Liquid masterbatch, colored resin composition, and molded article

Abstract

To provide a liquid master batch which enables formation of a molding that suppresses thickening by degradation of a resin component, prevents occurrence of color unevenness and coloring agent aggregate, and is excellent in appearance, even in the case of containing an anatase type titanium oxide, and a colored resin composition which does not affect mechanical physical properties such as tensile strength and thermal characteristics such as melting viscosity.SOLUTION: A liquid masterbatch contains an anatase type titanium oxide (A), a metal deactivator (B), a liquid dispersion medium (C) having viscosity at 25°C of 10,000 mPa s or less and a thermal decomposition start temperature of 200°C or higher, and a dispersion agent (D), wherein a percentage content of the anatase type titanium oxide (A) is 50-80 mass% in 100 mass% of the liquid masterbatch.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid masterbatch used for melt-kneading with a thermoplastic resin to form a plastic molded article, a colored resin composition, and a molded article formed therefrom. [Background technology]

[0002] Plastic molded products are easy to process and are therefore used in a wide range of fields, including electrical and electronic equipment parts, automotive parts, medical parts, food containers, synthetic fibers, etc. They are also colored and given functionality using dyes, organic and inorganic pigments, etc., depending on the application.

[0003] Among these, titanium dioxide is an inorganic pigment that is widely used for white coloring and matting plastics due to its high refractive index, good heat resistance, and chemical stability. Titanium dioxide is known to exist in three crystalline forms: rutile, anatase, and brookite, with rutile and anatase being used industrially. Compared to rutile, anatase has a more diffuse atomic arrangement and unstable physical properties, but is characterized by a bluish color and low hardness.

[0004] Therefore, the use of anatase-type titanium dioxide is desired, especially in synthetic fiber applications, because it is easy to suppress wear on mechanical parts and facilitates good passability through post-processing. Titanium dioxide is also used to control not only color but also gloss by adding it to fibers. For example, in clothing linings, gloss is a characteristic that consumers dislike, so approximately 0.2 to 1.9 mass % of titanium dioxide is added to the fibers to achieve a matte finish.

[0005] Known methods for adding inorganic pigments such as anatase titanium dioxide to plastic molded products such as synthetic fibers include dispersing the pigment in resin to form pellets or flakes as a solid masterbatch, or dispersing the pigment in a liquid resin at 25°C to form a liquid masterbatch (also known as liquid color), which is then melt-kneaded with diluted resin to form a molded product.

[0006] However, it is difficult to achieve uniform coloring of molded products using solid masterbatches, resulting in problems such as color unevenness and other poor appearance. This problem is particularly likely to occur when the colorant concentration of the molded product is low, and can occur when titanium oxide is added at a low concentration, such as 2% by mass or less, to achieve a matte finish. Therefore, to achieve uniform coloring of molded products, several methods have been investigated, including improving the molding conditions by increasing the melt-kneading time or strength of the melt-kneading between the solid masterbatch and the dilution resin used to form the molded product, and by decreasing the colorant concentration in the solid masterbatch and increasing the amount of solid masterbatch added during molding. However, the former method reduces productivity due to the long molding cycle time, and strong kneading can cause partial decomposition of the resin, resulting in a decrease in intrinsic viscosity and melt viscosity during molding. Furthermore, the latter method suffers from the problem of reduced physical properties of the molded product due to the increased amount of solid masterbatch added.

[0007] As a method for forming a molded body containing an inorganic pigment using a liquid masterbatch, for example, Patent Document 1 discloses a method using a pigment dispersion liquid that has good fluidity after storage at room temperature for 24 hours and is composed of a hydrophobic liquid (liquid dispersion medium), an inorganic pigment containing titanium oxide, and a phosphoric acid monoester compound as a dispersant.

[0008] Even when the titanium oxide colorant concentration in the molded body is low, the liquid masterbatch quickly comes into contact with the diluted resin molten in the molding machine, preventing poor appearance such as uneven color and enabling uniform coloring. However, the addition of a large amount of a low-molecular-weight liquid dispersion medium can reduce the intrinsic viscosity and melt viscosity during molding, which can lead to deterioration of moldability. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2015 / 023454 Summary of the Invention [Problem to be solved by the invention]

[0010] Thus, anatase titanium dioxide has a bluish hue and lower hardness than titanium dioxide with a rutile crystal structure, and therefore, when used as a colorant, it is highly effective in coloring and matting molded articles, resulting in molded articles with excellent appearance. However, because of its high catalytic activity, it can cause deterioration of resin components and thickening, particularly in liquid masterbatches.

[0011] Therefore, an object of the present invention is to provide a liquid masterbatch that, even when containing anatase titanium oxide, suppresses thickening due to deterioration of the resin component and is capable of forming molded articles with excellent appearance without generating uneven color or colorant aggregates, and a colored resin composition that does not affect mechanical properties such as tensile strength or thermal properties such as melt viscosity. Another object of the present invention is to provide a molded article with excellent appearance. [Means for solving the problem]

[0012] The present inventors have conducted extensive research to solve the above problems and have arrived at the following invention. Specifically, the present invention relates to a liquid masterbatch comprising anatase titanium oxide (A), a metal deactivator (B), a liquid dispersion medium (C) having a viscosity of 10,000 mPa s or less at 25°C and a thermal decomposition onset temperature of 200°C or higher, and a dispersant (D), wherein the content of the anatase titanium oxide (A) is 50 to 80 mass% relative to 100 mass% of the liquid masterbatch. [Effects of the Invention]

[0013] The present invention has made it possible to provide a liquid masterbatch that suppresses thickening due to deterioration of resin components, does not cause color unevenness or colorant aggregates, and is capable of forming molded articles with good appearance, even when containing anatase titanium oxide, and a colored resin composition that does not affect mechanical properties such as tensile strength or thermal properties such as intrinsic viscosity.Furthermore, it has become possible to form molded articles with excellent appearance from the colored resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0014] The liquid masterbatch, colored resin composition, molded article, and fiber of the present invention will be described in detail below, but are not limited thereto. In addition, the term "liquid" in the present invention refers to a liquid state at 25°C. Note that "a liquid dispersion medium (C) having a viscosity of 10,000 mPa·s or less at 25°C and a thermal decomposition temperature of 200°C or higher" may be abbreviated as "liquid dispersion medium (C)." Unless otherwise noted, the various components appearing in this specification may be used independently either alone or in combination of two or more.

