Liquid coloring composition, coloring resin composition, and molding

Abstract

To provide a liquid coloring composition which is excellent in dispersibility of a coloring agent, has good storage stability and supply accuracy, and enables uniform coloring of a molding without impairing appearance of the molding and mechanical properties and moldability of a dilution resin when being kneaded in the dilution resin, and a molding using the same, which is excellent in color unevenness, appearance, mechanical properties and moldability.SOLUTION: A liquid coloring composition contains a liquid dispersion medium (A), a surface active agent (B), and a coloring agent (C), wherein the liquid dispersion medium (A) has viscosity at 25°C of 10,000 mPa s or less and 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 surface active agent (B) is at least one selected from the group consisting of fatty acid ester, higher fatty acid metal salt and fatty acid amide.SELECTED DRAWING: None

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. to do.

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. due to their easy molding process. The plastic molded article is colored to enhance its decorativeness, and various coloring compositions are added in the molding process such as injection molding and extrusion molding. are added.

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

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

[0005] Solid masterbatch is a colored agent composition obtained by melt-kneading a colorant into a resin or the like and granulating it into granules. It 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 defects in the appearance such as color unevenness may occur.

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

[0007] However, in the former method, the productivity decreases because the molding cycle takes time. Also, strong kneading may cause problems such as decomposition of a part of the resin and deterioration of physical properties. In the latter method, there is concern about deterioration of the physical properties of the molded article due to an increase in the addition amount of the solid masterbatch. Especially when the diluting resin is a polycarbonate resin or a polymethyl methacrylate resin, plasticization is difficult due to its high mechanical properties, and uniform transparent color coloring is said to be difficult. For polyester resins and polyamide resins too, since the viscosity of the resin decreases during melting because of the high processing temperature, uniform coloring is difficult due to the loosening defect of the solid masterbatch containing a high concentration of the colorant. to be difficult, and for polyester resins and polyamide resins as well, since the viscosity of the resin decreases during melting because of the high processing temperature, uniform coloring is difficult due to the loosening defect of the solid masterbatch containing a high concentration of the colorant. For the purpose of solving the above problems, methods using a liquid masterbatch as in Patent Documents 1 and 2 are known. Since the liquid masterbatch is liquid, it has excellent distributability and can uniformly color a plastic molded article. Patent Document 1 describes a method of adding a liquid masterbatch containing a pigment and a vegetable oil resin 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, respectively. For the purpose of solving the above problems, methods using a liquid masterbatch as in Patent Documents 1 and 2 are known. Since the liquid masterbatch is liquid, it has excellent distributability and can uniformly color a plastic molded article. Patent Document 1 describes a method of adding a liquid masterbatch containing a pigment and a vegetable oil resin 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, respectively. are each described.

[0008]

Prior Art Documents

Patent Documents

Patent Documents

Patent Documents

Patent Documents

Prior Art Documents

Patent Documents

[0009] [Patent Document 1] JP 2018-188577 A [Patent Document 2] JP 2023-038867 A [Patent Document 3] JP 2023-089368 A [Patent Document 4] JP 2018-131615 A Summary of the Invention [Problem 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. Furthermore, when molding a molded product, the physical properties of the diluted resin may deteriorate. There may be cases where this occurs.

[0011] Patent Document 3 describes a method for producing a titanium oxide of anatase type, a metal deactivator, and a method for producing a titanium oxide of anatase type. A liquid masterbatch is disclosed that contains a liquid dispersion medium having a specified initial temperature and a dispersant. According to the disclosure of Patent Document 3, even when anatase type titanium is contained, the deterioration of the resin component is prevented. However, this technology has the following disadvantages in the liquid masterbatch: It does not improve the dispersibility and storage stability or the supply accuracy, but it is There is room for further study on the color unevenness in the molded product and the variation in color difference between molded products.

[0012] Patent Document 4 describes a liquid resin having a specific viscosity, a dispersant having a hindered amine structure, and The liquid coloring composition containing the coloring agent prevents the occurrence of color unevenness in the resulting molded product. However, the technology disclosed in Patent Document 4 has , and to examine the dispersibility, storage stability and supply accuracy of colorants in liquid coloring compositions. However, the color unevenness of the obtained molded product and the color difference between molded products are further reduced. Furthermore, the color unevenness and variation in these molded products are caused by the lack of transparency. This problem becomes apparent in molded articles with high mechanical strength, but conventional techniques have not yet been able to solve this problem.

[0013] Therefore, an object of the present disclosure is to provide a colorant dispersion medium having excellent dispersibility, storage stability, and supply accuracy. When mixed with diluted resin, it may impair the appearance of the molded product and the mechanical properties and moldability of the diluted resin. A liquid coloring composition capable of uniformly coloring without any color difference and capable of reducing the variation in color difference between molded products. The object of the present invention is to provide a method for manufacturing a molded article using the same that has excellent color uniformity, appearance, mechanical properties, and moldability. The object of the present invention is to provide a molded article having such a structure. [Means for solving the problem]

[0014] The present inventors have conducted extensive research to solve the above problems, and have now completed the present invention. The present invention includes the following embodiments, but is not limited to the following embodiments.

