as the extending | stretching speed | rate of the said longitudinal stretch, Although it can select suitably according to the objective, 10-36,000 mm / min is preferable, 800-24,000 mm / min is more preferable, 1,200 More preferably, 12,000 mm / min. When the stretching speed is 10 mm / min or more, it is preferable in that sufficient necking can be easily expressed. Further, when the stretching speed is 36,000 mm / min or less, uniform stretching is facilitated, the resin is not easily broken, and the cost is reduced without requiring a large stretching apparatus for high-speed stretching. It is preferable in that it can be performed. Therefore, when the stretching speed is 10 to 36,000 mm / min, sufficient necking is easily developed, uniform stretching is facilitated, the resin is difficult to break, and a large size intended for high-speed stretching. It is preferable at the point which can reduce cost, without requiring an extending | stretching apparatus.

  More specifically, the stretching speed in the case of one-stage stretching is preferably 1,000 to 36,000 mm / min, more preferably 1,100 to 24,000 mm / min, and 1,200 to 12,000 mm / min. Min is more preferable.

  In the case of two-stage stretching, it is preferable that the first-stage stretching is a preliminary stretching whose main purpose is to develop necking. The stretching speed of the preliminary stretching is preferably 10 to 300 mm / min, more preferably 40 to 220 mm / min, and still more preferably 70 to 150 mm / min.

  In the two-stage stretching, it is preferable that the second-stage stretching speed after the necking is expressed by the preliminary stretching (first-stage stretching) is changed from the preliminary stretching speed. The stretching speed of the second stage after causing necking by the preliminary stretching is preferably 600 to 36,000 mm / min, more preferably 800 to 24,000 mm / min, and 1,200 to 15,000 mm. / Min is more preferable.

The temperature during stretching is not particularly limited and can be appropriately selected according to the purpose.
When the stretching temperature is T (° C) and the glass transition temperature is Tg (° C),
(Tg-30) (° C.) ≦ T (° C.) ≦ (Tg + 50) (° C.)
It is preferable to stretch at a stretching temperature T (° C.) in the range indicated by
(Tg-25) (° C.) ≦ T (° C.) ≦ (Tg + 50) (° C.)
It is more preferable to stretch at a stretching temperature T (° C.) in the range indicated by
(Tg-20) (° C.) ≦ T (° C.) ≦ (Tg + 50) (° C.)
More preferably, the film is stretched at a stretching temperature T (° C.) in the range indicated by.

In general, the higher the stretching temperature (° C.), the lower the stretching tension and the easier the stretching, but the stretching temperature (° C.) is {glass transition temperature (Tg) −30} ° C. or more, {glass transition temperature ( Tg) +50} ° C. or lower is preferable in that the void content increases, the aspect ratio tends to be 10 or more, and the voids are sufficiently developed.
Here, the stretching temperature T (° C.) can be measured with a non-contact thermometer. The glass transition temperature Tg (° C.) can be measured by a differential thermal analyzer (DSC).

In addition, in the said extending | stretching, it is not necessary to carry out a horizontal extending | stretching in the range which does not interfere with the expression of a cavity. In the case of transverse stretching, the film may be relaxed or heat-treated by utilizing transverse stretching.
Further, the stretched void-containing resin film may be further subjected to treatment such as applying heat to cause shrinkage or applying tension for the purpose of shape stabilization.

Drawing 1 is a figure showing an example of a manufacturing method of a void content resin film, and is a flow figure of a biaxially stretched film manufacturing device.
As shown in FIG. 1, after the raw material resin 11 is hot-melted and kneaded inside an extruder 12 (a twin screw extruder or a single screw extruder is used depending on the raw material shape and production scale). , And discharged from the T-die 13 in a soft plate shape (film or sheet shape).
Next, the discharged film or sheet F is cooled and solidified by the casting roll 14 to form a film. The formed film or sheet F (corresponding to “polymer molded body”) is sent to the longitudinal stretching machine 15.
And the film or sheet | seat F formed into a film is again heated within the longitudinal stretch machine 15, and is stretched | stretched longitudinally between the rolls 15a from which speed differs. By this longitudinal stretching, a cavity is formed in the film or sheet F along the stretching direction. Then, the film or sheet F in which the cavity is formed is gripped at both ends by the left and right clips 16a of the transverse stretching machine 16, and is stretched laterally while being sent to the winder side (not shown). A resin film (void-containing resin molded body) 1 is obtained. In addition, in the said process, you may use the film or sheet | seat F which performed only the longitudinal stretch as the cavity containing resin film (cavity containing resin molding) 1 without using for the transverse stretcher 16. FIG.

--Coloring (cavity-containing resin film)-
As described above, a void-containing resin film can be obtained. The void-containing resin film is preferably further colored from the viewpoints of high chroma of appearance, glossiness of appearance, improvement of texture, and the like. The method for coloring the void-containing resin film is not particularly limited and may be appropriately selected depending on the purpose. For example, after producing the film, a colorant as shown below is used, and a conventional method is used. According to the above, the film may be colored, or a colored film may be directly produced by previously dispersing a colorant in the crystalline polymer at the time of producing the film.

  There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, blue No. 1, red No. 2, red No. 3, red No. 102, red No. 104 (1), red No. 105 (1), Red 106, Yellow 4, Yellow 5, Green 3, Blue 1, Blue 2, Red 201, Red 213, Red 214, Red 215, Red 227, Red 230 No. (1), Red No. 230 (2), Red No. 231, Red No. 232, Orange No. 205, Orange No. 207, Yellow No. 203, Green No. 201, Green No. 204, Green No. 205, Blue No. 202, Blue No. 203 No., Blue 205, Brown 201, Red 401, Red 502, Red 503, Red 504, Red 506, Orange 402, Yellow 402, Yellow 403 (1), Yellow 406, Yellow 407, green 401 Water-soluble tar dyes such as green 402, purple 401, black 401, red 202, red 218, red 223, red 226, red 228, orange 201, yellow 201, yellow 205 No., Blue 201, Blue 204, Purple 201, Red 404, Red 405, Orange 401, Yellow 401, Yellow 404, Yellow 405, Blue 403, Blue 404, etc. Tar pigments, gardenia pigments, safflower pigments, turmeric pigments, paprika pigments, annatto pigments, cochineal pigments and other natural pigments, acidic, basic pigments, disperse pigments, disperse dyes, etc., among which water-soluble tar pigments Is preferable in terms of obtaining a remarkable cosmetic effect because of its high colorability and stability. Moreover, these colorants can use 1 type (s) or 2 or more types, and can produce various color tone.

-Size (resin film containing voids)-
The void-containing resin film is desirably blended into the cosmetic of the present invention by cutting into an appropriate size. There is no restriction | limiting in particular as a size of the said void containing resin film mix | blended in the said cosmetics, Although it can select suitably according to the objective, Both width and length are preferable 0.01-5 mm, 0 0.1-3 mm is more preferable, and 0.2-2 mm is still more preferable. If the size of the void-containing resin film is less than 0.01 mm, the cosmetic effect may be difficult to appear due to being too small, and if it exceeds 5 mm, a highly saturated decorative film may not be provided. On the other hand, when the size of the void-containing resin film is within the further preferable range, it is advantageous in terms of a cosmetic effect at a use site, good usability, and formation of a uniform decorative film.

  The method for cutting the void-containing resin film into the preferred size as described above is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is cut using MS SHREDDER 120MW manufactured by Meiko Shokai Co., Ltd. The method of doing is mentioned.

-Content (Cavity-containing resin film)-
Further, the content of the void-containing resin film in the cosmetic is not particularly limited and can be appropriately selected according to the type of cosmetic to be applied, the degree of desired effect, and the like. 0.01-65 mass% is preferable, 0.1-40 mass% is more preferable, 0.3-35 mass% is still more preferable. If the content is less than 0.01% by mass, the cosmetic effect may be difficult to appear due to being too small, and if it exceeds 65% by mass, it may overlap and be unable to effectively form a highly saturated cosmetic film. is there. On the other hand, when the content is within the further preferable range, it is advantageous in terms of a cosmetic effect at the site of use, good usability and formation of a uniform decorative film.

