Composite material containing organic colorant

Abstract

The present disclosure provides a composite material comprising: an organic colorant; a first layer that is attached to the organic colorant and contains silicon oxide; and a second layer that is attached to the first layer and contains an organosilicon compound. The organic colorant may be, for example, a carotenoid-based colorant, a porphyrin-based colorant, a quinone-based colorant, a betacyanine-based colorant, an azaphilone-based colorant, an anthocyanin-based colorant, a flavonoid-based colorant, or a diketone-based colorant, or may be a chromoprotein.

Description

Composite materials containing organic dyes

[0001] This invention relates to a composite material containing an organic dye.

[0002] Dyes are broadly classified into organic and inorganic dyes, and organic dyes are further classified into synthetic and natural dyes. Composite materials containing dyes have also been proposed. For example, Patent Document 1 discloses a composite material in which a dye is coated with a predetermined matrix. The matrix in Patent Document 1 contains silica and polysilsesquioxane. The examples in Patent Document 1 show that the elution of highly water-soluble organic dyes into water is suppressed by the formation of the matrix.

[0003] International Publication No. 2019 / 039160

[0004] Patent Document 1 does not address the inherent function of organic dyes, namely color development. Compared to inorganic dyes, organic dyes exist in many varieties, allowing for a wide range of hues to be obtained. However, even with organic dyes, it is sometimes desirable to adjust or improve the color development. The present invention aims to provide a new composite material suitable for controlling the color development of organic dyes.

[0005] In one aspect, the present invention provides a composite material comprising: an organic dye; a first layer containing silicon dioxide attached to the organic dye; and a second layer containing an organosilicon compound attached to the first layer.

[0006] The present invention provides a composite material suitable for controlling the color development of organic dyes.

[0007] The present invention will be described below with reference to its embodiments, but the following description is not intended to limit the present invention to any particular embodiment. In the following, "main component" means the component that is present in the highest amount by mass. "Substantially absent" means that the content is less than 0.1% by mass, and even less than 0.01%. "Natural pigment" is used to include pigments obtained by various synthesis methods, not limited to pigments derived from natural products, that have the same molecular structure as pigments derived from natural products. Furthermore, in the following, the upper and lower limits indicating numerical ranges can be combined arbitrarily.

[0008] The composite material of this embodiment comprises an organic dye, a first layer containing silicon dioxide attached to the organic dye, and a second layer containing an organosilicon compound attached to the first layer. In this embodiment, it is believed that color development can be easily controlled by the refraction, reflection, and scattering of light at the interface between the first layer containing silicon dioxide and the second layer containing the organosilicon compound.

[0009] [Composite Materials] (Organic Dyes) Organic dyes may be synthetic dyes, but natural dyes are preferable. Unlike synthetic dyes, which can be designed at the molecular level, natural dyes are relatively few in number. Furthermore, natural dyes extracted from natural products tend to be obtained as mixtures of lower purity compared to synthetic dyes used at high purity, and bright, vivid colors may not be obtained. For these reasons, controlling the color development of natural dyes is highly useful.

[0010] The organic pigment may be at least one selected from the group consisting of carotenoid pigments, porphyrin pigments, quinone pigments, betacyanin pigments, azaphyllon pigments, anthocyanin pigments, flavonoid pigments, and diketone pigments. However, the organic pigment may also be caramel, gardenia blue pigment, gardenia red pigment, plant charcoal pigment, etc. The organic pigment may also be a carotenoid pigment and / or a porphyrin pigment. The organic pigments exemplified in this paragraph are also representative natural pigments.

[0011] Carotenoid pigments include, for example, annatto pigment, gardenia yellow pigment, carotenoid pigments, tomato pigment, chili pepper pigment, saffron pigment, and marigold pigment. Porphyrin pigments include, for example, chlorophyll pigment and spirulina pigment. Quinone pigments include, for example, cochineal pigment and lac pigment. An example of a betacyanin pigment is beet red. Azaphyllon pigments include, for example, red yeast rice pigment and red yeast rice yellow pigment. Anthocyanin pigments include, for example, red cabbage pigment, purple cabbage pigment, red radish pigment, perilla pigment, hibiscus pigment, grape juice pigment, grape skin pigment, purple sweet potato pigment, purple corn pigment, elderberry pigment, butterfly pea pigment, and boysenberry pigment. Flavonoid pigments include, for example, cocoa pigment, sorghum pigment, rosewood pigment, onion pigment, tamarind pigment, safflower red pigment, and safflower yellow pigment. However, natural organic pigments are not limited to those listed above and may include caramel, gardenia blue pigment, gardenia red pigment, turmeric yellow pigment, squid ink pigment, melanin pigment, plant charcoal pigment, and other natural pigments.

