WO2024019052A1 - Liquid coloring composition, and method for manufacturing polyester resin composition and polyester resin molding body - Google Patents

Liquid coloring composition, and method for manufacturing polyester resin composition and polyester resin molding body Download PDF

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Publication number
WO2024019052A1
WO2024019052A1 PCT/JP2023/026277 JP2023026277W WO2024019052A1 WO 2024019052 A1 WO2024019052 A1 WO 2024019052A1 JP 2023026277 W JP2023026277 W JP 2023026277W WO 2024019052 A1 WO2024019052 A1 WO 2024019052A1
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Prior art keywords
polyester resin
dye
coloring composition
liquid coloring
diol component
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PCT/JP2023/026277
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French (fr)
Japanese (ja)
Inventor
渓介 大久保
誠 柳澤
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東洋インキＳｃホールディングス株式会社
トーヨーカラー株式会社
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Publication of WO2024019052A1 publication Critical patent/WO2024019052A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • Embodiments of the present invention relate to a liquid coloring composition used when obtaining a polyester resin by polymerization, and a method for producing a polyester resin composition and a polyester resin molded article.
  • plastic molded bodies are easy to mold, they are used in a wide range of fields such as electrical and electronic equipment parts, automobile parts, medical parts, and food containers.
  • molded products using polyester resin have excellent chemical and physical properties, so they can be used in food containers such as plastic bottles, sanitary containers, polyester fibers, films, sheets, etc. It is used for a wide variety of purposes. Furthermore, in order to reduce costs and environmental impact, efforts are being made to reuse polyester resin.
  • polyester resins may have a yellowish hue, and polyester resin molded articles made using this may not be desirable in terms of appearance depending on the application. Specifically, since titanium catalysts have a faster reaction rate, they have a problem of being yellower than polyester resins obtained using conventional antimony catalysts.
  • polyamide MXD6 resin is sometimes used in combination, but it is difficult to separate it from polyamide MXD6 resin during chemical recycling of polyester resin. If this is mixed during polymerization, there is also a problem that the appearance of the obtained polyester resin becomes yellowish.
  • Patent Document 1 discloses a technique in which a phosphoric acid compound or a phosphorous acid compound is added during polymerization for the purpose of preventing coloration.
  • Patent Document 2 discloses a technique for obtaining polyester with low yellowness by a polyester manufacturing method.
  • cobalt compounds such as cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and their hydrates, other inorganic and organic pigments, dyes, optical brighteners, etc.
  • the method of adding these substances is as follows: during the polycondensation reaction, they are added as a powder or dissolved in one of the polyester monomers, or after the polycondensation reaction is complete, they are added as a powder or dissolved in one of the monomers of the polyester. , a method of adding it as a masterbatch is described.
  • the object of the present invention is to provide a liquid coloring composition that has excellent colorant dispersibility and storage stability, does not inhibit the polymerization reaction during the production of polyester resin, and can be uniformly blued without color unevenness. It is an object of the present invention to provide a polyester resin composition having no color migration property of a coloring material and a liquid coloring composition capable of producing a polyester resin molded article. Another object of the present invention is to provide a method for producing the polyester resin composition and a polyester resin molded article.
  • One embodiment of the present invention is a liquid coloring composition used when obtaining a polyester resin by polymerization, comprising: Contains a diol component (A), a surfactant (B), and a dye (C),
  • the dye (C) relates to a liquid coloring composition having a solubility in 100 mL of ethylene glycol at 25° C. of 0.5 g or less.
  • Another embodiment of the present invention is to polymerize a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol in the presence of a polymerization catalyst (Z) and a liquid coloring composition. Equipped with a process of reacting to produce polyester resin,
  • the liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
  • the dye (C) relates to a method for producing a polyester resin composition in which the solubility in 100 mL of ethylene glycol at 25° C. is 0.5 g or less.
  • Another embodiment of the present invention is to polymerize a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol in the presence of a polymerization catalyst (Z) and a liquid coloring composition.
  • the liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
  • the dye (C) relates to a method for producing a polyester resin molded article, in which the solubility in 100 mL of ethylene glycol at 25° C. is 0.5 g or less.
  • a liquid coloring composition that has excellent dispersibility and storage stability of the coloring material, and which inhibits the polymerization reaction of the polyester resin raw material by adding it during the polymerization reaction to obtain the polyester resin. It is possible to provide a liquid coloring composition that can be uniformly blued without any color unevenness, and can produce a polyester resin composition and a polyester resin molded article without color migration of the coloring material.
  • a dicarboxylic acid component (X) containing at least terephthalic acid "a diol component (Y) containing at least ethylene glycol”, “polyester resin composition”, and “polyester resin molded article” are respectively referred to as Sometimes referred to as “dicarboxylic acid component (X),”"diol component (Y),”""resincomposition,” or “resin molded article.”
  • liquid refers to being liquid at 25°C.
  • the term “main component” refers to the component that is included in the largest amount among the components. Unless otherwise noted, the various components appearing in this specification may be used individually or in combination of two or more.
  • the liquid coloring composition is a liquid coloring composition used when synthesizing a polyester resin, and includes a diol component (A), a surfactant (B), and a dye (C ), and the dye (C) has a solubility in 100 mL of ethylene glycol at 25° C. of 0.5 g or less.
  • the liquid coloring composition can be used by being added to a polyester resin raw material when synthesizing a polyester resin.
  • the coloring material By using a dye (C) as a coloring material and a liquid coloring composition containing a diol component (A) and a surfactant (B), the coloring material has excellent dispersibility and storage stability, and polyester resin When obtained through a polymerization process, it is possible to obtain a polyester resin composition that does not inhibit the polymerization reaction, can be blued without color unevenness, and has no dye color migration.
  • the diol component (A) has the role of a dispersion medium for the dye (C).
  • Diol is also called glycol, and also functions as one of the main raw materials constituting polyester resin. That is, the diol component (A) in the liquid coloring composition reacts with the dicarboxylic acid component (X) when producing a polyester resin by polymerizing the dicarboxylic acid component (X) and the diol component (Y). , forming a polyester resin.
  • the diol component (A) even if added during the synthesis of the polyester resin raw material, the liquid coloring composition does not inhibit the polymerization reaction and can uniformly blue the polyester resin.
  • the diol component (A) is not limited as long as it can be used as a raw material for polyester resin, and specific examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol. , 1,4-cyclohexanedimethanol and the like. Among them, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol are preferred from the viewpoint of suppressing color unevenness of the polyester resin, and from the viewpoint of dispersibility of the liquid coloring composition. Ethylene glycol is more preferred. Ethylene glycol is a glycol also called 1,2-ethanediol, and is one of the main raw materials for polyethylene terephthalate.
  • the diol component (A) preferably contains at least ethylene glycol, and more preferably contains ethylene glycol as a main component.
  • the main component means that the component with the highest content among the components constituting the diol component (A) is ethylene glycol.
  • the melting point of the diol component (A) is preferably -30°C to 50°C from the viewpoint of uniformity of the mixed liquid during polyester resin polymerization. This is preferable because it allows uniform bluing without color unevenness.
  • the melting point of the diol component (A) can be measured using a differential scanning calorimeter.
  • the blending amount of the diol component (A) in the liquid coloring composition is preferably 30 to 90% by mass, more preferably 35 to 70% by mass, based on the total mass of the liquid coloring composition, from the viewpoint of preventing precipitation of the dye. Preferably, 40 to 50% by mass is more preferable.
  • the molecular weight of the diol component (A) in the liquid coloring composition may be, for example, 1,000 or less, 500 or less, or 400 or less, and from the viewpoint of the physical properties of the resulting polyester resin, it is preferably 300 or less, and more Preferably it is 200 or less.