<< Cavity-containing resin fiber >>
-Crystalline polymer (void-containing resin fiber)-
In the void-containing resin fiber, the crystalline polymer is not particularly limited and can be appropriately selected depending on the purpose. For example, the same crystalline polymer that can be used in the void-containing resin film is used. can do. Among these, from the viewpoint of the mechanical strength of the void-containing resin fiber and the production, at least one of polyolefins, polyesters, and polyamides is preferable, and polyesters are more preferable. Two or more kinds of these polymers may be blended or copolymerized.
The details of polyesters (polyester resins) preferably used in the void-containing resin fibers are as described in the item of polyester resin of the void-containing resin film.

There is no restriction | limiting in particular as melt viscosity of the said crystalline polymer in the said cavity containing resin fiber, Although it can select suitably according to the objective, 50-1,000 Pa.s is preferable and 70-750 Pa.s is. More preferably, 80 to 450 Pa · s is still more preferable. When the melt viscosity is 50 to 1,000 Pa · s, it is preferable in that the shape of melt spinning discharged from the die at the time of melt spinning is stable and uniform yarn production is facilitated. Moreover, it is preferable that the melt viscosity is 50 to 1,000 Pa · s from the viewpoint that the viscosity at the time of melt spinning becomes appropriate and the extrusion becomes easy and the diameter at the time of spinning becomes stable.
Here, the melt viscosity can be measured by a plate type rheometer or a capillary rheometer.

The intrinsic viscosity (IV: Intrinsic Viscosity) of the crystalline polymer in the void-containing resin fiber is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.4 to 1.5, 0.6-1.2 are more preferable and 0.7-1.0 are still more preferable. When the IV is 0.4 to 1.5, the tensile strength of the yarn produced becomes high, and the yarn can be efficiently drawn.
Here, the IV can be measured by an Ubbelohde viscometer.

There is no restriction | limiting in particular as melting | fusing point (Tm) of the said crystalline polymer in the said void containing resin fiber, Although it can select suitably according to the objective, 40-350 degreeC is preferable and 100-300 degreeC is more preferable. 150 to 260 ° C is more preferable. The melting point is preferably 40 to 350 ° C. in that it is easy to keep the diameter in the temperature range expected for normal use, and even without using a special technique required for processing at a high temperature. It is preferable at the point which can produce uniform yarn.
Here, the melting point can be measured by a differential thermal analyzer (DSC).

There is no restriction | limiting in particular as a weight average molecular weight of the said crystalline polymer in the said void containing resin fiber, Although it can select suitably according to the objective, 5,000-1,000,000 are preferable and 10,000. -800,000 are more preferable, and 15,000-700,000 are still more preferable. If the weight average molecular weight is less than 5,000, there is a fear of insufficient mechanical strength as a fiber or breakage during stretching, and if it exceeds 1,000,000, it may be difficult to stretch, However, there is a concern that cavities are difficult to develop. On the other hand, when the weight average molecular weight is within the further preferable range, it is preferable in terms of both the ease of the stretching process and the ease of expression of the cavities.
Here, the weight average molecular weight can be measured by a gel permeation chromatography (GPC Gel Permeation Chromatography) method.

As described above, the void-containing resin fiber is made of a crystalline polymer as described above. The void-containing resin fiber is preferably made of at least one type of crystalline polymer, and more preferably made of only one type of crystalline polymer.
The void-containing resin fiber can be obtained from only a crystalline polymer without adding a void-forming agent such as inorganic fine particles and incompatible resin that have been added to form voids (cavities) in the prior art. A cavity can be formed by a simple process. Furthermore, no special equipment for dissolving the inert gas in the resin in advance is required.

  Here, the void-containing resin fiber may contain other components as necessary as long as it does not contribute to the development of the void. As said other component, the other component illustrated by the item of the said void containing resin film is mentioned similarly. Whether or not the other component contributes to the development of the cavity can be determined by whether or not a component other than the crystalline polymer (for example, each component described later) is detected in the cavity or at the interface portion of the cavity.

--Cavity (Cavity-containing resin fiber)-
The cavity-containing resin fiber has a cavity and is characterized by the cavity content of the cavity and the aspect ratio of the cavity.
The cavity means a domain in a vacuum state or a gas phase domain existing inside the cavity-containing resin fiber.

The void content means the total volume of the contained cavities relative to the sum of the total volume of the solid phase portion of the void-containing resin fibers and the total volume of the contained cavities.
There is no restriction | limiting in particular as long as the said void content rate does not impair the effect of this invention, According to the objective, it can select suitably, 3-50 volume% is preferable, 5-40 volume% is more preferable, 10 -30% by volume is more preferred.
Here, the void content can be calculated based on the specific gravity by measuring the specific gravity.
Specifically, the void content can be obtained by the following equation (1).
Cavity content (%) = {1- (Density of cavity-containing resin fiber after stretching) / (Density of fiber before stretching)} (1)

  4A to 4C are diagrams for explaining the aspect ratio of the cavity of the cavity-containing resin fiber, FIG. 4A is a perspective view of the cavity-containing resin fiber, and FIG. 4B is the perspective view of FIG. 4A. FIG. 4C is a cross-sectional view taken along the line AA ′ of the void-containing resin fiber, and FIG. 4C is a cross-sectional view taken along the line BB ′ of the void-containing resin fiber in FIG. 4A.

The aspect ratio of the cavity is defined as an average length of the cavity 100 in a direction orthogonal to the length direction of the cavity-containing resin fiber perpendicular to the orientation direction of the cavity, r (μm) (see FIG. 4B), It means L / r ratio when the average length of the cavity 100 in the cavity orientation direction is L (μm) (see FIG. 4C).
The aspect ratio of the cavity is not particularly limited as long as the effect of the present invention is not impaired, and can be appropriately selected according to the purpose, preferably 10 or more, more preferably 15 or more, and more preferably 20 or more. Further preferred.

  The orientation direction of the cavities indicates the uniaxial stretching direction (first stretching direction) when stretching is uniaxial. Usually, since longitudinal stretching is performed along the direction in which the molded body flows during production, this longitudinal stretching direction corresponds to the orientation direction of the cavities (first stretching direction).

The cavity-containing resin fibers have a cross-sectional area of fibers in an arbitrary cross-section orthogonal to the length direction as X (μm ² ) and a cross-sectional area of cavities in the cross-section as Y (μm ² ). The average of the ratio (Y / X) is preferably 0.05 or more and 0.4 or less.
In addition, each cross-sectional area in the said cross section can be measured with the image of an optical microscope or an electron microscope.

The void-containing resin fiber has an average number P of cavities in a direction orthogonal to the length direction of the fiber, a refractive index difference ΔN between the crystalline polymer portion and the cavities, and a product of the ΔN and the P. , Has features.
The number of cavities in the direction perpendicular to the length direction of the fibers is a plane perpendicular to the surface 10a of the void-containing resin fiber 10 and including a direction perpendicular to the orientation direction of the cavities (A- in FIG. 4A). In the A ′ cross section), it means the number of cavities 100 included in a direction orthogonal to the fiber length direction.
The crystalline polymer portion refers to a portion (a portion made of a crystalline polymer) other than a cavity in the fiber.
The average number P of cavities in the direction perpendicular to the length direction of the fibers is not particularly limited and can be appropriately selected according to the purpose, preferably 5 or more, more preferably 10 or more, 15 More than the number is more preferable.
Here, the number of cavities in the direction perpendicular to the length direction of the fibers can be measured by an image of an optical microscope or an electron microscope.

