Liquid coloring composition, colored resin composition, and molded article

Abstract

The present invention provides a liquid coloring composition that has excellent dispersibility of colorants, good storage stability and supply accuracy, and can uniformly color a molded product when kneaded into a diluted resin without impairing the appearance of the molded product or the mechanical properties and moldability of the diluted resin. It also provides a molded product using the same that has excellent color unevenness, appearance, mechanical properties, and moldability. [Solution] The problem is solved by a liquid coloring composition comprising a liquid dispersion medium (A), a surfactant (B), and a colorant (C), in which the liquid dispersion medium (A) has a viscosity at 25°C of 10,000 mPa·s or less and a decomposition onset temperature of 250°C or higher, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polycarboxylic acid ester, and the surfactant (B) is at least one selected from the group consisting of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide.

Description

Technical Field

[0001] The present disclosure relates to a liquid coloring composition, a colored resin composition, a molded article, and a colored resin composition.

Background Art

[0002] Plastic molded articles are used in a wide range of fields such as electrical and electronic equipment parts, automotive parts, medical parts, food and beverage containers, etc. because they are easy to mold. In order to enhance the decorativeness of plastic molded articles, coloring is performed, and various coloring compositions are added in molding processes such as injection molding and extrusion molding.

[0003] Examples of the above coloring compositions include dry color which is a powdery coloring composition, solid masterbatch which is a coloring composition in the form of pellets, granules or grains, or liquid masterbatch which is a liquid coloring composition.

[0004] Since dry color is a powdery coloring composition obtained by mixing a colorant such as a dye or a pigment with a dispersant, contamination of the production line due to scattering may be a problem. Also, even when dry color is melt-kneaded with the main resin of the molded article, aggregates of the colorant cannot be sufficiently loosened, and appearance defects may occur in the molded article.

[0005] Solid masterbatch is a coloring agent composition obtained by melt-kneading a colorant into a resin or the like and granulating it into a granular form, and is widely used. However, when using solid masterbatch for coloring a molded article with a low colorant concentration such as a transparent color, since the addition amount of the masterbatch is small, it is difficult to obtain a uniformly colored molded article, and appearance defects such as color unevenness may occur.

[0006] In order to uniformly color a molded article, methods for improving molding conditions such as increasing the melt-kneading time of melt-kneading a solid masterbatch and a diluting resin, strengthening the melt-kneading, reducing the colorant concentration in the solid masterbatch, and increasing the addition amount of the solid masterbatch used during molding are known.

[0007] However, in the former method, the molding cycle takes a long time, resulting in a decrease in productivity. In addition, due to strong kneading, some of the resin may decompose, causing problems such as a decrease in physical properties. In the latter method, there is a concern about a decrease in the physical properties of the molded body due to an increase in the addition amount of the solid masterbatch. In particular, when the diluent resin is a polycarbonate resin or a polymethyl methacrylate resin, it is difficult to plasticize due to its high mechanical properties, and it is said that it is difficult to achieve uniform permeation color coloring. For polyester resins and polyamide resins as well, since the viscosity of the resin decreases during melting due to the high processing temperature, it is difficult to achieve uniform coloring due to the loosening defect of the solid masterbatch containing a high concentration of the colorant.

[0008] To solve the above problems, methods using a liquid masterbatch as disclosed in Patent Documents 1 and 2 are known. Since the liquid masterbatch is in a liquid state, it has excellent distributability and can uniformly color a plastic molded body. Patent Document 1 describes a method of adding a liquid masterbatch containing a pigment and vegetable oil to a thermoplastic resin, and Patent Document 2 describes a method of adding a liquid masterbatch containing a fatty acid ester, solid particles, and a surfactant to a specific thermoplastic resin.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0010] However, in the liquid coloring compositions described in Patent Documents 1 and 2, the dispersibility of the colorant is not sufficient. Further, when molding a molded body, there may be a problem that the physical properties of the diluting resin deteriorate.

[0011] Patent Document 3 discloses a liquid masterbatch containing anatase-type titanium oxide, a metal deactivator, a liquid dispersion medium having a specific viscosity and thermal decomposition start temperature, and a dispersant. According to the disclosure of Patent Document 3, even when anatase-type titanium is included, thickening due to deterioration of the resin component can be suppressed. However, this technique does not enhance the dispersibility and storage stability in the liquid masterbatch and does not improve the supply accuracy, and there is still room for further study regarding color unevenness in the obtained molded body and variations in color differences between molded bodies.

[0012] Patent Document 4 discloses a technique for suppressing the occurrence of color unevenness in a obtained molded body and providing mechanical properties by means of a liquid coloring composition containing a liquid resin having a specific viscosity, a dispersant having a hindered amine structure, and a colorant. However, the technique disclosed in Patent Document 4 does not examine the dispersibility, storage stability, and supply accuracy of the colorant in the liquid coloring composition, and there is still room for further study regarding color unevenness in the obtained molded body and variations in color differences between molded bodies. Further, color unevenness and variations in these molded bodies become apparent in molded bodies having transparency and high mechanical strength, but have not been solved by conventional techniques.

[0013] Therefore, an object of the present disclosure is to provide a liquid coloring composition that is excellent in the dispersibility of a colorant, has good storage stability and supply accuracy, can be uniformly colored without impairing the appearance of a molded body, the mechanical properties of a diluting resin, and the moldability when kneaded into the diluting resin, and can reduce variations in color differences between molded bodies. Another object is to provide a molded body excellent in color unevenness, appearance, mechanical properties, and moldability using the same.

Means for Solving the Problems

[0014] As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. The present invention includes the following embodiments. The embodiments of the present invention are not limited to the following.

[0015] [1] A liquid coloring composition containing a liquid dispersion medium (A), a surfactant (B), and a colorant (C), wherein the liquid dispersion medium (A) has a viscosity at 25 ° C of 10,000 mPa · s or less, a decomposition start temperature of 250 ° C or higher, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polyvalent carboxylic acid ester, and the surfactant (B) is at least one selected from the group consisting of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide. [2] The liquid coloring composition according to [1], wherein the fatty acid ester contains a triglyceride. [3] The liquid coloring composition according to [1] or [2], wherein the mass ratio (B) / (C) of the content of the surfactant (B) to the content of the colorant (C) is 0.01 to 2. [4] The liquid coloring composition according to any one of [1] to [3], which contains 1 to 300 parts by mass of the colorant (C) with respect to 100 parts by mass of the liquid dispersion medium (A). [5] The liquid coloring composition according to any one of [1] to [4], which contains 0.5 to 30 parts by mass of the surfactant (B) with respect to 100 parts by mass of the liquid dispersion medium (A). [6] A colored resin composition containing the liquid coloring composition according to any one of [1] to [5] and a diluting resin (D). [7] The colored resin composition according to [6], wherein the diluting resin (D) is at least one selected from the group consisting of a polycarbonate resin, an acrylic resin, a polyester resin, and a polyamide resin. [8] A molded body formed from the colored resin composition according to [7]. [Advantages of the Invention]

[0016] According to the present disclosure, there can be provided a liquid coloring composition which is excellent in the dispersibility, storage stability, and supply accuracy of a colorant, can be uniformly colored without impairing the appearance, mechanical properties, and moldability of a molded article when mixed with a diluent resin to form a molded article, and can reduce the variation in color difference between molded articles. Further, a colored resin composition using the same can provide a molded article excellent in appearance, mechanical properties, and moldability.

Embodiments for Carrying Out the Invention

[0017] Hereinafter, the present invention will be described in detail. Needless to say, other embodiments are also included in the scope of the present invention as long as they are consistent with the gist of the present invention. In addition, the numerical range specified using "~" in this specification shall include the numerical values described before and after "~" as the range of the lower limit value and the upper limit value. Here, "liquid" means being in a liquid state at 25°C. Unless otherwise noted, the various components appearing in this specification may each be used alone or in combination of two or more.

