JP6467765B2 - Titanium oxide pigment - Google Patents

Description

  The present invention relates to a titanium oxide pigment. More specifically, the present invention relates to a titanium oxide pigment that, when used in a composition containing a fluorescent material, gives a visual effect of showing a small change in color appearance even under different light sources.

  Titanium oxide is used in a wide range of fields such as cosmetics, paints, inks, plastics, paper, and rubber. Of these fields, pigment-grade titanium oxide having a primary particle size of approximately 0.2 μm is generally used in fields where hiding power is required. Pigment grade titanium oxide not only has excellent visible light hiding properties, but also has a high blocking effect in the ultraviolet region. For example, Patent Documents 1 and 2 disclose titanium oxides suitable for cosmetics.

  When a bright color is used for cosmetics or paints, a fluorescent material is often used (for example, Patent Document 3). The fluorescent material has a solid or liquid form, and has a characteristic of absorbing visible light mainly from ultraviolet rays and emitting it to the visible light region. If fluorescence is added to the waveform of the irradiation light, the intensity of light of that wavelength becomes strong, so that the human eye feels vivid and highly saturated. A wide variety of fluorescent materials are known from natural sources to synthetic products. For example, organic pigments and dyes such as rose pigments, fluorescent brighteners incorporated in detergents, fluorescent pigments used in fluorescent inks, and the like.

JP 2000-191325 A JP 2013-28563 A JP 2005-206613 A

  In recent years, switching from incandescent lamps of lighting fixtures to LEDs and fluorescent lamps has been promoted as a countermeasure against global warming. However, under alternative light sources such as LEDs and fluorescent light sources, cosmetics, resins, inks, fibers, paints, papers, etc. that contain titanium oxide pigments appear dull, and when the light source changes There is a problem that the difference in color and impression is extreme. In Japan, since various light sources have been mixed in the living space, there has been a problem that changes in color and saturation due to the influence of the light sources are severe.

  The present inventors focused on this problem and studied the cause, and found that the cause was fluorescence. And earnestly examined in order to solve this subject by the pigment grade titanium oxide used as a masking agent. As a result, it has been found that the use of a titanium oxide pigment having specific properties can reduce the change in color appearance under different light sources, and the present invention has been completed.

That is, the present invention is a titanium oxide pigment, and a metric chroma C ^* _W of reflected light of a paste measured using a daylight white LED as a light source with respect to a paste in which the titanium oxide pigment and an organic red pigment are blended. , metric chroma difference between the metric chroma ^C _{* L} of the reflected light of the paste was measured using a warm white LED light source _{^{ΔC * (W-L) =}} | C * W -C * L | is 25 or less, oxidation Such as titanium pigment.

  The titanium oxide pigment of the present invention is used in cosmetics together with a material that absorbs ultraviolet light and / or visible light and emits fluorescence in the visible light region, thereby reducing the change in color appearance under different light sources. Can provide a fee. The same effect can be expected even when used for paints, inks, plastics, paper, rubber, and the like.

It is an apparatus arrangement | positioning figure at the time of measuring a metric chroma. It is the figure which showed the spectrum of various light sources. It is the figure which expanded the spectrum of the ultraviolet region of various light sources. It is the figure which showed the fluorescence spectrum at the time of irradiating an ultraviolet ray of 380 nm to a pigment pigment (Red-7). It is a spectral transmittance curve of each sample of an example and a comparative example.

The titanium oxide pigment of the present invention has a metric chroma C ^* _W of reflected light of a paste measured using a daylight white LED as a light source and a light bulb color as a light source with respect to a paste in which the titanium oxide pigment and an organic red pigment are blended. This is a titanium oxide pigment having a metric chroma difference ΔC ^* _(W−L) = | C ^* _W− C ^* _L | of 25 or less of the metric chroma C ^* _L of the reflected light of the paste measured using the LED.

As another aspect, the titanium oxide pigment of the present invention is a paste in which the titanium oxide pigment and the organic red pigment are blended, and the metric chroma C ^* _F of the reflected light of the paste measured using a fluorescent lamp as a light source. , metric chroma difference between the metric chroma ^C _{* L} of the reflected light of the paste was measured using a warm white LED light source _{^{ΔC * (F-L) =}} | C * F -C * L | is 35 or less, oxidation It is a titanium pigment.

As yet another aspect, the titanium oxide pigment of the present invention has a metric chroma C ^* _F of reflected light of a paste measured using a fluorescent lamp as a light source with respect to a paste in which the titanium oxide pigment and an organic red dye are blended. If, metric chroma difference between the metric chroma ^C _{* W} of the reflected light of the mixed paste was measured using a neutral white LED light source _{^{ΔC * (F-W) =}} | C * F -C * W | is less than 5 , A titanium oxide pigment.

The metric chroma C ^* is a numerical value representing saturation, and a higher numerical value indicates a pure chromatic color. The metric chroma difference ΔC ^* is a numerical value representing the saturation difference between the two colors. The lower the numerical value, the more the saturation is maintained, and the saturation difference under different light sources, that is, the color. It can also represent the difference in the appearance of

First, a method for measuring the metric chroma C ^* will be described. (Hereafter, the term “metric chroma” may be omitted.)

  First, 3000 g of titanium oxide pigment is charged in a Henschel mixer (for example, Mitsui HNSSCHEL method 1 manufactured by Mitsui Mining Co., Ltd.) and stirred at 38 Hz while triethoxyoctylsilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-3083 (LS-5580)). ) Is added to the titanium oxide over 5% by mass over 15 minutes. Then, it heats up with a vapor | steam and heat-processes for 30 minutes at 140 degreeC, It is set as a triethoxy octyl silane treatment titanium oxide pigment.

  Next, a paste in which the octyl silylation-treated titanium oxide pigment and an organic red pigment are blended is prepared. Prepare the materials listed in Table 1, weigh group B into the same container, mix with a homomixer (eg, TK ROBOMIX Ver. 5.4 manufactured by PRIMIX), and add group A to the mixture. To do. Subsequently, Group C is added and mixed well with a three roll (for example, EXAKT 50 I manufactured by EXAKT Advanced Technologies GmbH) to obtain a paste. (Hereafter, this paste may be referred to as “lip gloss”.)

  Next, 0.4 g of the prepared lip gloss is applied to HelioPlate HD6 (50 × 50 mm / manufactured by Labsphere, USA) so as to have a thickness of about 3 mm, and left as a measurement sample for about 10 minutes.

  A light source is installed in the direction of 45 ° on the HelioPlate HD6 measurement sample plane coated with lip gloss, and the distance is adjusted so that the illuminance becomes 1600 lux. The illuminance is measured with an illuminometer (for example, ANA-FII, manufactured by Tokyo Photoelectric Co., Ltd.) A spectral radiance meter (CS2000 manufactured by Konica Minolta) is installed at a distance of 500 mm from the measurement sample in the 90 ° direction of the measurement sample plane to construct a measurement system. The arrangement is shown in FIG. Hereinafter, FIG. 1 will be described. Reference numeral 1a denotes a light source, and a light source such as a fluorescent lamp, an LED, or an incandescent bulb can be used. 1b is a test piece coated with a sample. 1c is a spectral radiance meter.