The refractive index difference ΔN between the crystalline polymer portion and the cavity is specifically the difference between N1 and N2 when the refractive index of the crystalline polymer portion is N1 and the refractive index of the cavity is N2. It means a certain ΔN (= N1−N2) value. More specifically, the refractive index N1 of the crystalline polymer portion is made of a crystalline polymer of the same type as the cavity-containing resin fiber that is melt-spun, and the resin fiber that does not contain the cavity is passed through an Abbe refractometer and a transmission It can be measured with a two-beam interference microscope. Note that the refractive index of the cavity portion in the cavity-containing resin fiber was analyzed as a result of analysis of bubbles generated when the fiber forming the cavity was cut in water. Refractive index of air = N2 refractive index = 1. By calculating these differences, ΔN (= N1−N2) can be obtained. The refractive indexes N1 and N2 are preferably measured for light having a wavelength of 589 nm.
The product of ΔN and P is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 or more, more preferably 2.5 or more, and still more preferably 3 or more.

Furthermore, since the void-containing resin fiber has the void, the inorganic fine particles for expressing the void, the incompatible resin, and the inert gas which are added in the prior art are not added. Has excellent surface smoothness.
The surface smoothness of the void-containing resin fiber is not particularly limited and may be appropriately selected according to the purpose. However, Ra = 0.3 μm or less is preferable, Ra = 0.25 μm or less is more preferable, and Ra = 0.1 μm or less is particularly preferable.

Furthermore, the cavity-containing resin fiber is characterized in that not only a fiber surface but also a cavity is not formed at a predetermined distance from the fiber surface.
That is, for the 10 cavities having the shortest distance from the center of the cavity to the surface of the cavity-containing resin fiber in the cross section orthogonal to the orientation direction of the cavity in the cavity-containing resin fiber, the center to the cavity The distance h (i) to the surface of the contained resin fiber is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) is expressed by the following formula: h (avg)> T / 100 Meet.
However, T represents the arithmetic mean value of the radii in the cross section of the cavity-containing resin fiber, and the ten cavities are 360 ° in the circumferential direction along an arbitrary line segment indicating the radius of the cavity-containing resin fiber. It is selected from cavities existing in the rotated region.

The “center of the cavity” means the center when the cross-sectional shape of the cavity in the cross section is a perfect circle, and is arbitrarily set by, for example, the maximum square center method in the case of other shapes. The center of the circle that minimizes the sum of squares of the deviation from the reference circle is determined, and this is set as the center of the cavity.
The “surface of the void-containing resin fiber” means the outermost surface of the void-containing resin fiber in a direction orthogonal to the length direction of the fiber.

Specifically, a cross-section (see FIG. 4D) perpendicular to the orientation direction of the cavity in the cavity-containing resin fiber is examined at an appropriate magnification of 300 to 3000 times using a scanning electron microscope, and a cross-sectional photograph is taken. Take an image. In the cross-sectional photograph, an arithmetic average value T of radii is calculated. Here, the arithmetic average value of the radii is obtained by calculating the center of the cross section of the fiber by the method described later, and determining the distance from the center to the circumference as the radius, and determining and averaging the 10 arbitrary distances. Can do.
The center of the cross section of the fiber is the center when the cross sectional shape of the fiber is a perfect circle, and in the case of other shapes, for example, a reference circle arbitrarily set by the maximum square center method The center of the circle that minimizes the sum of squares of deviation from is determined, and this is taken as the center of the fiber cross section.
Next, an arbitrary line segment indicating a radius is drawn in the cross-sectional photograph, and the one line segment is rotated 360 ° in the circumferential direction around the center of the cross section of the fiber. Draw the area.
Then, in each cavity in the cross-sectional photograph, the center of a circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method is determined, and this is set as the center of the cavity.
Then, ten cavities having the shortest distance from the center of the cavity to the surface of the cavity-containing resin fiber are selected in a region obtained by rotating any one line segment indicating the radius 360 ° in the circumferential direction. Note that the “distance from the center of the cavity to the surface of the cavity-containing resin fiber” is obtained by sequentially increasing the radius of the circle to be drawn when drawing a circle centered on the “center of the cavity”. The radius of the circle when contacting the surface of the void-containing resin fiber.
Then, for the 10 selected cavities, a distance h (i) from each center to the surface of the cavity-containing resin fiber is calculated, and an arithmetic average value h (avg) of each calculated distance h (i) is calculated. It calculates with the following (1) formula.
h (avg) = (Σh (i)) / 10 (1)
The “distance h (i) from each center to the surface of the void-containing resin fiber” cannot be measured accurately if the void-containing resin fiber is curved or stressed. Therefore, it is preferable to measure in a state where it is placed on a flat surface during measurement.
4D is a diagram for specifically explaining the distance h (i) from each center of the cavity to the surface of the cavity-containing resin fiber, and is a cross-sectional view taken along the line AA ′ of the cavity-containing resin film in FIG. 4A. It is.
As described above, the void-containing resin fiber has excellent surface smoothness because the void is not formed near the surface of the void-containing resin fiber while containing the void.

  When the h (avg) satisfies the relationship of h (avg)> T / 100, the cosmetic of the present invention containing the void-containing resin fiber is advantageous in that it exhibits excellent glitter.

  The thickness of the void-containing resin fiber is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.01 to 20 denier (hereinafter simply referred to as “D”), 0.05-15D is more preferable and 0.1-13D is still more preferable. When the thickness is less than 0.01D, the number of cavities may decrease and the glitter may be deteriorated. When the thickness exceeds 20D, rigidity (stiffness) increases and it may be difficult to prepare cosmetics. is there. On the other hand, when the thickness is within the further preferable range, it is advantageous from the viewpoint of formulation and cosmetic properties.

-Properties (cavity-containing resin fibers)-
The void-containing resin fiber has various excellent characteristics in, for example, glossiness due to having the void inside. In other words, characteristics such as glossiness can be adjusted by changing the mode of the void-containing resin fiber (for example, the mode of the void and the thickness).

  The glossiness of the void-containing resin fiber is preferably 60 or more, more preferably 70 or more, and even more preferably 80 or more, like the void-containing resin film. Here, the glossiness can be measured by a variable glossmeter.

-Manufacturing method (cavity-containing resin fiber)-
The void-containing resin fiber can be produced, for example, by melt spinning a resin composition made of a crystalline polymer as described above and stretching the spun resin composition.

The resin composition is formed of a crystalline polymer, and the polymer component is only the crystalline polymer. However, components other than the polymer include additive components appropriately selected as necessary. Also good. The structure of the resin composition is not particularly limited as long as no cavity is formed therein, and can be appropriately selected depending on the purpose. Moreover, there is no restriction | limiting in particular as a shape of the said resin composition, According to the objective, it can select suitably, For example, a film form, a sheet form, etc. are mentioned.
Moreover, the production of the resin composition may be performed independently of a spinning process and a stretching process described later, or may be performed continuously.

  The spinning can be performed by extruding the resin composition from a nozzle in which a large number of small holes are formed to form a fiber. Examples of the spinning method include melt spinning, wet spinning, and dry spinning. However, among these, melt spinning is preferable.

  The melt spinning is a process in which a polymer is heated and melted to form a high-temperature viscous liquid, which is spun into a cold atmosphere (usually cold air), stretched, and solidified into fibers. Compared to wet spinning and dry spinning, the process is simpler and the spinning speed can be significantly increased, but it is limited to polymers that melt at about 300 ° C or less, such as polyester, nylon, polypropylene, PBT, PTT, and polylactic acid. It is done.

  The spinning step is a step of producing an undrawn yarn (UDY) in order to stretch the resin composition spun in the stretching step, which is a subsequent step. Here, the undrawn yarn refers to a yarn that is in the form of a fiber, but has a low degree of molecular chain orientation, and can be easily stretched up to 3 to 4 times and does not return. It is produced at a spinning speed of about 000 m / min or less.