[0015] Liquid masterbatch The liquid masterbatch of the present invention comprises anatase type titanium oxide (A), a metal deactivator (B), a liquid dispersion medium (C) having a viscosity of 10,000 mPa·s or less at 25°C and a thermal decomposition onset temperature of 200°C or higher, and a dispersant (D), wherein the content of the anatase type titanium oxide (A) is 50 to 80 mass% relative to 100 mass% of the liquid masterbatch. By mixing such a liquid masterbatch with the diluted resin (X) described later to form a colored resin composition, a molded article formed from the colored resin composition does not have color unevenness or colorant aggregates, and has an excellent appearance.

[0016] <Anatase-type titanium dioxide (A)> The anatase type titanium oxide (A) of the present invention is titanium oxide having an anatase type crystal structure. Anatase titanium dioxide has a bluish hue and lower hardness than titanium dioxide with a rutile crystal structure, so when used as a colorant, it can produce molded articles with excellent coloring and matte finish and excellent appearance. In particular, in synthetic fiber applications, anatase titanium dioxide has lower hardness than rutile titanium dioxide, making it easier to suppress wear on mechanical parts and allowing for good passability in subsequent processes. However, the commonly used anatase type titanium dioxide has higher catalytic activity than the rutile type, and therefore, particularly in a liquid masterbatch, it may deteriorate the liquid dispersion medium or resin components such as the dispersant, causing an increase in viscosity. In contrast, by using the liquid masterbatch of the present invention, even when anatase titanium oxide is used, thickening due to deterioration of the resin component is suppressed, and a molded product with excellent appearance can be obtained due to uniform coloring and matte finish. The anatase type titanium oxide (A) may be surface-treated with various organic or inorganic compounds. Examples of organic compounds include fatty acids such as stearic acid, alkylsilanes, and silicone oils, while examples of inorganic compounds include alumina, silica, zirconia, titania, zinc, and tin compounds.

[0017] The content of anatase titanium oxide (A) is 50 to 80 mass %, more preferably 65 to 75 mass %, based on 100 mass % of the liquid masterbatch. By being within the above range, a liquid masterbatch with high storage stability and good fluidity can be obtained, and a colored resin composition with excellent moldability and mechanical properties can be obtained.

[0018] The average particle size of the anatase type titanium oxide (A) is not particularly limited, but is preferably 1 μm or less, and more preferably 0.01 to 0.5 μm. In fiber applications, a particle size of 0.01 to 0.5 μm, which is smaller than the fiber diameter, is preferred because it prevents thread breakage during spinning, reduces the decrease in tensile strength, and allows for convenient use. In the case of surface-treated anatase-type titanium oxide, it is preferable that the average particle size of the titanium oxide after the surface treatment is within the above range. The average particle size can be measured using a dynamic light scattering particle size distribution analyzer LB-550 (manufactured by Horiba, Ltd.) or the like.

[0019] Specific examples of anatase-type titanium oxide (A) include, but are not limited to, Titone SA-1 (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.15 μm, surface untreated), Titone A-190 (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.15 μm, surface alumina treatment), and TA-100 (manufactured by Fuji Titanium Co., Ltd., average particle size 0.60 μm, surface untreated).

[0020] <Metal deactivator (B)> The metal deactivator (B) is not particularly limited as long as it has the function of capturing and stabilizing metal ions, which are deterioration factors, by chelating the metal ions. Examples include oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, triazole derivatives, and imidazole derivatives. However, oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, and triazole derivatives are preferred because they provide high storage stability to the liquid masterbatch, and salicylic acid derivatives are more preferred because they have excellent heat resistance and compatibility with the diluent resin (X). Anatase titanium dioxide has higher catalytic activity than rutile titanium dioxide, and therefore is prone to causing deterioration of the dispersant (D) in the liquid masterbatch and the diluent resin (X) in the colored resin composition. However, by using a metal deactivator (B) to supplement the factors that cause deterioration and achieve stabilization, the dispersibility of the anatase titanium dioxide (A) in the liquid masterbatch is maintained, and the viscosity of the liquid masterbatch is prevented from increasing over time, making it possible to maintain the moldability of the colored resin composition and the mechanical properties of the molded product.

[0021] Specific examples of these compounds include oxalic acid derivatives such as oxalo-bis-1,2-hydroxybenzylidenehydrazide and 2,2'-oxamidobis(ethyl 3-(3,5-tert-butyl-4-hydroxyphenyl)propionate), but are not particularly limited thereto. Specific examples of oxalic acid derivatives include Eastman Inhibitor OABH (manufactured by Eastman Kodak Co.), Naugard XL-1 (manufactured by Shiraishi Calcium Co.), and the like.

[0022] Examples of salicylic acid derivatives include, but are not limited to, 3-(N-salicyloyl)amino-1,2,4-triazole, decamethylenedicarboxylic acid disalicyloyl hydrazide, salicylidenesalicyloyl hydrazine, and the like. Specific examples of salicylic acid derivatives include Adekastab CDA-6 (manufactured by ADEKA Corporation) and Chel-180 (manufactured by BASF Corporation).

[0023] Examples of hydrazide derivatives include, but are not limited to, N,N'-bis((3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl))propionohydrazide. Specific examples of hydrazide derivatives include Adekastab CDA-10 (manufactured by ADEKA Corporation) and Qunox (manufactured by Mitsui Toatsu Fine Co., Ltd.).