Using a fluorescent lamp, a daylight white LED, and a light bulb color LED as a light source, the spectrum of reflected light from each light source is measured with a spectral radiance meter, and L ^* a ^* b ^* for each light source is calculated. Each light source used for the measurement has a spectrum shown in FIG. FL20SS EX-N manufactured by Mitsubishi Electric Corporation is used as the fluorescent lamp, and the LED white light mode and bulb color mode of LED ceiling light AE-08LDR manufactured by Odelic Co. are used as each LED light source.

C ^* is calculated by the following equation based on a ^* b ^* measured under each light source.
C ^* = (a ^{* 2} + b ^{* 2} ) ^1/2 , and for each light source:
_{^{Fluorescent: C * F = (a *}} F 2 + b * F 2) 1/2
Daylight white _{^{LED: C * W = (a}} * W 2 + b * W 2) 1/2
Warm white _{^{LED: C * L = (a}} * L 2 + b * L 2) 1/2

In the titanium oxide pigment of the present invention, ΔC ^* _(W−L) = | C ^* _W− C ^* _L | measured by the above method is 25 or less, and it is under a daylight white LED light source and a light bulb color LED light source. Since the metric chroma is smaller than the conventional titanium oxide pigment, the change in the color appearance under both light sources can be reduced.

In the titanium oxide pigment of the present invention, ΔC ^* _(F−L) = | C ^* _F− C ^* _L | measured by the above method is 35 or less, and the metric is measured under a fluorescent light source and a light bulb color LED light source. Since the chroma is smaller than the conventional titanium oxide pigment, the change in color appearance under both light sources can be reduced. In particular, ΔC ^* _(F−L) can be 25 or less.

In the titanium oxide pigment of the present invention, ΔC ^* _(F−W) = | C ^* _F− C ^* _W | measured by the above method is 5 or less, and the metric is measured under a fluorescent light source and under a daylight white LED light source. Since the chroma is smaller than the conventional titanium oxide pigment, the change in color appearance under both light sources can be reduced. In particular, ΔC ^* _(F−W) can be 3 or less.

  In the spectral transmittance of the titanium oxide pigment of the present invention, the average transmittance in the wavelength range of 370 to 400 nm is preferably 60% to 80%, and more preferably 65% to 75%.

  Fluorescence is often used for various items in the living space such as cosmetics, fashion, furniture, etc. Vivid lipstick color and clear white color of blouse are often technologies using fluorescence. In the case of a material that generates fluorescence, which is generally used in cosmetics and the like, the fluorescence occurs by absorbing visible light of ultraviolet to short wavelengths. For this reason, if light of this absorption wavelength is cut, no fluorescence is generated, and the color lacks completely different vividness. In addition, since the intensity of fluorescence depends on the intensity of light, the color changes when the amount of light having this absorption wavelength changes.

  Incandescent light bulbs are light sources that abundantly emit light in this absorption wavelength region, but fluorescent lamps and LED lighting have relatively little light in this region, and some manufacturers do not emit light. Although LED lighting and general lighting appear to be similar light sources to the human eye, their spectra are actually very different. For example, LED lighting does not have a broad spectrum that spreads over the entire visible light like an incandescent bulb, and often forms a color by a combination of light and intensity in a specific wavelength range. Further, the daylight white, daylight white, and light bulb colors of general LED lighting are often realized by changing the balance between the intensity of blue light and the intensity of yellow light without changing the wavelength band itself. For this reason, when the light source is changed, that is, when the balance of the combination of the wavelength and intensity of light is changed, the vividness of the fluorescent material is reduced. This phenomenon has a great influence on lipstick color, dress color and blouse texture.

  On the other hand, pigment grade titanium oxide is often used for cosmetics, resins, inks, fibers, paints, papers, etc. (hereinafter sometimes referred to as cosmetics, etc.) for the purpose of securing a hiding power. Titanium also has a certain degree of ultraviolet shielding properties, so it cuts ultraviolet rays in the long wavelength range considerably. Then, the ultraviolet rays from the light source are weak, and it will be further cut with pigment grade titanium oxide, the amount of ultraviolet rays necessary to emit fluorescence cannot be secured, the saturation is low, and the appearance is not vivid It will be. The titanium oxide pigment of the present invention has a significantly higher transmittance in the long wavelength ultraviolet region, particularly in the range of 370 to 400 nm, compared with the conventional pigment grade titanium oxide, so it absorbs ultraviolet to short wavelength visible light and emits fluorescence. Cosmetics that have a small change in color appearance even when the light source changes because the amount of ultraviolet rays necessary to emit fluorescence can be secured when used in combination with fluorescent materials that generate (hereinafter simply referred to as fluorescent materials) Is obtained.

  Further, the titanium oxide pigment of the present invention preferably has an average transmittance of less than 50% and more preferably 45% or less in the spectral transmittance of the wavelength region of 320 to 340 nm. With such a spectral transmittance, it is possible to balance the protection effect of UVA, which also affects the blackening of the skin, and the vividness of the color. Since skin darkening is mainly effective at 320 to 340 nm, the transmittance in the wavelength range of 370 to 400 nm, which has a large absorption band of fluorescence, while suppressing the skin blackening while maintaining the shielding ability in this wavelength range. As a result, the cosmetics and the like can be designed so that even if the light source changes, the change in color appearance is small and the color becomes vivid. There is no particular limitation on the lower limit of the average transmittance.

  Further, the titanium oxide pigment of the present invention preferably has an average transmittance of 65% to 90% and more preferably 70% to 87% in the wavelength range of 400 to 700 nm in the spectral transmittance. In particular, when used in cosmetics, it is a preferable characteristic that cosmetics have a sense of transparency, but it is not preferable that there is no covering power. Therefore, by setting the spectral transmittance within the above range, it is possible to design a cosmetic that can ensure a sufficient covering power while having a transparent feeling.

  The titanium oxide used in the present invention further has a transmittance as it goes from the long wavelength side to the short wavelength side among the bending points of the transmittance curve when the transmittance is measured so that the presence or absence of the bending point and the waveform can be recognized. The lowering bending point is preferably in the wavelength range of 370 to 400 nm. In the spectral transmittance curve of a titanium oxide pigment, there are usually two inflection points on the long wavelength side and the short wavelength side. In the present invention, the inflection point appearing on the long wavelength side is used as a reference. If the inflection point of the transmittance curve exceeds 400 nm, the transmittance of light in the range of 370 to 400 nm is excessively reduced, and there is a problem in that the amount of ultraviolet light that can be absorbed by the fluorescent material is reduced. When the bending point is less than 370 nm or when the bending point is not clear, the hiding power may be insufficient, which is not preferable. The inflection point means “the inflection point is the point where the curvature changes suddenly, that is, the apex of the convex angle”.

The above-described transmittance measurement is performed by the following method.
<Sample preparation>
The contents described in Table 2 are put into a 140 mL glass container (M-140 manufactured by Saya Glass Industrial Co., Ltd.). The ratio of the (liquid paraffin / white petrolatum / stearic acid) mixture in Table 2 is shown in Table 3.