[0015] [1] A liquid coloring composition comprising 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 more at 25°C. The decomposition temperature is 250°C or higher, and the decomposition temperature is 250°C or higher. Kylene glycol resin, polyether ester resin, and aromatic polycarboxylic acid ester The surfactant (B) is at least one selected from the group consisting of fatty acid esters. At least one selected from the group consisting of esters, higher fatty acid metal salts, and fatty acid amides. A liquid coloring composition. [2] The liquid coloring composition according to [1], wherein the fatty acid ester contains a triglyceride. [3] The mass ratio of the content of the surfactant (B) to the content of the colorant (C) (B The liquid coloring composition according to [1] or [2], wherein (a) / (C) is 0.01 to 2. [4] The colorant (C) is added in an amount of 1 to 300 parts by mass per 100 parts by mass of the liquid dispersion medium (A). The liquid coloring composition according to any one of [1] to [3], [5] The surfactant (B) is added in an amount of 0.5 to 100 parts by mass of the liquid dispersion medium (A). The liquid coloring composition according to any one of [1] to [4], wherein the liquid coloring composition contains 30 parts by mass of the water-soluble polymer. [6] A liquid coloring composition according to any one of [1] to [5] and a diluent resin (D). A colored resin composition. [7] The diluent resin (D) is a polycarbonate resin, an acrylic resin, a polyester resin, or the like. [6] The composition according to [6], which is at least one selected from the group consisting of a polyester resin, a polyester resin, and a polyamide resin. Colored resin composition. [8] A molded article obtained by molding the colored resin composition according to [7]. Effect of the Invention

[0016] The present disclosure provides a colorant that is excellent in dispersibility, storage stability, and supply accuracy, and is easily mixed with a diluent resin. When the molded product is molded using this method, it adheres uniformly without impairing the appearance, mechanical properties, or moldability of the molded product. To provide a liquid coloring composition which is capable of coloring and reducing the variation in color difference between molded articles. In addition, the colored resin composition using the same can improve the appearance, mechanical properties, and moldability. It is possible to provide a molded article having excellent properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[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, in this specification, the numerical range specified using "~" shall include the numerical values described before and after "~" as the lower limit value and the upper limit value range. Here, "liquid" refers to being liquid at 25°C. Unless otherwise noted, each of the various components appearing in this specification may 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 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 at 25°C of 10,000 mP a·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. 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, at least one selected from the group consisting of a fatty acid ester, a higher fatty acid metal salt, and a fatty acid amide is used as the surfactant (B), and the colorant is added to a specific liquid dispersion medium (A). ​​​​​​​By dispersing the colorant (C), a liquid coloring composition excellent in storage stability and supply accuracy can be obtained. Furthermore, by mixing the obtained liquid coloring composition with the diluting resin (D) to form a molded article, a liquid coloring composition capable of uniformly coloring the molded article without impairing the appearance, mechanical properties, and moldability of the molded article can be provided. 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] From the viewpoints of the dispersibility of the colorant (C) and the supply accuracy of the liquid coloring composition, 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 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 according to JIS K7117-1.

[0022] Also, the decomposition start temperature of the liquid dispersion medium (A) is 250°C or higher from the viewpoints of the moldability and appearance of the molded article. It is 0 °C or higher, preferably 260 °C or higher, and more preferably 270 °C or higher. Regarding the decomposition start temperature the upper limit 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 occurs when heating at a rate of 10 °C / min using "STA7 200" manufactured by Hitachi High-Tech Science 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, poly ether ester resins, and aromatic polyvalent carboxylic acid esters. From the viewpoint of compatibility with the diluting resin (D), when the diluting 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 diluting 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 diluting resin (D ) is a polyester resin, the liquid dispersion medium (A) is preferably an aliphatic polyester resin, poly alkylene glycol resin, or polyether ester resin. Even in such a combination of the liquid dispersion medium (A) and the diluting resin (D), by using the surfactant (B ), the dispersibility, storage stability, and supply accuracy of the liquid coloring composition can be further improved. ) ​​​​It is possible to prevent a decrease in mechanical strength in the resulting molded article and suppress the occurrence of variations in color difference between molded articles. Among them, when a polycarbonate resin is used as the diluting resin (D), although it is difficult to obtain compatibility with a normal liquid coloring composition, more excellent effects can be exhibited by using the surfactant (B). In particular, when using a polycarbonate resin as the diluting resin (D), although it is difficult to obtain compatibility with a normal liquid coloring composition, more excellent effects can be exhibited by using the surfactant (B). In particular, when a polycarbonate resin is used as the diluting resin (D), although it is difficult to obtain compatibility with a normal liquid coloring composition, more excellent effects can be exhibited by using the surfactant (B). In particular, when a polycarbonate resin is used as the diluting resin (D), although it is difficult to obtain compatibility with a normal liquid coloring composition, more excellent effects can be exhibited by using the surfactant (B).

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

[0026] The aliphatic polyvalent carboxylic 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. For example, 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. can be mentioned. These aliphatic carboxylic acids may be used alone or in combination of two or more. The aliphatic polyvalent carboxylic 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. For example, 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. can be mentioned. These aliphatic carboxylic acids may be used alone or in combination of two or more. The aliphatic polyvalent carboxylic 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. For example, 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. can be mentioned. These aliphatic carboxylic acids may be used alone or in combination of two or more. The aliphatic polyvalent carboxylic 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. For example, 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. can be mentioned. These aliphatic carboxylic acids may be used alone or in combination of two or more. The aliphatic polyvalent carboxylic 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. For example, 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. can be mentioned. These aliphatic carboxylic acids may be used alone or in combination of two or more. The aliphatic polyvalent carboxylic 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. For example, 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. can be mentioned. 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. For example, 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 other aliphatic glycols and 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. For example, 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 other aliphatic glycols and 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. For example, 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 other aliphatic glycols and 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. For example, 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 other aliphatic glycols and 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. For example, 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 other aliphatic glycols and 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. For example, 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 other aliphatic glycols and Examples of the polyalkylene glycol include diethylene glycol and dipropylene glycol. These may be used alone or in combination of two or more.

[0028] A specific example of an aliphatic polyester resin is ADEKA Cizer PN-7160 (ADEKA Viscosity 150mPa·s (25℃), freezing point -42℃, adipic acid polyester resin ), Adeka Cizer PN-5090 (ADEKA, viscosity 10,000 mPa·s (2 5℃), freezing point -10℃, adipic acid polyester resin).