[0024] Examples of triazole derivatives include, but are not limited to, benzotriazole, 3-amino-1,2,4-triazole, 2-mercaptobenzotriazole, 2,5-dimercaptobenzotriazole, 4-alkylbenzotriazole, 5-alkylbenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, 5,5'-methylenebisbenzotriazole, 1-[di(2-ethylhexyl)aminomethyl]-1,2,4-triazole, 1-(1-butoxyethyl)-1,2,4-triazole, acylated 3-amino-1,2,4-triazole, and 1,2,3-benzotriazole. A specific example of the triazole derivative is BT-120 (manufactured by Johoku Chemical Co., Ltd.).

[0025] Examples of imidazole derivatives include, but are not limited to, 4,4'-methylenebis(2-undecyl-5-methylimidazole), bis[(N-methyl)imidazol-2-yl]carbinol octyl ether, and the like.

[0026] The content of the metal deactivator (B) is preferably 0.01 to 5 mass%, more preferably 0.05 to 4 mass%, and even more preferably 0.1 to 1 mass%, based on 100 mass% of the liquid masterbatch. By keeping the content within the above range, deterioration of resin components such as the liquid dispersion medium (C) and dispersant (D) due to the high catalytic activity of anatase titanium oxide is suppressed, thereby making it possible to form a liquid masterbatch with high storage stability and excellent dispersibility of anatase titanium oxide (A), as well as a colored resin composition with excellent moldability and thermal properties.

[0027] <Liquid dispersion medium (C)> The liquid dispersion medium (C) of the present invention serves as a dispersion medium for dispersing the anatase type titanium oxide (A). The liquid dispersion medium (C) is characterized by having a viscosity of 10,000 mPa·s or less at 25°C and a thermal decomposition onset temperature of 200°C or higher. This makes it possible to obtain a liquid masterbatch with excellent dispersibility of anatase-type titanium dioxide (A). Furthermore, when a molded product is obtained by melt-kneading with the diluted resin (X), the liquid dispersion medium (C) decomposes little, so molding defects such as silver streaks do not occur, and molded products can be obtained stably.

[0028] From the viewpoint of dispersibility of anatase type titanium oxide (A), the viscosity at 25° C. is more preferably 10 to 5,000 mPa·s, and even more preferably 20 to 3,000 mPa·s. A viscosity of 10 mPa·s or more is preferred from the viewpoint of moldability. The thermal decomposition starting temperature is more preferably 220° C. or higher, and even more preferably 240° C. or higher. When the temperature is within this range, when a molded article is obtained by melt-kneading with the diluted resin (X), decomposition of the liquid dispersion medium (C) is reduced, so that molding defects such as silver streaks do not occur, and molded articles can be obtained stably. The viscosity in this specification is a value measured at 25°C using a B-type viscometer in accordance with JIS K7117-1:1999. The thermal decomposition onset temperature can be determined using a thermogravimetric and differential thermal analyzer (TG / DTA).

[0029] The content of the liquid dispersion medium (C) is preferably 10% by mass or more, more preferably 10 to 45% by mass, and even more preferably 15 to 35% by mass, based on 100% by mass of the liquid masterbatch. By keeping the content within the above range, the fluidity of the liquid masterbatch can be maintained during the stirring and dispersion steps in production, and a molded product with excellent moldability and mechanical properties can be obtained.

[0030] The liquid dispersion medium (C) preferably has a number average molecular weight (Mn) of 100 to 3000, more preferably 200 to 2000, and even more preferably 400 to 1500. An Mn of 100 or more is preferred in terms of screw slip properties, and an Mn of 3000 or less is preferred in terms of dispersibility. The number average molecular weight is a value calculated as the molecular weight of standard polystyrene, determined by gel permeation chromatography (GPC).

[0031] Examples of the liquid dispersion medium (C) include liquid resins such as epoxy resins such as epoxidized soybean oil and epoxidized linseed oil, fatty acid polyester resins, polyalkylene glycol resins, polyether ester resins, and acetyl tributyl citrate. However, even when the diluent resin (X) is a polyethylene terephthalate (PET) or polyamide resin that requires a high molding temperature, fatty acid polyester resins, polyalkylene glycol resins, polyether ester resins, and acetyl tributyl citrate are preferred, with polyether ester resins being more preferred, because they have high heat resistance and excellent moldability.

[0032] [Fatty acid polyester resin] Examples of fatty acid polyester resins include polyester resins obtained by reacting aliphatic polycarboxylic acids with polyhydric alcohols.

[0033] The aliphatic polycarboxylic acid constituting the fatty acid polyester resin is not particularly limited as long as it is an aliphatic carboxylic acid having two or more carboxyl groups, and examples thereof include aliphatic polycarboxylic acids such as succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-hexanetricarboxylic acid, etc. These aliphatic carboxylic acids may be used alone or in combination of two or more.

[0034] The polyhydric alcohol constituting the fatty acid polyester resin is not particularly limited as long as it is an alcohol having two or more hydroxyl groups, and examples thereof include 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, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2 Examples of the glycol include aliphatic glycols such as n-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-octadecanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol. These may be used alone or in combination of two or more.

[0035] The freezing point of the fatty acid polyester resin is preferably -5°C or lower, more preferably -60°C to -10°C.

[0036] A specific example of fatty acid polyester resin is ADEKA Cizer PN-170 (ADEKA Corporation). Examples of suitable resins include Adeka Cizer P-200 (manufactured by Adeka Corporation, viscosity at 25°C 800 mPa·s, freezing point -15°C, adipic acid polyester resin), Adeka Cizer P-200 (manufactured by Adeka Corporation, viscosity at 25°C 2,600 mPa·s, freezing point -20°C, adipic acid polyester resin), and Adeka Cizer PN-250 (manufactured by Adeka Corporation, viscosity at 25°C 4,500 mPa·s, freezing point -20°C, adipic acid polyester resin).

[0037] [Polyalkylene glycol resin] Polyalkylene glycol resins are generally composed of alkylene glycols with repeating units containing 1 to 6 carbon atoms, but various polyalkylene glycols can be used as long as their viscosity at 25°C is 10,000 mPa s or less. From the viewpoints of compatibility, water absorption, and screw slip properties, polyalkylene glycol resins with repeating units containing 2 to 4 carbon atoms are preferred.