As shown in FIG. 3, the melt-spun raw yarn 21 obtained as described above is inserted into, for example, a heating furnace 30 adjusted to 25 to 150 ° C., and the rotational speed difference between the nip rolls 41 and 42 is set. A fiber having a cavity is produced by stretching by applying a tensile force and applying a tensile force and causing necking. In some cases, the same void-containing resin fiber 10 can be produced simply by heating the nip roll (25 to 150 ° C.) except for the heating furnace. In FIG. 3, 31 represents an annealing furnace, and 32 represents a winding part.
Specifically, the spun resin composition (undrawn yarn) is drawn at least uniaxially. And by the said extending process, while the resin composition is extended | stretched, the said cavity containing resin fiber 10 is obtained by forming the cavity which made the 1st extending | stretching direction the long axis in the inside.

The reason why cavities are formed by stretching is that at least one crystalline polymer constituting the resin composition is a phase containing crystals that do not easily stretch during stretching, and the resin between hard crystals is torn. By peeling and stretching, it is considered that this serves as a cavity forming source to form a cavity.
Note that such void formation by stretching is possible not only when there is only one kind of crystalline polymer, but also when two or more kinds of crystalline polymers are blended or copolymerized.

Generally, in stretching, the number of longitudinal stretching stages and the stretching speed can be adjusted by the combination of rolls and the speed difference between the rolls.
The stretching speed of the longitudinal stretching is not particularly limited as long as the effect of the present invention is not impaired, and can be appropriately selected according to the purpose, but is preferably 10 to 2,000 m / min, and preferably 15 to 1,000 m. / Min is more preferable, and 20 to 1,000 m / min is still more preferable. When the stretching speed is 10 m / min or more, it is preferable in that sufficient necking can be easily expressed. Further, when the stretching speed is 2,000 m / min or less, uniform stretching is facilitated, the yarn is not easily broken, and a large-scale stretching apparatus for high-speed stretching is not particularly required, and the cost is reduced. Is preferable in that it can be reduced.

The temperature during stretching is not particularly limited and can be appropriately selected according to the purpose.
When the stretching temperature is T (° C) and the glass transition temperature is Tg (° C),
(Tg-30) ≦ T ≦ (Tg + 50)
It is preferable to stretch at a stretching temperature T (° C.) in the range indicated by
(Tg-25) ≦ T ≦ (Tg + 45)
It is more preferable to stretch at a stretching temperature T (° C.) in the range indicated by
(Tg−20) ≦ T ≦ (Tg + 40)
More preferably, the film is stretched at a stretching temperature T (° C.) in the range indicated by.

In general, the higher the stretching temperature (° C.), the lower the stretching tension, and the easier it can be stretched. However, when the stretching temperature (° C.) is {glass transition temperature (Tg) +50} ° C. or less, cavities are formed. The volume ratio is high, and the aspect ratio is preferably 10 or more. Moreover, it is preferable that the stretching temperature (° C.) is {glass transition temperature (Tg) −30} ° C. or higher in that a cavity is sufficiently developed.
Here, the stretching temperature T (° C.) can be measured with a non-contact thermometer. The glass transition temperature Tg (° C.) can be measured by a differential thermal analyzer (DSC).

  In the stretching step, the stretched resin composition (cavity-containing resin fibers) is further subjected to heat shrinkage by applying heat or treatment such as tension for the purpose of shape stabilization. Also good.

--Coloring (cavity-containing resin film)-
As described above, void-containing resin fibers can be obtained. The void-containing resin fibers are preferably further colored in view of high chroma of appearance, glossiness of appearance, improvement of texture, and the like. The method for coloring the void-containing resin fiber is not particularly limited and may be appropriately selected depending on the purpose. For example, after the fiber is produced, a colorant as shown below is used, and a conventional method is used. According to the above, the fibers may be colored, or colored fibers may be directly produced by dispersing a colorant in the crystalline polymer in advance during the production of the fibers.

  There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, the same coloring agent as the case of the said void containing resin film can be used.

-Length (resin fiber containing voids)-
The void-containing resin fiber is desirably blended into the cosmetic of the present invention by cutting into an appropriate length. There is no restriction | limiting in particular as the length of the said void containing resin fiber mix | blended in the said cosmetics, Although it can select suitably according to the objective, 0.01-5 mm is preferable and 0.1-3 mm is preferable. More preferably, 0.2-2 mm is still more preferable. If the length of the void-containing resin fiber is less than 0.01 mm, the cosmetic effect may be difficult to appear due to being too small, and if it exceeds 5 mm, a highly saturated decorative film may not be provided. On the other hand, when the length of the void-containing resin fiber is within the further preferable range, it is advantageous in terms of a cosmetic effect at a use site, good usability, and formation of a uniform decorative film.

  The method for cutting the void-containing resin fiber into a preferable length as described above is not particularly limited and may be appropriately selected depending on the purpose. For example, a method of cutting using a blade such as a razor Can be mentioned.

-Content (Cavity-containing resin fiber)-
Further, the content of the void-containing resin fiber in the cosmetic is not particularly limited, and can be appropriately selected according to the type of cosmetic to be applied, the degree of desired effect, and the like. 0.01-65 mass% is preferable, 0.1-40 mass% is more preferable, 0.3-35 mass% is still more preferable. If the content is less than 0.01% by mass, the cosmetic effect may be difficult to appear due to being too small, and if it exceeds 65% by mass, it may overlap and be unable to effectively form a highly saturated cosmetic film. is there. On the other hand, when the content is within the further preferable range, it is advantageous in terms of a cosmetic effect at the site of use, good usability and formation of a uniform decorative film.

<< Cavity-containing resin film + Cavity-containing resin fiber >>
In addition, only one of the void-containing resin film and the void-containing resin fiber may be used alone, or both may be used in combination. In the case where both the void-containing resin film and the void-containing resin fiber are used in combination, the total content of the void-containing resin film and the void-containing resin fiber in the cosmetic is not particularly limited. Although it can select suitably according to the objective, 0.01-65 mass% is preferable, for example, 0.1-40 mass% is more preferable, 0.3-35 mass% is still more preferable. If the total content is less than 0.01% by mass, the cosmetic effect may be difficult to appear when the amount is too small. If the total content exceeds 65% by mass, they may overlap and cannot effectively form a highly saturated cosmetic film. There is. On the other hand, when the total content is within the further preferable range, it is advantageous in terms of the cosmetic effect at the site of use, good usability and formation of a uniform decorative film.

  The content ratio of the void-containing resin film and the void-containing resin fiber in the cosmetic when using both the void-containing resin film and the void-containing resin fiber is particularly as follows. Although there is no restriction | limiting and can be suitably selected according to the objective, For example, by mass ratio, void-containing resin film: void-containing resin fiber = 0.1: 99.9-99.9: 0.1 is preferable, 10: 90-90: 10 is more preferable, and 30: 70-70: 30 is still more preferable. When the content ratio of the void-containing resin film to the void-containing resin fiber is less than 0.001 times in terms of mass ratio, the color developability from one direction by the film may be inferior, and when it exceeds 9990 times , The color developability from one direction by the film becomes strong, and the texture may be inferior. On the other hand, when the content ratio is within the further preferable range, it is advantageous in terms of the balance between color development property and texture from one direction.

The void-containing resin film has a feature that the appearance changes depending on the viewing direction. Therefore, the void-containing resin film is advantageous in that it has excellent aesthetic properties and is excellent in effects such as adhesion because it is flat.
Further, the void-containing resin fiber has the characteristics that the same high saturation and glitter can be obtained from any point of view, and is therefore advantageous in that it has an excellent effect of adjusting the glitter.
Any of these void-containing resin films and void-containing resin fibers can be suitably used for the purpose of blending into the cosmetic of the present invention.