[0012] The organic pigment may be a pigment protein. The pigment that binds to the protein may be one of the natural pigments exemplified above.

[0013] The organic dye may not have a sulfonic acid group or a sulfonic acid base. Furthermore, excluding the pigment protein, the molecular weight of the molecules constituting the organic dye may be 50 or more but less than 5000, 100 or more but 2500 or less, or even 200 or more but 1000 or less. The molecular weight of the pigment protein may be, for example, 5000 or more but 150000 or less. The organic dye may also be a natural pigment having the molecular weights described above.

[0014] (First layer) The first layer contains silicon dioxide. The first layer may have silicon dioxide as its main component. The first layer may contain components other than silicon dioxide. Examples of components other than silicon dioxide include oxides such as aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, tin oxide, iron oxide, tantalum oxide, and niobium oxide. Components other than silicon dioxide may include carbides, nitrides, etc. The first layer may contain organic functional groups bonded to the silicon atoms of the silicon dioxide. Examples of organic functional groups are alkyl groups having 1 to 10 carbon atoms, especially methyl groups. The first layer may substantially not contain organic substances other than organic functional groups. Furthermore, the first layer may substantially not contain organic substances.

[0015] The deposition of the first layer onto the organic dye is preferably carried out by a wet film deposition method. The sol-gel method is an example of a wet film deposition method. In the sol-gel method, a layer containing silicon oxide is formed through hydrolysis and dehydration condensation of a hydrolyzable silicon-containing compound.

[0016] The first layer only needs to be attached to the organic dye, and may cover part of the organic dye or all of it. The first layer may be dense or porous.

[0017] (Second layer) The second layer contains an organosilicon compound. A typical organosilicon compound is silicone. Silicone is a polymer that has siloxane bonds as its main chain and contains organic groups. Silicone may also be an organosilicon compound that is liquid at room temperature, called silicone oil. Silicone may have constituent units represented by the following formula.

[0018]

[0019] In formula (I), R represents an organic group, and n is an arbitrary integer. However, a part of R may be a hydrogen atom. The organic group is, for example, an alkyl group having 1 to 20 carbon atoms, further 1 to 10 carbon atoms, or a phenyl group, and typically a methyl group. The alkyl group and the phenyl group may have a substituent of a hydrogen atom. A part of the alkyl group and the phenyl group may be modified with at least one substituent selected from a hydroxy group, an amino group, an epoxy group, a mercapto group, a carboxyl group, an alkoxy group, an aralkyl group, an acrylic group, a methacrylic group, a polyether group, and an amide group.

[0020] The second layer only needs to be attached to the first layer, and may cover a part or the whole of the first layer. A part of the second layer may be in contact with the organic dye.

[0021] (Material ratio) The ratio of the organosilicon compound contained in the second layer to the silicon oxide contained in the first layer, expressed on a mass basis, may be 0.01 or more and less than 0.5, 0.02 or more and 0.4 or less, 0.03 or more and 0.3 or less, and further 0.05 or more and 0.2 or less. By appropriately adjusting this ratio, it becomes easy to control the hydrophilicity (hydrophobicity) of the composite material as well as the optical properties.

[0022] The ratio of the silicon oxide contained in the first layer to the organic dye, expressed on a mass basis, may be 1 or more and 500 or less, 3 or more and 400 or less, and further 5 or more and 300 or less.

[0023] (Characteristic) L * a * b * In the color space, the lightness is indicated by L * and the hue is indicated by a * and b * The chroma C * is ((a * )) 2 +(b * )) 2 )) 1 / 2 According to the present embodiment, compared with the state of only the organic dye, L * , a * , and b *A composite material can be provided which is prepared by selecting at least one from the group consisting of the following. According to this embodiment, L * and C * It is also possible to increase at least one selected from the group consisting of the following. This means that the composite of this embodiment can improve the brightness and / or saturation of the organic dye's color development.

[0024] Saturation C * This can be significantly improved by the composite material of this embodiment. The composite material of this embodiment has a carbon content of 5 or more, 10 or more, and even 15 or more than the organic dye alone. * It may have C. * The difference is based on values ​​for an acrylic resin coating film with a thickness of 75 to 90 μm containing composite materials or dyes in a volume ratio of 0.1 to 1.0%, or an acrylic resin coating film with a thickness of 25 to 35 μm containing composite materials or dyes in a volume ratio of 5.0%.