[0038] Specific examples of polyalkylene glycol resins include polyethylene glycol, both of which have 2 carbon atoms in their repeating units, polytrimethylene glycol and polypropylene glycol, both of which have 3 carbon atoms in their repeating units, and polytetramethylene glycol and polybutylene glycol, both of which have 4 carbon atoms in their repeating units. Polypropylene glycol is particularly preferred from the viewpoints of compatibility and water absorbency.

[0039] [Polyetherester resin] The polyether ester resin is obtained by esterifying the aliphatic polycarboxylic acid and the alkylene glycol described above in the fatty acid polyester resin.

[0040] Specific examples of polyetherester resins include Adeka Cizer RS-107 (manufactured by Adeka Corporation, viscosity at 25°C 20 mPa·s, freezing point -47°C, adipic acid ether ester resin) and Adeka Cizer RS-700 (manufactured by Adeka Corporation, viscosity at 25°C 30 mPa·s, freezing point -53°C, polyetherester resin).

[0041] <Dispersant (D)> The dispersant (D) is not particularly limited as long as it interacts with anatase titanium oxide (A), and examples thereof include hindered amine compounds (HALS), phosphate ester compounds, and resin-type dispersants having a pigment-affinity moiety that has the property of adsorbing to inorganic pigments such as titanium oxide, and a relaxation moiety that has high affinity with components other than the pigment and causes steric repulsion between pigment particles.

[0042] The dispersant (D) is preferably a phosphate ester compound because it has a strong interaction with the anatase titanium dioxide (A). The use of such a dispersant (D) allows for stable preparation of a liquid masterbatch. Furthermore, a molded product with excellent moldability and mechanical properties can be obtained without causing a decrease in strength.

[0043] The acid value of the dispersant (D) is preferably 180 mgKOH / g or less, and more preferably 0 to 140 mgKOH / g or less, from the viewpoint of the dispersibility of the anatase type titanium oxide (A) and the mechanical properties of the molded product.

[0044] The amine value of the dispersant (D) is preferably 180 mgKOH / g or less, and more preferably 0 to 140 mgKOH / g or less, from the viewpoint of the dispersibility of the anatase type titanium oxide (A) and the mechanical properties of the molded product.

[0045] The amount of dispersant (D) in the liquid masterbatch is preferably 0.01 to 20 mass%, more preferably 0.5 to 10 mass%, based on 100 mass% of the liquid masterbatch, from the viewpoint of the dispersibility of anatase titanium oxide (A) and compatibility with the diluent resin (X). Furthermore, from the viewpoint of the dispersibility of anatase type titanium oxide (A) and compatibility with the diluent resin (X), the amount of dispersant (D) to be blended is preferably 0.01 to 40 parts by mass, more preferably 0.5 to 20% by mass, per 100 parts by mass of anatase type titanium oxide (A).

[0046] [Resin-type dispersant] Examples of resin-type dispersants that can be used include resin-based polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, and ethylene oxide / propylene oxide adducts.

[0047] Specific examples of resin-type dispersants include Disper BYK-108 (manufactured by BYK, amine value 71 mg KOH / g), Disper BYK-109 (manufactured by BYK, amine value 140 mg KOH / g), Disper BYK-111 (manufactured by BYK, acid value 95 mg KOH / g, amine value 129 mg KOH / g), Disper BYK-180 (manufactured by BYK, acid value 94 mg KOH / g, amine value 94 mg KOH / g), and Disper BYK-2013 (manufactured by BYK). Examples of such copolymers include Disper BYK-2055 (manufactured by BYK-Chemie, acid value 8 mg KOH / g, amine value 18 mg KOH / g), Disper BYK-2055 (manufactured by BYK-Chemie, amine value 40 mg KOH / g), Disper BYK-2155 (manufactured by BYK-Chemie, amine value 48 mg KOH / g), Disper BYK-2157 (manufactured by BYK-Chemie, acid value 35 mg KOH / g, amine value 5 mg KOH / g), and Disper BYK-9076 (manufactured by BYK-Chemie, acid value 38 mg KOH / g, amine value 44 mg KOH / g).

[0048] [Phosphate ester compounds] Examples of phosphate ester compounds include alkyl phosphates such as tributyl phosphate, trioctyl phosphate, tris(β-chloroethyl)phosphate, tris(β-chloropropyl)phosphate, and tris(dichloropropyl)phosphate; phenyl phosphates such as triphenyl phosphate, tricresyl phosphate, tris(i-properphenyl)phosphate, cresyl diphenyl phosphate, and octyl diphenyl phosphate; alkyl polyoxyethylene phosphate esters such as tributoxyethyl phosphate; alkylphenol polyoxyethylene phosphate esters; and their neutralized salts with sodium, potassium, ammonia, amine, or the like. These phosphate ester compounds may have an acid value or an amine value. These phosphate ester compounds may be used alone or in combination of two or more. From the viewpoint of dispersibility of anatase titanium dioxide (A), the phosphate ester compound is preferably an alkyl polyoxyethylene phosphate ester or alkylphenol polyoxyethylene phosphate ester having an acid value or an amine value.

[0049] Specific examples of the phosphate ester compound include ADEKA REASOAP PP-70 (manufactured by ADEKA Corporation), DISPER BYK-102 (manufactured by BYK-Chemie, acid value 101 mgKOH / g), and DISPER BYK-145 (manufactured by BYK-Chemie, acid value 76 mgKOH / g, amine value 71 mgKOH / g).

[0050] <Method for manufacturing liquid masterbatch> The method for producing the liquid masterbatch in the present invention is not particularly limited, and for example, the liquid masterbatch can be obtained by adding anatase titanium oxide (A), a metal deactivator (B), a liquid dispersion medium (C), a dispersant (D), and, if necessary, other functionality-imparting agents, mixing them in a Henschel mixer, tumbler, disperser, or the like, and dispersing them using a Silverson mixer (manufactured by Silverson) or the like. In addition to the above, any other dispersing device can also be used, such as a kneader, roll mill, ball mill, or sand mill. It is preferable to use a Silverson mixer or roll mill because of their ease of molding and excellent dispersibility.