<Other ingredients>
The other components that can be contained in the cosmetic are not particularly limited and can be appropriately selected according to the purpose from components that can be usually contained in cosmetics. Examples of specific components include: Oily components such as hydrocarbons, higher fatty acid esters, animal and vegetable oils and fats, silicone oils, fluorine-based oils, etc. for imparting an emollient feeling, and water-soluble polymers, alcohols, water and other aqueous components for imparting a feeling of moisture In addition, surfactants, film forming agents, ultraviolet absorbers, moisturizers, antioxidants, cosmetic ingredients, preservatives, fragrances and the like for imparting various other effects can be mentioned, and these can be appropriately blended. . Further, the cosmetic powder is not particularly limited by the shape such as spherical shape, plate shape, needle shape, haze shape, fine particle, particle size such as pigment grade, particle structure such as porous, nonporous, etc. Those used in general cosmetics such as bodies, glitter powders, organic powders, pigment powders, metal powders and composite powders can be used without particular limitation.

  The cosmetic is water or a mixture of water and a hydrophilic organic solvent (such as alcohol) (particularly, water and a straight chain having 2 to 5 carbon atoms such as ethanol, isopropanol, n-propanol). Alternatively, a branched lower monoalcohol, glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol, a mixture with a polyol such as polyethylene glycol) may be included. Moreover, the hydrophilic phase of the cosmetic may contain C2 ether or C2-C4 aldehyde which is hydrophilic. Water or a mixture of water and a hydrophilic organic solvent is preferably contained in an amount of 0 to 90% by weight (particularly 0.1 to 90% by weight) based on the total weight of the cosmetic. 60% by weight (particularly 0.1 to 60% by weight) is preferably contained.

  The cosmetic comprises a fatty substance that is liquid at room temperature (usually 25 ° C.), a fatty substance that is solid at room temperature (such as wax), a fatty substance that is pasty at room temperature, rubber, and a mixture thereof. It may contain a fatty phase. Furthermore, this fatty phase may contain a lipophilic organic solvent.

  Examples of fatty substances that can be used in the cosmetics and are generally liquid at room temperature called oil include perhydrosqualene as animal-derived hydrocarbon oil, heptanoic acid or octanoic acid triglyceride as liquid triglyceride Fatty acids having 4 to 10 carbon atoms such as sunflower oil, corn oil, soybean oil, grape seed oil, sesame oil, apricot oil, macadamia oil, castor oil and avocado oil, caprylic acid / caprin Synthetic esters of fatty acids derived from synthesis, such as triglycerides of acids, jojoba oil, vegetable oils such as shea butter, paraffin oils and their derivatives, mineral oils such as petroleum jelly, polydecene, hydrogenated polyisobutenes such as parleam Perserine oil (Pur ellino oil), isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, malic acid Diisostearyl, triisocetyl citrate, fatty alcohol heptanoate, octanoate, decanoate, polyol ester, dioctanoic acid propylene glycol, diheptanoic acid neopentyl glycol, diisononanoic acid diethylene glycol, etc., pentaerythritol ester, octyl Dodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol Oleyl alcohol, etc. (esters with aliphatic alcohols having 12 to 26 carbon atoms), phenyltrimethicone, phenyltrimethylsiloxydiphenylsiloxane, diphenylmethyl as partially hydrocarbon- and / or silicone-based fluorinated oils Dimethyltrisiloxane, diphenyldimethicone, phenyldimethicone, polymethylphenylsiloxane, cyclomethicone having a phenyl group, dimethicone, etc., linear or cyclic polymethylsiloxane (PDMS) that is liquid or pasty at room temperature, etc. And silicone oils, and mixtures thereof.

  The cosmetic may contain one or more cosmetically acceptable organic solvents within acceptable toxicity and feel.

  Examples of the organic solvent that can be used in the cosmetics include acetates such as methyl acetate, ethyl, butyl, amyl, 2-methoxyethyl, and isopropyl, ketones such as methyl ethyl ketone and methyl isobutyl ketone, toluene, xylene, Examples thereof include hydrocarbons such as hexane and heptane, aldehydes having 5 to 10 carbon atoms, ethers having at least 3 carbon atoms, and mixtures thereof.

  Further, as described above, the cosmetic may contain a fatty substance that is solid or pasty at room temperature, such as rubber and wax. The wax may be hydrocarbon-based, fluoride-based, and / or silicone-based, and may be of plant, mineral, animal, or synthetic origin.

  Examples of the “wax” that can be used in the cosmetic include, for example, beeswax, carnauba wax or candelilla wax as natural waxes, paraffin, microcrystalline wax, ceresin wax or ozokerite, polyethylene or Fischer-Tropsch wax as a synthetic wax, 16 Mention may be made of silicone waxes such as alkyl or alkoxy dimethicones having 45 carbon atoms.

  The rubber used in the cosmetic is usually high molecular weight polydimethylsiloxane (PDMS), cellulose rubber, or polysaccharide, and the pasty substance is usually lanolin and its derivatives, or PDMS. It is a hydrocarbon compound.

  There is no restriction | limiting in particular also as content of the said other component in the said cosmetics, It can select suitably according to the objective within the range which does not impair the effect of this invention.

<Manufacturing method of cosmetics>
The method for producing the cosmetic is not particularly limited and can be appropriately selected according to the dosage form, type, and the like of the cosmetic to be described later. For example, at least the void-containing resin film and the void-containing resin fiber can be selected. It can be produced by uniformly mixing any one of the other components. There is no restriction | limiting in particular as an apparatus used for the said mixing, For example, a conventionally well-known mixing apparatus etc. can be utilized suitably.

<Cosmetic formulation>
There is no restriction | limiting in particular as a dosage form of the said cosmetics, According to the objective, it can select suitably, For example, water type, oil type, emulsification type (water-in-oil type, oil-in-water type etc.), powder type, solvent And the like.
The form of the cosmetic is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include solid, semi-solid, and liquid, among which gel is preferable, and transparent and translucent. Opaque, can be used as a cosmetic for each.

<Types of cosmetics>
There is no restriction | limiting in particular as a kind of said cosmetics, According to the objective, it can select suitably, For example, makeup cosmetics, base makeup cosmetics, skin care cosmetics etc. are mentioned. Specifically, for example, makeup cosmetics such as mascara, eyeliner, eye color, eyebrow, lipstick, nail polish, body color, foundation makeup teak color, face color, base makeup cosmetics such as makeup base, cream, Examples include skin care cosmetics such as emulsions and lotions. Among these, the cosmetics can impart a highly saturated cosmetic film, optically change the texture of the application site, and provide a sense of transparency and stereoscopic effect. Is particularly suitable for make-up cosmetics. In addition, the above cosmetics can make makeup hair, cleansing material that removes dirt from sebum, and make hair appear thicker and thicker without using hair dyes due to chemical reaction. It can be applied to hair cosmetics that can change the texture and give a high-saturation cosmetic film to the hair.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention, and modifications may be made without departing from the spirit described above and below. Included in the technical scope.

(Production Example 1: void-containing resin film: polyester)
PBT1 (100% polybutylene terephthalate resin, polyester) having an intrinsic viscosity (IV) = 0.72 is extruded from a T-die at 245 ° C. using a melt extruder and solidified by a casting drum to a thickness of about 120 μm. A polymer molded body (polymer film) was obtained. This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, in a heated atmosphere at 40 ° C., after uniaxial stretching at a speed of 100 mm / min and confirming that necking has occurred, it is further performed at the speed of 6,000 mm / min in the same direction as the beginning. Uniaxial stretching was performed.
As described above, a void-containing resin film having a thickness of 20 μm was obtained. In addition, the cavity content rate of the obtained cavity containing resin film was 22 volume%, and the aspect ratio of the cavity was L / r = 16. Further, h (avg) of the obtained void-containing resin film was 7.0 μm. The method for measuring the void content and the aspect ratio of the void and the method for measuring h (avg) are as follows.
The obtained void-containing resin film was cut into a size of 2 mm in width using MS SHREDDER 120 MW manufactured by Meiko Shokai, and further cut into a size of 1 mm (length) × 2 mm (width) using a razor. This was used as a void-containing resin film in Production Example 1.