[0025] The composite material of this embodiment may provide a composite material having an improved tactile feel compared to the state of organic dyes alone. The composite material of this embodiment may have an MIU of 0.60 or less, 0.55 or less, and even 0.53 or less. MIU is the average value of the coefficient of friction. The lower the MIU, the better the slipperiness. The composite material of this embodiment may have an MMD of 0.005 or less, 0.0045 or less, even 0.004 or less, and in some cases 0.0035 or less. MMD is the average deviation of the coefficient of friction. The smaller the MMD, the smoother the tactile feel. The composite material of this embodiment may have a relatively low MMD compared to the state of organic dyes alone. The difference between the MMD of the composite material of this embodiment and the MMD of the state of organic dyes alone is, for example, 0.001 or more, and even 0.002 or more.

[0026] The composite material of this embodiment can improve the uniformity of the appearance of the coating film compared to the case where only organic pigments are dispersed. Specifically, it is possible to alleviate color variations caused by uneven distribution of organic pigments and grainy appearance caused by aggregation of organic pigments.

[0027] According to the combination in this embodiment, the diffusibility of incident light may be improved as compared with the case of being dispersed in the state of only the organic dye. The composite material of this embodiment may have a relatively high haze ratio as compared with the state of only the organic dye. The difference between the haze ratio of the composite material of this embodiment and the haze ratio in the state of only the organic dye is, for example, 20% or more, further 30% or more, and in some cases 40% or more. The difference in the haze ratio is also based on the value in the above-mentioned acrylic resin coating film.

[0028] [Dye-containing composition] The composite material of this embodiment can be blended and used in various products. An example of the product is a dye-containing composition. The dye-containing composition may be at least one selected from the group consisting of cosmetics, inks, paints, and resin compositions.

[0029] As described above, this specification discloses the following technologies. (Technology 1) A composite material including an organic dye, a first layer containing silicon oxide attached to the organic dye, and a second layer containing an organosilicon compound attached to the first layer.

[0030] (Technology 2) The composite material of Technology 1, wherein the organic dye is a natural dye.

[0031] (Technology 3) The composite material of Technology 1 or 2, wherein the organic dye is at least one selected from the group consisting of carotenoid dyes, porphyrin dyes, quinone dyes, betacyanin dyes, azaphilone dyes, anthocyanin dyes, flavonoid dyes, and diketone dyes.

[0032] (Technology 4) The composite material of Technology 1 or 2, wherein the organic dye is a pigment protein.

[0033] (Technology 5) The composite material of any one of Technologies 1 to 4, wherein the ratio of the organosilicon compound to the silicon oxide is 0.01 or more and less than 0.5 based on mass.

[0034] (Technology 6) The composite material of any one of Technologies 1 to 5, wherein the ratio of the silicon oxide to the organic dye is 1 or more and 500 or less based on mass.

[0035] (Technology 7) A composite material according to any one of Technologies 1 to 6, having an average deviation (MMD) of the coefficient of friction of 0.005 or less.

[0036] (Technology 8) A dye-containing composition containing a composite material according to any one of Technologies 1 to 7.

[0037] Hereinafter, the present embodiment will be described more specifically by way of examples. (Example 1) A carotene dye (manufactured by Fujifilm Wako Pure Chemical Corporation) was prepared as an organic dye. The dye and water were mixed so that the dye concentration became 9.4% by mass. On the other hand, 411.5 g of tetramethoxysilicate (TMOS) was weighed into a flask, and while stirring this, 5003 g of pure water was added and further stirred for 1 hour to obtain a TMOS hydrolysis solution of 3% by mass in terms of silica. 320 g of a 9.4% dye dispersion was added to this hydrolysis solution to obtain a TMOS hydrolysis solution in which the dye was dispersed. Next, 1N tetramethylammonium (TMAH) was prepared and dropped into the above hydrolysis solution so that the pH was in the range of 8 to 9. The obtained dye dispersion was spray-dried to remove the solvent, and the obtained powder was dried at 100° C. for 2 hours to obtain a powder in which the dye and silicon oxide were complexed.