<Preparation method>
The glass container containing the contents is shaken with a paint shaker (manufactured by Red Devil) for 10 minutes, and then the glass beads are separated with a metal net to obtain a sample.

<Application method>
Using a 2 mil (50.8 μm) applicator (manufactured by Dazai Equipment Co., Ltd.), apply the prepared sample to a film (Lonza TAC100 manufactured by Panac) so that the film thickness in a wet (wet) state is about 50 μm. And a coating film is obtained.

<Measurement method>
The coating film prepared above is subjected to spectral transmittance measurement with an ultraviolet-visible spectrophotometer (V-660 manufactured by JASCO Corporation).

  The average transmittance in each wavelength range is calculated as follows. The measured transmittance in the wavelength region measured by the above method is added at intervals of 5 nm, and the average value is defined as “average transmittance”.

The titanium oxide pigment of the present invention preferably has an average primary particle diameter measured by electron microscopy in the range of 0.30 to 0.60 μm. Within this range, it is possible to obtain a titanium oxide pigment that gives a visual effect of showing a small change in color appearance even under different light sources. When the average primary particle size is less than 0.30 μm, light scattering of titanium oxide becomes strong, so that there is a problem that fluorescence is not emitted efficiently or absorption of ultraviolet rays is suppressed. When the average primary particle diameter exceeds 0.60 μm, there is a problem that the hiding power becomes weak and the function as a hiding agent becomes weak. When there are a plurality of titanium oxide particle size distributions, one particle size distribution falls within the scope of the present invention, and when the effect of reducing the change in metric chroma C ^* can be exhibited, it falls within the scope of the present invention. The average primary particle diameter is obtained by taking a transmission electron micrograph (magnification 20000 times) of a titanium oxide pigment, measuring the major axis diameter and minor axis diameter of 100 or more particles, respectively, and averaging all of them.

The titanium oxide pigment of the present invention preferably has a coefficient of variation in particle size distribution of 1 or less. When the average primary particle diameter is in the above-mentioned range and the coefficient of variation is 1 or less, the shielding ability in the wavelength region of 340 nm or less is relatively high, and the shielding ability in the wavelength region of 370 to 400 nm is relatively low. Therefore, the effect of the present invention is enhanced because most of the particles have moderate transparency with a small ultraviolet ray shielding ability and a small scattering ability in the red region. On the other hand, when the coefficient of variation is larger than 1, it means that the variation in the particle diameter is large, and the number of particles that deviate from the particle diameter having an appropriate ultraviolet shielding ability and an appropriate transparency with a small scattering ability in the red region increases. Appropriate ultraviolet shielding ability cannot be obtained, the scattering ability in the red region is increased, and the degree of reduction in the change in color appearance under different light sources is weakened. The variation coefficient of the particle diameter is more preferably 0.6 or less, and further preferably 0.2 or less. The particle size distribution of titanium oxide is preferably unimodal. However, if there are a plurality of titanium oxide particle size distributions, the variation coefficient of one particle size distribution is within the scope of the present invention, and the metric chroma C ^* changes. When the reduction effect can be exhibited, it falls within the scope of the present invention. The variation coefficient of the particle size distribution is obtained by obtaining a standard deviation from all the major axis diameters and minor axis diameters measured at the time of calculating the average primary particle diameter, and dividing it by the average primary particle diameter.

  The crystal form of the titanium oxide of the present invention may be any of anatase type, rutile type and brookite type, and may be a mixture containing two or more of these. These may be properly used according to the required characteristics. The crystal system can be confirmed by measuring a diffraction pattern by a powder X-ray diffraction method and comparing it with PDF (powder diffraction file) data.

  The shape of the titanium oxide pigment of the present invention is not particularly limited, such as a spherical shape, a spindle shape, a rod shape, a plate shape, an indefinite shape, a polygonal plate shape, a petal shape, or a bundle shape. In addition, when using the titanium oxide pigment of this invention for cosmetics, it is preferable that the shape of the particle | grains which comprise it is spherical shape-substantially spherical shape. When the particles have such a shape, a good feeling is exhibited when used in a cosmetic. The shape of the particles can be observed with an electron micrograph, and may be roughly spherical to substantially spherical. Specifically, the aspect ratio is preferably 1.0 to 1.5, and preferably 1.0 to 1.5. 1.2 is more preferable. The aspect ratio is obtained by calculating the average major axis diameter and the average minor axis diameter from the major axis diameter and the minor axis diameter measured at the time of calculating the average primary particle diameter, and dividing the average major axis diameter by the average minor axis diameter.

  In the titanium oxide pigment of the present invention, the surface of titanium oxide particles is preferably coated with silicon oxide and / or aluminum oxide. Examples of the silicon oxide and the aluminum oxide include at least one compound selected from silicon, an anhydrous oxide of aluminum, a hydrated oxide, a hydrated oxide, and a hydroxide. As long as the photocatalytic activity is sufficiently suppressed, it may be porous or dense, and can be appropriately selected. Each of them can be coated alone, or can be used in combination by laminating or mixing them. In particular, it is more preferable to coat the surface of titanium oxide particles with silicon oxide and then coat the surface with aluminum oxide or hydroxide.

These preferable coating amounts are in the range of 3.0 to 13.0% by mass of silicon oxide in terms of SiO _{2 with} respect to the mass standard of titanium oxide particles in terms of TiO ₂ , and aluminum (water) oxide is Al. It is in the range of 0.1 to 5.0% by mass in terms of ₂ O ₃ . More preferably, each coating amount is in the range of 6 to 10% by mass and 0.3 to 3.0% by mass with respect to the mass standard of titanium oxide particles in terms of TiO ₂ . The coating amount can be confirmed by fluorescent X-ray analysis or ICP emission spectroscopic analysis.

  In the present invention, in addition to silicon oxide and aluminum (water) oxide, an inorganic compound other than these may be coated. Examples of inorganic compounds include oxides such as zirconium, tin, titanium, and antimony, hydroxides, phosphates, apatite, titanium silicate, iron hydroxide, iron oxide, and the like.

  Moreover, various surface treatments may be further applied to the particle surface of the titanium oxide pigment of the present invention. Examples of the surface treatment include silane compounds, silicone compounds, fluorine surfactants, metal soaps, resins, and the like. Examples of the silane compound include alkyl alkoxysilanes such as octyltrimethoxysilane and octyltriethoxysilane. Examples of the silicone compound include methyl hydrogen polysiloxane, trimethylsiloxysilicic acid, fluoroalkyl / polyoxyalkylene co-modified silicone, and the like. Examples of the fluorine surfactant include perfluoroalkyl phosphate esters and perfluoroalkyl carboxylates.

Depending on the industrial application, for example, a polyol compound (trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol, etc.), an alkanolamine compound (monoethanolamine, monopropanolamine, diethanolamine, diethanolamine) (Propanolamine, triethanolamine, tripropanolamine, etc.) and derivatives thereof (acetate, oxalate, tartrate, formate, benzoate, etc.) are also preferable. Among these, a polyol compound is preferable because it has a high effect of improving dispersibility, and trimethylolpropane and trimethylolethane are more preferable. More preferably, the silicone compound, the fluorine surfactant and other organic compounds are coated on a coating of an inorganic compound such as silicon oxide or aluminum oxide. More preferably, the silicone compound, the fluorosurfactant and other organic compounds are further coated on a coating of an inorganic compound such as silica or alumina. The coating amount at the time of the surface treatment also depends on the specific surface area of the titanium oxide particles, but is preferably in the range of 0.1 to 20% by mass with respect to the mass standard of the titanium oxide particles in terms of TiO _2. The range of 10% by mass is more preferable.