[0029] [Polyalkylene glycol resin] Polyalkylene glycol resins are generally alkylene glycols having repeating units with 1 to 6 carbon atoms. It is often composed of alkylene glycol, but has a viscosity of 10,000m at 25°C. Various polyalkylene glycols can be used as long as their molecular weight is below Pa·s. From the viewpoint of solubility and water absorption, polyalkylene glycols having repeating units with 2 to 4 carbon atoms are used. Mol resins are preferred.

[0030] A specific example of the polyalkylene glycol resin is a polyalkylene glycol resin having a repeating unit with 2 carbon atoms. Polyethylene glycol and polypropylene glycol, which have three carbon atoms in the repeating unit, and polybutylene glycol having 4 carbon atoms in the repeating unit.

[0031] A specific example of the polyalkylene glycol resin is PEG#300 (NOF Corporation, viscosity 7. 0 mPa·s (25°C), polyethylene glycol), Uniol D-1200 (NOF Corporation Examples include polypropylene glycol).

[0032] [Polyether ester resin] The polyether ester resin is obtained by esterifying an aliphatic polycarboxylic acid and an alkylene glycol, and the aforementioned aliphatic polycarboxylic 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, viscosity 20 mPa·s (25°C), freezing point -47°C), Adeka Sizer RS-700 (manufactured by ADEKA, viscosity 30 mPa·s (25°C), freezing point -53°C), and the like. (manufactured by ADEKA, viscosity 30 mPa·s (25°C), freezing point -53°C), etc. can be mentioned.

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

[0035] The aromatic polycarboxylic acid constituting the aromatic polycarboxylic acid ester is not particularly limited as long as it is an aromatic carboxylic acid having two or more carboxyl groups. For example, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid can be mentioned. 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) methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol , tridecanol, tetradecanol, pentadecanol, hexadecanol, heptade canol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosano l, heptacosanol, octacosanol, nonacosanol, triacontanol, etc. linear chain alkyl alcohols, (2) isopropanol, isobutanol, isohexanol, 2-ethylhexanol, isononanol, isodecanol, isododecanol, isot ridecanol, isotetradecanol, isopentadecanol, isohexadecanol, isoheptadecanol, isooctadecanol, isononadecanol, isoeicosano l, isoheneicosanol, isodocosanol, isotricosanol, isotetracos anol, 2-decyltetradecanol, isopentacosanol, isohexacosanol, isoheptacosanol, isooctacosanol, isononacosanol, isotriacont anol, etc. branched alkyl alcohols, (3) tetradecenol, hexadecenol, hep tadeceneol, octadecenol, oleyl alcohol, nonadecenol, etc. linear alken yl alcohols, (4) isohexadecenol, isooctadecenol, etc. branched alkenyl alcohols, (5) cyclopentanol, cyclohexanol, etc. cyclic alkyl alcoh ols, etc. may be mentioned. Furthermore, polyhydric alcohols may be used, and examples of polyhydric alcohols include , for example, 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. Further, alkyl glycol alkyl ethers, polyalkylene glycol alkyl ethers, or acetate salts thereof in which at least one hydroxy group other than one hydroxy group of these polyhydric alcohols is substituted with an alkyl group are included. 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 - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. ylene glycol, 1,2 - butanediol, 1,3 - butanediol, 2 - methyl - 1,3 - prop anediol, 1,4 - butanediol, 1,5 - pentanediol, 1,6 - hexa anediol, 1,8 - octanediol, 1,10 - decanediol, 1,12 - octa decanediol, etc., and polyalkylene glycols such as diethylene glycol and dipropylene glycol. 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 - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. Among these polyhydric alcohols, alkyl glycol alkyl ethers, polyalkylene glycol alkyl ethers, or acetate salts thereof in which at least one hydroxy group other than one hydroxy group is substituted with an alkyl group are included. 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 - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. ylene glycol alkyl ether, polyalkylene glycol alkyl ether, or acetate salts thereof are included. 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 - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. 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 - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. Among them, monohydric aliphatic alcohols are preferred. Particularly preferred is a monohydric branched - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. Among them, monohydric aliphatic alcohols are preferred. Particularly preferred is a monohydric branched - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. Among them, monohydric aliphatic alcohols are preferred. Particularly preferred is a monohydric branched - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges. Among them, monohydric aliphatic alcohols are preferred. Particularly preferred is a monohydric branched - chain aliphatic alkyl alcohol. Also, the number of carbon atoms of the alcohol may be 3 - 22, 4 - 18, or 6 - 12, and it is even better when the number of carbon atoms of the monohydric branched - chain aliphatic alkyl alcohol is within these ranges.

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

[0038] The liquid dispersion medium (A) uses one of the above - described various resins alone or a combination of two or more. It may be. 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 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 with respect to the total mass of the liquid coloring composition, and may be, for example, 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 fatty acid esters or higher fatty acid metal salts are preferred. . By containing these compounds, the liquid coloring composition can enhance the dispersibility of the colorant (C) and maintain storage stability. Furthermore, 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 products in the obtained molded article. This can more effectively confirm the phenomenon that even when there is no obvious difference in supply accuracy 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 the function of reducing the interfacial tension by strong adsorption to the interface of substances that do not mix with each other and molecular orientation.

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

[0041] By using a liquid dispersion medium (A) and a surfactant (B), the dispersibility of the colorant (C) is excellent, the storage stability and supply accuracy are good, and when kneaded into the diluting resin (D), the appearance of the molded body can be uniformly colored without impairing the mechanical properties and moldability, and a liquid coloring composition can be provided. 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), the supply accuracy can be further improved, and the variation in color difference among molded bodies 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 body with suppressed strength reduction, uniformly colored, and excellent appearance. Furthermore, the variation in color difference among the obtained molded bodies can be reduced.

[0043] The variation in color difference among molded bodies may occur among molded bodies continuously molded by injection molding, extrusion molding, etc. when molding a molded body using a colored resin composition containing a liquid coloring composition and a diluting resin (D). In injection molding, although one part is molded for each shot, there may be a variation in color difference among 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. The following applies. 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, for example, 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, preferably are glycerin, propylene glycol, pentaerythritol, and dipentaerythritol, and more preferably glycerin and dipentaerythritol.