  • the surfactant (B) has the role of a dispersant that disperses the dye (C) in the diol component (A).
  • Surfactants have hydrophilic groups and lipophilic groups in their molecules, and reduce interfacial tension by strongly adsorbing mutually immiscible substances to the interface and orienting the molecules.
  • Surfactants are classified into surfactants that dissociate into ions when made into an aqueous solution and surfactants that do not dissociate. Dissociable surfactants are further divided into anionic surfactants and cationic surfactants according to the ionic nature of the surfactant moiety. Furthermore, there are surfactants in which the part exhibiting surface activity becomes an anion when the hydrogen ion concentration (pH) of the solution is high, and becomes a cation when the pH is low. This is called an amphoteric surfactant. Surfactants that do not dissociate when made into an aqueous solution are called nonionic surfactants.
  • the surfactant (B) is preferably a nonionic surfactant or an amphoteric surfactant, more preferably a nonionic surfactant.
  • a nonionic surfactant By using these surfactants, the dispersibility and storage stability of the dye (C) in the liquid coloring composition are better, and it is possible to perform blueing without inhibiting the polymerization of the polyester resin and with even color unevenness.
  • a liquid colored composition is obtained.
  • surfactant (B) is preferably poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, alkyl betaine. , and alkylamine oxide.
  • the blending amount of the surfactant (B) in the liquid coloring composition is 0 to 100 parts by mass of the diol component (A) from the viewpoint of dispersibility of the dye (C) and not inhibiting the polymerization reaction of the polyester resin raw material. .1 to 50 parts by weight is preferable, 1 to 20 parts by weight is more preferable, and even more preferably 2 to 10 parts by weight.
  • Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester , glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, etc., but are not particularly limited to poly(12-hydroxystearic acid)-polyethyleneimine copolymer.
  • Polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, and sorbitan fatty acid esters are preferred, and polyoxyalkylene derivatives are more preferred.
  • the above is preferable because the dye (C) in the liquid coloring composition has excellent dispersibility and storage stability, and does not inhibit the polymerization reaction of the polyester resin raw material.
  • the HLB value of the nonionic surfactant (B) is preferably 15 or less, more preferably 1 to 15, from the viewpoint of dispersibility of the dye (C).
  • HLB Hydrophilicity-Lipophile Balance
  • the HLB value is one of the parameters representing the hydrophilicity or hydrophobicity of a material, and the smaller the value, the higher the hydrophobicity, and the higher the HLB value, the higher the hydrophilicity.
  • Various methods are known for calculating the HLB value from a chemical structure, and various methods for actual measurement are also known, but in the embodiment of the present invention, the HLB value is calculated using the Griffin method.
  • polyoxyethylene alkyl ether examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyl dodecyl ether, etc., but are not particularly limited.
  • polyoxyethylene alkyl ethers include Emulgen 109P (manufactured by Kao Corporation, liquid at 25°C, HLB value 13.6) and Emulgen 102KG (manufactured by Kao Corporation, liquid at 25°C, HLB value 6.3). .
  • the polyoxyalkylene derivative may be, for example, an ether having a polyoxyalkylene structure (excluding compounds corresponding to polyoxyethylene alkyl ether).
  • polyoxyalkylene derivatives include polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene glyceryl ether, and polyoxyethylene. Examples include diglyceryl ether, but are not particularly limited.
  • polyoxyalkylene derivatives include Emulgen LS-114 (manufactured by Kao Corporation, liquid at 25°C, HLB value 14), Emulgen B-66 (manufactured by Kao Corporation, liquid at 25°C, HLB value 13.2), Adeka.
  • Pluronic L-61 manufactured by ADEKA, liquid at 25°C, HLB value 3
  • Adeka Pluronic L-43 manufactured by ADEKA, liquid at 25°C, HLB value 12
  • ADEKA Pluronic L-35 manufactured by ADEKA, liquid at 25°C) liquid, HLB value 18.5), etc.
  • sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, Examples include polyoxyethylene monooleate, polyoxyethylene monostearate, etc., but are not particularly limited.
  • sorbitan fatty acid esters include Rheodol SP-O30-V (manufactured by Kao Corporation, liquid at 25°C, HLB value 1.8), Rheodol SP-L10 (manufactured by Kao Corporation, liquid at 25°C, HLB value 8.6). ), Emazol L-120V (manufactured by Kao Corporation, liquid at 25°C, HLB value 16.7), and the like.
  • ampholytic surfactant examples include alkyl betaine, alkyl amine oxide, etc., and are not particularly limited.
  • alkyl betaines include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and the like, but are not particularly limited.
  • alkylbetaine include Amhitol 20BS (manufactured by Kao Corporation, liquid at 25° C.), Amhitol 20Y-B (manufactured by Kao Corporation, liquid at 25° C.), and the like.
  • alkylamine oxide examples include lauryl dimethylamine oxide, but are not particularly limited.
  • Specific examples of the alkylamine oxide include Amhitol 20N (manufactured by Kao Corporation, liquid at 25° C.) and the like.
  • the surfactant (B) is preferably liquid at 25°C because it has excellent compatibility with the diol component (A) and dispersibility of the dye (C).
  • the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C. In an embodiment of the present invention, it is used for blueing during the polymerization reaction of polyester resin.
  • a polyester resin composition obtained using dye (C) as a dye (C) is better than a polyester resin composition obtained without using dye (C) according to CIE1976L*a*b* It is possible to select and use dyes that can lower b* expressed in the color system.
  • the dye (C) has a solubility of 0.5 g or less in the ethylene glycol contained in the diol component (Y)
  • polymerization of the polyester resin raw material containing the dicarboxylic acid component (X) and the diol component (Y) is possible. It is possible to obtain a polyester resin composition that does not inhibit the reaction, uniformly blues the polyester resin without color unevenness, and has no color migration of the coloring material.
  • the dye (C) preferably has low solubility in ethylene glycol, which is a hydrophilic component. Therefore, it is preferably hydrophobic and has a solubility in ethylene glycol of 0.5 g or less, preferably 0.48 g or less, and more preferably 0.45 g or less.
  • ethylene glycol 0.5 g or less, preferably 0.48 g or less, and more preferably 0.45 g or less.
  • dyes and pigments include, for example, C.I. It can be identified according to the classification in I Name (Color Index Generic Name).
  • a dye having a solubility in 100 mL of ethylene glycol at 25°C is higher than 0.5 g as a coloring material is used as a liquid coloring composition by dissolving it in ethylene glycol, it is more effective during the polymerization reaction of polyester resin raw materials or during molding. Bleed is suppressed at temperatures as low as 100 mph, and color migration does not occur.
  • bluing refers to a change in the hue of the obtained polyester resin composition or polyester resin molded article to a bluish tone when visually observed.
  • b* expressed in the CIE1976L*a*b* color system is higher in a polyester resin composition obtained by adding dye (C) than in a polyester resin composition obtained without adding dye (C). It can be expressed that the composition is lower.
  • the solubility of a dye in 100 mL of ethylene glycol at 25 °C is the upper limit of the amount of dye that can dissolve in 100 mL of ethylene glycol at 25 °C.
  • the dye is added to 100 mL of ethylene glycol at 25 °C, stirred for 1 minute, This is the upper limit of the mass of the dye when no solids or crystals are observed when filtered on a 5 ⁇ m cotton cloth.
  • the blending amount of the dye (C) in the liquid coloring composition is preferably 1 to 150 parts by weight, and 2 to 130 parts by weight, based on 100 parts by weight of the diol component (A). More preferably, 5 to 120 parts by mass is even more preferred.
  • the amount of the dye (C) to be blended is preferably 5 to 100 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the diol component (A).