The titanium oxide pigment of the present invention preferably has a specific surface area of 18 to 33 m ² / g. When the specific surface area is within the above range, it is preferable because the particle diameter has an appropriate ultraviolet shielding ability and an appropriate transparency with a small red light scattering ability. The specific surface area is more preferably in the range of 20 to 30 m ² / g. The specific surface area may be measured by a general BET single point method based on nitrogen adsorption in which nitrogen gas is adsorbed to the sample while cooling the sample tube with liquid nitrogen.

The titanium oxide pigment of the present invention preferably has an oil absorption of 20 to 40 mL / 100 g. When the amount of oil absorption is in the above range, stickiness, makeup collapse and powderiness can be improved when the cosmetic is made. In addition, the stability over time can be maintained at a high level. The oil absorption is more preferably 22 to 37 mL / 100 g, and more preferably 25 to 35 mL / 100 g. The oil absorption is measured according to JIS K-5101-13-2. Specifically, the sample and boiled linseed oil are mixed little by little, and the amount of boiled linseed oil used per 100 g of the sample (formula a) when it can be spirally wound using a spatula is expressed (formula a).
(Formula a) Oil absorption (g / 100 g) = Amount of boiled linseed oil (g) / Sample mass (g) × 100

  The titanium oxide pigment of the present invention has a whiteness comparable to that of a conventional titanium dioxide pigment, but inside the titanium oxide particles, iron, copper, cerium, vanadium, antimony, chromium, tungsten, manganese, cobalt In this case, it has various hues. In particular, when an iron compound such as iron oxide is contained, a beige color that is preferable for cosmetics is obtained. In addition, titanium oxide particles may contain a metal compound such as aluminum, zinc, phosphorus, iron, etc. In this case, the oxidation activity and photoactivity peculiar to titanium oxide are suppressed, which is preferable.

  The titanium oxide pigment of the present invention has a number average particle diameter measured by a laser diffraction / scattering method of approximately 0.2 to 1.1 μm. Since the average primary particle diameter determined by the electron microscopic method is in the range of 0.3 to 0.6 μm, it can be seen that the titanium oxide pigment of the present invention is not agglomerated and behaves in a state close to monodispersion. .

  There is no restriction | limiting in particular in the manufacturing method of the titanium oxide pigment of this invention, What is necessary is just to use the arbitrary methods which can manufacture the titanium oxide powder which has the above-mentioned characteristic. A specific manufacturing method will be described.

  Titanyl sulfate was hydrolyzed at a temperature of 170 ° C. or higher and at a pressure equal to or higher than the saturated vapor pressure of the temperature to obtain spherical hydrous titanium dioxide, and then the spherical hydrous titanium dioxide was immersed in hydrochloric acid after 400 to 400 It can be manufactured by firing at a temperature of 700 ° C. Details of each step will be described below.

  First, spherical water-containing titanium dioxide is produced by hydrolyzing titanyl sulfate at a temperature of 170 ° C. or higher and a pressure equal to or higher than the saturated vapor pressure of the temperature.

  The titanyl sulfate solution is a purified titanyl sulfate solution, a solution containing impurities such as iron sulfate obtained by leaching titanium ore with sulfuric acid, metatitanic acid or hydrous titanium dioxide obtained by neutralizing titanyl sulfate with an alkali, etc. For example, a solution prepared by dissolving sulfuric acid in sulfuric acid.

The titanyl sulfate solution is put in a pressure vessel, and the vessel is sealed, and then heated to a predetermined temperature for hydrolysis. The concentration of titanyl sulfate from 0.05 to 5 mol / L approximately in terms of TiO ₂ basis, preferably from 0.5 to 3 mol / L. Moreover, when adjusting the density | concentration of a titanyl sulfate as needed, you may adjust the density | concentration of a free sulfuric acid to about 50-800 g / L, Preferably it is 150-400 g / L.

  The temperature at the time of hydrolysis is 170 ° C. or higher, desirably 180 ° C. to 300 ° C. When the temperature is lower than 170 ° C., it becomes difficult to obtain spherical hydrous titanium dioxide having a desired size and shape.

The pressure at the time of hydrolysis is about the saturated vapor pressure at the temperature or higher than the saturated vapor pressure, preferably about 0 to 10 kg / cm ² higher than the saturated vapor pressure at the temperature. When the temperature at the time of hydrolysis is higher than 300 ° C. or when the pressure at the time of hydrolysis is significantly higher than the saturated vapor pressure, it is not preferable because usable devices are limited.

  The reaction time for hydrolysis is suitably 0.5 to 10 hours. After being hydrolyzed in this manner, it is cooled to an appropriate temperature, separated, washed as necessary, and dried to obtain spherical hydrous titanium dioxide.

  Next, the spherical hydrous titanium dioxide thus obtained is immersed in hydrochloric acid and then baked at a temperature of 400 to 700 ° C. Spherical hydrous titanium dioxide contains a large amount of sulfate radicals, but when immersed in hydrochloric acid, the residual amount of sulfate radicals can be reduced by a substitution reaction.

  Specifically, spherical water-containing titanium dioxide obtained by immersing in hydrochloric acid and then washing and drying as necessary is fired at a temperature of 400 to 700 ° C. When the firing temperature is higher than 700 ° C., it is not desirable because the particles strongly sinter and the pulverization must be strengthened or the resulting titanium oxide pigment feels bad. On the other hand, when the temperature is lower than 400 ° C., the number of particles deviating from the particle diameter having an appropriate ultraviolet shielding ability and an appropriate transparency (small scattering ability in the red region) increases, and an appropriate ultraviolet shielding ability cannot be obtained. When used in a composition containing a fluorescent material, the change in saturation under different light sources becomes large, which is not desirable.

  In the above production method, the firing time is suitably about 0.5 to 10 hours. As a device used for firing, a general firing furnace such as a rotary furnace can be used. The titanium oxide powder thus obtained may be pulverized or pulverized by a crusher or the like, if necessary. In this way, the titanium oxide pigment of the present invention is obtained.

  The firing temperature is preferably higher than 600 ° C. and 700 ° C. or lower. After firing in this temperature range, the sized titanium oxide pigment produced through a pulverization step (a classification step if necessary) has a bending point that changes sharply in a range of about 370 to 390 nm, It shows a more ideal spectral transmittance curve in which the transmittance in the long wavelength ultraviolet to visible light region is relatively high. Therefore, when used in a composition containing a fluorescent material, changes in color appearance under different light sources can be further reduced.