<Measurement method of void content (film)>
Specific gravity was measured and calculated based on this specific gravity.
Specifically, the void content was calculated by the following equation (1).
Cavity content (%) = {1- (density of resin film after stretching) / (density of polymer film before stretching)} (1)

<Measurement method of cavity aspect ratio (film)>
A cross section perpendicular to the surface of the resin film and perpendicular to the longitudinal stretching direction (see FIG. 2B), and a cross section perpendicular to the surface of the resin film and parallel to the longitudinal stretching direction (see FIG. 2C). Using a scanning electron microscope, the microscope was examined at an appropriate magnification of 300 to 3000 times, and a measurement frame was set in each cross-sectional photograph. This measurement frame was set so that 50 to 100 cavities were included in the measurement frame. Moreover, it confirmed that the cavity was orientating along the vertical extending | stretching direction by the examination by the said scanning electron microscope.
Next, the number of cavities included in the measurement frame is measured, and the number of cavities included in the measurement frame having a cross section perpendicular to the longitudinal stretching direction (see FIG. 2B) is m and the cross section parallel to the longitudinal stretching direction. The number of cavities included in the measurement frame (see FIG. 2C) was n.
Then, the longitudinal stretching direction perpendicular cross section of the measurement frame to measure the thickness (r _i) of each one of the cavities included in (Fig. 2B see), and the thickness of the average and r. Further, the length (L _i ) of each cavity included in the measurement frame (see FIG. 2C) having a cross section parallel to the longitudinal stretching direction was measured, and the average length was defined as L.
That is, r and L can be represented by the following formulas (2) and (3), respectively.
r = (Σr _i ) / m (2)
L = (ΣL _i ) / n (3)
Then, L / r was calculated as an aspect ratio.

<Measurement method of the distance from the cavity located closest to the film surface to the film surface>
A cross section perpendicular to the surface of the resin film and perpendicular to the longitudinal stretching direction (see FIG. 2D) was examined using a scanning electron microscope at an appropriate magnification of 300 to 3000 times, and a cross-sectional photograph was taken.
At the time of imaging, the resin film was set on a scanning electron microscope in a state where the resin film was placed on a plane, and the imaging was performed.
In the cross-sectional photograph, an arithmetic average value T of thickness was calculated. The arithmetic average value T of the thicknesses calculated for each resin film is a thickness measured using a long range contact displacement meter AF030 (measuring unit), AF350 (indicating unit) manufactured by Keyence Corporation (of the manufacturing example 1). In the case, 20 μm).
Next, an arbitrary straight line parallel to the thickness direction was drawn in the cross-sectional photograph, and another straight line parallel to the single straight line and separated by 20 × T was drawn. Moreover, it confirmed that the cavity was orientating along the vertical extending | stretching direction by the examination by the said scanning electron microscope.
Then, in each cavity in the cross-sectional photograph, the center of the circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method was determined, and this was set as the center of the cavity.
Then, in the region sandwiched between the one straight line and the other straight line, ten cavities having the shortest distance from the center of the cavity to the upper surface of the resin film were selected. The “distance from the center of the cavity to the top surface of the resin film” refers to increasing the radius of the circle to be drawn in order when drawing a circle centered on the “center of the cavity”. The radius of the circle when touching the surface of.
And about 10 selected cavities, the distance h (i) from each center to the upper surface of the resin film is calculated, and the arithmetic average value h (avg) of each calculated distance h (i) is as follows ( 4) Calculated by the equation.
h (avg) = (Σh (i)) / 10 (4)

(Production Example 2: void-containing resin film: polyolefin)
Isotactic polypropylene (100% polypropylene resin, manufactured by Aldrich, weight average molecular weight 190,000, number average molecular weight 50,000, MFI: 35 g / 10 min (ASTM D1238, 230 ° C., 2.16 kg), Tm: 170 to 175 ° C.) Was extruded from a T-die at 210 ° C. using a melt extruder and solidified with a casting drum to obtain a polymer film having a thickness of about 150 μm. This polymer film was uniaxially stretched (longitudinal stretching).
Specifically, uniaxial stretching was performed in one step at a speed of 12,000 mm / min in a heated atmosphere at 35 ° C. to obtain a 50 μm thick void-containing resin film.
In addition, the void content of the obtained void-containing resin film was 32% by volume, and the void aspect ratio was L / r = 55. In addition, h (avg) of the obtained void-containing resin film was 1.3 μm. The method for measuring the cavity content and the aspect ratio of the cavity and the method for measuring the h (avg) are as described above.
The obtained void-containing resin film was cut into a size of 2 mm in width using MS SHREDDER 120 MW manufactured by Meiko Shokai, and further cut into a size of 1 mm (length) × 2 mm (width) using a razor. This was used as a void-containing resin film in Production Example 2.

(Production Example 3: void-containing resin film: polyamide)
Nylon MXD6 S6007 (manufactured by Mitsubishi Gas Chemical Co., Inc.) (polyamides) having a relative viscosity of 2.7 and MI = 2 (polyamides) was extruded from a T-die at 260 ° C. using a melt extruder, and solidified with a casting drum. A polymer molded body (polymer film) having a thickness of about 120 μm was obtained. This polymer molded body (polymer film) was uniaxially stretched (longitudinal stretching).
Specifically, in a heated atmosphere at 80 ° C., uniaxially stretching at a speed of 100 mm / min and confirming that necking has occurred, and then further in the same direction as the beginning at a speed of 6,000 mm / min. Uniaxial stretching was performed to obtain a void-containing resin film having a thickness of 35 μm.
In addition, the void content of the obtained void-containing resin film was 16% by volume, and the void aspect ratio was L / r = 55. Further, h (avg) of the obtained void-containing resin film was 8.7 μm. The method for measuring the cavity content and the aspect ratio of the cavity and the method for measuring the h (avg) are as described above.
The obtained void-containing resin film was cut into a size of 2 mm in width using MS SHREDDER 120 MW manufactured by Meiko Shokai, and further cut into a size of 1 mm (length) × 2 mm (width) using a razor. This was used as a void-containing resin film in Production Example 3.

(Production Example 4: Colored cavity-containing resin film)
With respect to the void-containing resin film having a thickness of 50 μm obtained by the same method as in Production Example 1, 0.1% by mass of a colorant (Blue No. 1) was used and colored according to a conventional method. This is cut into a size of 2 mm in width using MS SHREDDER 120 MW Meiko Shokai Co., Ltd., and further cut into a size of 1 mm (length) × 2 mm (width) using a razor. Used as a void-containing resin film.

(Production Example 5: void-containing resin fiber)
The intrinsic viscosity (IV) of 100% polybutylene terephthalate resin PBT2 (produced in FUJIFILM Corporation) was measured with an Ubbelohde viscometer and found to be 0.8. The PBT2 was extruded from the die at 245 ° C. using a melt spinning machine to obtain a resin composition (undrawn yarn).
Next, the obtained (unstretched yarn) was uniaxially stretched at a speed of 200 m / min in a heated atmosphere at 45 ° C. (magnification: 5 times), and after confirming that necking had occurred, it was 200 m / min. Fibers were produced at the same speed and in the same direction as the beginning.
As described above, void-containing resin fibers having a thickness of 30 μm (radius) were obtained. In addition, the cavity content rate of the obtained cavity containing resin fiber was 22 volume%, and the aspect ratio of the cavity was L / r = 23. Further, h (avg) of the obtained void-containing resin fiber was 6.4 μm. The method for measuring the void content and the aspect ratio and the method for measuring the h (avg) are as follows.
The obtained void-containing resin fiber was cut into a length of 2 mm using a razor and used as the void-containing resin fiber of Production Example 5.