  • the dye (C) is not particularly limited as long as it has a solubility in 100 mL of ethylene glycol at 25° C. of 0.5 g or less, and can be selected according to the color tone of the polyester resin.
  • Dyes (C) include anthraquinone dyes, perinone dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, xanthene dyes, phthalocyanine dyes, quinoline dyes, azine dyes, and indigoid dyes.
  • Examples include dyes, xanthene dyes, azine dyes, acridine dyes, methine dyes, thiazole dyes, thiazine dyes, rhodamine dyes, and triarylmethane dyes.
  • anthraquinone dyes or perinone dyes are preferred because they have a high bluing effect and excellent dispersibility in liquid coloring compositions.
  • the anthraquinone or perinone dyes include Solvent Red52, 117, 135, 169, 176, Disperse Red5, Solvent Orange63, 67, 68, 72, 78, Solvent Yellow98, 103, 105, 113, 116, Di sparse Yellow 54, 64, 160, Solvent Green 3, 20, 26, Solvent Blue 35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 33, 36, etc. It will be done.
  • Solvent Red52, 117, 135, 169, 176, Solvent Green3, 20, 26, Solvent Blue35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 33, 36 are preferred, Solvent Red 135, Solvent Blue 35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 3 3, 36 is more preferred.
  • the liquid coloring composition may contain other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, matting agents, optical brighteners, stabilizers, antioxidants. , a viscosity modifier, and other additives may also be contained.
  • antioxidants aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphorus-based, sulfur-based, and amine-based stabilizers such as phosphoric acid and phosphoric acid esters can be used. is available.
  • the liquid coloring composition preferably does not contain any organic solvent other than the diol component (A). This is a concept that excludes intentional addition, and means that it is substantially free, and the content of other organic solvents is 1% by mass or less, 0.5% by mass based on the total mass of the liquid coloring composition. or less, or 0.1% by mass or less, or 0% by mass.
  • the total amount of any other components other than the diol component (A), surfactant (B), and dye (C) is 10% by mass or less and 5% by mass or less based on the total mass of the liquid coloring composition. , or 1% by weight or less, or 0% by weight.
  • the method for producing the liquid coloring composition in the embodiment of the present invention is not particularly limited, and includes, for example, a diol component (A), a surfactant (B), a dye (C), and, if necessary, a method for producing a liquid coloring composition.
  • a liquid coloring composition can be obtained by adding other additives and mixing with a Henschel mixer, tumbler, disper, etc., and dispersing using a Silverson mixer (manufactured by Silverson).
  • a silverson mixer manufactured by Silverson.
  • any device other than the above-mentioned devices such as a kneader, roll mill, ball mill, sand mill, etc. can be used.
  • the liquid colored composition is a dye dispersion in which the dye (C) is dispersed, and can be used as a bluing agent-containing composition.
  • a polyester resin composition is obtained by using a liquid coloring composition when producing a polyester resin by polymerizing a polyester resin raw material.
  • the polyester resin can be uniformly blued without uneven coloring without inhibiting the polymerization reaction of the polyester resin raw material containing the dicarboxylic acid component (X) and the diol component (Y).
  • a polyester resin composition can be obtained that does not have the color migration property of the coloring material.
  • the diol component (A) in the liquid coloring composition also undergoes a polymerization reaction as a diol component with the dicarboxylic acid component (X) to become a polyester resin, and thus also functions as a polyester resin raw material.
  • the diol component (A) is also preferably ethylene glycol, which is a component contained in the diol component (Y).
  • the liquid colored composition can be used by being added to a reaction vessel for polymerization. The step of adding the liquid coloring composition may be performed before the start of polymerization or during the polymerization reaction.
  • the polyester resin composition is a polyester resin obtained by a polymerization reaction of a dicarboxylic acid component (X), a diol component (A), and a diol component (Y) in the presence of a polymerization catalyst (Z), and a surfactant. agent (B) and dye (C).
  • the dicarboxylic acid component (X) is a dicarboxylic acid component containing at least terephthalic acid, and is a raw material for polyester resin.
  • the dicarboxylic acid component (X) may include terephthalic acid and, for example, terephthalic acid, dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, and the like.
  • terephthalic acid it is preferable that terephthalic acid is the main component.
  • the main component means that the component with the highest content rate among the components constituting the dicarboxylic acid component (X) is terephthalic acid.
  • the dicarboxylic acid component (X) a component obtained by synthesis from raw materials may be used, or a component obtained by depolymerizing a polyester resin by recycling or the like may be used.
  • the liquid coloring composition has a high effect of blueing the polyester resin without color unevenness, so even when a dicarboxylic acid component obtained by depolymerizing the polyester resin by recycling is used. , a resin molded article with good color tone can be obtained.
  • the diol component (Y) is a diol component containing at least ethylene glycol, and is a raw material for polyester resin.
  • the diol component (Y) may contain ethylene glycol and a diol component other than ethylene glycol explained in the diol component (A), such as diethylene glycol, triethylene glycol, polyethylene glycol, etc.
  • ethylene glycol is the main component.
  • the diol component (A) contained in the liquid coloring composition is excluded as the diol component (Y).
  • a liquid coloring composition containing a diol component (A) and a diol component (Y) are used separately from the liquid coloring composition, and the raw material for the polyester resin is a diol component (A). ) and a diol component (Y) separately from the diol component (A).
  • the diol component (Y) may contain the same diol as the diol contained in the diol component (A), or may contain a diol different from the diol contained in the diol component (A), and further, It may contain both the same diol and different diols.
  • the main component means that the component with the highest content rate among the components constituting the diol component (Y) is ethylene glycol.
  • the diol component (Y) a component obtained by synthesis from raw materials may be used, or a component obtained by depolymerizing a polyester resin by recycling may be used.
  • the liquid coloring composition has a high effect of blueing the polyester resin evenly, so even when using a component obtained by depolymerizing the polyester resin by recycling etc. A resin molded article with good color tone can be obtained.
  • the polymerization catalyst (Z) is a catalyst that accelerates the polymerization reaction of the polyester resin raw material, and there are no particular restrictions on the polymerization of the polyester resin.
  • examples include titanium-based catalysts such as titanium tetraalkoxide, tetrabutoxytitanium, and titanium oxide; Tin-based catalysts such as dibutyltin oxide, tin acetate, zinc acetate, and tin disulfide, antimony-based catalysts such as antimony trioxide, and polymerization catalysts such as germanium dioxide and magnesium acetate can be used.
  • the liquid coloring composition uses a titanium catalyst that has a high reaction rate because it has a high effect of uniformly blueing the polyester resin without color unevenness during the polymerization reaction of the polyester resin raw material. Even in the case where the resin molded article has a good color tone, it is possible to obtain a resin molded article with good color tone.
  • the polymerization catalyst (Z) is a titanium-based catalyst.
  • the amount of the polymerization catalyst (Z) is preferably 0.5% by mass or less based on the total of 100% by mass of the dicarboxylic acid component (X) and the diol component (Y) from the viewpoint of the physical properties of the resulting polyester resin. Yes, and more preferably 0.2% by mass or less.
  • the blending amount of the polymerization catalyst (Z) is preferably 0.001% by mass or more, and 0.05% by mass or more based on the total of 100% by mass of the dicarboxylic acid component (X) and diol component (Y). preferable.
  • the polyester resin composition may contain components other than those described above, as long as they do not inhibit the polymerization reaction of the polyester resin raw material and the blueing of the polyester resin.
  • Other ingredients may include arbitrary polymers, antistatic agents, antifoaming agents, dyeability improvers, matting agents, optical brighteners, stabilizers, antioxidants, and other additives. good.
  • antioxidants aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphorus-based, sulfur-based, and amine-based stabilizers such as phosphoric acid and phosphoric acid esters can be used. is available.