  Moreover, you may coat | cover the titanium oxide particle surface with a silicon oxide or an aluminum oxide as needed. For this purpose, first, an aqueous slurry is prepared by dispersing titanium oxide powder in water and preferably performing wet pulverization using a vertical sand mill, horizontal sand mill or the like. This aqueous slurry may be subjected to a particle size distribution control operation through a mesh or the like for adjusting the particle size distribution. At this time, it is preferable to adjust the pH of the aqueous slurry to 9 or more because the titanium oxide powder is stably dispersed in water. Moreover, you may use dispersing agents, such as silicic acid compounds, such as phosphoric acid compounds, such as sodium hexametaphosphate and sodium pyrophosphate, sodium silicate, and potassium silicate, as needed. The solid content concentration of the titanium oxide powder in the aqueous slurry is in the range of 50 to 800 g / L, preferably in the range of 100 to 500 g / L.

  Then, after adding a silicon compound and an aluminum compound to an aqueous slurry, a neutralizing agent is added, or if a silicon compound, an aluminum compound and a neutralizing agent are added simultaneously, the silicon oxide and the aluminum compound are added. Covered. Examples of the salt of the silicon compound include sodium silicate and potassium silicate. Examples of the aluminum compound salt include sodium aluminate, aluminum sulfate, and aluminum nitrate. Further, as the neutralizing agent, if it is a basic compound, hydroxides or carbonates such as alkali metals and alkaline earth metals, ammonium compounds such as ammonia, amines, etc., if acidic compounds, sulfuric acid And inorganic acids such as hydrochloric acid, and organic acids such as acetic acid and formic acid.

  As for the silicon oxide coated on the particle surface of titanium oxide, porous treatment and dense treatment are known, and the coating of porous silicon oxide can be obtained by the above-described method. If the dense silicon oxide is coated, a known method described in JP-A-53-33228 can be applied. If the method described in JP-A-53-33228 is used, the slurry preferably has a pH of 9 to 10.5 while maintaining the slurry of titanium oxide powder at a temperature in the range of 80 to 100 ° C. While maintaining the range, sodium silicate is rapidly added and then neutralized at a pH of 9-10.5, after which a temperature in the range of 80-100 ° C. is held for 50-60 minutes. Or the method of neutralizing a silicic acid compound over 30 minutes can also be used. In this method, the neutralization is more preferably performed over 1 hour. If the neutralization pH is in the range of 4 to 7.5 and the temperature of the aqueous slurry at the time of neutralization is 80 ° C. or higher, it is preferable because a denser coating is easily formed. The range of more preferable neutralization pH is 4.5-7, and the neutralization temperature is 90 degreeC or more.

  Moreover, you may coat | cover the particle | grain surface of a titanium oxide pigment with the above-mentioned surface treating agents, such as a silane compound, a silicone compound, and a fluorine surfactant, as needed. For example, a titanium oxide pigment powder and a surface treatment agent such as a silane compound can be coated by using a dry pulverizer or a high-speed stirrer and stirring and mixing them. In particular, a method using a dry pulverizer is preferable because the pulverization of the titanium oxide pigment and the coating of the organic compound can be performed simultaneously. As the dry pulverizer, an airflow pulverizer such as a jet mill having good pulverization efficiency and excellent mixing properties is preferably used. Moreover, it can also coat | cover by adding a silane compound, a silicone compound, a fluorine surfactant, etc. to the aqueous slurry of a titanium oxide pigment powder.

  In the present invention, when an inorganic compound other than silicon oxide and aluminum oxide is coated on the surface of titanium oxide particles, the same method as that for coating silicon oxide and aluminum oxide can be used. Also, when the surface of the titanium oxide particles is coated with an organic compound other than the silane compound, silicone compound, and fluorine surfactant, the same method as that for coating the silane compound, silicone compound, and fluorine surfactant can be used. . If the particle surface of titanium oxide pigment powder is to be coated with an organic compound, use a titanium oxide pigment coated with silicon oxide or aluminum oxide, a dry pulverizer or a high-speed stirrer, and stir and mix them. Is preferred. Titanium oxide pigments coated with inorganic compounds such as silicon oxide and aluminum oxide, organic compounds such as silane compounds, silicone compounds and fluorine surfactants are dehydrated, solid-liquid separated from the slurry, and dried. Can be dry pulverized. For dehydration, for example, a filter press, a roll press, or the like can be used. For example, a band heater, a batch heater, or the like can be used for drying. For the dry pulverization, for example, an impact pulverizer such as a hammer mill or a pin mill, a pulverizer or the like, a grinding pulverizer, an airflow pulverizer such as a jet mill, or a spray dryer such as a spray dryer can be used.

  The particle size distribution of the titanium oxide pigment can be adjusted by a known method. Specifically, a known classification step may be included in any step of the manufacturing method described above. Classification may be performed by either wet or dry methods, and known methods such as mesh pass and fluid classification can be used, and there is no particular limitation. You may carry out in combination with them in a crushing process or a transportation process. In particular, classification is performed after wet pulverization in the inorganic surface treatment process, classification is performed in the pulverization process after firing, or classification is performed in the pulverization process after surface treatment, because classification efficiency is high and the process is simple, which is preferable. . In particular, it is preferable to perform pulverization and / or classification after the completion of all surface treatments because the particle size distribution can be precisely controlled. Examples of the classifier include a cyclone, a superclone, a centrifuge, and a vibrating sieve.

  The titanium oxide pigment of the present invention is particularly effective when used as a composition together with a material that has absorption in the ultraviolet to low wavelength visible region and emits fluorescence in the visible light region, and particularly absorbs at a wavelength of 370 to 400 nm. It is preferable to use together with the fluorescent material which has. The fluorescent material is not particularly limited as long as it is a known material, but when applied to the human body or when there are legal regulations, it is necessary to use materials that comply with safety and regulations. The fluorescent material may be either organic or inorganic. Further, for the purpose of enhancing the performance of the fluorescent material, it may be a composite pigment or various surface treatments. Examples of fluorescent materials include natural pigments, parts of colored plant extracts, fluorescent brighteners, fluorescent dyes, fluorescent pigments, etc., but they also fluoresce even those that are not recognized as fluorescent materials. Since many things exist, when a color change is observed visually by applying long-wavelength ultraviolet rays, the fluorescent spectrum can be selected. Specific examples of fluorescent materials include Brilliant Sulfoflavin FF (CI56205) as a material that emits green to yellowish green, and basic yellow HG (CI46040) as a material that emits yellowish green to yellow. Examples of materials that emit red fluorescent color include D & C Red No. 7 (CI15850), D & C Red No. 27 (CI45410), and D & C Red No. 28 (CI45410). .

  It is preferable to mix | blend the said fluorescent material in 0.001-15 mass% with respect to a composition in conversion of solid content, More preferably, it may mix | blend in the range of 0.1-10 mass%. preferable.

  In the case where the fluorescent material has a powder shape, the primary particle diameter is preferably in the range of 1 nm to 20 μm. Since this fluorescent material has a characteristic of absorbing ultraviolet rays and releasing them into the visible light region, it is preferable that the specific surface area be as large as possible because the emission luminance of fluorescence per unit mass can be increased. When the particle diameter is within this range, the luminous efficiency of fluorescence can be increased.