[0051] 《Colored resin composition》 The colored resin composition of the present invention is used to form a molded article containing anatase type titanium oxide (A), and contains a liquid masterbatch and a diluent resin (X).

[0052] The method for producing the colored resin composition is not particularly limited, and for example, a liquid masterbatch and diluted resin (X), and further various additives and colorants as necessary, are mixed in a Henschel mixer, tumbler, disperser, etc., and then mixed or melt-kneaded in a batch mixer such as a kneader, roll mill, super mixer, high-speed mixer, ball mill, sand mill, attritor, or Banbury mixer, a single-screw extruder, a twin-screw extruder, a rotor-type twin-screw kneader, etc., to form a pellet-shaped, powder-shaped, granular, or bead-shaped resin composition. It is preferable to form a pellet-shaped colored resin composition using a twin-screw extruder because it is easy to mold.

[0053] These colored resin compositions can be used, for example, as a compound for forming a molded body by melting and kneading a pellet-shaped colored resin composition consisting of a mixture of a liquid masterbatch containing anatase titanium oxide (A) and a diluted resin (X) without diluting it with other resins or the like, or as a solid masterbatch for forming a molded body by further melting and kneading it with the diluted resin (X).

[0054] Specifically, the compound preferably contains 0.1 to 5 parts by mass, more preferably 0.4 to 3 parts by mass, of the liquid masterbatch relative to 100 parts by mass of the diluted resin (X). By using the compound within the above range, it is possible to obtain a molded product that has excellent appearance without color unevenness or colorant aggregates, and that is excellent in mechanical properties such as tensile strength and thermal properties such as intrinsic viscosity.

[0055] When preparing a solid masterbatch, it is preferable to blend 0.1 to 10 parts by mass of the liquid masterbatch with 100 parts by mass of the diluted resin (X). This does not affect the processability of the solid masterbatch. When the obtained solid masterbatch is mixed with the diluted resin (X) and molded, the blending amount of the solid masterbatch is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. By keeping it within the above range, it is possible to suppress deterioration in the physical properties of the molded product.

[0056] <Diluted Resin (X)> The diluent resin (X) is a resin that serves as the main resin of the molded body, and is preferably a thermoplastic resin. However, this does not include the case where the dispersion medium (C) is a liquid. Preferably, the diluent resin (X) is a solid at 25°C. Examples of the diluent resin (X) include polycarbonate resin, polyester resin, acrylic resin, polyamide resin, fluororesin, polystyrene resin, cycloolefin copolymer (COC), polyvinyl chloride resin, etc. Among these, polyester-based resin or polyamide-based resin is preferred because it has high compatibility with the liquid dispersion medium (C) and therefore tends to maintain mechanical properties such as tensile strength.

[0057] [Polycarbonate resin] Polycarbonate resins can be easily produced by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or a carbonate diester, etc. The reaction can be carried out by a known method, for example, an interfacial method when phosgene is used, or a transesterification method in which the reaction is carried out in a molten state when a carbonate diester is used.

[0058] Examples of the aromatic dihydroxy compound include bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; Examples of suitable hydroxyaryl compounds include bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; and dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. These compounds may be used alone or in combination. In addition to these compounds, piperazine, dipiperidyl hydroquinone, resorcinol, and 4,4'-dihydroxydiphenyl compounds may also be used in combination. Furthermore, branched aromatic polycarbonate resins containing polyfunctional compounds such as phloroglucin can also be used.

[0059] Examples of the carbonate precursor to be reacted with the aromatic dihydroxy compound include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0060] A specific example of the polycarbonate resin is Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation).

[0061] [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).

[0062] Examples of carboxylic acid components constituting the polyester resin include benzoic acid, p-tert-butylbenzoic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, tetrachlorophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride, methylcyclohexene tricarboxylic anhydride, pyromellitic anhydride, and ε-caprolactone.

[0063] Examples of hydroxyl group components that constitute the polyester resin include diols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, 3-methylpentanediol, and 1,4-cyclohexanedimethanol, as well as polyfunctional alcohols having three or more hydroxyl groups such as glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, and dipentaerythritol.

[0064] Specific examples of polyester resins include Polyester MA-2101M (PET resin, manufactured by Unitika Co., Ltd.) and Duranex 700FP (PBT resin, manufactured by Polyplastics Co., Ltd.).

[0065] [Acrylic resin] Acrylic resins 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, and styrene. In this specification, "(meth)acrylic" means "acrylic and / or methacrylic," and "(meth)acrylate" means "acrylate and / or methacrylate." Among these, polymethyl methacrylate (PMMA) resin is preferred.

[0066] A specific example of the acrylic resin is Acrypet VH (polymethyl methacrylate resin, manufactured by Mitsubishi Chemical Corporation).

[0067] [Polyamide resin] The polyamide resin can be obtained, for example, by reacting the above-mentioned carboxylic acid component with a compound having two or more amino groups, for example, by subjecting the carboxylic acid component to a dehydration condensation reaction with a compound (Am) having two or more amino groups.

[0068] The compound (Am) having two or more amino groups may be any known compound, and examples thereof include aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diaminoalcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine.

[0069] A specific example of the polyamide resin is Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, Inc.).

[0070] [Fluorine resin] Fluorine resins can be obtained by copolymerization of fluorine-containing monomers. Examples of fluorine-containing monomers include fluorine-containing ethylenically unsaturated compounds such as vinyl fluoride, tetrafluoroethylene, trifluorochloroethylene, hexafluoropropylene, hexafluoroisobutylene, perfluoroacrylic acid, perfluoromethacrylic acid, and fluoroalkyl esters of acrylic acid or methacrylic acid, as well as fluorine-free ethylenically unsaturated compounds such as cyclohexyl vinyl ether and hydroxyethyl vinyl ether. Monomers copolymerizable with the fluorine-containing monomers may also be fluorine-free diene compounds such as butadiene, isoprene, and chloroprene. Examples of fluorine resins include polyvinylidene fluoride resin (PVDF resin), which is a homopolymer of vinylidene fluoride; polytetrafluoroethylene resin (PTFE resin), which is a homopolymer of tetrafluoroethylene; and ethylene-tetrafluoroethylene copolymer (ETFE resin), which is a copolymer of ethylene and tetrafluoroethylene.