[0038] 60 g of the obtained powder, 60 g of isopropyl alcohol (IPA), and 4.5 g of dimethylpolysiloxane (dimethicone), which is a silicone, were mixed in a flask. While stirring with a stirring blade, the flask was heated at 90° C. to volatilize the IPA. Approximately 500 ml of water was added to the flask and stirred at 200 rpm with a stirring blade. After stirring for 1 hour, the water and the solid matter were separated with filter paper. This step was repeated once more, and the solid matter was washed with water. Then, it was dried at 100° C. for 2 hours to obtain a composite powder containing a dye, silicon oxide, and silicone. Table 1 shows the content rates and ratios of the components constituting the composite powder.

[0039] (Examples 2-4) As shown in Table 1, each composite powder was obtained in the same manner as in Example 1, except that the type of dye was changed and the amount of silicon dioxide and silicone added was adjusted. The additive in Example 1 was a dye additive such as gum arabic. Chlorophyll dye (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.) was used in Example 2, annatto dye (manufactured by Kanto Chemical Co., Ltd.) was used in Example 3, and Linablue (Linablue G1 (manufactured by DIC Corporation), Linablue is a registered trademark) was used in Example 4.

[0040] (Example 5) Anthocyanin dye (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared as an organic dye. The dye and water were mixed to a dye concentration of 9.4% by mass. Meanwhile, 373.2 parts by mass of deionized water, 15.9 parts by mass of 1% by mass acetic acid, and 207.0 parts by mass of orthosilicate ethyl (manufactured by Tama Chemical Industry Co., Ltd.) were mixed in a flask and stirred at room temperature for about 12 hours to obtain a clear hydrolysis solution. 159.1 g of 9.4% dye dispersion was added to this hydrolysis solution. Next, the dispersion was spray-dried to remove the solvent, and the resulting powder was dried at 100°C for 2 hours to obtain a powder in which the dye and silicon dioxide were compounded. From there, a composite powder containing the dye, silicon dioxide, and silicone was obtained in the same manner as in Example 1.

[0041] In each example, approximately 120 g of the compounded powder of the dye and silicon dioxide was obtained, and approximately 60 g of the composite powder containing the dye, silicon dioxide, and silicone was obtained.

[0042]

[0043] The following evaluations were performed on each composite powder obtained from the examples. In addition, the dyes used in each example were evaluated in their pigment-only state and designated as reference examples with corresponding numbers.

[0044] <Hue Evaluation> A coating film was formed for each composite powder and pigment. The thickness of the coating film was 75 to 90 μm for Examples 1 to 3, 5 and Reference Examples 1 to 3, 5 (Examples 1 to 3, 5: 75 μm, Reference Example 1: 90 μm, Reference Example 2: 80 μm, Reference Example 3: 85 μm, Reference Example 5: 85 μm), and 27 to 32 μm for Example 4 and Reference Example 4 (Example 4: 27 μm, Reference Example 4: 32 μm). A thermosetting acrylic resin was used together with the composite powder or pigment to form the coating film. The volume ratio of the composite powder or pigment in the paint prepared to form the coating film was 0.1% for Example 1 and Reference Example 1, 1.0% for Examples 2 to 3, 5 and Reference Examples 2 to 3, 5, and 5.0% for Example 4 and Reference Example 4.

[0045] The details of film formation are described below using Example 1 as an example. First, 3.33 g of composite powder, 12.62 g of thermosetting acrylic resin (solids concentration: 50%, solvent: xylene / ethyl acetate = 60 / 40, manufactured by DIC Corporation), and 2.90 g of a mixed solvent of xylene / ethyl acetate = 60 / 40 were placed in a glass bottle, and 3 mm diameter glass beads were added. The mixture was then dispersed in paint conditioner for 20 minutes. After that, 3.92 g of isocyanate-based curing agent (solids concentration: 75%, solvent: propylene glycol monomethyl ether acetate / xylene = 50 / 50, manufactured by Sumika Covestro Urethane Co., Ltd.) was added and dispersed in paint conditioner for 5 minutes to obtain the paint. The obtained paint was applied to BYK Optical Chart paper with an applicator and dried to obtain the film.

[0046] The appearance of the obtained coating film was visually observed, and its uniformity was measured using a 5-point scale, with 5 being the highest level of uniformity. The graininess caused by the aggregation of composite powders or organic dyes in the coating film was also measured using a 2-point scale: "NG" if graininess was visible, and "OK" if it was not visible. Furthermore, the hue was measured using a spectrophotometer "DC650" (manufactured by datacolor).