[0045] The fatty acid constituting the fatty acid ester is a monovalent carboxylic acid 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, plaslinic acid, erucic acid, and ricinoleic acid; hydroxy fatty acids such as 12 - hydroxystearic 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 Acids, palmitic acid, stearic acid, oleic acid, erucic acid, and 12-hydroxystearic acid Acids, particularly preferably stearic acid and 12-hydroxystearic acid. As the fatty acid ester, particularly preferably, it is a triglyceride.

[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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. 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 constituting the triglyceride may be the same as each other, or part or all of them 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 particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred.

[0047] Hydrogenated castor oil is a hydrogenated castor oil obtained by adding hydrogen to the unsaturated bonds of castor oil, and is a triglyceride of 12-hydroxystearic acid. Specific examples of hydrogenated castor oil include KAWASUTER CR (manufactured by Kawaken Fine Chemicals Co., Ltd.). Hydrogenated castor oil is a hydrogenated castor oil obtained by adding hydrogen to the unsaturated bonds of castor oil, and is a triglyceride of 12-hydroxystearic acid. Specific examples of hydrogenated castor oil include KAWASUTER CR (manufactured by Kawaken Fine Chemicals Co., Ltd.). Hydrogenated castor oil is a hydrogenated castor oil obtained by adding hydrogen to the unsaturated bonds of castor oil, and is a triglyceride of 12-hydroxystearic acid. Specific examples of hydrogenated castor oil include KAWASUTER CR (manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0048] Higher fatty acid metal salts are metal salts of higher fatty acids, and preferably non-alkali metal salts of higher fatty acids. The carbon number of 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 their derivatives, and particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. Higher fatty acid metal salts are metal salts of higher fatty acids, and preferably non-alkali metal salts of higher fatty acids. The carbon number of 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 their derivatives, and particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. Higher fatty acid metal salts are metal salts of higher fatty acids, and preferably non-alkali metal salts of higher fatty acids. The carbon number of 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 their derivatives, and particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. Higher fatty acid metal salts are metal salts of higher fatty acids, and preferably non-alkali metal salts of higher fatty acids. The carbon number of 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 their derivatives, and particularly preferably fatty acids having a hydroxy group. Examples of the triglyceride include castor oil, coconut oil, olive oil, and hydrogenated products thereof, and among them, hydrogenated castor oil is preferred. Examples include locked fatty acids and their derivatives. The fatty acid of the higher fatty acid metal salt may have a substituent such as a hydroxy group to enhance the adsorbability 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. Metal soaps with good adsorbability to the colorant (C) are preferably magnesium stearate and its derivatives, and 12-hydroxy magnesium stearate is more preferred. Specific examples of the higher fatty acid metal salt include Sinac Red SAK-MS-P (manufactured by San Ace Co., magnesium stearate), MS-6 (manufactured by Nitto Kasei Kogyo Co., 12-hydroxy magnesium stearate), etc.

[0049] [Fatty acid amide] 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 amines having 10 or more carbon atoms. For example, oleylamine, stearyl amine, etc. are 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, and more preferably stearic acid, 12-hydroxy stearic acid, and erucic acid.

[0051] Examples of the fatty acid amide include lauric acid amide, palmitic acid amide, oleic acid Amides, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide , and aliphatic monocarboxylic acid amides such as hydroxystearic acid amide; N-oleyl oleic acid amide, N-oleyl stearic acid amide, and N-stearyl oleic acid amide and other N-substituted aliphatic monocarboxylic acid amides; methylene bis stearic acid amide, and aliphatic biscarboxylic acid amides such as ethylene bis stearic acid amide; N,N'-ethyl ene-bis-oleylamide; N,N'-ethylene bis stearic acid amide; N,N'- methylene bis stearic acid amide; and the like. Preferably, stearic acid amide, e rucic acid amide, N,N'-ethylene bis stearic acid amide.

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

[0053] The amine value of the surfactant (B) is preferably 180 mgKOH / g or less, more preferably 140 mgKOH / g or less, 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, the decrease in the heat distortion temperature can be suppressed.

[0054] The content of the surfactant (B) is preferably 0.5 part by mass or more, more preferably 0.8 part by mass or more, still more preferably 1 part by mass or more, based on 100 parts by mass of the liquid dispersion medium (A), from the viewpoint of the mechanical properties due to the compatibility between the colorant (C) and the diluting resin (D), for example, the decrease in the heat distortion temperature can be suppressed. Also, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less. ​​​​​​​The surfactant (B) is a fatty acid ester. If two or more of the following are contained, the total It is preferred that the weighting is within the above range.

[0055] The liquid coloring composition is a colorant that contains a fatty acid ester, a higher fatty acid metal salt, a fatty acid amide, or In addition to the combination of the above, the liquid coloring composition may further contain other surfactants. The dispersion may further comprise a dispersant.

[0056] As the dispersant, a dispersant-type acrylic resin can be used. The acrylic resin is a (meth) A polymer containing structural units derived from acrylic monomers, such as (meth)acrylic resin and styrene. -Acrylic resins, etc. Acrylic resins are made of (meth)acrylic monomers. It is preferred to have at least one polymer block of units.

[0057] The weight average molecular weight of the acrylic resin depends on its solubility in the liquid dispersion medium (A) and the property of the dilution resin (D). From the viewpoint of the molecular weight, the molecular weight is preferably 500 to 20,000, and more preferably 1,000 to 15,000. In this specification, the weight average molecular weight is determined by gel permeation chromatography (GPC method). The values ​​were measured using polystyrene as the standard and tetrahydrofuran as the eluent. (Measured values ​​obtained by

[0058] Examples of the (meth)acrylic monomer constituting the acrylic resin include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate Acrylate, butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl Xyl(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, di ethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclo pentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclo pentenyloxyethyl (meth)acrylate, etc. (meth)acrylates, (poly)ethyl ene glycol, (poly)propylene glycol, (poly)butylene glycol, etc. (poly alkylene glycol group-containing mono(meth)acrylates, etc. (meth)acrylic acid or its esters, etc. may be mentioned.