  • a polyester resin composition can be manufactured using a dicarboxylic acid component (X), a diol component (Y), a polymerization catalyst (Z), and a liquid colored composition according to an embodiment of the present invention.
  • the method for producing a polyester resin composition includes, for example, adding a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol in the presence of a polymerization catalyst (Z) and a liquid coloring composition. It includes a step of producing a polyester resin composition by conducting a polymerization reaction.
  • This step may include respectively adding a dicarboxylic acid component (X), a diol component (Y), a polymerization catalyst (Z), and a liquid coloring composition to a reaction vessel.
  • the order in which the dicarboxylic acid component (X), diol component (Y), polymerization catalyst (Z), and liquid coloring composition are added is not particularly limited. Two or more of these may be added at the same time.
  • the diol component (A) also undergoes a polymerization reaction with the dicarboxylic acid component (X).
  • the liquid coloring composition may be added before the start of polymerization or during the polymerization reaction. Further optional components may be used in the polymerization reaction.
  • the polymerization method for obtaining the polyester resin is not particularly limited, but for example, the dicarboxylic acid component (X) and the diol component (Y) are charged into a reaction container, and then the liquid colored composition according to the embodiment of the present invention is added. After that, a polymerization catalyst (Z) is added, and the product obtained by the esterification reaction or transesterification reaction of the dicarboxylic acid component (X) and the diol component (Y) is subjected to a polycondensation reaction to produce a polyester resin.
  • a manufacturing method is mentioned. In this specification, these reactions may be referred to as polymerization reactions.
  • the ratio of the polymerization reaction of the polyester resin raw material is preferably such that the molar ratio of dicarboxylic acid component (X) to diol component (Y) is in the range of 1:1.03 to 1:2.5, and 1:1.05. More preferably, the ratio is in the range of 1:1.2. By being within the above range, a polyester resin molded article with excellent mechanical properties can be obtained.
  • At least one of the dicarboxylic acid component (X) containing at least terephthalic acid and the diol component (Y) containing at least ethylene glycol is a component obtained by depolymerizing a polyester resin. good.
  • the amount of the liquid coloring composition to be blended is preferably 0.0001 to 100% based on the total of 100% by mass of the dicarboxylic acid component (X) and the diol component (Y). 1% by mass, more preferably 0.00015 to 0.5% by mass, still more preferably 0.0002 to 0.5% by mass.
  • the ratio of the diol component (Y) used in the polymerization reaction and the diol component (A) contained in the liquid coloring composition used in the polymerization reaction is , the diol component (A) is preferably 0.0001 to 2% by mass, more preferably 0.0002 to 1.5% by mass, and even more preferably It is 0.0005 to 1% by mass.
  • the diol component (Y) used in the polymerization reaction and the surfactant (B) contained in the liquid coloring composition used in the polymerization reaction are preferably 0.000001 to 0.8% by mass, more preferably 0.000005 to 0.5% by mass. %, more preferably 0.00001 to 0.3% by mass.
  • the content of the dye (C) is preferably more than 0 ppm and 10 ppm or less, more preferably 5 ppm or less, and even more preferably 3 ppm, based on 100% by mass of the polyester resin composition. It is as follows.
  • the reaction temperature for polymerization is not particularly limited, but is preferably in the range of 180°C to 280°C.
  • productivity tends to be good, and when it is 280°C or lower, it tends to suppress resin decomposition and volatile by-products that cause odor. It is in.
  • the lower limit of the polymerization reaction temperature is more preferably 200°C, particularly preferably 220°C.
  • the upper limit of the polymerization reaction temperature is more preferably 270°C.
  • the degree of vacuum during polymerization is preferably 0.5 kPa or more. When it is 0.5 kPa or more, reactivity tends to be good and productivity is improved.
  • the obtained polyester resin composition can be in the form of pellets (such as cylindrical chips), powder, granules, or beads. It is preferable to use a pellet form produced by a single-screw extruder or a twin-screw extruder because the kneading force is strong and the subsequent molding process is easy.
  • the polyester resin molded article is a molded article using a polyester resin, and is obtained by molding the above-mentioned polyester resin composition. Specifically, it can be manufactured, for example, by melt-kneading a polyester resin composition and molding it using a conventionally known molding machine. Examples of the molding machine include, but are not limited to, injection molding machines, extrusion molding machines, rotary molding machines, and the like.
  • polyester resin molded product examples include films, laminates, coatings, fibers, injection molded products for foods and daily necessities, compression injection molded products, rotary molded products, extrusion molded products, and the like.
  • the polyester resin molded product is uniformly blued without any color unevenness, so that it can be seen by consumers during use, and is particularly suitable for applications that require a good appearance. Even if there is, it can be used suitably.
  • a liquid coloring composition used when obtaining a polyester resin by polymerization Contains a diol component (A), a surfactant (B), and a dye (C),
  • the dye (C) is a liquid coloring composition having a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
  • the surfactant (B) is at least one of a nonionic surfactant and an amphoteric surfactant.
  • Surfactant (B) consists of poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, alkyl betaine, and alkyl amine oxide.
  • [5] The liquid coloring composition according to any one of [1] to [4], wherein the dye (C) is an anthraquinone dye or a perinone dye.
  • a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol are polymerized to form a polyester resin. Equipped with a manufacturing process,
  • the liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C), A method for producing a polyester resin composition, wherein the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
  • the polymerization catalyst (Z) is a titanium-based catalyst.
  • At least one of the dicarboxylic acid component (X) containing at least terephthalic acid and the diol component (Y) containing at least ethylene glycol is a component obtained by depolymerizing a polyester resin, [6] or [7] The method for producing the polyester resin composition described in [7]. [9] In the presence of a polymerization catalyst (Z) and a liquid coloring composition, a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol are polymerized to form a polyester resin composition.
  • the liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C), A method for producing a polyester resin molded article, in which the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
  • parts and % represent parts by mass and % by mass, respectively, unless otherwise specified.
  • the blending amounts in the table are parts by mass and are nonvolatile content equivalent values.
  • a blank column in the table indicates that it is not blended.
  • ⁇ Diol component (A)> A1: Ethylene glycol (manufactured by Maruzen Petrochemical Co., Ltd., melting point -13°C, molecular weight 62)
  • B1 ADEKA Pluronic L-61 (manufactured by ADEKA)
  • B2 ADEKA Pluronic L-43 (manufactured by ADEKA)
  • B3 ADEKA Pluronic L-35 (manufactured by ADEKA)
  • B4 Poly(12-hydroxystearic acid)-polyethyleneimine copolymer
  • B5 Emulgen 109P (manufactured by Kao Corporation)
  • B6 Rheodor SP-O30-V (manufactured by Kao Corporation)
  • B7 Anhitor 20BS (manufactured by Kao Corporation)
  • B8 Amhitol 20N (manufactured by Kao Corporation)
  • B9 Ramtel PD-105 (manufactured by Kao Corporation)
  • B10 Cortamine 24P (manufactured by Kao Corporation)
  • surfactant (B) The structure and physical properties of surfactant (B) are shown below.
  • C1 Macrolex Blue RR (Dye: Anthraquinone dye, Solvent Blue 97, manufactured by Lanxess, solubility in 100 mL of ethylene glycol at 25°C is 0.2 g)
  • C2 Sumiplast Violet B (Dye: Anthraquinone dye, SolventViolet 13, manufactured by Sumika Chemtex Co., Ltd., solubility in 100 mL of ethylene glycol at 25 ° C. is 0.45 g)
  • C3 Diamond Resin Red HS (Dye: perinone dye, Solvent Red 135, manufactured by Mitsubishi Chemical Corporation, solubility in 100 mL of ethylene glycol at 25 ° C.