<Measurement method of void content (fiber)>
Specific gravity was measured and calculated based on this specific gravity.
Specifically, the void content was calculated by the following equation (1).
Cavity content (%) = {1- (Density of cavity-containing resin fiber after stretching) / (Density of fiber before stretching)} (1)

<Measurement method of hollow aspect ratio (fiber)>
A cross section perpendicular to the fiber surface and perpendicular to the longitudinal stretching direction (see FIG. 4B) and a cross section perpendicular to the fiber surface and parallel to the longitudinal stretching direction (see FIG. 4C) are scanned. Using an electron microscope, the microscope was examined at an appropriate magnification of 300 to 3,000 times, and a measurement frame was set in each cross-sectional photograph. The measurement frame was set so that 50 to 100 cavities were included in the measurement frame.
Next, the number of cavities included in the measurement frame is measured, and the number of cavities included in the measurement frame (see FIG. 4B) perpendicular to the longitudinal stretching direction is m, and the cross section parallel to the longitudinal stretching direction. The number of cavities included in the measurement frame (see FIG. 4C) was n.
Then, the longitudinal stretching direction orthogonal cross section of the measurement frame measured (Figure 4B refer) to one by one of the length of the cavity included a (r _i), and the length of the average and r. Further, the length (L _i ) of each cavity included in the measurement frame (see FIG. 4C) having a cross section parallel to the longitudinal stretching direction was measured, and the average length was defined as L.
That is, r and L can be represented by the following formulas (2) and (3), respectively.
r = (Σr _i ) / m (2)
L = (ΣL _i ) / n (3)
Then, L / r was calculated as an aspect ratio.

<Measurement method of distance from cavity closest to fiber surface to fiber surface>
A cross section (see FIG. 4D) of the void-containing resin fiber perpendicular to the orientation direction of the void was examined with an appropriate magnification of 300 to 3000 using a scanning electron microscope, and a cross-sectional photograph was taken. At the time of imaging, the resin fiber was set on a scanning electron microscope in a state where the resin fiber was placed on a plane, and the imaging was performed.
In the cross-sectional photograph, the arithmetic average value T of the radii was calculated. The arithmetic average value T of the radii was obtained by calculating the center of the cross section of the fiber by a method described later, and determining the average distance from the center to the circumference and calculating and averaging the 10 arbitrary distances. That is, the center of the cross-section of the fiber is the center when the cross-sectional shape of the fiber is a perfect circle, and in the case of other shapes, for example, from the reference circle arbitrarily set by the maximum square center method The center of the circle that minimizes the sum of the squares of the deviations was determined and used as the center of the fiber cross section.
Next, in the cross-sectional photograph, an arbitrary straight line indicating a radius was drawn, and a region obtained by rotating the single straight line by 360 ° in the circumferential direction was drawn.
Moreover, it confirmed that the cavity was orientating along the vertical extending | stretching direction by the examination by the said scanning electron microscope.
Then, in each cavity in the cross-sectional photograph, the center of the circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method was determined, and this was set as the center of the cavity.
Then, ten cavities having the shortest distance from the center of the cavity to the resin fiber surface were selected in a region obtained by rotating any one straight line indicating the radius 360 ° in the circumferential direction. Note that the “distance from the center of the cavity to the surface of the resin fiber” indicates that when drawing a circle centered on the “center of the cavity”, the radius of the circle to be drawn is sequentially increased, and the arc is the resin fiber first. The radius of the circle when touching the surface of.
Then, for the selected 10 cavities, the distance h (i) from each center to the surface of the resin fiber is calculated, and the calculated arithmetic average value h (avg) of each calculated distance h (i) is as follows ( 4) Calculated by the equation.
h (avg) = (Σh (i)) / 10 (4)

(Production Example 6: Colored cavity-containing resin fiber)
The void-containing resin fiber having a thickness of 30 μm (radius) obtained by the same method as in Production Example 5 was colored according to a conventional method using 0.1% by weight of a colorant (Blue No. 1). This was cut into a length of 2 mm using a razor and used as the colored void-containing resin fiber of Production Example 6.

(Comparative Production Example 1: Polyethylene terephthalate)
Using a commercially available PET film (Teroton film G2 thickness 25 μm, manufactured by Teijin), MS SHREDDER 120 MW, manufactured by Meiko Shokai Co., Ltd., cut to a size of 2 mm in width, and further 1 mm (length) using a razor It was cut into a size of 2 mm (width) and used as polyethylene terephthalate of Comparative Production Example 1.
In addition, it confirmed that the said polyethylene terephthalate did not contain a cavity with the scanning electron microscope (made by S-4800 Hitachi High Technology).

(Comparative Production Example 2: Colored polyethylene terephthalate)
The same polyethylene terephthalate as in Comparative Production Example 1 was colored according to a conventional method using 0.1% by weight of a colorant (Blue No. 1). This was cut into a size of 2 mm in width using MS SHREDDER 120 MW manufactured by Meiko Shokai, and further cut into a size of 1 mm (length) × 2 mm (width) using a razor. Used as colored polyethylene terephthalate.
In addition, it confirmed that the said colored polyethylene terephthalate did not contain a cavity with the scanning electron microscope (made by S-4800 Hitachi High Technology).

(Comparative Production Example 3: colored fiber)
According to the method described in JP-A-11-1829, 51 layers of polyethylene terephthalate and nylon are alternately laminated, and a fiber colored with 0.1% by weight of a colorant (blue No. 1) is prepared. (6D, 2 mm) (presents blue interference light). This was used as a colored fiber of Comparative Production Example 3.
In addition, it confirmed that the said colored fiber did not contain a cavity with the scanning electron microscope (made by S-4800 Hitachi High Technology).

[Examples 1-7, Comparative Examples 1-4]
According to the formulation shown in Table 1, cosmetics (manicure) of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared. Specifically, after mixing and dissolving an alkyd resin (Teslac 2053-70, manufactured by Hitachi Chemical Co., Ltd.), ethyl acetate (manufactured by Wako Pure Chemical Industries), and butyl acetate (manufactured by Wako Pure Chemical Industries), a void-containing resin film or a void-containing resin Fibers (Examples 1 to 7) or comparative components thereof (Comparative Examples 1 to 4) were added and mixed uniformly. The obtained mixture was filled in a container (reagent glass bottle 10 ml) to obtain a product.

For each of the obtained cosmetics, (1) the effect of imparting high saturation to the appearance of the cosmetic (manicure) (high chroma of appearance), and (2) the effect of imparting glitter to the appearance of the cosmetic (manicure) (Glossiness of appearance), (3) The effect of imparting high saturation to the site of use (nail coated with nail polish) (high chroma of the makeup film), (4) Transparency to the site of use (nail coated with nail polish) The sensory evaluation was performed by the following method for the effect of giving a three-dimensional effect (texture improvement effect).
Each item of said (1)-(4) was evaluated in seven steps according to the following evaluation criteria about each cosmetic by 10 sensory test panels. Furthermore, based on the average score of 10 panelists, the items (1) to (4) were determined according to the following criteria. The results are shown in Table 1.

-Evaluation criteria-
6 points: Very good.
5 points: Good.
4 points: Somewhat good.
3 points: Normal.
2 points: Somewhat bad.
1 point: Bad.
0 points: Very bad.
-Criteria-
A: The average score of 10 people exceeds 5 points.
○: The average score of 10 people exceeds 3 points and is 5 points or less.
(Triangle | delta): The average score of 10 people exceeds 2 points and is 3 points or less.
X: The average score of 10 people is 2 or less.

  From the results shown in Table 1, the cosmetics of Examples 1 to 7 were superior in appearance to high-saturation appearance, glossiness of appearance, high-saturation feeling of the cosmetic film, and texture improvement effect, compared to the cosmetics of Comparative Examples 1 to 4. It turned out to be a fee. Moreover, the cosmetics of Examples 1 to 7 were not only excellent in the effects as described above, but also excellent in usability and uniformity of the cosmetic film.