[0018] ≪Liquid Coloring Composition≫ The liquid coloring composition can be used as a liquid masterbatch for coloring a molded article. When molding a plastic molded article, the liquid coloring composition can be used by melt-kneading it with a diluent resin as a main component. The liquid coloring composition is a liquid coloring composition containing a liquid dispersion medium (A), a surfactant (B), and a colorant (C). The liquid dispersion medium (A) has a viscosity of 10,000 mPa·s or less at 25°C, a decomposition start temperature of 250°C or higher, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polyvalent carboxylic acid ester. The surfactant (B) is at least one selected from the group consisting of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide.

[0019] Thus, by using at least one selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides as the surfactant (B) and dispersing the colorant (C) in a specific liquid dispersion medium (A), a liquid coloring composition excellent in storage stability and supply accuracy can be obtained. Further, by mixing the obtained liquid coloring composition with a diluting resin (D) to form a molded article, it is possible to provide a liquid coloring composition capable of uniformly coloring the molded article without impairing the appearance, mechanical properties, and moldability of the molded article. Thereby, the obtained molded article is excellent in appearance, mechanical properties, and moldability.

[0020] <Liquid dispersion medium (A)> The liquid dispersion medium has the role of a dispersion medium for dispersing the colorant. The liquid coloring composition contains a liquid dispersion medium (A). The liquid dispersion medium (A) has a viscosity at 25°C of 10,000 mPa·s or less, a decomposition start temperature of 250°C or higher, and is at least one selected from the group consisting of aliphatic polyester resins, polyalkylene glycol resins, polyether ester resins, and aromatic polyvalent carboxylic acid esters.

[0021] The viscosity of the liquid dispersion medium (A) at 25°C is 10,000 mPa·s or less, preferably 10 to 7,000 mPa·s, and more preferably 20 to 5,000 mPa·s, from the viewpoints of the dispersibility of the colorant (C) and the supply accuracy of the liquid coloring composition. From the viewpoints of improving the supply accuracy and reducing the variation in color difference between the obtained molded articles, the viscosity of the liquid dispersion medium (A) at 25°C may be 600 mPa·s or less, 500 mPa·s or less, 200 mPa·s or less, or 100 mPa·s or less. The viscosity in this specification is a value measured using a B-type viscometer in accordance with JIS K7117-1.

[0022] In addition, from the viewpoints of the moldability and appearance of the molded article, the decomposition start temperature of the liquid dispersion medium (A) is 250°C or higher, preferably 260°C or higher, and more preferably 270°C or higher. The upper limit of the decomposition start temperature is not particularly limited, but from the viewpoint of the viscosity of the liquid dispersion medium (A), it is preferably 320°C or lower. The decomposition start temperature in this specification is the temperature at which 10% of the weight loss on heating occurs when the temperature is raised at a rate of 10°C / min using "STA7200" manufactured by Hitachi High-Tech Sciences Corporation.

[0023] The freezing point of the liquid dispersion medium (A) is preferably -5°C or lower, and more preferably -50°C to -10°C. The freezing point in this specification is the value measured according to JIS K0065.

[0024] The liquid dispersion medium (A) contains at least one selected from the group consisting of aliphatic polyester resins, polyalkylene glycol resins, polyether ester resins, and aromatic polyvalent carboxylic acid esters. From the viewpoint of compatibility with the diluent resin (D), when the diluent resin (D) is a polycarbonate resin, the liquid dispersion medium (A) is preferably an aliphatic polyester resin or an aromatic polyvalent carboxylic acid ester. When the diluent resin (D) is an acrylic resin or a polyamide resin, the liquid dispersion medium (A) is preferably a polyalkylene glycol resin or a polyether ester resin. When the diluent resin (D) is a polyester resin, the liquid dispersion medium (A) is preferably an aliphatic polyester resin, a polyalkylene glycol resin, or a polyether ester resin. Even in such a combination of the liquid dispersion medium (A) and the diluent resin (D), by using the surfactant (B), the dispersibility, storage stability, and supply accuracy of the liquid coloring composition can be further improved, the decrease in mechanical strength in the obtained molded article can be prevented, and the occurrence of variations in color difference between molded articles can be suppressed. Among them, when a polycarbonate resin is used as the diluent resin (D), it is usually difficult to obtain compatibility with the liquid coloring composition, but by using the surfactant (B), excellent effects can be exhibited.

[0025] [Aliphatic polyester resin] An aliphatic polyester resin is a polyester resin obtained by the reaction of an aliphatic polycarboxylic acid and a polyhydric alcohol.

[0026] The aliphatic polycarboxylic acid constituting the aliphatic polyester resin is not particularly limited as long as it is an aliphatic carboxylic acid having two or more carboxyl groups. Examples include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-hexanetricarboxylic acid, etc. These aliphatic carboxylic acids may be used alone or in combination of two or more.

[0027] The polyhydric alcohol constituting the aliphatic polyester resin is not particularly limited as long as it is an alcohol having two or more hydroxyl groups. Examples include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-octadecanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol. These may be used alone or in combination of two or more.

[0028] Specific examples of the aliphatic polyester resin include Adeka Sizer PN-7160 (manufactured by ADEKA, viscosity 150 mPa·s (25°C), freezing point -42°C, adipic acid polyester resin), Adeka Sizer PN-5090 (manufactured by ADEKA, viscosity 10,000 mPa·s (25°C), freezing point -10°C, adipic acid polyester resin), etc.

[0029] [Polyalkylene Glycol Resin] Polyalkylene glycol resins generally consist of alkylene glycols having repeating units with 1 to 6 carbon atoms, but various polyalkylene glycols can be used as long as the viscosity at 25 °C is 10,000 mPa·s or less. From the viewpoints of compatibility and water absorption, polyalkylene glycol resins having repeating units with 2 to 4 carbon atoms are preferred.

[0030] Specific examples of polyalkylene glycol resins include polyethylene glycol having 2 carbon atoms in the repeating unit, polypropylene glycol having 3 carbon atoms in the repeating unit, polybutylene glycol having 4 carbon atoms in the repeating unit, and the like.

[0031] Specific examples of polyalkylene glycol resins include PEG#300 (manufactured by NOF Corporation, viscosity 70 mPa·s (25 °C), polyethylene glycol), Unionol D-1200 (manufactured by NOF Corporation, viscosity 200 mPa·s (25 °C), polypropylene glycol), and the like.

[0032] [Polyether ester resin] The polyether ester resin is obtained by esterifying an aliphatic polyvalent carboxylic acid and an alkylene glycol, and the aforementioned aliphatic polyvalent carboxylic acid and the aforementioned alkylene glycol can be used.

[0033] Specific examples of the polyether ester resin include Adeka Sizer RS-107 (manufactured by ADEKA Corporation, viscosity 20 mPa·s (25 °C), freezing point -47 °C), Adeka Sizer RS-700 (manufactured by ADEKA Corporation, viscosity 30 mPa·s (25 °C), freezing point -53 °C), and the like.

[0034] [Aromatic polyvalent carboxylic acid ester] An aromatic polyvalent carboxylic acid ester is an ester compound obtained by the reaction of an aromatic polyvalent carboxylic acid and an alcohol. The aromatic polyvalent carboxylic acid ester may be either a low molecular weight compound or a high molecular weight compound. In one example, the aromatic polyvalent carboxylic acid ester may be an esterified product of an aromatic polyvalent carboxylic acid and a monoalcohol. In another example, the aromatic polyvalent carboxylic acid ester may be a polycondensate of an aromatic polyvalent carboxylic acid and a polyalcohol, or may be a polycondensate of an aromatic polyvalent carboxylic acid and a glycol.