  • D1 Ultramarine No. 1500 (inorganic pigment, ultramarine blue, manufactured by Daiichi Kasei Kogyo Co., Ltd., solubility in 100 mL of ethylene glycol at 25°C is 0.4 g)
  • D2 Lionol Blue FG7330 (organic pigment, phthalocyanine blue, manufactured by Toyo Color Co., Ltd., solubility in 100 mL of ethylene glycol at 25°C is 0.2 g)
  • X1 Terephthalic acid obtained by synthesis from raw materials
  • X2 Terephthalic acid obtained by depolymerizing polyester resin
  • Y1 Ethylene glycol obtained by synthesis from raw materials
  • Y2 Ethylene glycol obtained by depolymerizing polyester resin
  • Example 1 Manufacture of liquid colored composition (T1) 100 parts by mass of diol component (A), 15 parts by mass of surfactant (B1), and 120 parts by mass of dye (C1) were mixed and dispersed in a bead mill to obtain a liquid colored composition (T1).
  • Liquid coloring compositions (T36, 37) were manufactured in the same manner as liquid coloring composition (T1), except that the materials and blending amounts (parts by mass) shown in Table 5 were changed. It was not possible to obtain a good liquid coloring composition due to poor dispersibility and storage stability.
  • D 90 The particle size (D 90 ) at a cumulative volume percentage of 90% was measured using a dynamic light scattering particle size distribution analyzer LB-550 (manufactured by Horiba, Ltd.). Evaluation was performed based on the following criteria. [Evaluation criteria] ⁇ : D90 is less than 10 ⁇ m, very good ⁇ : D90 is 10 ⁇ m or more and less than 30 ⁇ m, good ⁇ : D90 is 30 ⁇ m or more and less than 50 ⁇ m, suitable for practical use ⁇ : D90 is 50 ⁇ m or more, Impractical
  • Example 34 Manufacture of polyester resin composition
  • a reaction vessel equipped with a distillation column 69 parts by mass of dicarboxylic acid component (X1) (terephthalic acid obtained by synthesis from raw materials) and 30 parts by mass of diol component (Y1) (ethylene glycol obtained by synthesis from raw materials).
  • X1 dicarboxylic acid component
  • Y1 diol component
  • T1 liquid coloring composition
  • Z1 polymerization catalyst
  • the rotational speed of the stirring blade in the reaction vessel was maintained at 200 rpm, and the temperature was started to increase to bring the temperature inside the reaction system to 265° C., and this temperature was maintained.
  • the temperature in the reaction system was raised to 250°C, and the pressure in the reaction system was reduced over about 40 minutes, and the degree of vacuum was set to 0.5 kPa.
  • the condensation reaction was carried out while distilling the diol component from the reaction system.
  • the viscosity of the reaction system increases with the reaction, and when the torque of the stirring blade reaches the specified torque, the stirring is stopped, the reaction system is returned to normal pressure, and the strand is extruded from the nozzle, cooled with water, and then cut.
  • a polyester resin composition in the form of pellets (about 2.5 mm in diameter and about 2.5 mm in length) was obtained.
  • Examples 35 to 69, Comparative Examples 6 and 7 Polyester resin compositions were produced in the same manner as for the polyester resin composition of Example 34, except that the materials and blending amounts (parts by mass) shown in Table 6 were changed.
  • Polymerization time evaluation Calculate the ratio of the polymerization time (b) required for the obtained polyester resin composition to the polymerization time (a) required for the polyester resin composition produced without adding a liquid coloring composition using the following formula. and evaluated.
  • Polymerization time ratio (%) (b) / (a) x 100 [Evaluation criteria] ⁇ : Polymerization time ratio is less than 120%, good. ⁇ : Polymerization time ratio is 120% or more and less than 150%, practical. ⁇ : Polymerization time ratio is 150% or more, not practical.
  • the obtained polyester resin pellets were blow molded at 280° C. using a blow molding machine to produce 50 PET bottles each having a thickness of 1 mm.
  • An impact test was conducted on 10 of the obtained PET bottles. Specifically, a plastic bottle was filled 80% with water and dropped from a height of 1 m.
  • the evaluation criteria were as follows. [Evaluation criteria] ⁇ : No holes were observed in any of the 10 bottles, and less than 5 bottles were found to be deformed. ⁇ : No holes were observed in any of the 10 bottles, but deformation was observed in 5 or more but less than 10 bottles. ⁇ : Deformation was observed in all 10 bottles, and less than 2 bottles had holes. ⁇ : Deformation was observed in all 10 bottles, and two or more bottles had holes.
  • the liquid coloring composition according to the embodiment of the present invention has excellent dispersibility and storage stability of the coloring material, and furthermore, by using the liquid coloring composition, it is possible to improve the coloring composition when producing polyester resin. It was confirmed that the polymerization reaction of the polyester resin raw material was not inhibited, uniform bluing was possible without color unevenness, and a polyester resin molded article without color migration of the coloring material was obtained. It was confirmed that even when a titanium catalyst was used as the polymerization catalyst (Z), a polyester resin molded article with good color tone could be formed.
  • the dicarboxylic acid component (X) and the diol component (Y) is a compound obtained by depolymerizing a polyester resin, evaluation of polymerization time, hue, color unevenness, and color migration property It was confirmed that this method has excellent properties and can be effectively applied to the reuse of polyester resin.
  • the liquid coloring composition of Comparative Example 1 in which the dye (C) was dispersed in a plasticizer, was practical in terms of dispersibility and storage stability, but the polymerization of the polyester resin composition It took a long time, and the color was uneven, so the result was not practical.
  • the liquid coloring composition of Comparative Example 2 which uses a coloring material that dissolves in the raw material of polyester resin, that is, a hydrophilic coloring material, causes color migration of the dye from the molded product, and can be used for various purposes, especially as a beverage container. The result was that it could not be put to practical use as a polyester resin composition or a molded article thereof that may be used.

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Abstract

One embodiment pertains to a liquid coloring composition that is added when polymerizing a polyester resin and contains a diol composition (A), a surfactant (B), and a dye (C). The dye (C) has a solubility of 0.5 g or less for 100 mL of ethylene glycol at 25°C.

Description

液状着色組成物、ならびにポリエステル樹脂組成物およびポリエステル樹脂成形体の製造方法Liquid coloring composition, and method for producing polyester resin composition and polyester resin molded article
　本発明の実施形態は、ポリエステル樹脂を重合により得る際に使用される液状着色組成物、ならびにポリエステル樹脂組成物およびポリエステル樹脂成形体の製造方法に関する。 Embodiments of the present invention relate to a liquid coloring composition used when obtaining a polyester resin by polymerization, and a method for producing a polyester resin composition and a polyester resin molded article.
　プラスチック成形体は、成形加工が容易なことから、電気および電子機器部品、自動車部品、医療用部品、食品容器などの幅広い分野で使用されている。特にポリエステル樹脂を用いた成形体（ポリエステル樹脂成形体）は化学的及び物理的性質に優れているため、ペットボトル等に代表される食品容器、サニタリー容器、ポリエステル繊維、またはフィルムやシート等、非常に多岐の用途に利用されている。また、コスト及び環境への負荷低減のため、ポリエステル樹脂の再利用も進められている。 Because plastic molded bodies are easy to mold, they are used in a wide range of fields such as electrical and electronic equipment parts, automobile parts, medical parts, and food containers. In particular, molded products using polyester resin (polyester resin molded products) have excellent chemical and physical properties, so they can be used in food containers such as plastic bottles, sanitary containers, polyester fibers, films, sheets, etc. It is used for a wide variety of purposes. Furthermore, in order to reduce costs and environmental impact, efforts are being made to reuse polyester resin.