[0071] Specific examples of fluororesins include KF Polymer W#1100 (manufactured by Kureha Corporation, PVDF resin), Fluon PTFE CD123E (manufactured by Asahi Glass Co., Ltd., PTFE resin), and Fluon ETFE C-55AP (manufactured by Asahi Glass Co., Ltd., ETFE resin).

[0072] <<Molded body>> The molded article of the present invention is formed from a colored resin composition containing the liquid masterbatch of the present invention and a diluent resin (X), and the liquid masterbatch is preferably blended in an amount of 0.1 to 5 parts by mass, more preferably 0.40 to 3 parts by mass, per 100 parts by mass of the diluent resin (X). By blending in the above range, it is possible to obtain a molded article that has excellent appearance without color unevenness or colorant aggregates, and is excellent in mechanical properties such as tensile strength and thermal properties such as intrinsic viscosity.

[0073] Examples of molded articles include various pipes, films, laminates, coatings, fibers, injection molded articles, compression injection molded articles, rotational molded articles, extrusion molded articles, etc. for food and daily necessities, etc. In particular, the liquid masterbatch of the present invention has anatase type titanium oxide uniformly and finely dispersed therein, colors molded articles without unevenness, and does not affect mechanical properties such as tensile strength, so that molded articles with higher dispersibility than conventional ones can be obtained, and the masterbatch is particularly suitable for use in fibers.

[0074] The molded article of the present invention can be obtained by molding the colored resin composition by any of extrusion molding, injection molding, blow molding, compression molding, transfer molding, film molding, calender molding, spinning molding and the like.

[0075] Specifically, for example, there are mentioned (Method 1) a method in which a liquid masterbatch and pellets of diluted resin (X) or the like are melt-kneaded to form a colored resin composition, and a molded body is obtained; (Method 2) a method in which a liquid masterbatch and diluted resin (X) are melt-kneaded to form a masterbatch, and the colored resin composition is then melt-kneaded together with pellets of diluted resin (X) or the like to form a molded body; and (Method 3) a method in which a liquid masterbatch and diluted resin (X) are melt-kneaded to form a compound, and the compound is then melt-kneaded as is to form pellets or the like to form a molded body.

[0076] The colored resin composition of the present invention can be subjected to injection molding, blow molding, or extrusion molding to obtain a molded article. From the viewpoint of the dispersibility of anatase titanium oxide (A) and the physical properties of the colored resin composition, it is preferable to obtain the molded article by mixing a liquid masterbatch with a diluent resin (X) (Method 1) or by diluting the masterbatch with a diluent resin (X) (Method 2).

[0077] When producing fibers as a molded article, they can be produced by a conventional melt spinning method, and a two-step method or a one-step method of spinning and drawing can be used. Furthermore, all known fiber production methods, such as staple production methods and monofilament production methods, which include crimping, heat setting, and cutting steps, can be applied. [Example]

[0078] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the examples, parts and % represent parts by mass and % by mass, respectively, unless otherwise specified. The blending amounts in the table are in mass % and are calculated as non-volatile content. Blank spaces in the table indicate that no blending was performed. The average particle size of the anatase type titanium oxide (A), the number average molecular weight and viscosity of the liquid dispersion medium (C), and the acid value and amine value of the dispersant (D) were measured by the following methods.

[0079] <Measurement of the average particle size of anatase-type titanium dioxide (A)> The average particle size was measured using a dynamic light scattering particle size distribution measuring device LB-550 (manufactured by Horiba, Ltd.).

[0080] <Measurement of number average molecular weight of liquid dispersion medium (C)> The number-average molecular weight is the number-average molecular weight converted to standard polystyrene molecular weight and was measured using a high-performance liquid chromatograph (Tosoh Corporation, "HLC-8320GPC") with two TSKgel SuperMultipore HZ-M columns in series (exclusion limit: 2 x 106, theoretical plate number: 16,000 plates / column, packing material: styrene-divinylbenzene copolymer, packing particle size: 4 μm, column temperature: 40°C). GPC is a liquid chromatograph that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on differences in their molecular size.

[0081] <Measurement of viscosity of liquid dispersion medium (C)> The viscosity is a value measured at 25°C using a B-type viscometer in accordance with JIS K7117-1:1999.

[0082] <Measurement of the thermal decomposition temperature of the liquid dispersion medium (C)> The thermal decomposition starting temperature is the temperature at which the weight loss rate reaches 10% when the weight loss is measured using a thermogravimetric and differential thermal analyzer (TG / DTA) under the following conditions at a constant rate of temperature increase. Measuring equipment: Seiko Instruments TG / DTA 6200 Measurement range: RT to 400°C Heating rate: 10°C / min Atmosphere: Nitrogen

[0083] <Measurement of the acid value of dispersant (D)> Approximately 1 g of sample was accurately weighed into a stoppered Erlenmeyer flask and dissolved in 100 mL of cyclohexanone solvent. Phenolphthalein test solution was added as an indicator and the mixture was allowed to stand for 30 seconds. The solution was then titrated with 0.1 N alcoholic potassium hydroxide solution until it turned a pale pink color. The acid value was calculated using the following formula (unit: mgKOH / g). Acid value (mgKOH / g)=(5.611×a×F) / S however, S: Amount of sample collected (g) a: Amount of 0.1N alcoholic potassium hydroxide solution consumed (mL) F: Potency of 0.1N alcoholic potassium hydroxide solution

[0084] <Measurement of the amine value of dispersant (D)> Approximately 1 g of sample was accurately weighed into a stoppered Erlenmeyer flask and dissolved in 100 mL of cyclohexanone solvent. A few drops of an indicator prepared separately by dissolving 0.20 g of Methyl Orange in 50 mL of distilled water and 0.28 g of Xylene Cyanol FF in 50 mL of methanol were added and the mixture was left to stand for 30 seconds. The solution was then titrated with 0.1 N alcoholic hydrochloric acid until it turned blue-gray. The amine value was calculated using the following formula (unit: mgKOH / g). Acid value (mgKOH / g)=(5.611×a×F) / S however, S: Amount of sample collected (g) a: Consumption volume of 0.1N alcoholic hydrochloric acid solution (mL) F: Potency of 0.1N alcoholic hydrochloric acid solution