[0035] The aromatic polyvalent carboxylic acid constituting the aromatic polyvalent carboxylic acid ester is not particularly limited as long as it is an aromatic carboxylic acid having two or more carboxyl groups. Examples thereof include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. These aliphatic carboxylic acids may be used alone or in combination of two or more.

[0036] The alcohol constituting the aromatic polyvalent carboxylic acid ester is not particularly limited. For example, (1) linear alkyl alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, triacontanol, etc.; (2) branched alkyl alcohols such as isopropanol, isobutanol, isohexanol, 2-ethylhexanol, isononanol, isodecanol, isododecanol, isotridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, isooctadecanol, isononadecanol, isoeicosanol, isoheneicosanol, isodocosanol, isotricosanol, isotetracosanol, 2-decyltetradecanol, isopentacosanol, isohexacosanol, isoheptacosanol, isooctacosanol, isononacosanol, isotriacontanol, etc.; (3) linear alkenyl alcohols such as tetradecenol, hexadecenol, heptadecenol, octadecenol, oleyl alcohol, nonadecenol, etc.; (4) branched alkenyl alcohols such as isohexadecenol, isooctadecenol, etc.; (5) cyclic alkyl alcohols such as cyclopentanol, cyclohexanol, etc. Further, polyhydric alcohols may be used. Examples of the polyhydric alcohols include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-octadecanediol, etc., and polyalkylene glycols such as diethylene glycol, dipropylene glycol, etc.In addition, examples include alkylene glycol alkyl ethers, polyalkylene glycol alkyl ethers, or acetate salts thereof, in which a hydroxy group excluding at least one hydroxy group of these polyhydric alcohols is substituted with an alkyl group. These may be used alone or in combination of two or more. Among them, monohydric aliphatic alcohols are preferred. Particularly preferred is a monohydric branched aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 to 22, 4 to 18, or 6 to 12, and it is even better if the number of carbon atoms of the monohydric branched aliphatic alkyl alcohol is within these ranges.

[0037] Specific examples of the aromatic polyvalent carboxylic acid ester include Adeka Stab UL-80 (manufactured by ADEKA, viscosity 450 mPa·s (25°C), 2-ethylhexyl pyromellitate), Adeka Stab UL-100 (manufactured by ADEKA, viscosity 176 mPa·s (25°C), alkyl pyromellitate), and the like.

[0038] The liquid dispersion medium (A) may be used alone or in combination of two or more of the above-mentioned various resins. Since the liquid dispersion medium (A) serves as a dispersion medium for the colorant (C), the liquid coloring composition may not contain components other than the resin as an additional liquid dispersion medium. For example, the liquid coloring composition may be a non-aqueous liquid coloring composition, and water may not be substantially contained in the total mass of the liquid coloring composition, for example, it may be less than 1% by mass.

[0039] <Surfactant (B)> The surfactant (B) is at least one selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides, and a fatty acid ester or a higher fatty acid metal salt is preferred. By containing these compounds, the liquid coloring composition can enhance the dispersibility of the colorant (C) and maintain storage stability. Further, by containing these compounds, the supply accuracy of the liquid coloring composition can be enhanced. By increasing the supply accuracy of the liquid coloring composition, it is possible to reduce the variation in color difference between molded articles in the obtained molded article. This makes it possible to more effectively confirm the phenomenon that even when no obvious difference in supply accuracy is observed in the liquid coloring composition, variation in color difference occurs between the obtained molded articles. Here, a surfactant is a compound having a hydrophilic group and a lipophilic group in its molecule, and means a substance having a function of reducing the surface tension by strong adsorption to the interface of substances that do not mix with each other and the orientation of molecules.

[0040] The surfactant (B) can also function as a dispersant in the liquid coloring composition. Here, a dispersant means a substance that interacts with a colorant and has a role of uniformly dispersing the colorant in a liquid dispersion medium.

[0041] By using the liquid dispersion medium (A) and the surfactant (B), it is possible to provide a liquid coloring composition having excellent dispersibility of the colorant (C), good storage stability and supply accuracy, and capable of uniformly coloring without impairing the appearance, mechanical properties, and moldability of the molded article when kneaded into the diluting resin (D). By the surfactant (B) containing at least one of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide, the supply accuracy can be further enhanced and the variation in color difference between molded articles can be reduced.

[0042] Since the surfactant (B) has a strong interaction with the colorant (C), the dispersibility of the colorant (C) can be further enhanced. Therefore, even when the colorant (C) is at least one of an inorganic pigment and a dye, it does not cause a decrease in the dispersibility of the liquid coloring composition, and the storage stability and supply accuracy can be improved. As a result, it is possible to provide a molded article with suppressed strength reduction, uniform coloring, and excellent appearance. Furthermore, the variation in color difference between the obtained molded articles can be reduced.

[0043] The variation in color difference between molded articles may occur between molded articles that are continuously molded by injection molding, extrusion molding, etc. when a molded article is molded using a colored resin composition containing a liquid coloring composition and a diluting resin (D). Also, in injection molding, although one part is molded per shot, a variation in color difference may occur between parts.

[0044] [Fatty acid ester] The fatty acid ester has a structure in which one or more fatty acids are ester-bonded to an alcohol. Examples of the alcohol include monohydric or polyhydric alcohols. Preferably, the number of oxygen atoms is 8 or less. The monohydric alcohol is preferably a higher alcohol having 6 or more carbon atoms, more preferably a higher alcohol having 10 or more carbon atoms. For example, myristyl alcohol, stearyl alcohol, and oleyl alcohol can be mentioned. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol; polyhydric alcohols having 3 or more valences such as glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, and sorbitol; Among them, glycerin, propylene glycol, pentaerythritol, and dipentaerythritol are preferable, and glycerin and dipentaerythritol are more preferable.

[0045] The fatty acids that make up the fatty acid ester are monocarboxylic acids having a carboxy group in the hydrocarbon chain. For example, saturated fatty acids such as caproic acid, caprylic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid; unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, plaidic acid, erucic acid, and ricinoleic acid; hydroxy fatty acids such as 12-hydroxy stearic acid; aliphatic dicarboxylic acids such as adipic acid; etc. are mentioned. Preferably, it is a fatty acid having 6 or more carbon atoms, more preferably a fatty acid having 13 or more carbon atoms. Among them, myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid, and 12-hydroxy stearic acid are particularly preferred, and stearic acid and 12-hydroxy stearic acid are particularly preferred. As the fatty acid ester, triglyceride is particularly preferred.

[0046] Triglyceride is an ester of fatty acid and glycerin. The carbon number of the fatty acid of the triglyceride is preferably 10 to 22, more preferably 12 to 20, and even more preferably 14 to 18. The three fatty acids that make up the triglyceride may be the same as each other, or partially or all may be different. Examples of the fatty acid of the triglyceride include long-chain fatty acids such as stearic acid, lauric acid, ricinoleic acid, octylic acid, montanic acid, palmitic acid, and their derivatives, and fatty acids having a hydroxy group are particularly preferred. Examples of the triglyceride include castor oil, coconut oil, olive oil, etc., and hydrogenated products thereof, and hydrogenated castor oil is particularly preferred.

[0047] Hydrogenated castor oil is a hydrogenated castor oil obtained by adding hydrogen to the unsaturated bond of castor oil, and is a triglyceride of 12-hydroxy stearic acid. Specific examples of hydrogenated castor oil include Kawaster CR (manufactured by Kawaken Fine Chemical Co., Ltd.).