　また、ポリエステル樹脂は、重合時に用いる原料や重合条件により、色相が黄味になることがあり、これを用いたポリエステル樹脂成形体は、用途によっては、外観上好ましくない場合がある。具体的には、チタン触媒は反応速度が早いため、従来のアンチモン触媒を用いて得られたポリエステル樹脂よりも、黄味であることが問題となっている。 Furthermore, depending on the raw materials used during polymerization and the polymerization conditions, polyester resins may have a yellowish hue, and polyester resin molded articles made using this may not be desirable in terms of appearance depending on the application. Specifically, since titanium catalysts have a faster reaction rate, they have a problem of being yellower than polyester resins obtained using conventional antimony catalysts.
　さらに、ポリエステル樹脂からなる食品包装容器や飲料ボトルにガスバリア性を付与する目的で、例えばポリアミドＭＸＤ６樹脂が併用されることがあるが、ポリエステル樹脂のケミカルリサイクル時にポリアミドＭＸＤ６樹脂と分別することが難しく、これが重合時に混在すると、得られたポリエステル樹脂の外観が黄味になるという問題もある。 Furthermore, for the purpose of imparting gas barrier properties to food packaging containers and beverage bottles made of polyester resin, for example, polyamide MXD6 resin is sometimes used in combination, but it is difficult to separate it from polyamide MXD6 resin during chemical recycling of polyester resin. If this is mixed during polymerization, there is also a problem that the appearance of the obtained polyester resin becomes yellowish.
　このような問題を解決する方法として、特許文献１には着色を防止する目的で、リン酸化合物や亜リン酸化合物を重合時に添加する技術が開示されている。特許文献２には、ポリエステルの製造方法により、黄色度の低いポリエステルを得る技術が開示されている。さらに色調改善等の目的で、酢酸コバルト、硝酸コバルト、塩化コバルト、コバルトアセチルアセトネート、ナフテン酸コバルトおよびそれらの水和物等のコバルト化合物、その他無機および有機の顔料、染料、蛍光増白剤などを使用する手法が記載されており、これらの添加方法として、重縮合反応中には、粉末や、ポリエステルのモノマーの１つに溶解させて添加する手法、または重縮合反応終了後には、粉末や、マスターバッチとして添加する手法が記載されている。 As a method for solving such problems, Patent Document 1 discloses a technique in which a phosphoric acid compound or a phosphorous acid compound is added during polymerization for the purpose of preventing coloration. Patent Document 2 discloses a technique for obtaining polyester with low yellowness by a polyester manufacturing method. Furthermore, for the purpose of improving color tone, cobalt compounds such as cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and their hydrates, other inorganic and organic pigments, dyes, optical brighteners, etc. The method of adding these substances is as follows: during the polycondensation reaction, they are added as a powder or dissolved in one of the polyester monomers, or after the polycondensation reaction is complete, they are added as a powder or dissolved in one of the monomers of the polyester. , a method of adding it as a masterbatch is described.
特開２００６－３３５９７４号公報Japanese Patent Application Publication No. 2006-335974 特開２００５－３１４５１５号公報Japanese Patent Application Publication No. 2005-314515
　しかしながら、これらのような従来の方法では、粉末状または顆粒状であるブルーイング剤となる色材を、ポリエステル樹脂組成物中で均一に分散することは難しく、得られた成形体は、色調整が十分でなく、色ムラも起こるという問題がある。
　また、色材をポリエステル樹脂の原料に分散して用いただけでは、相溶性が悪く均一に分散できないことから、これを用いて得られた成形体は色ムラが発生する。
　さらに、重縮合反応終了後にマスターバッチを添加する場合には、別途計量設備や混合設備が必要になることからコスト増の要因となるだけでなく、マスターバッチ製造時の熱により劣化した樹脂が成形体に含まれることとなり、機械物性の低下が起こる。 However, with conventional methods such as these, it is difficult to uniformly disperse a powdered or granular coloring material that serves as a bluing agent in a polyester resin composition, and the resulting molded product cannot be used for color adjustment. There is a problem in that the color is not sufficient and color unevenness occurs.
Furthermore, if the coloring material is simply dispersed in the raw material of the polyester resin, it has poor compatibility and cannot be uniformly dispersed, resulting in uneven coloring in the molded product obtained using the coloring material.
Furthermore, if a masterbatch is added after the polycondensation reaction is completed, separate measuring equipment and mixing equipment are required, which not only increases costs, but also causes molding of resin that has deteriorated due to heat during masterbatch production. It will be included in the body, resulting in a decrease in mechanical properties.
　そこで本発明の課題は、色材の分散性と保存安定性に優れる液状着色組成物であって、ポリエステル樹脂を製造する際の重合反応を阻害せず、色ムラなく均一にブルーイングができ、色材の色移行性が無いポリエステル樹脂組成物およびポリエステル樹脂成形体を製造できる液状着色組成物を提供することである。また、本発明の課題は、前記ポリエステル樹脂組成物、およびポリエステル樹脂成形体の製造方法を提供することである。 Therefore, the object of the present invention is to provide a liquid coloring composition that has excellent colorant dispersibility and storage stability, does not inhibit the polymerization reaction during the production of polyester resin, and can be uniformly blued without color unevenness. It is an object of the present invention to provide a polyester resin composition having no color migration property of a coloring material and a liquid coloring composition capable of producing a polyester resin molded article. Another object of the present invention is to provide a method for producing the polyester resin composition and a polyester resin molded article.
　本発明者は、上記課題を解決するため鋭意検討を行った結果、本発明を完成するに至った。
　すなわち、本発明は、以下の実施形態を含む。本発明の実施形態は以下に限定されない。
　本発明の一実施形態は、ポリエステル樹脂を重合により得る際に使用される液状着色組成物であって、
　ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、液状着色組成物に関する。
　本発明の他の一実施形態は、重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂を製造する工程を備え、
　前記液状着色組成物は、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、ポリエステル樹脂組成物の製造方法に関する。
　本発明の他の一実施形態は、重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂組成物を製造する工程と、
　得られたポリエステル樹脂組成物を成形する工程とを備え、
　前記液状着色組成物は、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、ポリエステル樹脂成形体の製造方法に関する。 The present inventor conducted extensive studies to solve the above problems, and as a result, completed the present invention.
That is, the present invention includes the following embodiments. Embodiments of the present invention are not limited to the following.
One embodiment of the present invention is a liquid coloring composition used when obtaining a polyester resin by polymerization, comprising:
Contains a diol component (A), a surfactant (B), and a dye (C),
The dye (C) relates to a liquid coloring composition having a solubility in 100 mL of ethylene glycol at 25° C. of 0.5 g or less.
Another embodiment of the present invention is to polymerize a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol in the presence of a polymerization catalyst (Z) and a liquid coloring composition. Equipped with a process of reacting to produce polyester resin,
The liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
The dye (C) relates to a method for producing a polyester resin composition in which the solubility in 100 mL of ethylene glycol at 25° C. is 0.5 g or less.
Another embodiment of the present invention is to polymerize a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol in the presence of a polymerization catalyst (Z) and a liquid coloring composition. A step of reacting to produce a polyester resin composition;
and a step of molding the obtained polyester resin composition,
The liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
The dye (C) relates to a method for producing a polyester resin molded article, in which the solubility in 100 mL of ethylene glycol at 25° C. is 0.5 g or less.
　本発明の実施形態により、色材の分散性と保存安定性に優れる液状着色組成物であって、ポリエステル樹脂を得るための重合反応の際に添加することで、ポリエステル樹脂原料の重合反応を阻害せず、色ムラなく均一にブルーイングし、色材の色移行性が無いポリエステル樹脂組成物およびポリエステル樹脂成形体を製造できる液状着色組成物を提供することができる。 According to an embodiment of the present invention, there is provided a liquid coloring composition that has excellent dispersibility and storage stability of the coloring material, and which inhibits the polymerization reaction of the polyester resin raw material by adding it during the polymerization reaction to obtain the polyester resin. It is possible to provide a liquid coloring composition that can be uniformly blued without any color unevenness, and can produce a polyester resin composition and a polyester resin molded article without color migration of the coloring material.