  The titanium oxide pigment of the present invention is particularly suitable for cosmetics. The amount blended into the cosmetic can not be defined unconditionally depending on the dosage form of the cosmetic and other blending components in view of a more specific purpose, but is generally 0.1 to 0.1% of the entire cosmetic. 60.0 mass% is preferable and it is especially preferable that it is 1.0-40.0 mass%. If it is less than 0.1% by mass, sufficient effects may not be obtained, and if it exceeds 60.0% by mass, usability may be deteriorated.

  In cosmetics, in addition to the titanium oxide pigment of the present invention and fluorescent material, other components usually used in cosmetics and pharmaceuticals, etc., as long as the effect is not impaired, such as other powder components, liquid fats and oils, solid fats and oils, Wax, hydrocarbon, higher alcohol, ester, silicone, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water-soluble polymer, thickener, film agent, UV absorption Agent, sequestering agent, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient, vitamin, antioxidant, antioxidant aid, fragrance, water, etc. are required Depending on the dosage form, it can be prepared by a conventional method according to the intended dosage form. At this time, when blending a component that suppresses ultraviolet absorption of the fluorescent material, it is preferable to adjust the blending amount within a range in which the saturation of the composition is maintained.

  Cosmetics can be widely applied to cosmetics, pharmaceuticals, and quasi drugs that are applied to the outer skin. The dosage form is arbitrary, such as solution system, solubilization system, emulsification system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, gel, aerosol, mist, capsule, etc. It can be provided in the form. In addition, the product form of the cosmetic is also arbitrary, facial cosmetics such as lotion, milky lotion, cream, pack, etc .; makeup cosmetics such as foundation, funny, blusher, lipstick, eye shadow, eyeliner, mascara, sunscreen, etc .; Body cosmetics; aromatic cosmetics; skin cleansers such as makeup removers, facial cleansers, body shampoos; hair cosmetics such as hair rinses and shampoos; ointments; bath preparations; oil blotting paper, etc. It can be applied in any form. The titanium oxide pigment of the present invention can be particularly suitably used for point makeup cosmetics such as lipsticks, glosses (lip glosses), and teaks in which a relatively large amount of fluorescent material is used.

  The titanium oxide pigment of the present invention can also be used as a resin composition by blending with a resin component. By selecting the type of the resin component, it is a resin composition useful for various applications such as paint, paper, fiber and the like. be able to. Among them, it is useful as a resin composition for paints, a resin composition for inks, and a resin composition for plastics. The specific pigment concentration varies depending on the application. For example, in the case of a resin composition for paint or a resin composition for ink, 0.5 to 10 parts by mass of titanium oxide pigment is used for plastics with respect to 1 part by mass of the resin component. If it is a resin composition, 0.05-2 mass parts of titanium oxide pigments are preferable with respect to 1 mass part of resin components. In the present invention, in addition to the titanium oxide pigment and the resin component, a solvent, an additive, a filler, and the like may be included. At this time, when blending a component that suppresses ultraviolet absorption of the fluorescent material, it is preferable to adjust the blending amount within a range in which the saturation of the composition is maintained.

  The resin composition containing a coating resin can be used for coating a wide range of substrates such as metal, wood, plastics, concrete, and the like, but is particularly suitable for coating indoor members. As the coating method, known methods such as brush coating, roller coating, spray coating, dip coating, and electrostatic coating can be applied, and there is no particular limitation.

  Examples of the resin component for paint include alkyd resins, acrylic resins, polyester resins, epoxy resins, amino resins, fluorine resins, modified silicone resins, urethane resins, vinyl resins, and the like. You can choose. These resin components for paint are not particularly limited, such as an organic solvent-soluble type, a water-soluble type, and an emulsion type, and the curing method is not limited such as a heat curing type, a room temperature curing type, an ultraviolet curing type, and an electron beam curing type. The resin composition containing a coating resin contains an organic solvent such as alcohols, esters, ethers, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, water, or a mixed solvent thereof as a solvent. The solvent may be selected according to suitability with the resin component. In addition, colorants such as organic pigments, inorganic pigments, dyes, extenders, surfactants, plasticizers, curing aids, dryers, antifoaming agents, thickeners, emulsifiers, flow regulators, depending on the purpose Various additives such as anti-skinning agents, anti-color separation agents, ultraviolet absorbers and anti-fungal agents, fillers and the like may be included. Or it can also be set as the two-component coating material which uses a hardening | curing agent, a hardening adjuvant, and a curable resin component separately as a hardening liquid, and mixes with a coating material at the time of coating. It is preferable to add a photopolymerization initiator, a photosensitizer and the like to the resin composition containing an ultraviolet curable resin.

  When a resin for coating is used as the resin component, the resin composition is added with various solvents as necessary to the titanium oxide pigment and the resin component for coating, and a sand mill, a disper, a ball mill, a paint shaker, It can be obtained by dispersing using a disperser such as a present roll mill or a three roll mill. The various additives and fillers can be added at the time of dispersion or added to the paint after dispersion.

  The resin composition containing the resin for ink is useful for various printing inks used for gravure printing, flexographic printing, other intaglio printing, letterpress printing, planographic printing, stencil printing, and the substrate to be printed is a plastic film, Paper, metal foil, etc. are not particularly limited. Further, the present invention is applied not only as a final printing ink but also as an intermediate product such as a toning ink and a color chip.

  The resin component for ink to be used can be appropriately selected depending on the printing method, the type of base material to be printed, and the like. For example, urethane resin, vinyl chloride resin, chlorinated polypropylene resin, polyamide resin, acrylic resin, maleic acid Resin, cyclized rubber resin, nitrified cotton, rosin and the like can be used. These resin components for ink are not particularly limited, such as an organic solvent-soluble type, a water-soluble type, and an emulsion type, and the curing method is not limited to room temperature curing type, heat curing type, ultraviolet curing type, electron beam curing type, and the like. In the resin composition containing the ink resin of the present invention, an organic solvent such as alcohols, esters, ethers, ketones, aromatic hydrocarbons, aliphatic hydrocarbons, water, or a mixed solvent thereof, It may be contained as a solvent, and the solvent can be selected according to suitability with the resin component. In addition, colorants such as organic pigments, inorganic pigments, dyes, extenders, surfactants, antistatic agents, plasticizers, curing aids, antifoaming agents, lubricants, antioxidants, ultraviolet rays, depending on the situation of use Various additives such as an absorbent and a chelating agent, a filler and the like may be contained.

  When the resin composition uses an ink resin as a resin component, various solvents are added to the titanium oxide pigment and the ink resin component as necessary, and a sand mill, attritor, disper, ball mill, paint It can be obtained by dispersing using a dispersing machine such as a shaker, 2-roll mill, 3-roll mill or the like. Alternatively, the pigment and the resin component can be kneaded to form a chip. The various additives and fillers can be added at the time of dispersion or can be added to the ink after dispersion.

  A resin composition containing a resin for plastics is useful for uses such as laminate products such as water-resistant paper, injection molded products, extrusion molded products, inflation processed products, and calendar processed products. Furthermore, the present invention is applied not only as a final molded product but also to intermediate products such as color pellets and master batches (color concentration).