[0048] The higher fatty acid metal salt is a metal salt of a higher fatty acid, preferably a non-alkali metal salt of a higher fatty acid. The number of carbon atoms in the fatty acid of the higher fatty acid metal salt is preferably 10 to 22, more preferably 12 to 20, and even more preferably 14 to 18. Examples of the fatty acid of the higher fatty acid metal salt include long-chain fatty acids such as stearic acid, lauric acid, ricinoleic acid, octylic acid, montanic acid, palmitic acid, and derivatives thereof. The fatty acid of the higher fatty acid metal salt may have a substituent such as a hydroxy group to enhance the adsorptivity to the colorant (C). Examples of the metal include lithium, magnesium, calcium, barium, zinc, etc. Among them, alkaline earth metals are preferred, and magnesium is more preferred. Magnesium stearate and its derivatives are preferred as the metal soap because of their good adsorptivity to the colorant (C), and magnesium 12-hydroxystearate is more preferred. Specific examples of the higher fatty acid metal salt include Sinacared SAK-MS-P (manufactured by San Ace Co., magnesium stearate), MS-6 (manufactured by Nitto Kasei Kogyo Co., magnesium 12-hydroxystearate), etc.

[0049] [Fatty acid amide] The fatty acid amide has a structure in which one or more fatty acids are amide-bonded to an amine. Examples of the amine include monovalent or polyvalent amines. The monovalent amine is preferably ammonia and an amine having 10 or more carbon atoms. For example, oleylamine and stearylamine can be mentioned. The polyvalent amine preferably has 3 or less nitrogen atoms. Among them, diamines having 6 or less carbon atoms such as ethylenediamine and hexamethylenediamine are preferred.

[0050] Examples of the fatty acid constituting the fatty acid amide include the above-mentioned fatty acids. Preferably, it is a long-chain fatty acid having 13 or more carbon atoms, more preferably stearic acid, 12-hydroxystearic acid, and erucic acid.

[0051] Examples of the fatty acid amide include aliphatic monocarboxylic acid amides such as lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, and hydroxystearic acid amide; N-substituted aliphatic monocarboxylic acid amides such as N-oleyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl oleic acid amide; aliphatic dicarboxylic acid amides such as methylene bisstearic acid amide and ethylene bisstearic acid amide; N,N'-ethylene-bis-oleylamide; N,N'-ethylene bisstearic acid amide; N,N'-methylene bisstearic acid amide. Preferably, they are stearic acid amide, erucic acid amide, and N,N'-ethylene bisstearic acid amide.

[0052] From the viewpoint of the dispersibility of the colorant (C) and the mechanical properties due to the compatibility with the diluting resin (D), the acid value of the surfactant (B) is preferably 180 mgKOH / g or less, more preferably 140 mgKOH / g or less.

[0053] From the viewpoint of the dispersibility of the colorant (C) and the mechanical properties due to the compatibility with the diluting resin (D), for example, since the decrease in the heat distortion temperature can be suppressed, the amine value of the surfactant (B) is preferably 180 mgKOH / g or less, more preferably 140 mgKOH / g or less.

[0054] From the viewpoint of the mechanical properties due to the compatibility between the colorant (C) and the diluting resin (D), for example, since the decrease in the heat distortion temperature can be suppressed, the content of the surfactant (B) is preferably 0.5 part by mass or more, more preferably 0.8 part by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of the liquid dispersion medium (A). Also, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. When the surfactant (B) contains two or more of fatty acid esters, higher fatty acid metal salts, and fatty acid amides, the total amount thereof is preferably within the above range.

[0055] The liquid coloring composition may further contain other surfactants in addition to fatty acid esters, metal salts of higher fatty acids, fatty acid amides, or combinations thereof. Further, the liquid coloring composition may further contain a dispersant.

[0056] A dispersant-type acrylic resin can be used as the dispersant. The acrylic resin is a polymer containing structural units derived from (meth)acrylic monomers, and examples thereof include (meth)acrylic resins and styrene-acrylic resins. The acrylic resin preferably has at least one polymer block composed of structural units derived from (meth)acrylic monomers.

[0057] From the viewpoints of solubility in the liquid dispersion medium (A) and physical properties of the diluting resin (D), the weight average molecular weight of the acrylic resin is preferably 500 to 20,000, more preferably 1,000 to 15,000. In this specification, the weight average molecular weight is a value measured by gel permeation chromatography (GPC method) (a measured value obtained using polystyrene as a standard substance and tetrahydrofuran as an eluent).

[0058] Examples of the (meth)acrylic monomer constituting the acrylic resin include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and other (meth)acrylates, (poly)ethylene glycol, (poly)propylene glycol, mono(meth)acrylate having a (poly)alkylene glycol group such as (poly)butylene glycol, and (meth)acrylic acid or its ester.

[0059] The styrene-acrylic resin is a copolymer of a styrene monomer and the above (meth)acrylic monomer. Examples of the styrene monomer include styrene, α-methylstyrene and the like. The styrene-acrylic resin preferably has a styrene polymer block and a (meth)acrylic polymer block.

[0060] The acrylic resin may have a functional group. Examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group and the like.

[0061] Specific examples of the acrylic resin include Alphon UP-1000 (manufactured by Toagosei Co., Ltd., weight-average molecular weight 3,000, acrylic resin), Alphon UP-2170 (manufactured by Toagosei Co., Ltd., weight-average molecular weight 14,000, styrene-acrylic resin), and the like.

[0062] The phosphate ester compound is a surfactant and can also be used as a dispersant. Examples of the phosphate ester compound include alkyl phosphates such as tributyl phosphate, trioctyl phosphate, tris(β-chloroethyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, etc., phenyl phosphates such as triphenyl phosphate, tricresyl phosphate, tris(i-propylphenyl) phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, etc., alkyl polyoxyethylene phosphate esters such as tributoxyethyl phosphate, alkylphenol polyoxyethylene phosphate esters, and neutral salts thereof such as sodium, potassium, ammonia, and amines. These phosphate ester compounds may have an acid value or an amine value. These phosphate ester compounds may be used alone or in combination of two or more. From the viewpoints of the dispersibility and storage stability of the colorant (C), the phosphate ester compound is preferably an alkyl polyoxyethylene phosphate ester or an alkylphenol polyoxyethylene phosphate ester having an acid value or an amine value.

[0063] Specific examples of the phosphate ester compound include Adeka Resope PP-70 (manufactured by ADEKA Corporation, phosphate ester), Disper BYK-102 (manufactured by BYK-Chemie GmbH, acid value 101 mg KOH / g), Disper BYK-145 (manufactured by BYK-Chemie GmbH, acid value 76 mg KOH / g, amine value 71 mg KOH / g), and the like.

[0064] In addition to fatty acid esters, higher fatty acid metal salts, fatty acid amides, or combinations thereof, when other surfactants and dispersants are further used, the total amount of other surfactants and dispersants may be 0 to 50 parts by mass, 0 to 20 parts by mass, or 0 to 10 parts by mass with respect to 100 parts by mass of surfactant (B). Even when other surfactants and dispersants are not used, the effects of the liquid coloring composition can be expected by using fatty acid esters, higher fatty acid metal salts, fatty acid amides, or combinations thereof, and the effects of the resulting molded article can also be expected.

[0065] <Colorant (C)> The colorant (C) is not particularly limited, and generally used dyes, pigments, etc. can be used. Examples of the dyes include methine dyes, perinone dyes, anthraquinone dyes, etc. Examples of the pigments include inorganic pigments such as titanium oxide, chrome titanium yellow, cadmium yellow, ultramarine blue, carbon black, etc., or organic pigments such as azo pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, etc. Titanium oxide is preferably of the rutile type rather than the anatase type because the rutile type has lower activity and is less likely to induce resin deterioration. From the viewpoint of heat resistance, pigments are preferred, and from the viewpoint of transparency, dyes are preferred.