　以下、本発明について詳細に説明する。なお、本発明の趣旨に合致する限り、他の実施形態も本発明の範疇に含まれることは言うまでもない。また、本明細書において「～」を用いて特定される数値範囲は、「～」の前後に記載される数値を下限値及び上限値の範囲として含むものとする。
　なお、本明細書では、「少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）」、「少なくともエチレングリコールを含むジオール成分（Ｙ）」、「ポリエステル樹脂組成物」、「ポリエステル樹脂成形体」を、それぞれ「ジカルボン酸成分（Ｘ）」、「ジオール成分（Ｙ）」、「樹脂組成物」、「樹脂成形体」と称することがある。
　ここで、「液状」とは、２５℃において液状であることを指す。
　また、「主成分」とは、その成分中、最も配合量が多い成分であることをいう。
　本明細書中に出てくる各種成分は特に注釈しない限り、それぞれ独立に一種単独でも二種以上を併用してもよい。 The present invention will be explained in detail below. It goes without saying that other embodiments are also included in the scope of the present invention as long as they meet the spirit of the present invention. Further, in this specification, a numerical range specified using "~" includes the numerical values written before and after "~" as the lower limit value and upper limit value range.
In this specification, "a dicarboxylic acid component (X) containing at least terephthalic acid", "a diol component (Y) containing at least ethylene glycol", "polyester resin composition", and "polyester resin molded article" are respectively referred to as Sometimes referred to as "dicarboxylic acid component (X),""diol component (Y),""resincomposition," or "resin molded article."
Here, "liquid" refers to being liquid at 25°C.
Furthermore, the term "main component" refers to the component that is included in the largest amount among the components.
Unless otherwise noted, the various components appearing in this specification may be used individually or in combination of two or more.
《液状着色組成物》
　本発明の実施形態によれば、液状着色組成物は、ポリエステル樹脂を合成する際に使用される液状着色組成物であって、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である。例えば、液状着色組成物は、ポリエステル樹脂を合成する際に、ポリエステル樹脂原料に添加して使用することができる。
　色材として、染料（Ｃ）を用い、さらにジオール成分（Ａ）と界面活性剤（Ｂ）を含む液状着色組成物を用いることにより、色材の分散性と保存安定性に優れ、ポリエステル樹脂を重合工程によって得る際に、重合反応を阻害せず、色ムラなくブルーイングでき、染料の色移行性が無いポリエステル樹脂組成物を得ることができる。 《Liquid coloring composition》
According to an embodiment of the present invention, the liquid coloring composition is a liquid coloring composition used when synthesizing a polyester resin, and includes a diol component (A), a surfactant (B), and a dye (C ), and the dye (C) has a solubility in 100 mL of ethylene glycol at 25° C. of 0.5 g or less. For example, the liquid coloring composition can be used by being added to a polyester resin raw material when synthesizing a polyester resin.
By using a dye (C) as a coloring material and a liquid coloring composition containing a diol component (A) and a surfactant (B), the coloring material has excellent dispersibility and storage stability, and polyester resin When obtained through a polymerization process, it is possible to obtain a polyester resin composition that does not inhibit the polymerization reaction, can be blued without color unevenness, and has no dye color migration.
＜ジオール成分（Ａ）＞
　ジオール成分（Ａ）は、染料（Ｃ）の分散媒の役割を有する。ジオールはグリコールともよばれ、ポリエステル樹脂を構成する主原料の１つとしても機能する。
　すなわち、液状着色組成物中のジオール成分（Ａ）は、ジカルボン酸成分（Ｘ）及びジオール成分（Ｙ）を重合反応させて、ポリエステル樹脂を製造する際に、ジカルボン酸成分（Ｘ）と反応し、ポリエステル樹脂を形成する。
　ジオール成分（Ａ）を用いることで、ポリエステル樹脂原料の合成の際に添加しても重合反応を阻害せず、ポリエステル樹脂を均一にブルーイングすることができる液状着色組成物となる。 <Diol component (A)>
The diol component (A) has the role of a dispersion medium for the dye (C). Diol is also called glycol, and also functions as one of the main raw materials constituting polyester resin.
That is, the diol component (A) in the liquid coloring composition reacts with the dicarboxylic acid component (X) when producing a polyester resin by polymerizing the dicarboxylic acid component (X) and the diol component (Y). , forming a polyester resin.
By using the diol component (A), even if added during the synthesis of the polyester resin raw material, the liquid coloring composition does not inhibit the polymerization reaction and can uniformly blue the polyester resin.
　ジオール成分（Ａ）は、ポリエステル樹脂の原料として使用できるものであれば制限されず、具体的には、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，３－プロピレングリコール、１，４－ブチレングリコール、１，４－シクロヘキサンジメタノール等に例示される脂肪族グリコールが挙げられる。
　中でも、ポリエステル樹脂の色ムラを抑制する観点から、エチレングリコール、１，３－プロピレングリコール、１，４－ブチレングリコール、１，４－シクロヘキサンジメタノールが好ましく、液状着色組成物の分散性の観点からエチレングリコールがより好ましい。
　エチレングリコールは、１，２－エタンジオール（１，２－ｅｔｈａｎｅｄｉｏｌ）ともよばれるグリコール類であり、ポリエチレンテレフタレートの主原料の１つである。 The diol component (A) is not limited as long as it can be used as a raw material for polyester resin, and specific examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, and 1,4-butylene glycol. , 1,4-cyclohexanedimethanol and the like.
Among them, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol are preferred from the viewpoint of suppressing color unevenness of the polyester resin, and from the viewpoint of dispersibility of the liquid coloring composition. Ethylene glycol is more preferred.
Ethylene glycol is a glycol also called 1,2-ethanediol, and is one of the main raw materials for polyethylene terephthalate.
　ジオール成分（Ａ）は、エチレングリコールを少なくとも含むことが好ましく、エチレングリコールを主成分として含むことがより好ましい。主成分とは、ジオール成分（Ａ）を構成する成分中、最も含有率が高い成分がエチレングリコールであることをいう。 The diol component (A) preferably contains at least ethylene glycol, and more preferably contains ethylene glycol as a main component. The main component means that the component with the highest content among the components constituting the diol component (A) is ethylene glycol.
　ジオール成分（Ａ）の融点は、ポリエステル樹脂重合時の混合液の均一性の観点から、－３０℃～５０℃であることが好ましい。これにより、色ムラなく均一にブルーイングができるために好ましい。
　ジオール成分（Ａ）の融点は、示差走査熱量測定装置を用いて測定することができる。 The melting point of the diol component (A) is preferably -30°C to 50°C from the viewpoint of uniformity of the mixed liquid during polyester resin polymerization. This is preferable because it allows uniform bluing without color unevenness.
The melting point of the diol component (A) can be measured using a differential scanning calorimeter.
　液状着色組成物におけるジオール成分（Ａ）の配合量は、染料の沈降を防止できるという観点から、液状着色組成物の全質量に対し、３０～９０質量％が好ましく、３５～７０質量％がより好ましく、４０～５０質量％が更に好ましい。 The blending amount of the diol component (A) in the liquid coloring composition is preferably 30 to 90% by mass, more preferably 35 to 70% by mass, based on the total mass of the liquid coloring composition, from the viewpoint of preventing precipitation of the dye. Preferably, 40 to 50% by mass is more preferable.