[0059] 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, etc. Styrene-acrylic resin is preferably a polymer having 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, etc.

[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. The phosphate ester compound includes, for example, alkyl phosphates such as tributyl phosphate, trioctyl phosphate, tris(β-chloroethyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, and phenyl phosphates such as triphenyl phosphate, tricresyl phosphate, tris(i-propylphenyl) phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, alkyl polyoxyethylene phosphate esters such as tributoxyethyl phosphate, alkylphenol polyoxyethylene phosphate esters, and neutral salts thereof such as sodium, potassium, ammonia, and amines. Further, these phosphate ester compounds may have an acid value and 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 and 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 KOH / g), Disper BYK-145 (manufactured by BYK Chemie, acid value 76 mg KOH / g , amine value 71 mg KOH / g), etc. can be mentioned.

[0064] In addition to fatty acid esters, higher fatty acid metal salts, fatty acid amides, or combinations thereof when further using other surfactants and dispersants, for 100 parts by mass of surfactant (B) 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. Even when not using other surfactants and dispersants in the case, by using fatty acid esters, higher fatty acid metal salts, fatty acid amides, or combinations thereof the effect of the liquid coloring composition can be expected, and the effect of the obtained molded body 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, valve handle, ultramarine blue, carbon black , or organic pigments such as azo pigments, quinacridone pigments, perylene pigments, diketo pyrrolopyrrole pigments, phthalocyanine pigments, etc. Titanium oxide is less active and less likely to induce resin deterioration than the anatase type, so the rutile type is preferred. 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. is obtained. Examples of the perinone dyes include, for example, C.I. Solvent Red 135, 1 79. Examples of the anthraquinone dyes include, for example, C.I. Solvent Red 52, 1 51, Solvent Violet 13, 36, Solvent Blue 97, etc. Incidentally, "C.I." means Color Index.

[0067] Specific examples of the methine dyes include, for example, Macrolex Yellow 3G-FG (manufactured by Lanxess, Solvent Yellow 93), Macrolex Yellow 6G (manufactured by Lanxess , Solvent Yellow 179), etc. Specific examples of the perinone dyes include , for example, Macrolex Red EG GRAN (manufactured by Lanxess, Solvent Red 1 35), Macrolex Red E2G GRAN (manufactured by Lanxess, Solvent Red 1 79), etc. Specific examples of the anthraquinone dyes include, for example, Sumipra Stred HL5B (manufactured by Sumitomo Chemical Tex Co., Ltd., Solvent Red 52), Sumipra Stred HL2B (manufactured by Sumitomo Chemical Tex Co., Ltd., 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), etc. Examples of the inorganic pigments include, for example, C.I. Pigment White 6, Pigment Brown

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

[0069] Specific examples of the inorganic pigments include, for example, Ty-Pake PF-740 (manufactured by Ishihara Sangyo Co., Ltd., rutile-type titanium oxide, Pigment White 6), Tomatec 42-118A (manufactured by Toa Titanium 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), etc. Specific examples of the organic pigments include, for example, the following. Specific examples of the azo-based pigments include, for example, PV Fast Yellow HG (manufactured by Clariant, Pigment Yellow 180), PV Fast Yellow H3R (manufactured by Clariant, Pigment Yellow 18 1), Chromophthal Orange K2960 (manufactured by BASF, Pigment Orange 64), Chromophthal Red K3890FP (manufactured by BASF, Pigment Red 144), Chrome Chromophthal Scarlet K3540 (manufactured by BASF, Pigment Red 166), Chrome mo Scarlet K3540 (manufactured by BASF, Pigment Red 166), Chrome mo Scarlet K3540 (manufactured by BASF, Pigment Red 166), Chrome mo Scarlet K3540 (manufactured by BASF, Pigment Red 166), Chrome Phthal Red K3900 (manufactured by BASF, Pigment Red 214), Chromophthal Red K4035 (manufactured by BASF, Pigment Red 221), etc. can be mentioned. The above quinacridone Specific examples of quinacridone-based pigments include, for example, PV Fast Red E4G (manufactured by Clariant Co., Pigment Violet 19), PV Fast Pink E-01 (manufactured by Clariant Co., Pigment Red 122), etc. Specific examples of the above perylene-based pigments include For example, Pariox Red K3580 (manufactured by BASF, Pigment Red 149), Pariox Red K3911 (manufactured by BASF, Pigment Red 178), etc. can be mentioned. The above diketopyrrolopyrrole-based pigments Specific examples include, for example, Irgazin Red K3840 (manufactured by BASF, Pigment Red 254), etc. Specific examples of the above phthalocyanine-based pigments include, for example, Lionol Blue CB7801 (manufactured by Toyo Color Co., Pig ment Blue 15:1), Lionol Blue FG7351 (manufactured by Toyo Color Co., Pigment Blue 15:3), Lionol Green Y-102 (manufactured by Toyo Color Co., Pigment Green 7), Lionol Green 6Y-501 (manufactured by Toyo Color Co., Pigment Green 36), etc. can be mentioned.

[0070] 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), from the viewpoints of the dispersibility of the colorant (C) and the supply accuracy of the liquid coloring composition.

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

[0072] From the viewpoints of the dispersibility and 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] In the liquid coloring composition, the total of the liquid dispersion medium (A), the surfactant (B), and the colorant (C) 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, from the viewpoints of dispersibility and storage stability, with respect to 100 parts by mass of the liquid coloring composition.