[0066] Examples of the above methine dyes include C.I. Solvent Yellow 93, 179, etc. Examples of the above perinone dyes include C.I. Solvent Red 135, 179. Examples of the above anthraquinone dyes include C.I. Solvent Red 52, 151, Solvent Violet 13, 36, Solvent Blue 97, etc. Incidentally, "C.I." means Color Index.

[0067] Specific examples of the above methine dyes include, for example, Macrolex Yellow 3G-FG (manufactured by Lanxess, Solvent Yellow 93), Macrolex Yellow 6G (manufactured by Lanxess, Solvent Yellow 179), and the like. Specific examples of the above perinone dyes include, for example, Macrolex Red EG GRAN (manufactured by Lanxess, Solvent Red 135), Macrolex Red E2G GRAN (manufactured by Lanxess, Solvent Red 179), and the like. Specific examples of the above anthraquinone dyes include, for example, Sumipra Red HL5B (manufactured by Sumitomo Chemical Tex, Solvent Red 52), Sumipra Red HL2B (manufactured by Sumitomo Chemical Tex, Solvent Red 151), Macrolex Violet B-FG (manufactured by Lanxess, Solvent Violet 13), Macrolex Violet 3R-FG (manufactured by Lanxess, Solvent Violet 36), Macrolex Blue RR GRAN (manufactured by Lanxess, Solvent Blue 97), and the like.

[0068] Examples of the above inorganic pigments include, for example, C.I. Pigment White 6, Pigment Brown 24, Pigment Red 101, Pigment Blue 29, Pigment Black 7, and the like. Examples of the above organic pigments include the following organic pigments. Examples of the above azo pigments include, for example, C.I. Pigment Yellow 180, 181, Pigment Orange 64, Pigment Red 144, 166, 214, 221, and the like. Examples of the above quinacridone pigments include, for example, C.I. Pigment Violet 19, Pigment Red 122, and the like. Examples of the above perylene pigments include, for example, C.I. Pigment Red 149, 178, and the like. Examples of the above diketopyrrolopyrrole pigments include, for example, C.I. Pigment Red 254, and the like. Examples of the above phthalocyanine pigments include, for example, C.I. Pigment Blue 15:1, 15:3, Pigment Green 7, 36, and the like. These colorants (C) may be used alone or in combination of two or more.

[0069] Specific examples of the inorganic pigment include, for example, Typecoat PF-740 (manufactured by Ishihara Sangyo Co., Ltd., rutile type titanium oxide, Pigment White 6), Tomatec 42-118A (manufactured by Toa Kankyo Material Technology Co., Ltd., Pigment Brown 24), Todacolor 120ED (manufactured by Toda Kogyo Co., Ltd., Pigment Red 101), Ultramarine No1500 (manufactured by Daiichi Kasei Kogyo Co., Ltd., Pigment Blue 29), and the like. Specific examples of the organic pigment include, for example, the following. Specific examples of the azo pigment include, for example, PV Fast Yellow HG (manufactured by Clariant, Pigment Yellow 180), PV Fast Yellow H3R (manufactured by Clariant, Pigment Yellow 181), Chromophthal Orange K2960 (manufactured by BASF, Pigment Orange 64), Chromophthal Red K3890FP (manufactured by BASF, Pigment Red 144), Chromophthal Scarlet K3540 (manufactured by BASF, Pigment Red 166), Chromophthal Red K3900 (manufactured by BASF, Pigment Red 214), Chromophthal Red K4035 (manufactured by BASF, Pigment Red 221), and the like. Specific examples of the quinacridone pigment include, for example, PV Fast Red E4G (manufactured by Clariant, Pigment Violet 19), PV Fast Pink E-01 (manufactured by Clariant, Pigment Red 122), and the like. Specific examples of the perylene pigment include, for example, Parioxene Red K3580 (manufactured by BASF, Pigment Red 149), Parioxene Red K3911 (manufactured by BASF, Pigment Red 178), and the like. Specific examples of the diketopyrrolopyrrole pigment include, for example, Irgazin Red K3840 (manufactured by BASF, Pigment Red 254), and the like. Specific examples of the phthalocyanine pigment include, for example, Lionol Blue CB7801 (manufactured by Toyo Color Co., Ltd., Pigment Blue 15:1), Lionol Blue FG7351 (manufactured by Toyo Color Co., Ltd., Pigment Blue 15:3), Lionol Green Y-102 (manufactured by Toyo Color Co., Ltd., Pigment Green 7), Lionol Green 6Y-501 (manufactured by Toyo Color Co., Ltd., Pigment Green 36), and the like.

[0070] From the viewpoints of the dispersibility of the colorant (C) and the supply accuracy of the liquid coloring composition, the content of the colorant (C) in the liquid coloring composition is preferably 1 to 300 parts by mass, more preferably 5 to 250 parts by mass, based on 100 parts by mass of the liquid dispersion medium (A).

[0071] When the colorant (C) is an inorganic pigment, the dispersibility can be further improved by including at least one of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide as the surfactant (B), and hydrogenated castor oil is more preferable among them. When the colorant (C) is a dye, the dispersibility can be further improved by including at least one of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide as the surfactant (B), and hydrogenated castor oil is more preferable among them. When the colorant (C) is an organic pigment, the dispersibility can be further improved by including at least one of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide as the surfactant (B), but it is preferable to use an acrylic resin as a dispersant from the viewpoint of further improving the dispersibility. By being these surfactants (B), the adsorptivity to the colorant (C) is further improved, the sedimentation stability of the colorant (C) becomes better, and it becomes possible to achieve both the dispersibility and the storage stability of the liquid coloring composition.

[0072] From the viewpoints of the dispersibility and the storage stability of the colorant (C), the content ratio (B) / (C) of the surfactant (B) to the content of the colorant (C) is preferably 0.01 to 2, more preferably 0.05 to 1, and still more preferably 0.1 to 0.5.

[0073] From the viewpoints of the dispersibility and the storage stability, the total of the liquid dispersion medium (A), the surfactant (B), and the colorant (C) in the liquid coloring composition is preferably 50 to 100 parts by mass, more preferably 70 to 100 parts by mass, and still more preferably 80 to 100 parts by mass, based on 100 parts by mass of the liquid coloring composition.

[0074] <Other Additives> The liquid coloring composition may contain other optional polymers, antistatic agents, defoamers, matting agents, fluorescent brighteners, stabilizers, antioxidants, viscosity modifiers, and other additives. Also, within a range that does not interfere with the effects of the present invention, it may contain a liquid dispersion medium other than the liquid dispersion medium (A), a surfactant other than the surfactant (B), and a dispersant.

[0075] <Method for Producing Liquid Coloring Composition> The method for producing the liquid coloring composition is not particularly limited. For example, the liquid dispersion medium (A), the surfactant (B), the coloring agent (C), and further other additives as required are added, mixed with a Henschel mixer, tumbler, disper, etc., and dispersed using a Silver Son mixer (manufactured by Silver Son Co., Ltd.) etc. to obtain the liquid coloring composition. As the dispersion device, in addition to the above, any device such as a kneader, roll mill, ball mill, sand mill, etc. can be used. It is preferable to use a bead mill, Silver Son mixer, or roll mill because of easy molding processing and excellent dispersibility.

[0076] ≪Colored Resin Composition≫ The colored resin composition contains the liquid coloring composition and the diluting resin (D) described above, and is used for molding a molded article. The diluting resin (D) is the main resin to be colored by the liquid coloring composition when molding a molded article, and becomes the main component of the molded article. Mainly thermoplastic resins are used and are appropriately selected according to the use of the molded article.