  The resin component for plastics can be appropriately selected depending on the processing method, for example, polyolefin resin, vinyl chloride resin, vinyl acetate resin, polystyrene resin, ABS resin, polyester resin, aromatic resin, nylon resin, polycarbonate resin, cellulose resin. Thermosetting resins such as polylactic acid resins and thermoplastic resins such as phenolic resins, urethane resins, and unsaturated polyester resins can be used without any particular limitation. In addition to the titanium oxide pigment and the resin component for plastics, the resin composition containing the plastic resin of the present invention includes an organic pigment, an inorganic pigment, a coloring agent such as a dye, a filler, a surface active agent, depending on the purpose. Contains various additives such as additives, plasticizers, lubricants / stabilizers, antistatic agents, antioxidants, UV absorbers, light stabilizers, flame retardants, brighteners, bactericides, reinforcing materials, fillers, etc. It may be.

  In the case where a plastic resin is used as the resin component, the resin composition may be added with the above-mentioned additives and fillers to the titanium oxide pigment and the plastics resin component as necessary, thereby uniaxial or biaxial extension. It can be obtained by dispersing by a known method using an extrusion molding machine such as a ruder, a roll molding machine such as a calender roll, a pressure mixer such as a Banbury mixer. Or after pelletizing using an extrusion molding machine or a pressure mixer, you may shape | mold with an injection molding machine or said various molding machines.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

<Preparation of titanium oxide sample>
An aqueous solution of titanyl sulfate with a concentration of 150 g / dm ^{3 in} terms of TiO ₂ was charged into an autoclave, a nucleating agent for hydrolysis was added, and the pressure was higher than the saturated vapor pressure of 100 kg / cm ² at a temperature of 250 ° C. over 4 hours. After hydrolyzing, filtration, washing and drying were performed to obtain a spherical hydrous titanium dioxide dry powder. 150 g of this dry powder was suspended in 500 cm ³ of 7% hydrochloric acid, heated to 60 ° C. and stirred for 1 hour, neutralized with 20% aqueous sodium hydroxide solution, filtered and washed. The obtained washed cake was baked at 650 ° C. to obtain a titanium oxide pigment (sample a).

After adjusting the titanium oxide pigment of sample a to an aqueous slurry having a TiO ₂ concentration of 200 g / dm ³ , adding sodium hexametaphosphate as P ₂ O ₅ by 0.4 mass% with respect to the titanium dioxide mass, and wet-pulverizing with a bead mill The particle size adjusting operation was performed with 150 mesh to obtain a titanium oxide slurry. A part thereof was washed and dried to obtain a titanium oxide pigment (sample b).

The remainder of the titanium oxide slurry was further sized with 200 mesh, and then adjusted so that the TiO ₂ concentration was 200 g / dm ³ . The slurry was heated to 70 ° C., a 3 mass% sodium silicate aqueous solution in terms of SiO ₂ was added to TiO ₂ minutes over 30 minutes, and the temperature was raised to 85 ° C. After stirring for 30 minutes, dilute sulfuric acid was slowly added dropwise over 40 minutes to neutralize to pH 7.0. Subsequently, this titanium dioxide slurry was cooled to 70 ° C., adjusted to pH 5.5 with dilute sulfuric acid, and a 1% by mass sodium aluminate aqueous solution in terms of Al ₂ O ₃ was added over 30 minutes to TiO ₂ minutes. did. After stirring for 30 minutes, the pH was adjusted again to 5.5 with dilute sulfuric acid, washed by filtration, and dried at 120 ° C. The dried product was subjected to airflow pulverization and sizing operation to obtain a titanium oxide pigment (sample c).

  In addition, titanium oxide pigments CR-60, CR-50, and CR-58 (all manufactured by Ishihara Sangyo) were prepared as samples df.

<Measurement of physical properties>
Table 4 shows the average primary particle diameter, standard deviation, coefficient of variation, and shape of samples a to f. The number average particle size, standard deviation, and coefficient of variation were determined by image analysis of 100 particles using an image analyzer manufactured by Nireco, based on a transmission electron micrograph (magnification 20000 times) of each sample. The shape was judged visually. As a result of measuring the oil absorption and the aspect ratio of Sample c, they were 30 mL / 100 g and 1.2, respectively. Moreover, it was 0.78 micrometer as a result of measuring the average particle diameter by the laser diffraction / scattering method.

(Examples 1 and 2, Comparative Examples 1 to 4)
Using samples a to f, lip gloss was prepared according to the above formulation. Table 5 shows the specific composition. All titanium oxide samples were blended as octyltriethoxysilane-treated titanium oxide treated with 5% by mass using octyltriethoxysilane. The unit in Table 5 is mass%.

<Measurement of metric chroma C ^* >
Using the lip glosses of Examples 1 and 2 and Comparative Examples 1 to 4, metric chroma C ^* was measured according to the method described above. Using a fluorescent lamp, a daylight white LED, and a light bulb color LED as the light source, the spectrum of the reflected light from each light source was measured with a spectral radiance meter, and L ^* a ^* b ^* for each light source was calculated. The actual measurement distance was 410 mm for a fluorescent lamp, 500 mm for a white LED, and 430 mm for a light bulb color LED. C ^* was calculated based on this a ^* b ^* value. The reason why the fluorescent lamp and the LED are compared as the light source is that the influence of this combination is most presumed in Japan. FL20SS EX-N manufactured by Mitsubishi Electric Corporation was used as the fluorescent light, and the daylight white mode and light bulb color mode of LED ceiling light AE-08LDR manufactured by Odelic Co. were used as the light sources of the LEDs.

<Measurement of spectral distribution of various light sources>
FIG. 2 shows the results of measuring the spectral distribution of various light sources in accordance with the method described above. In FIG. 2, 2a) indicates a fluorescent lamp, 2b) indicates a Japanese daytime white LED, 2c) indicates a Japanese-made bulb color LED, and 2d) indicates an incandescent lamp. It can be seen that the fluorescent lamp shows an emission line spectrum, whereas the LED has a broad two-wavelength type spectrum. FIG. 3 shows an enlarged view of the wavelength range of 350 to 450 nm. In FIG. 3, 3a) shows a fluorescent lamp, 3b) shows a Japanese daytime white LED, 3c) shows a Japanese-made bulb color LED, and 3d) shows an incandescent bulb. It can be seen that LEDs have very little ultraviolet light compared to incandescent bulbs and fluorescent lamps. In addition, although the LED made in Europe is a little stronger than the LED made in Japan, the absolute amount is considerably smaller than that of the incandescent bulb.

<Measurement of fluorescence spectrum of fluorescent material>
FIG. 4 shows a fluorescence spectrum when the pigment pigment (Red-7) used as the fluorescent material is irradiated with ultraviolet rays of 380 nm. It can be seen that there is strong fluorescence in the red region.

(Evaluation 1)
Table 6 shows the metric chroma difference ΔC ^* _(F−W) = | C ^* _F− C ^* _W | between the fluorescent lamp and the daylight white LED light source. It can be seen that the lip glosses of Examples 1 and 2 have little change in metric chroma under fluorescent light and daylight white LED light sources. In particular, it can be seen that the change in metric chroma is small in Example 2 where the variation coefficient of the particle size distribution of the titanium oxide pigment is small.