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

[0075] <Method for Producing Liquid Color Composition> The method for producing the liquid color composition is not particularly limited. For example, the liquid dispersion medium (A), the surfactant (B), the colorant (C), and, if necessary, other additives are added, and they are mixed using a Henschel mixer, a tumbler, a disper, etc., and dispersed using a Silverton mixer (manufactured by Silverton Co., Ltd.) or the like to obtain a liquid color composition. As the dispersing device, in addition to the above, a kneader, a roll mill, a ball mill, a sand mill, etc., any device can be used. For reasons such as easy molding processability and excellent dispersibility, it is preferable to use a bead mill, a Silverton mixer, or a roll mill.

[0076] ≪Colored Resin Composition≫ The colored resin composition contains the liquid color 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 color composition when molding a molded article, and becomes the main component of the molded article. Mainly, a thermoplastic resin is used, and it is appropriately selected according to the use of the molded article.

[0077] The content of the liquid color composition is preferably 0.001 part by mass or more, more preferably 0.005 part 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 part by mass or less. ​​​​​​​​​​​As a result, it is possible to obtain those having more excellent processability and mechanical properties. Furthermore, it is possible to obtain a molded article excellent in appearance without color unevenness of the molded article and generation of aggregations of the colorant.

[0078] The resin colored by the liquid coloring composition is not particularly limited, but as the diluting resin (D), polycarbonate resin, acrylic resin, polyester resin, polyamide resin, polyvinyl chloride resin, polystyrene resin, cycloolefin copolymer (COC), etc. may be mentioned. By using the liquid coloring composition of the invention, it is also suitable for coloring polycarbonate resin, acrylic resin, polyester-based resin, and polyamide-based resin, which are generally difficult to color uniformly. As the acrylic resin, polymethyl methacrylate resin is preferable.

[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 is a known reaction. For example, when phosgene is used, it can be obtained by an interfacial method, and when a carbonic acid diester is used, it can be obtained by a transesterification method in which the reaction is carried out in a molten state. For example, when phosgene is used, it is by an interfacial method, and when a carbonic acid diester is used, it is obtained by a transesterification method in which the reaction is carried out in a molten state.

[0080] Examples of the aromatic dihydroxy compound include 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 )alkanes such as propane, 1,1-bis(4-hydroxy phenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane and other bis(hydroxyaryl)cycloalkanes 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether and other dihydro xydiaryl ethers, 4,4'-dihydroxydiphenyl sulfide, 4,4' -dihydroxy-3,3'-dimethyldiphenyl sulfide and other dihydroxydiaryl sulfides, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydro xy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfox ides, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3, 3'-dimethyldiphenyl sulfone and other dihydroxydiaryl sulfones, etc. are mentioned. These are used alone or in a mixture of two or more. In addition to these, piperazine, dipiper idyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyls may be mixed and used. Further, a branched aromatic polycarbonate resin combined with a polyfunctional compound such as phloroglucinol can also be used. As the carbonate precursor to react with the aromatic dihydroxy compound, for example, phosgene can also be used.

[0081] Diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and the like , dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, and the like may be mentioned.

[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. In addition, 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 the 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. may be mentioned.

[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 addition, in this specification, "(meth)acrylic" means "acrylic and / or methacrylic", and "(meth)acrylate" means "acrylate and / or methacrylate". "Takuryrate" means each. Specifically, polymethyl methacrylate (PMM A) resin is preferred.

[0085] [Polyester resin] The 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-butyl benzoic 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-cyclohexanedicarbo nic acid, trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, ε-caprolactone, and the like.

[0087] Examples of the hydroxyl group component constituting the polyester resin include 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 other diols, and tri methylol ethane, trimethylol propane, tris(hydroxymethyl)aminomethane, pentaerythritol, dipentaerythritol and other polyfunctional alcohols having three or more hydroxyl groups can be mentioned.

[0088] [Polyamide resin] The polyamide resin is, for example, the above-mentioned carboxylic acid component and a compound having two or more amino groups It can be obtained by reacting compounds. For example, it can be obtained by subjecting a 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, tetramethyl ethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetra mine, etc.; aliphatic polyamines including alicyclic polyamines such as isophoronediamine, dicyclohexylmethane-4,4’- diamine, etc.; aromatic polyamines such as phenylenediamine, xylylenediamine diamine, etc.; 1,3-diamino-2-propanol, 1,4-diamino -2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclo hexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecane -2-ol, 3-(2-hydroxypropyl)-o-xylene-α,α’-diamine, etc. diaminoalcohols are exemplified.

[0090] The diluting resin (D) may be used alone or in combination of two or more of the above-mentioned 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. When the liquid coloring composition contains the liquid dispersion medium (A) and the surfactant (B) in which the resin type is specified, 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 obtained molded article can be prevented. In particular, the microscopic Since the supply accuracy is improved, color unevenness within the molded body and variations in color difference between molded bodies can be reduced in the resulting molded body. For example, for the colored resin composition or the molded body obtained by molding this, the content of the colorant (C) can be 0.01 to 10% by mass, 0.03 to 5 % by mass, or 0.05 to 3% by mass. Furthermore, due to such an effect, even in a molded body with high transparency, color unevenness and variations can be reduced even with a low concentration of the colorant (C). For example, for the colored resin composition or the molded body obtained by molding this, the content of the colorant (C) can be 0.01 to 1% by mass, 0.03 to 0.5% by mass, or 0.05 to 1% by mass. When the diluting resin (D) is a polycarbonate resin and an acrylic resin, particularly a polycarbonate resin and a methyl methacrylate resin, uniform transparent coloring can be obtained. The liquid coloring composition can enhance dispersibility, storage stability, and supply accuracy even when containing the colorant (C) at a high concentration by including the liquid medium (A) with a specified resin type and the surfactant (B). By using a liquid coloring composition containing a high concentration of the colorant (C), the contents of the liquid medium (A) and the surfactant (B) can be relatively reduced in the resulting molded body, and the mechanical strength of the molded body can be further enhanced. For example, for 100 parts by mass of the liquid medium (A), the colorant (C) can be 0.1 to 500 parts by mass, 1 to 300 parts by mass, or 10 to 120 parts by mass. Furthermore, in this case, it is advisable to use the surfactant (B) in an appropriate amount with respect to the colorant (C). For example, for 100 parts by mass of the colorant (C), the surfactant (B) can be 0.01 part by mass to 2, 0.05 to 1 part by mass, or 0.1 to 0.5 part 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 coloring can be obtained.