[0077] The content of the liquid coloring composition is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, based on 100 parts by mass of the diluting resin (D). Also, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less. Thereby, it can be made to have more excellent processability and mechanical properties. Furthermore, a molded article excellent in appearance without color unevenness or generation of coloring agent aggregates in the molded article can be obtained.

[0078] The resin colored by the liquid coloring composition is not particularly limited. Examples of the diluent resin (D) include polycarbonate resin, acrylic resin, polyester resin, polyamide resin, polyvinyl chloride resin, polystyrene resin, cycloolefin copolymer (COC), and the like. By using the liquid coloring composition of the invention, it can also be suitably used for coloring polycarbonate resin, acrylic resin, polyester resin, and polyamide resin, which are generally difficult to be uniformly colored. As the acrylic resin, polymethyl methacrylate resin is preferred.

[0079] [Polycarbonate resin] The polycarbonate resin can be easily produced by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or a carbonic acid diester. The reaction can be obtained by a known reaction, for example, in the case of using phosgene, by the interfacial method, and in the case of using a carbonic acid diester, by the transesterification method of reacting in a molten state.

[0080] Examples of the aromatic dihydroxy compound include bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. These may be used alone or in admixture of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyls may be used in admixture. Further, an aromatic polycarbonate resin having a branch and using a polyfunctional compound such as phloroglucin in combination may also be used.

[0081] Examples of the carbonate precursor to be reacted with the aromatic dihydroxy compound include diaryl carbonates such as phosgene, diphenyl carbonate, ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0082] The viscosity-average molecular weight of the polycarbonate resin is preferably from 15,000 to 30,000, more preferably from 16,000 to 27,000. The viscosity-average molecular weight in this specification is a value converted from the solution viscosity measured at a temperature of 25 ° C using methylene chloride as a solvent.

[0083] Specific examples of the polycarbonate resin include Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity-average molecular weight 16,000), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity-average molecular weight 23,000), Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity-average molecular weight 27,000), and the like.

[0084] [Acrylic resin] The acrylic resin can be obtained by polymerizing the (meth)acrylic monomers exemplified below. Examples of the monomers include (meth)acrylic monomers having an alkyl group, (meth)acrylic monomers having a hydroxyl group, (meth)acrylic monomers having a carboxyl group, (meth)acrylic monomers having a glycidyl group, vinyl esters such as vinyl acetate and vinyl propionate, maleic anhydride, vinyl ether, styrene, and the like. In this specification, "(meth)acrylic" means "acrylic and / or methacrylic", and "(meth)acrylate" means "acrylate and / or methacrylate", respectively. Specifically, a polymethyl methacrylate (PMMA) resin is preferred.

[0085] [Polyester resin] A polyester resin can be obtained by polymerizing a carboxylic acid component (a compound having a carboxyl group) and a hydroxyl group component (a compound having a hydroxyl group).

[0086] Examples of the carboxylic acid component constituting the polyester resin include benzoic acid, p-tert-butylbenzoic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, tetrachlorophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, ε-caprolactone, and the like.

[0087] Examples of the hydroxyl group component constituting the polyester resin include diols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, 3-methylpentanediol, 1,4-cyclohexanedimethanol, and polyfunctional alcohols having three or more hydroxyl groups such as trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, and dipentaerythritol.

[0088] [Polyamide resin] A polyamide resin can be obtained, for example, by reacting the above-described carboxylic acid component with a compound having two or more amino groups. For example, it can be obtained by subjecting the carboxylic acid component and a compound (Am) having two or more amino groups to a dehydration condensation reaction.

[0089] As the compound (Am) having two or more amino groups, known compounds can be used. For example, aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diaminoalcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecane-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine can be mentioned.

[0090] The diluting resin (D) may be used alone or in combination of two or more of the above-described various resins. When the diluting resin (D) is a polycarbonate resin, an acrylic resin, a polyester resin, and a polyamide resin, a molded article having high transparency and excellent mechanical strength can be provided. By including the liquid dispersion medium (A) and the surfactant (B) whose resin types are specified in the liquid coloring composition, the compatibility between the liquid coloring composition and the diluting resin (D) is enhanced, and a decrease in the transparency and mechanical strength of the resulting molded article can be prevented. In particular, since the microscopic supply accuracy of the liquid coloring composition is improved, color unevenness within the molded article and variations in color difference between molded articles can be reduced in the resulting molded article. For example, the content of the colorant (C) in the colored resin composition or the molded article formed therefrom can be 0.01 to 10% by mass, 0.03 to 5% by mass, or 0.05 to 3% by mass. Further, due to such an action, color unevenness and variations can be reduced even at a low concentration of the colorant (C) in a molded article having high transparency. For example, the content of the colorant (C) in the colored resin composition or the molded article formed therefrom can be 0.01 to 1% by mass, 0.03 to 0.5% by mass, or 0.05 to 0.1% by mass. Even when the diluting resin (D) is a polycarbonate resin and an acrylic resin, particularly a polycarbonate resin and a methyl methacrylate resin, uniform transparent color coloring can be obtained.

[0091] Since the liquid coloring composition contains the liquid medium (A) with a specific resin type and the surfactant (B), even if it contains the colorant (C) at a high concentration, the dispersibility, storage stability, and supply accuracy can be improved. By using the liquid coloring composition containing the high-concentration colorant (C), the contents of the liquid medium (A) and the surfactant (B) can be relatively reduced in the obtained molded body, and the mechanical strength of the molded body can be further increased. For example, the colorant (C) may be 0.1 to 500 parts by mass, 1 to 300 parts by mass, or 10 to 120 parts by mass with respect to 100 parts by mass of the liquid medium (A). Further, in this case, the surfactant (B) may be used in an appropriate amount with respect to the colorant (C). For example, the surfactant (B) may be 0.01 part by mass to 2, 0.05 to 1 part by mass, or 0.1 to 0.5 part by mass with respect to 100 parts by mass of the colorant (C).

[0092] <Method for producing colored resin composition> The method for producing the colored resin composition is not particularly limited. For example, the colored resin composition, the diluting resin (D), and further various additives and colorants are added as necessary, and after mixing with a Henschel mixer, tumbler, disper, etc., it is melt-kneaded with a batch kneader such as a kneader, roll mill, super mixer, high-speed mixer, ball mill, sand mill, attritor, Banbury mixer, single-screw extruder, twin-screw extruder, rotor-type twin-screw kneader, etc. to obtain a pellet-shaped, powder-shaped, granular or bead-shaped colored resin composition. Since the molding process is easy, it is preferable to obtain a pellet-shaped colored resin composition with a twin-screw extruder. As a production method for making the colored resin composition into a pellet shape, a general method such as granulating using a pelletizer after extrusion processing by an extruder can be adopted. Further, by pulverizing these pellet-shaped molded bodies, a powder-shaped or granular colored resin composition can be obtained. Alternatively, without passing through the pellet-shaped colored resin composition, a molded body may be directly molded from the colored resin composition obtained by melt-kneading the colored resin composition and the diluting resin (D).

[0093] ≪Molded body≫ The molded article is formed from the colored resin composition described above. The molding method for obtaining the molded article by molding the colored resin composition is not particularly limited. By using the liquid coloring composition, it is possible to uniformly color without degrading the mechanical properties of the diluent resin (D) regardless of the molding method such as injection molding or extrusion molding. Therefore, even a molded article with a low coloring agent concentration such as a transparent color can be made into a uniformly colored molded article, and appearance defects such as color unevenness can be suppressed. For example, even when the content of the coloring agent (C) is as low as 5 ppm or less, such as in a food packaging sheet using recycled PET resin, uniform coloring can be achieved.