[0085] The materials used in the examples and comparative examples are listed below. <Anatase-type titanium dioxide (A)> (A-1): Tytone SA-1 (Sakai Chemical Industry Co., Ltd., particle size 0.15 μm, surface untreated) (A-2): A-190 (Sakai Chemical Industry Co., Ltd., particle size 0.15 μm, surface alumina treatment) (A-3): TA-100 (manufactured by Fuji Titanium Industries, particle size 0.60 μm, surface untreated)

[0086] <Metal deactivator (B)> (B-1): Chel-180 (BASF, salicylic acid derivative) (B-2): Naugard XL-1 (Shiraishi Calcium Co., Ltd., oxalic acid derivative) (B-3): CDA-10 (ADEKA, hydrazide derivative) (B-4): BT-120 (manufactured by Johoku Chemical Co., Ltd., triazole derivative) (B-5): 4,4'-methylenebis(2-undecyl-5-methylimidazole)

[0087] <Liquid dispersion medium (C)> (C1): Adeka Cizer RS-700 (manufactured by ADEKA Corporation, polyetherester resin, number average molecular weight 500, viscosity 30 mPa·s, thermal decomposition temperature 290°C) (C2): PEG-400 (manufactured by Sanyo Chemical Industries, Ltd., polyalkylene glycol resin, polyethylene glycol resin, number average molecular weight 400, viscosity 90 mPa·s, thermal decomposition temperature 234°C) (C3): Uniol D-400 (NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa·s, thermal decomposition temperature 242°C) (C4): Uniol D-1200 (NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 1200, viscosity 200 mPa·s, thermal decomposition temperature 276°C) (C5): Adeka Cizer PN-6810 (ADEKA Corporation, acetyl tributyl citrate, number average molecular weight 190, viscosity 43 mPa·s, thermal decomposition temperature 218°C) (C6): Adeka Cizer PN-250 (manufactured by ADEKA Corporation, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa·s, thermal decomposition temperature 314°C)

[0088] <Dispersant (D)> (D1): Disper BYK-102 (manufactured by BYK-Chemie, phosphate ester compound, acid value 101 mg KOH / g) (D2): Adeka Reasoap PP-70 (manufactured by ADEKA Corporation, phosphate ester compound) (D3): Disper BYK-145 (manufactured by BYK-Chemie, phosphate ester compound, acid value 76 mg KOH / g, amine value 71 mg KOH / g) (D4): Disper BYK-108 (manufactured by BYK-Chemie, resin-type dispersant, amine value 71 mg KOH / g) (D5): Disper BYK-109 (manufactured by BYK-Chemie, resin-type dispersant, amine value 140 mg KOH / g) (D6): Disper BYK-111 (manufactured by BYK-Chemie, resin-type dispersant, acid value 95 mg KOH / g, amine value 129 mg KOH / g) (D7): Disper BYK-180 (manufactured by BYK-Chemie, resin-type dispersant, acid value 94 mg KOH / g, amine value 94 mg KOH / g) (D8): Disper BYK-2013 (manufactured by BYK-Chemie, resin-type dispersant, acid value 8 mg KOH / g, amine value 18 mg KOH / g) (D9): Disper BYK-2055 (manufactured by BYK-Chemie, resin-type dispersant, amine value 40 mg KOH / g) (D10): Disper BYK-2155 (manufactured by BYK-Chemie, resin-type dispersant, amine value 48 mg KOH / g) (D11): Disper BYK-2157 (manufactured by BYK-Chemie, resin-type dispersant, acid value 35 mg KOH / g, amine value 5 mg KOH / g) (D12): Disper BYK-9076 (manufactured by BYK-Chemie, resin-type dispersant, acid value 38 mg KOH / g, amine value 44 mg KOH / g)

[0089] <Diluted Resin (X)> X1: Polyester MA-2101M (polyester resin, manufactured by Unitika) X2: Amilan CM3001-N (polyamide resin, manufactured by Toray)

[0090] Example 1 (Production of liquid masterbatch (S-1)) 75 parts by mass of anatase-type titanium oxide (A1), 0.10 parts by mass of metal deactivator (B1), 16.9 parts by mass of liquid dispersion medium (C1), and 8 parts by mass of dispersant (D1) were mixed and dispersed in a bead mill to obtain a liquid masterbatch (S-1).

[0091] <Examples 2 to 33 and Comparative Examples 1 to 4> (Production of Liquid Masterbatches (S-2 to 33) and (S'-1 to 4)) Liquid masterbatches (S-2 to 33) and (S'-1 to 4) were produced in the same manner as liquid masterbatch (S-1), except that the materials and blending amounts (parts by mass) were changed to those shown in Tables 1 and 2, respectively.

[0092] <Comparative Example 5> (Production of solid masterbatch (T-1)) 75 parts by mass of anatase type titanium oxide (A1) and 25 parts by mass of a thermoplastic resin (polyester MA-2101M, polyester resin, manufactured by Unitika) were mixed, melted and kneaded in a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.) to obtain a solid masterbatch (T-1).

[0093] <Comparative Examples 6 to 8> (Production of solid masterbatches (T-2 to T-4)) Solid masterbatches (T-2 to T-4) were produced in the same manner as for the solid masterbatch (T-1), except that the materials and blending amounts (mass %) were changed to those shown in Table 4.

[0094] <Evaluation of liquid masterbatch and solid masterbatch> The dispersibility and storage stability of the obtained liquid masterbatch and solid masterbatch were evaluated by the following methods, and the results are shown in Tables 1 to 4.