(Evaluation 2)
Table 7 shows the metric chroma difference ΔC ^* _(W−L) = | C ^* _W− C ^* _L | under the daylight white LED light source and the light bulb color LED light source. It can be seen that the lip gloss of Example 2 has a small change in metric chroma even under a daylight white LED light source and a light bulb color LED light source.

(Evaluation 3)
Table 8 shows the metric chroma difference ΔC ^* _(F−L) = | C ^* _F− C ^* _L | under the fluorescent lamp and the light bulb color LED light source. It can be seen that the lip gloss of Example 2 shows little change in metric chroma even under fluorescent lamps and light bulb color LED light sources.

<Measurement of spectral transmittance>
FIG. 5 shows a transmittance curve obtained by measuring the spectral transmittances of the samples a to f in accordance with the above method, and Table 9 shows an average transmittance in each wavelength region. In FIG. 5, the titanium oxide pigments (samples b and c) suitable for the present invention have a point in which the transmittance curvature changes abruptly from the long wavelength side toward the short wavelength side (the apex of the convex angle, sample c in FIG. In other words, the bending point is in the range of 370 to 400 nm. Therefore, as shown in Table 9, it can be confirmed that the transmittance at 370 to 400 nm is high. Since all of the points (indicated by arrows in FIG. 5 for the sample f) are 400 nm or more, it is estimated that the transmittance in the range of 370 to 400 nm is low as shown in Table 9 and inhibits the ultraviolet absorption of the fluorescent material. Is done. These experimental results are in good agreement with the above-mentioned metric chroma difference evaluation results, and when existing titanium oxide pigments are used as a masking agent, the amount of ultraviolet light that is originally less is further reduced, making it impossible to emit fluorescence. I understand. Sample a is not sufficiently classified and includes relatively large particles. As a result, the bending point is not included in the range of 370 to 400 nm, which is not a suitable application.

(Example 2, Comparative Examples 6 and 7)
Next, test examples using ink will be shown.
The ink was evaluated according to the formulations and production methods shown in Tables 10 and 11. The fluorescent material used is a yellow to green fluorescent dye having absorption in the vicinity of ultraviolet to 450 nm.

  Titanium oxide pigments (samples c, a, and d) were charged into a 220 mL glass container (M-220 manufactured by Saiya Glass Industry Co., Ltd.) according to the formulation shown in Table 10, and shaken for 30 minutes using a paint shaker. After the adjustment, an ink composition of 4 parts by mass of a titanium oxide pigment was obtained with respect to 1 part by mass of the ink resin according to the formulation shown in Table 11. These were designated as Example 3 (Sample C), Comparative Example 5 (Sample A), and Comparative Example 6 (Sample D), respectively.

Evaluation method and result <Evaluation of color tone>
Toluene / isopropyl alcohol / methyl ethyl ketone (= 3/2/5 mass ratio) so that the ink compositions (samples c, a and d) obtained in Example 3 and Comparative Examples 5 and 6 have a practical printing viscosity. The mixture was diluted and the viscosity was adjusted so that the # 3 Zahn cup viscosity was 15 to 16 seconds. This diluted ink is applied onto a smooth PET film with a thickness of 75 μm using a # 1 bar coater (manufactured by Dazai Equipment Co., Ltd.), and is naturally dried for 30 minutes to form a coating film. Resin (IB-422; manufactured by Sanyo Chemical Industries, solid content concentration: 30.0%) was applied with a # 3 bar coater (produced by Dazai Equipment Co., Ltd.), and an OPP film (Torphan BO2535 manufactured by Toray Industries Inc.) was applied thereon. Bonded to the coating. This film is visually observed under daylight white LED, light bulb color LED, fluorescent lamp, and the change in saturation is in the range of 5 points (less change) to 0 point (changes) using 10 panelists. The average score was used as the evaluation result. Therefore, the higher the score, the smaller the change in saturation. The results are shown in Table 12.
In Table 12, the saturation change 1 is the result of visual observation of the saturation change under the fluorescent lamp and the daylight white LED light source, and the saturation change 2 is the daylight white LED light source and the light bulb color LED light source. It is the result of the visual observation of the saturation change below, and the saturation change 3 is the result of the visual observation of the saturation change under the fluorescent lamp and the light bulb color LED light source.

  From the results shown in Table 12, the ink composition containing the titanium oxide pigment of the example of the present invention has a small change in saturation due to the difference in the light source as compared with the comparative example in the case of cosmetics, and vividness is maintained. It was confirmed in human tests.

1a Light source 1b Sample 1c Spectral radiance meter

Claims (6)

When the transmittance is measured, the average transmittance in the wavelength range of 370 to 400 nm of the transmittance curve is 60% to 80%, and the inflection point of the transmittance curve is from the long wavelength side toward the short wavelength side. A titanium oxide pigment having a bending point in which the transmittance decreases according to the range of 370 to 400 nm ,
For a paste containing the titanium oxide pigment and organic red pigment,
The metric chroma difference C ^* _W of the paste reflected light measured using a daylight white LED as the light source and the metric chroma C ^* _L of the paste reflected light measured using the light bulb color LED as the light source ΔC ^* _{( W−L)} = | C ^* _W− C ^* _L | is a titanium oxide pigment having 25 or less. When the transmittance is measured, the average transmittance in the wavelength range of 370 to 400 nm of the transmittance curve is 60% to 80%, and the inflection point of the transmittance curve is from the long wavelength side toward the short wavelength side. A titanium oxide pigment having a bending point in which the transmittance decreases according to the range of 370 to 400 nm ,
For a paste containing the titanium oxide pigment and organic red pigment,
The metric chroma difference C ^* _F of the reflected light of the paste measured using a fluorescent lamp as the light source and the metric chroma C ^* _L of the reflected light of the paste measured using a light bulb color LED as the light source ΔC ^* _{(F -L)} = Titanium oxide pigment wherein | C ^* _F- C ^* _L | is 35 or less. When the transmittance is measured, the average transmittance in the wavelength range of 370 to 400 nm of the transmittance curve is 60% to 80%, and the inflection point of the transmittance curve is from the long wavelength side toward the short wavelength side. A titanium oxide pigment having a bending point in which the transmittance decreases according to the range of 370 to 400 nm ,
For a paste containing the titanium oxide pigment and organic red pigment,
And metric chroma C ^* _F of the reflected light of the paste was measured using a fluorescent lamp as the light source, the metric chroma difference between the metric chroma C ^* _W of the reflected light of the mixed paste was measured using a neutral white LED light source [Delta] C ^* _{( FW)} = | C ^* _F- C ^* _W | is a titanium oxide pigment having 5 or less. The average transmittance in the wavelength range of 320 to 340 nm of the transmittance curve when the transmittance is measured is less than 50%, and the average transmittance in the wavelength range of 400 to 700 nm is 65% to 90%. The titanium oxide pigment according to any one of 1 to 3 . The titanium oxide pigment according to any one of claims 1 to 4 , wherein the average primary particle diameter measured by electron microscopy is 0.30 to 0.60 µm. The titanium oxide pigment according to any one of claims 1 to 5 , wherein the coefficient of variation of the particle size distribution is 1 or less.

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