[0091] The liquid coloring composition can enhance dispersibility, storage stability, and supply accuracy even when containing the colorant (C) at a high concentration by including the liquid medium (A) with a specified resin type and the surfactant (B). By using a liquid coloring composition containing a high concentration of the colorant (C), the contents of the liquid medium (A) and the surfactant (B) can be relatively reduced in the resulting molded body, and the mechanical strength of the molded body can be further enhanced. For example, for 100 parts by mass of the liquid medium (A), the colorant (C) can be 0.1 to 500 parts by mass, 1 to 300 parts by mass, or 10 to 120 parts by mass. Furthermore, in this case, it is advisable to use the surfactant (B) in an appropriate amount with respect to the colorant (C). For example, for 100 parts by mass of the colorant (C), the surfactant (B) can be 0.01 part by mass to 2, 0.05 to 1 part by mass, or 0.1 to 0.5 part by mass. For example, for 100 parts by mass of the liquid medium (A), the colorant (C) can be 0.1 to 500 parts by mass, 1 to 300 parts by mass, or 10 to 120 parts by mass. Furthermore, in this case, it is advisable to use the surfactant (B) in an appropriate amount with respect to the colorant (C). For example, for 100 parts by mass of the colorant (C), the surfactant (B) can be 0.01 part by mass to 2, 0.05 to 1 part by mass, or 0.1 to 0.5 part by mass. For example, for 100 parts by mass of the colorant (C), the surfactant (B) can be 0.01 part by mass to 2, 0.05 to 1 part by mass, or 0.1 to 0.5 part by mass.

[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 is mixed with a diluting resin (D), and further, various additives and colorants are added as necessary, and then mixed with a Henschel mixer or a tumbler, a disperser, etc., and after that, melt-kneaded with a batch kneader such as a kneader, a roll mill, a super mixer , a high-speed mixer, a ball mill, a sand mill, an attritor, a Banbury mixer to obtain a colored resin composition in the form of pellets, powder, granules or beads. Since it is easy to perform molding processing, it is preferable to obtain a pellet-shaped colored resin composition using a twin-screw extruder. As a production method for making the colored resin composition into pellets, a general method such as granulating using a pelletizer after extrusion processing by an extruder can be adopted. Also, by pulverizing these pellet-shaped molded bodies, a powdered or granular colored resin composition can be obtained. As a production method for making the colored resin composition into pellets, a general method such as granulating using a pelletizer after extrusion processing by an extruder can be adopted. Also, by pulverizing these pellet-shaped molded bodies, a powdered or granular colored resin composition can be obtained. Moreover, 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) without passing through the pellet-shaped colored resin composition. Moreover, 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) without passing through the pellet-shaped colored resin composition.

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

[0094] Specifically, for example, (Method 1) a colored resin composition and pellets of a diluent resin (D) are dissolved in water. (Method 2) Melting and kneading the colored resin composition to obtain a molded product, and (Method 3) Diluting the colored resin composition. Resin (D) is melt-kneaded to prepare a solid master batch or the like of a colored resin composition, and then diluted with the resin. (Method 3) A method in which the resin (D) is melt-kneaded together with pellets of the resin (D) to obtain a molded product. The composition and diluent resin (D) are melt-kneaded to form a compound, which is then pelletized. and the like, which is then melt-kneaded to obtain a molded product. EXAMPLES

[0095] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and percentages are by weight and percentages, respectively, unless otherwise specified. The figures are in mass %. Note that blank spaces in the table indicate that no ingredient was added.

[0096] The materials used in the examples and comparative examples are shown below. <Liquid dispersion medium (A), etc.> A-1: Adeka Cizer PN-7160 (ADEKA, aliphatic polyester resin, Viscosity at 25℃: 150mPa·s, Decomposition temperature: 278℃) A-2: Adeka Cizer PN-5090 (ADEKA, aliphatic polyester resin, Viscosity at 25℃: 10,000mPa·s, Decomposition temperature: 295℃) 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 Corporation, aromatic polyvalent carboxylic acid ester , viscosity at 25°C: 450 mPa·s, decomposition start temperature: 310°C) A-5: Adeka Sizer RS-700 (manufactured by ADEKA Corporation, 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 Kawaken Fine Chemicals 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-Chemie Japan Co., Ltd., surfactant: phosphoric acid 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 AG, anthraquinone dye, Solvent Violet 13 ) C-2: Macrolex Red E2G GRAN (manufactured by Lanxess, perinone dye, Solvent Red 179) C-3: Taypek CR-60 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide, Pigment White 6) C-4: Pariox 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-based 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 in 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 the liquid dispersion medium (A-1) and 25 parts by mass of the colorant (C-1) were mixed and dispersed in 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 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 (densely packed point) at which distinct spots began to appear in the liquid coloring composition was observed, and evaluation was performed according to the following criteria. [Evaluation Criteria] +++: Densely packed point ≤ 30 μm, very good ++: 30 μm < densely packed point ≤ 50 μm, good +: 50 μm < densely packed point ≤ 70 μm, practical NG: 70 μm < densely packed point, unpractical

[0106] <Storage Stability Evaluation> For storage stability, the obtained liquid coloring composition was allowed to stand for 30 days, and separation and sedimentation of the colorant (C) in the liquid coloring composition were visually confirmed, and evaluation was performed 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 exist, but becomes uniform when stirred, practical NG: Separation and sedimentation exist, and does not become uniform even when stirred, unpractical