[0094] Specifically, for example, (Method 1) a method of melting and kneading a colored resin composition and pellets of the diluent resin (D) to obtain a colored resin composition and then obtaining a molded article; (Method 2) a method of melting and kneading a colored resin composition and the diluent resin (D), using the obtained colored resin composition in the form of a solid masterbatch or the like, and further melting and kneading it together with pellets of the diluent resin (D) to obtain a molded article; (Method 3) a method of melting and kneading a colored resin composition and the diluent resin (D) to form a compound, using the compound once made into pellets or the like and directly melting and kneading it to obtain a molded article, etc. can be mentioned.

Examples

[0095] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. In the examples, parts and % represent parts by mass and mass % respectively unless otherwise specified. The blanks in the table indicate that they are not blended.

[0096] The materials used in the examples and comparative examples are shown below. <Liquid dispersion medium (A), etc.> A-1: Adeka Sizer PN-7160 (manufactured by ADEKA, aliphatic polyester resin, viscosity at 25°C: 150 mPa·s, decomposition start temperature: 278°C) A-2: Adeka Sizer PN-5090 (manufactured by ADEKA, aliphatic polyester resin, viscosity at 25°C: 10,000 mPa·s, decomposition start temperature: 295°C) A-3: Unionol D-1200 (manufactured by NOF Corporation, polyalkylene glycol resin, viscosity at 25°C: 200 mPa·s, decomposition start temperature: 276°C) A-4: Adeka Sizer UL-80 (manufactured by ADEKA, aromatic polycarboxylic acid ester, viscosity at 25°C: 450 mPa·s, decomposition start temperature: 310°C) A-5: Adeka Sizer RS-700 (manufactured by ADEKA, polyether ester resin, viscosity at 25°C: 30 mPa·s, decomposition start temperature: 300°C) A’-6: BIOCIZER (manufactured by Riken Vitamin Co., Ltd., acetylated monoglyceride, viscosity at 25°C: 30 mPa·s, decomposition start temperature: 228°C)

[0097] <Surfactant (B), etc.> B-1: Kawaster CR (manufactured by Kawa Ken Fine Chemical Co., Ltd., surfactant: hydrogenated castor oil) B-2: MS-6 (manufactured by Nitto Kasei Kogyo Co., Ltd., surfactant: magnesium 12-hydroxystearate) B-3: Shinakared SAK-CS-P (manufactured by Sun Ace Co., Ltd., surfactant: magnesium stearate) B’-4: DISPERBYK-145 (manufactured by BYK Japan K.K., surfactant: phosphate ester compound, acid value: 76 mgKOH / g, amine value 71 mgKOH / g) B’-5: ARUFON UP-1000 (manufactured by Toagosei Co., Ltd., acrylic resin) B’-6: Yumex 1010 (manufactured by Sanyo Chemical Industries, Ltd., maleic anhydride-modified PP resin, acid value: 52 mKOH / g)

[0098] <Colorant (C)> C-1: Macrolex Violet B (manufactured by Bayer, anthraquinone dye, Solvent Violet 13) C-2: Macrolex Red E2G GRAN (manufactured by Lanxess, perinone dye, Solvent Red 179) C-3: Type Tape CR-60 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, Pigment White 6) C-4: Parion Red K3911 (manufactured by BASF, perylene pigment, Pigment Red 178) C-5: #45L (manufactured by Mitsubishi Chemical Corporation, carbon black, Pigment Black 7)

[0099] <Diluent Resin (D)> D-1: Iupilon H-4000 (polycarbonate resin (PC), manufactured by Mitsubishi Engineering-Plastics Corporation) D-2: Acrypet VH (acrylic resin, polymethyl methacrylate resin (PMMA), manufactured by Mitsubishi Chemical Corporation) D-3: Polyester MA-2101M (polyester resin (PET), manufactured by Unitika Ltd.) D-4: Amilan CM3001-N (polyamide resin (PA), manufactured by Toray Industries, Inc.)

[0100] [Example 1] <Production of Liquid Coloring Composition (X-1)> 100 parts by mass of liquid dispersion medium (A-1), 1 part by mass of surfactant (B-1), and 10 parts by mass of colorant (C-1) were mixed and dispersed with a bead mill to obtain a liquid coloring composition (X-1).

[0101] [Examples 2 to 23] <Production of Liquid Coloring Compositions (X-2 to 23)> Liquid coloring compositions (X-2 to 23) were each produced in the same manner as the liquid coloring composition (X-1), except that the materials and contents (parts by mass) shown in Table 1 were changed respectively.

[0102] [Comparative Example 1] (Production of Liquid Coloring Composition (Y-1)) 100 parts by mass of liquid dispersion medium (A-1) and 25 parts by mass of colorant (C-1) were mixed and dispersed with a bead mill, but a liquid resin composition (Y-1) could not be obtained because of high viscosity.

[0103] [Comparative Examples 2 to 6] Liquid coloring compositions (Y-2 to Y-6) were each produced in the same manner as the liquid coloring composition (X-1), except that the materials and contents (parts by mass) shown in Table 1 were changed respectively.

[0104] <Evaluation of Liquid Coloring Composition> The dispersibility, storage stability, and supply accuracy of the obtained liquid coloring compositions were evaluated by the following methods. The results are shown in Table 1.

[0105] <Dispersibility Evaluation> In accordance with JIS K5600-2-5, using a 100 μm gauge, the point (dense point) at which distinct spots began to appear in the liquid coloring composition was observed, and evaluation was carried out according to the following criteria. [Evaluation Criteria] +++: Dense point ≦ 30 μm or less, very good ++: 30 μm < dense point ≦ 50 μm, good +: 50 μm < dense point ≦ 70 μm, practical NG: 70 μm < dense point, not practical

[0106] <Storage Stability Evaluation> For storage stability, the obtained liquid coloring composition was allowed to stand for 30 days, and the separation and sedimentation of the colorant (C) in the liquid coloring composition were visually confirmed, and evaluation was carried out according to the following criteria based on sedimentation stability. [Evaluation Criteria] +++: No separation or sedimentation, very good ++: Slight separation and sedimentation, but becomes uniform when stirred, good +: Separation and sedimentation, but becomes uniform when stirred, practical NG: Separation and sedimentation, does not become uniform even when stirred, not practical

[0107] <Supply Accuracy> The obtained liquid coloring composition was supplied at a flow rate of 10 mL / min for 10 minutes using a tube color roller pump RP-NBC (manufactured by Sanyo Technos Co., Ltd.) and a high-strength silicone tube with a tube size of 1.6 mm × 3.2 mm. The average value of the discharge amount was calculated every 10 seconds, and the discharge amount Q x furthest from the set value during the 10-minute supply time: Q 0(=10 mL / min) ratio Qx / Q 0 From the value of, the supply accuracy was evaluated according to the following criteria. [Evaluation Criteria] +++: 0.9 ≤ Qx / Q 0 ≤ 1.1, very good ++: 0.85 ≤ Qx / Q 0 < 0.9 or 1.1 < Qx / Q 0 ≤ 1.15, good +: 0.8 ≤ Qx / Q 0 < 0.85 or 1.15 < Qx / Q 0 ≤ 1.2, practical NG: Qx / Q 0 < 0.8 or 1.2 < Qx / Q 0 , unpractical

[0108]

Table 1-1

[0109]

Table 1-2

[0110] [Example 24] <Manufacture of Colored Resin Composition> 1 part by mass of liquid coloring composition (X-1) and 100 parts by mass of diluting resin (D-1) were mixed and kneaded at a kneading temperature of 280°C and a screw rotation speed of 200 rpm using a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX25αIII) to obtain a colored resin composition (Z-1).

[0111] [Examples 25 to 49, Comparative Examples 7 to 11] Colored resin compositions (Z-2 to 30) were each manufactured in the same manner as in Example 24, except that the materials and contents (parts by mass) shown in Table 2 were changed respectively.