[0047] <Haze Evaluation> The paint prepared for hue evaluation was applied to a 188 μm PET film using an applicator and dried to obtain coatings of the thickness described above for each example and reference example. The linear transmittance and total light transmittance of the obtained coatings from 380 nm to 780 nm were measured using a spectrophotometer "V-770" (manufactured by JASCO Corporation), and the haze (%) was obtained by calculating (total light transmittance - linear transmittance) / total light transmittance × 100.

[0048] <Particle Characterization Evaluation> Using the friction tester "KES-SE" (manufactured by Kato Tech Co., Ltd.), the average value MIU and average deviation MMD of the friction coefficient were measured by placing a sensor on the composite material spread on the sample stage and sliding it. A silicon sensor was used. The composite material was 1.6 mg / cm² on black artificial leather (protein leather, manufactured by Ideatex Japan Co., Ltd.) 2 The material was applied in the manner described above. The measurement conditions were a static load of 25 gf and a measurement speed of 1 mm / second. For accuracy, the data for the initial 5 mm and the final 5 mm were omitted, and the data for the 20 mm in between was used. A smaller MIU value indicates better slipperiness, and a smaller MMD value indicates a smoother particle surface and a smoother feel.

[0049] The results of the characteristic evaluation are shown in Tables 2 and 3.

[0050]

[0051]

[0052] In each embodiment, compared to the state with only the dye (reference example), a * and / or b * The brightness L changed significantly. * and / or saturation C * The values ​​increased. In each embodiment, compared to the reference example, the haze rate increased, MIU and MMD decreased, and uniformity and / or graininess also improved.

[0053] Pressed powder cosmetics, cream-to-powder cosmetics, and BB (blemish balm) cream cosmetics containing the complex pigments obtained from the examples or the pigments from the reference examples were prepared and evaluated.

[0054] <Preparation of Pressed Powder Cosmetics> The raw materials used are shown in Table 4. After mixing the materials shown in the main phase (Base) using a blender, the materials shown in phase A were added and mixed further using a blender. The mixed powder was placed on a pan for a press machine and pressed to form the shape of the pan, thereby obtaining pressed powder cosmetics.

[0055] <Preparation of Cream-to-Powder Cosmetic> The raw materials used are shown in Table 5. The materials shown in Phase A were weighed into a container and heated while stirring until melted, then the materials shown in Phase B were added. Heating was stopped, the materials shown in Phase C were added, and the mixture was stirred until uniform. Then the materials shown in Phase D were added and stirred until uniform to obtain the cream-to-powder cosmetic.

[0056] <Preparation of BB Cream Cosmetic Formulation> The raw materials used are shown in Table 6. Water shown in Phase A was weighed into a container and heated to 75-85°C. The remaining materials shown in Phase A were added while stirring. Meanwhile, the materials shown in Phase B were weighed into another container and heated to 75-85°C. After stirring until Phase A and Phase B were homogeneous, Phase B was slowly added to Phase A and stirred further until homogeneous. After cooling the mixed phase to 45°C, the materials shown in Phase C were added and stirred until homogeneous to obtain the BB cream cosmetic formulation.

[0057] Each cosmetic composition using the composite powder obtained from each example was superior to similar cosmetic compositions using only the corresponding pigment instead of the composite powder in terms of water resistance, roughness, color unevenness, and makeup durability. When using only the corresponding pigment instead of the composite powder, the amount added was adjusted appropriately so that the ratio of pigment in each cosmetic composition was equivalent to that when the composite powder was used.

[0058]

[0059]

[0060]

Claims

1. A composite material comprising: an organic dye; a first layer containing silicon dioxide attached to the organic dye; and a second layer containing an organosilicon compound attached to the first layer.

2. The composite material according to claim 1, wherein the organic dye is a natural dye.

3. The composite material according to claim 1, wherein the organic dye is at least one selected from the group consisting of carotenoid dyes, porphyrin dyes, quinone dyes, betacyanin dyes, azaphyllon dyes, anthocyanin dyes, flavonoid dyes, and diketone dyes.

4. The composite material according to claim 1, wherein the organic dye is a pigment protein.

5. The composite material according to claim 1, wherein the ratio of the organosilicon compound to the silicon oxide is 0.01 or more and less than 0.5, expressed by mass.

6. The composite material according to claim 1, wherein the ratio of silicon dioxide to the organic dye is 1 or more and 500 or less, expressed by mass.

7. The composite material according to claim 1, wherein the mean deviation (MMD) of the coefficient of friction is 0.005 or less.

8. A dye-containing composition comprising the composite material according to any one of claims 1 to 7.

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