[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 volume was calculated every 10 seconds, and the discharge volume: Q that deviated the most from the set value within the supply time of 10 x minutes and the set flow rate: Q0 (= 10 mL / min). The ratio Q x / Q0 was used to evaluate the supply accuracy according to the following criteria. [Evaluation criteria] +++: 0.9 ≤ Qx / Q0 ≤ 1.1, very good ++: 0.85 ≤ Qx / Q0 < 0.9 or 1.1 < Qx / Q0 ≤ 1.15, good +: 0.8 ≤ Qx / Q0 < 0.85 or 1.15 < Qx / Q0 ≤ 1.2, practical Possible NG: Qx / Q0 < 0.8 or 1.2 < Qx / Q0, not practical

[0108] [Table 1-1]

[0109] [Table 1-2]

[0110] [Example 24] [Manufacture of colored resin composition] 1 part by mass of a liquid coloring composition (X-1) and 100 parts by mass of a 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] Except for changing to the materials and contents (parts by mass) shown in Table 2, respectively, in the same manner as in Example 24 colored resin compositions (Z-2 to 30) were each produced.

[0112] [Comparative Example 11] 0.1 part by mass of a colorant (C-1) and 100 parts by mass of a 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). (Z-31).

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

[0114] [Processability] The discharge amount (Q0) when extruding only the diluting resin (D) and the discharge amount (Q ) of the colored resin composition when adding the liquid coloring composition x ) of the colored resin composition when adding the liquid coloring composition x The ratio (Q / Q0) was calculated and evaluated according to the following criteria x . The higher the value of Q / Q0, the smaller the change in discharge due to the addition of the liquid coloring composition, and the better the processability can be said. [Evaluation Criteria] +++: Q x / Q0 ≧ 0.95, very good ++: 0.90 ≦ Q x / Q0 < 0.95, good +: 0.85 ≦ Q x / Q0 < 0.90, practical NG: Q x / Q0 < 0.85, unpractical

[0115] [Color Unevenness] Using the obtained colored resin composition, 10 plates of 15 0 mm × 130 mm × 2 mm were produced using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., injection pressure 100 t), and the plates were molded from the 6th to the 10th Five plates were visually evaluated according to the following criteria. [Evaluation Criteria] +++: No color unevenness on all five plates, very good ++: One plate with color unevenness confirmed, good +: Two plates with color unevenness confirmed, practical NG: Three or more plates with color unevenness confirmed, not practical

[0116] <Appearance> The surfaces of the five plates used for color unevenness evaluation were observed, and the number of plates with bubbles or flash (volatile components generated during molding appearing on the surface of the molded body) confirmed was counted and evaluated according to the following criteria. [Evaluation Criteria] +++: No bubbles or flash on all five plates, very good ++: One plate with bubbles or flash confirmed, good +: Two plates with bubbles or flash confirmed, practical NG: Three or more plates with bubbles or flash 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., Ltd., injection pressure 100t). The color difference (ΔE) of the plates from the 10th shot to the 49th shot was measured with a spectrocolorimeter 36dG (manufactured by Konica Minolta Sensing Inc.) using the plate of the 50th shot as the standard, and evaluated according to the following criteria. [Evaluation Criteria] +++: ΔE ≤ 0.3 for all plates, very good ++: Five or fewer plates with ΔE > 0.3, good +: Ten or fewer plates with ΔE > 0.3, practical

[0118] NG: Fifteen or more plates with ΔE > 0.3, not practical

[0118] <Mechanical properties> Using the obtained colored resin composition, a multi-purpose test piece with a length of 80 mm, a width of 10 mm, and a height of 4 mm was molded. The heat distortion temperature at a load of 1.80 MPa was measured according to JIS K7191-2. The heat distortion temperature (T0) of the uncolored diluted resin (D) and the ratio (T / T0) of the colored resin composition (T x ) after coloring were calculated, and evaluation was performed according to the following criteria. T x The higher the value of / T0 x / T0 , the less the mechanical properties are deteriorated by the liquid coloring composition, and it can be said to be good. [Evaluation criteria] +++: T x / T0 ≥ 0.95, very good ++: 0.90 ≤ T x / T0 < 0.95, good +: 0.85 ≤ T x / T0 < 0.90, practical NG: T x / T0 < 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 with excellent color uniformity and appearance can be obtained without deteriorating the processability and mechanical properties of the diluted resin (D). Moreover, 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 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 body be molded.

Claims

1. A liquid coloring composition comprising a liquid dispersion medium (A), a surfactant (B), and a colorant (C). So, The liquid dispersion medium (A) has a viscosity at 25° C. of 10,000 mPa s or less, The decomposition temperature is 250°C or higher, and aliphatic polyester resin, polyalkylene glycol It is made of cholester resin, polyether ester resin, and aromatic polycarboxylic acid ester. At least one selected from the group The surfactant (B) is selected from the group consisting of fatty acid esters, higher fatty acid metal salts, and fatty acid amides. At least one selected from the group consisting of A liquid coloring composition.

2. 2. The liquid coloring composition of claim 1, wherein said fatty acid ester comprises a triglyceride.

3. The mass ratio (B) / ( 2. The liquid coloring composition according to claim 1, wherein C) is 0.01 to 2.

4. Contains 1 to 300 parts by mass of the colorant (C) per 100 parts by mass of the liquid dispersion medium (A). nothing, The liquid coloring composition according to claim 1.

5. The surfactant (B) is added in an amount of 0.5 to 30 parts by mass per 100 parts by mass of the liquid dispersion medium (A). Including quantity, The liquid coloring composition according to claim 1.

6. A colored resin comprising the liquid colored composition according to any one of claims 1 to 5 and a diluent resin (D). composition.

7. The diluent resin (D) is a polycarbonate resin, an acrylic resin, a polyester resin, or and at least one selected from the group consisting of polyamide resins, The colored resin composition according to claim 6.

8. A molded article obtained by molding the colored resin composition according to claim 7.

Images