[0095] (Dispersibility evaluation) The particle size at a cumulative volume percentage of 90% (D 90 ) was measured using a dynamic light scattering particle size distribution analyzer LB-550 (manufactured by Horiba, Ltd.) and was evaluated according to the following criteria. In the case of a solid masterbatch, the solid masterbatch is dissolved in a phenol / 1,1,2,2-tetrachloroethane = 1 / 1 mixture at 150 °C to prepare a solution, and the average dispersed particle size and D 90 was measured. [Evaluation criteria] ◎:D 90 is less than 3 μm, which is very good 〇:D 90 is 3 μm or more and less than 10 μm, which is good △:D 90is between 10 μm and 30 μm, and is practically usable ×:D 90 is 30μm or more, and is unacceptable

[0096] (Storage stability evaluation) The fluidity of the obtained liquid masterbatch at 25°C was checked one month and three months after production, and evaluated according to the following criteria. The solid masterbatch was not evaluated because it was solid at 25°C and its fluidity did not change. [Evaluation criteria] 〇: Flows well and has the same fluidity as immediately after production, good △: Flows, but fluidity is lower than immediately after production, and usable ×: Not flowing, not practical

[0097] [Table 1]

[0098] [Table 2]

[0099] [Table 3]

[0100] [Table 4]

[0101] The thermoplastic resins used in Table 4 were: MA-2101M; Polyester MA-2101M (polyester resin, manufactured by Unitika) Amilan CM3001-N: Amilan CM3001-N (polyamide resin, manufactured by Toray)

[0102] Example 34 (Production of Molded Body) 0.4 parts by mass of the liquid master batch (S-1) and 100 parts by mass of the diluted resin (X1) were mixed together and a 90 denier fiber was obtained using a spinning machine.

[0103] <Examples 35 to 99 and Comparative Examples 9 to 12> Fibers were obtained in the same manner as in Example 25, except that the materials and blending amounts (parts by mass) were changed to those shown in Tables 4 and 5, respectively. The liquid masterbatches (S'-1, 4) and solid masterbatches (T-1, 2) had poor dispersibility and frequently caused thread breakage during the spinning process, making it impossible to obtain fibers.

[0104] <Evaluation of molded products> The resulting molded articles were evaluated for dispensability, tensile strength, and intrinsic viscosity retention by the following methods. The results are shown in Tables 5 and 6.

[0105] (Distributive Assessment) The obtained fibers were evaluated based on whether or not there was uneven coloring. [Evaluation criteria] 〇: No uneven color, good △: There is some color unevenness, but it is usable ×: Color unevenness, not practical

[0106] (Tensile strength evaluation) The tensile strength [cN / dtex] of the obtained fiber was measured in accordance with JIS L1013 under the conditions of a length of 300 mm, a pulling speed of 300 mm / min, and five measurements. [Evaluation criteria] 〇: Tensile strength 4.0cN / dtex or more, good △: Tensile strength 3.5cN / dtex or more, less than 4.0cN / dtex, usable ×: Tensile strength less than 3.5 cN / dtex, not practical

[0107] (Intrinsic viscosity retention rate) The intrinsic viscosity retention was calculated from the solution viscosity of the obtained fiber measured at 30°C in a mixed solvent of phenol:tetrachloroethane = 1:1. The measurement was carried out using a capillary automatic viscosity measuring device (manufactured by Shibayama Scientific Instruments Manufacturing Co., Ltd.). The intrinsic viscosity of the diluted resin (X) used in the fiber was set to 100, and the intrinsic viscosity retention was calculated as the ratio of the intrinsic viscosity of the diluted resin (X) to the intrinsic viscosity of the fiber. [Evaluation criteria] 〇: Retention rate 80% or more, good △: Retention rate 70% or more, less than 80%, usable ×: retention rate less than 70%, not practical

[0108] [Table 5]

[0109] [Table 6]

[0110] As shown in Tables 1 to 6, it was confirmed that the liquid masterbatch of the present invention can suppress thickening due to deterioration of the resin component, and can form molded articles with no color unevenness or colorant aggregates, even when containing anatase titanium oxide, and with no defective appearance.

Claims

1. The dispersion medium (C) contains an anatase type titanium oxide (A), a metal deactivator (B), a liquid dispersion medium (C) having a viscosity of 10,000 mPa s or less at 25°C and a thermal decomposition onset temperature of 200°C or more, and a dispersant (D), the metal deactivator (B) is at least one selected from the group consisting of oxalic acid derivatives, salicylic acid derivatives, hydrazide derivatives, triazole derivatives, and imidazole derivatives; the dispersant (D) is at least one selected from the group consisting of a hindered amine compound, a phosphate ester compound, and a resin-type dispersant; The content of the anatase type titanium oxide (A) is 50 to 80 mass % in 100 mass % of the liquid master batch.

2. 2. The liquid masterbatch according to claim 1, wherein the content of the metal deactivator (B) is 0.01 to 5 mass% in 100 mass% of the liquid masterbatch.

3. 3. The liquid masterbatch according to claim 1, wherein the liquid dispersion medium (C) is at least one selected from the group consisting of a fatty acid polyester resin, a polyalkylene glycol resin, a polyether ester resin, and acetyl tributyl citrate.

4. The liquid masterbatch according to any one of claims 1 to 3, wherein the dispersant (D) is a phosphate ester compound.

5. The liquid masterbatch according to any one of claims 1 to 4, wherein the content of the dispersant (D) is 0.01 to 20 mass% in 100 mass% of the liquid masterbatch.

6. A colored resin composition comprising the liquid masterbatch according to any one of claims 1 to 5 and a diluting resin (X) (excluding the case where the diluting resin (X) is a liquid dispersion medium (C)).

7. A colored resin composition, which is a melt-kneaded mixture of the liquid masterbatch according to any one of claims 1 to 5 and a diluting resin (X) (excluding the case where the diluting resin is a liquid dispersion medium (C)).

8. 8. The colored resin composition according to claim 6, wherein the diluent resin (X) is at least one of a polyester resin and a polyamide resin.

9. A molded article formed from the colored resin composition according to any one of claims 6 to 8.

10. A fiber formed from the colored resin composition according to any one of claims 6 to 8.

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