[0112] [Comparative Example 11] 0.1 part by mass of coloring agent (C-1) and 100 parts by mass of diluting resin (D-1) were mixed and kneaded at 280 °C using a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX25αIII) to obtain a colored resin composition (Z-31).

[0113] <Evaluation of Colored Resin Composition> The processability, color unevenness, appearance, and mechanical properties of the obtained colored resin composition were evaluated by the following methods. The results are shown in Table 2.

[0114] <Processability> The discharge amount (Q 0 ) when extruding only the diluting resin (D) and the discharge amount (Q x ) of the colored resin composition when adding the liquid coloring composition were used to calculate the ratio (Q x / Q 0 ). Evaluation was carried out according to the following criteria. The higher the value of Q x / Q 0 , the less the change in discharge due to the addition of the liquid coloring composition, and it can be said that the processability is good. [Evaluation Criteria] +++: Q x / Q 0 ≥0.95, very good ++: 0.90 ≤ Q x / Q 0 < 0.95, good +: 0.85 ≤ Q x / Q 0 < 0.90, practical NG: Q x / Q 0 < 0.85, unpractical

[0115] <Color Unevenness> Using the obtained colored resin composition, 10 plates of 150 mm × 130 mm × 2 mm were produced with an injection molding machine (manufactured by Toshiba Machine Co., Ltd., injection pressure 100 t). Five plates molded from the 6th to the 10th were visually evaluated according to the following criteria. [Evaluation Criteria] +++: There is no color unevenness in all 5 plates, very good ++: There is 1 plate with color unevenness confirmed, good +: 2 plates with visible color unevenness, practical NG: 3 or more plates with visible color unevenness, not practical

[0116] <Appearance> Observe the surfaces of the 5 plates used for color unevenness evaluation, count the number of plates where bubbles or flash (volatile components generated during molding appearing on the surface of the molded body) can be confirmed, and evaluate according to the following criteria. [Evaluation Criteria] +++: No bubbles or flash on all 5 plates, very good ++: 1 plate with bubbles or flash can be confirmed, good +: 2 plates with bubbles or flash can be confirmed, practical NG: 3 or more plates with bubbles or flash can be confirmed, not practical

[0117] <Shot - to - shot Variation> Using the obtained colored resin composition, 50 plates of 150 mm × 130 mm × 2 mm were produced with an injection molding machine (manufactured by Toshiba Machine Co., injection pressure 100t). The color difference (ΔE) of the plates from the 10th shot to the 49th shot was measured using a spectrocolorimeter 36dG (manufactured by Konica Minolta) with the 50th shot plate as the standard, and evaluated according to the following criteria. [Evaluation Criteria] +++: ΔE ≤ 0.3 for all plates, very good ++: 5 or fewer plates with ΔE > 0.3, good +: 10 or fewer plates with ΔE > 0.3, practical NG: 15 or more plates with ΔE > 0.3, not practical

[0118] <Mechanical Properties> Using the obtained colored resin composition, multi - purpose test pieces of 80 mm in length × 10 mm in width × 4 mm in height were molded, and the heat distortion temperature at a load of 1.80 MPa was measured according to JIS K7191 - 2. The heat distortion temperature (T 0 ) of the uncolored diluted resin (D) and the heat distortion temperature (T x ) of the colored resin composition after coloring, and their ratio (T x / T0 ) was calculated and evaluated according to the following criteria. T x / T 0 The higher the value of, the less the decrease in mechanical properties due to the liquid coloring composition, and it can be said to be good. [Evaluation Criteria] +++: T x / T 0 ≧0.95, very good ++: 0.90 ≦ T x / T 0 < 0.95, good +: 0.85 ≦ T x / T 0 < 0.90, practical NG: T x / T 0 < 0.85, not practical

[0119]

Table 2

[0120] As shown in Tables 1 and 2, the liquid coloring composition of the present disclosure is excellent in dispersibility, storage stability, and supply accuracy. Furthermore, by using the liquid coloring composition, a molded article excellent in color unevenness and appearance can be obtained without deteriorating the processability and mechanical properties of the diluted resin (D), and the variation between shots of the molded article was also reduced. By using the liquid coloring composition of the present disclosure, even in the coloring of polycarbonate resin, acrylic resin, polyester resin, and polyamide resin, which are generally difficult to color uniformly, a molded article without color unevenness, excellent in appearance, and having good mechanical properties can be molded. It was confirmed that there was. In Comparative Example 1, the viscosity was high and a liquid coloring composition could not be obtained. In Comparative Example 3, the dispersibility of the liquid coloring composition was poor, and in neither case could a molded article be molded.

Claims

1. A liquid coloring composition for a molded body, comprising a liquid dispersion medium (A), a surfactant (B), and a colorant (C), the liquid dispersion medium (A) has a viscosity at 25° C. of 10,000 mPa s or less and a decomposition onset temperature of 250° C. or more, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polyvalent carboxylate ester; The surfactant (B) is at least one selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides. A liquid coloring composition for moldings.

2. A liquid coloring composition comprising a liquid dispersion medium (A), a surfactant (B), and a colorant (C), the total amount of the liquid dispersion medium (A), the surfactant (B), and the colorant (C) is 50 to 100 parts by mass with respect to 100 parts by mass of the liquid coloring composition; the liquid dispersion medium (A) has a viscosity at 25° C. of 10,000 mPa s or less and a decomposition onset temperature of 250° C. or more, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polyvalent carboxylate ester; The surfactant (B) is at least one selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides. A liquid coloring composition.

3. The liquid coloring composition according to claim 1 or 2, wherein the fatty acid ester comprises a triglyceride.

4. 3. The liquid colored composition according to claim 1, wherein the mass ratio (B) / (C) of the content of the surfactant (B) to the content of the colorant (C) is 0.01 to 2.

5. The colorant (C) is contained in an amount of 1 to 300 parts by mass relative to 100 parts by mass of the liquid dispersion medium (A); The liquid coloring composition according to claim 1 or 2.

6. The surfactant (B) is contained in an amount of 0.5 to 30 parts by mass relative to 100 parts by mass of the liquid dispersion medium (A), The liquid coloring composition according to claim 1 or 2.

7. A colored resin composition comprising the liquid colored composition according to claim 1 and a diluent resin (D).

8. The diluent resin (D) is at least one selected from the group consisting of polycarbonate resins, acrylic resins, polyester resins, and polyamide resins. The colored resin composition according to claim 7.

9. A liquid coloring composition and a diluent resin (D), wherein the liquid coloring composition is 10 parts by mass or less per 100 parts by mass of the diluent resin (D), The liquid coloring composition contains a liquid dispersion medium (A), a surfactant (B), and a colorant (C), the liquid dispersion medium (A) has a viscosity at 25° C. of 10,000 mPa s or less and a decomposition onset temperature of 250° C. or more, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polyvalent carboxylate ester; The colored resin composition, wherein the surfactant (B) is at least one selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides.

10. The diluent resin (D) is at least one selected from the group consisting of polycarbonate resin, acrylic resin, polyester resin, and polyamide resin. The colored resin composition according to claim 9.

11. A molded article obtained by molding the colored resin composition according to any one of claims 7 to 10.

12. A method for producing a liquid coloring composition comprising mixing a liquid coloring composition with a diluent resin (D) in an amount of 10 parts by weight or less per 100 parts by weight of the diluent resin (D), The liquid coloring composition contains a liquid dispersion medium (A), a surfactant (B), and a colorant (C), the liquid dispersion medium (A) has a viscosity at 25° C. of 10,000 mPa s or less and a decomposition onset temperature of 250° C. or more, and is at least one selected from the group consisting of an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and an aromatic polyvalent carboxylate ester; The method for producing a colored resin composition, wherein the surfactant (B) is at least one selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides.

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