The void-containing resin film (uncolored or colored, Production Examples 1 to 4) is a colored fiber (51 layers of polyethylene terephthalate and nylon alternately laminated according to JP-A-11-1829) (Comparative Production Example). Since the aspect ratio of the film is larger than that of 3) (the thickness of the hollow-containing resin film is 0.02 mm and the width is 2 mm is 100 with respect to 3.5 of the colored fibers), even a small amount is excellent in high chroma and the like. Here, the aspect ratio of the void-containing resin film is the ratio of width / thickness, and the aspect ratio of the colored fiber is the flatness ratio (long) of the cross section when the cross section of the fiber is flat. (Ratio of axis / short axis).
The void-containing resin fibers (uncolored or colored, Production Examples 5 to 6) have an aspect ratio of fibers (when the cross section of the fiber is flat, the flatness ratio of the cross section (ratio of major axis / minor axis)). Since it is less than 3.5, the high saturation feeling is somewhat insufficient compared to the void-containing resin films (Production Examples 1 to 4), but since it reflects in all directions, colored fibers (polyethylene terephthalate and nylon are disclosed in In accordance with Japanese Patent Application Laid-Open No. 11-1829, 51 layers are alternately laminated) (Comparative Production Example 3).

[Examples 8 to 9, Comparative Examples 5 to 6]
According to the formulation shown in Table 2, cosmetics (eyeliners) of Examples 8 to 9 and Comparative Examples 5 to 6 were prepared. Specifically, acrylic acid / butyl acrylate copolymer emulsion, 40% by mass (prepared in FUJIFILM Corporation), distilled water (prepared in FUJIFILM Corporation), triethanolamine (manufactured by Wako Pure Chemical Industries, Ltd.) ), Carbon black MA100 (manufactured by Mitsubishi Chemical), glycerin (manufactured by Wako Pure Chemical Industries), phenoxyethanol (manufactured by Wako Pure Chemical Industries) are mixed and dissolved, and then a void-containing resin film or void-containing resin fibers (Examples 8 to 9), or The comparative component with them (Comparative Examples 5 to 6) was added and mixed uniformly. The obtained mixture was filled in a container (reagent glass bottle 10 ml) to obtain a product.

For each of the obtained cosmetics, (1) the effect of imparting high chroma to the appearance of the cosmetic (eyeliner) (high chroma of the appearance), and (2) the glittering appearance of the cosmetic (eyeliner). (3) Effect of imparting high saturation to the site of use (skin coated with eyeliner) (high chroma of the cosmetic film), (4) Site of use (skin coated with eyeliner) ) Was subjected to sensory evaluation by the following method with respect to the effect of imparting transparency and stereoscopic effect (texture improvement effect).
Each item of said (1)-(4) was evaluated in seven steps according to the following evaluation criteria about each cosmetic by 10 sensory test panels. Furthermore, based on the average score of 10 panelists, the items (1) to (4) were determined according to the following criteria. The results are shown in Table 2.

-Evaluation criteria-
6 points: Very good.
5 points: Good.
4 points: Somewhat good.
3 points: Normal.
2 points: Somewhat bad.
1 point: Bad.
0 points: Very bad.
-Criteria-
A: The average score of 10 people exceeds 5 points.
○: The average score of 10 people exceeds 3 points and is 5 points or less.
(Triangle | delta): The average score of 10 people exceeds 2 points and is 3 points or less.
X: The average score of 10 people is 2 or less.

  From the results shown in Table 2, the cosmetics of Examples 8 to 9 were superior in appearance to high-saturation feeling, appearance glossiness, high-saturation feeling of the cosmetic film, and texture improvement effect as compared with the cosmetics of Comparative Examples 5 to 6. It turned out to be a fee. Moreover, the cosmetics of Examples 8 to 9 were not only excellent in the effects as described above, but also excellent in usability and uniformity of the cosmetic film.

Drawing 1 is a figure showing an example of a manufacturing method of a void content resin film, and is a flow figure of a biaxially stretched film manufacturing device. FIG. 2A is a diagram for specifically explaining the aspect ratio of the void-containing resin film, and is a perspective view of the void-containing resin film. FIG. 2B is a diagram for specifically explaining the aspect ratio of the void-containing resin film, and is a cross-sectional view taken along the line A-A ′ of the void-containing resin film in FIG. 2A. FIG. 2C is a diagram for specifically explaining the aspect ratio of the void-containing resin film, and is a B-B ′ sectional view of the void-containing resin film in FIG. 2A. FIG. 2D is a diagram for specifically explaining the distance h (i) from each center of the cavity to the surface of the cavity-containing resin film, and is a cross-sectional view taken along the line AA ′ of the cavity-containing resin film in FIG. 2A. is there. FIG. 3 is a diagram illustrating an example of a stretching process in the method for producing void-containing resin fibers. FIG. 4A is a diagram for specifically explaining the aspect ratio of the void-containing resin fiber, and is a perspective view of the void-containing resin fiber. FIG. 4B is a diagram for specifically explaining the aspect ratio of the void-containing resin fiber, and is a cross-sectional view taken along the line A-A ′ of the void-containing resin fiber in FIG. 4A. FIG. 4C is a diagram for specifically explaining the aspect ratio of the void-containing resin fiber, and is a B-B ′ cross-sectional view of the void-containing resin fiber in FIG. 4A. FIG. 4D is a diagram for specifically explaining a distance h (i) from each center of the cavity to the surface of the cavity-containing resin fiber, and is a cross-sectional view taken along the line AA ′ of the cavity-containing resin fiber in FIG. 4A. is there.

Explanation of symbols

1 void-containing resin film (hollow-containing resin molding)
DESCRIPTION OF SYMBOLS 1a Surface of cavity containing resin film 10 Cavity containing resin fiber 10a Surface of cavity containing resin fiber 100 Cavity L Length of cavity in orientation direction of cavity r Thickness direction of cavity containing film or cavity containing resin orthogonal to orientation direction of cavity Cavity length in the direction perpendicular to the fiber length direction h (i) Distance from the center of the cavity to the surface of the cavity-containing resin film or cavity-containing resin fiber T Cross section perpendicular to the orientation direction of the cavity of the cavity-containing resin film Arithmetic mean value of thickness or the mean mean value of radii in the cross section perpendicular to the orientation direction of the cavity of the resin fiber containing voids

Claims (5)

A void-containing resin film comprising a crystalline polymer and containing cavities therein, and at least one of a void-containing resin fiber comprising a crystalline polymer and containing cavities therein, the void-containing resin film and / or Alternatively, the cavity-containing resin fiber contains an elongated cavity in a state in which the length direction is oriented in one direction, and in the cross section perpendicular to the orientation direction of the cavity, For the ten cavities having the shortest distance to the surface of the cavity-containing resin film and / or the cavity-containing resin fiber, the distance h (from each center to the surface of the cavity-containing resin film and / or the cavity-containing resin fiber h ( i) is calculated, and the calculated arithmetic mean value h (avg) of the distances h (i) is expressed by the following formula: h (avg)> T / 100 [where T is The arithmetic mean value of the thickness in the cross section of the sinusoidal resin film and / or the radius in the cross section of the void-containing resin fiber is represented, and the ten cavities are any one straight line parallel to the thickness direction of the void-containing resin film. And a cavity existing in a region sandwiched between another straight line parallel to the one straight line and separated by 20 × T, and / or of the void-containing resin fiber Selected from the cavities existing in a region obtained by rotating any one line segment indicating the radius 360 ° in the circumferential direction].   The cosmetic according to claim 1, wherein at least one of the void-containing resin film and the void-containing resin fiber is colored.   Orientation of the cavities, where r (μm) is the average length of the cavities in the thickness direction of the cavity-containing resin film and / or the direction perpendicular to the length direction of the cavity-containing resin fibers. The cosmetic according to any one of claims 1 to 2, wherein an L / r ratio when the average length of the cavities in the direction is L (µm) is 10 or more.   The crystalline polymer in at least one of the void-containing resin film and the void-containing resin fiber is at least one selected from polyolefins, polyesters, and polyamides. Cosmetics.   The cosmetic according to any one of claims 1 to 4, wherein the content of at least one of the void-containing resin film and the void-containing resin fiber is 0.1 to 65 mass%.