　液状着色組成物におけるジオール成分（Ａ）の分子量は、例えば、１，０００以下、５００以下、又は、４００以下であってよく、得られるポリエステル樹脂の物性の観点から好ましくは３００以下であり、より好ましくは２００以下である。 The molecular weight of the diol component (A) in the liquid coloring composition may be, for example, 1,000 or less, 500 or less, or 400 or less, and from the viewpoint of the physical properties of the resulting polyester resin, it is preferably 300 or less, and more Preferably it is 200 or less.
＜界面活性剤（Ｂ）＞
　界面活性剤（Ｂ）は、ジオール成分（Ａ）に、染料（Ｃ）を分散させる分散剤の役割を有する。界面活性剤は、その分子中に親水性基と親油性基を有しており、相互に混ざり合わない物質の界面への強い吸着と分子の配向によって、界面張力を低下させる。 <Surfactant (B)>
The surfactant (B) has the role of a dispersant that disperses the dye (C) in the diol component (A). Surfactants have hydrophilic groups and lipophilic groups in their molecules, and reduce interfacial tension by strongly adsorbing mutually immiscible substances to the interface and orienting the molecules.
　界面活性剤は、水溶液にしたときにイオンに解離する界面活性剤と解離しない界面活性剤に分類される。解離する界面活性剤は、界面活性を示す部分のイオンの性質に従ってアニオン系界面活性剤あるいはカチオン系界面活性剤にさらに分けられる。また、溶液の水素イオン濃度（ｐＨ）が高いときには界面活性を示す部分が陰イオンとなり、ｐＨが低くなるとそれが陽イオンになる界面活性剤がある。これは両性界面活性剤とよばれる。水溶液にした場合、解離をしない界面活性剤はノニオン系界面活性剤とよばれる。 Surfactants are classified into surfactants that dissociate into ions when made into an aqueous solution and surfactants that do not dissociate. Dissociable surfactants are further divided into anionic surfactants and cationic surfactants according to the ionic nature of the surfactant moiety. Furthermore, there are surfactants in which the part exhibiting surface activity becomes an anion when the hydrogen ion concentration (pH) of the solution is high, and becomes a cation when the pH is low. This is called an amphoteric surfactant. Surfactants that do not dissociate when made into an aqueous solution are called nonionic surfactants.
　界面活性剤（Ｂ）は、ノニオン系界面活性剤または両性界面活性剤が望ましく、ノニオン系界面活性剤がより望ましい。これらの界面活性剤を用いることで液状着色組成物中の染料（Ｃ）の分散性と保存安定性がより優れ、よりポリエステル樹脂の重合を阻害せず、色ムラなくブルーイングを行うことができる液状着色組成物が得られる。後述する具体例の中でも、界面活性剤（Ｂ）は、好ましくは、ポリ（１２－ヒドロキシステアリン酸）－ポリエチレンイミン共重合体、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレン誘導体、ソルビタン脂肪酸エステル、アルキルベタイン、及びアルキルアミンオキサイドからなる群より選ばれる少なくともいずれかである。 The surfactant (B) is preferably a nonionic surfactant or an amphoteric surfactant, more preferably a nonionic surfactant. By using these surfactants, the dispersibility and storage stability of the dye (C) in the liquid coloring composition are better, and it is possible to perform blueing without inhibiting the polymerization of the polyester resin and with even color unevenness. A liquid colored composition is obtained. Among the specific examples described below, surfactant (B) is preferably poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, alkyl betaine. , and alkylamine oxide.
　液状着色組成物における界面活性剤（Ｂ）の配合量は、染料（Ｃ）の分散性と、ポリエステル樹脂原料の重合反応を阻害しないという観点から、ジオール成分（Ａ）１００質量部に対し、０．１～５０質量部が好ましく、１～２０質量部がより好ましく、２～１０質量部が更に好ましい。 The blending amount of the surfactant (B) in the liquid coloring composition is 0 to 100 parts by mass of the diol component (A) from the viewpoint of dispersibility of the dye (C) and not inhibiting the polymerization reaction of the polyester resin raw material. .1 to 50 parts by weight is preferable, 1 to 20 parts by weight is more preferable, and even more preferably 2 to 10 parts by weight.
［ノニオン系界面活性剤］
　ノニオン系界面活性剤は、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレン誘導体、ソルビタン脂肪酸エステル、ポリ（１２－ヒドロキシステアリン酸）－ポリエチレンイミン共重合体、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルアミン、アルキルアルカノールアミド等が挙げられ、特に制限されないが、ポリ（１２－ヒドロキシステアリン酸）－ポリエチレンイミン共重合体、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレン誘導体、ソルビタン脂肪酸エステルが好ましく、ポリオキシアルキレン誘導体がより好ましい。上記であることで、液状着色組成物中の染料（Ｃ）の分散性と保存安定性に優れ、ポリエステル樹脂原料の重合反応を阻害しないために好ましい。 [Nonionic surfactant]
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester , glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, etc., but are not particularly limited to poly(12-hydroxystearic acid)-polyethyleneimine copolymer. Polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, and sorbitan fatty acid esters are preferred, and polyoxyalkylene derivatives are more preferred. The above is preferable because the dye (C) in the liquid coloring composition has excellent dispersibility and storage stability, and does not inhibit the polymerization reaction of the polyester resin raw material.
　ノニオン系界面活性剤（Ｂ）のＨＬＢ値は、染料（Ｃ）の分散性の観点から、ＨＬＢ値１５以下が好ましく、１～１５が更に好ましい。 The HLB value of the nonionic surfactant (B) is preferably 15 or less, more preferably 1 to 15, from the viewpoint of dispersibility of the dye (C).
　なお、ＨＬＢ（Ｈｙｄｒｏｐｈｉｌｅ－ＬｉｐｏｐｈｉｌｅＢａｌａｎｃｅ）値とは、材料の親水性又は疎水性を表すパラメータの一つであり、小さいほど疎水性が高く、大きいほど親水性が高いことを表す。化学構造からＨＬＢ値を算出する方法は種々知られており、また実測する方法も様々知られているが、本発明の実施形態では、グリフィン法を用いてＨＬＢ値の算出を行う。なおグリフィン法とは、対象の材料の分子構造と分子量を用いて、下記式を用いてＨＬＢ　値を算出する方法である。
式：ＨＬＢ値＝　２０×（親水性部分の分子量の総和）÷（材料の分子量） Note that the HLB (Hydrophile-Lipophile Balance) value is one of the parameters representing the hydrophilicity or hydrophobicity of a material, and the smaller the value, the higher the hydrophobicity, and the higher the HLB value, the higher the hydrophilicity. Various methods are known for calculating the HLB value from a chemical structure, and various methods for actual measurement are also known, but in the embodiment of the present invention, the HLB value is calculated using the Griffin method. Note that the Griffin method is a method of calculating the HLB value using the following formula using the molecular structure and molecular weight of the target material.
Formula: HLB value = 20 x (sum of molecular weights of hydrophilic parts) ÷ (molecular weight of material)
　ポリオキシエチレンアルキルエーテルの具体例として、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンミリスチルエーテル、ポリオキシエチレンオクチルドデシルエーテル等が挙げられるが、特に限定されない。
　ポリオキシエチレンアルキルエーテルの具体例として、エマルゲン１０９Ｐ（花王社製、２５℃で液体、ＨＬＢ値１３．６）、エマルゲン１０２ＫＧ（花王社製、２５℃で液体、ＨＬＢ値６．３）が挙げられる。 Specific examples of polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyl dodecyl ether, etc., but are not particularly limited.
Specific examples of polyoxyethylene alkyl ethers include Emulgen 109P (manufactured by Kao Corporation, liquid at 25°C, HLB value 13.6) and Emulgen 102KG (manufactured by Kao Corporation, liquid at 25°C, HLB value 6.3). .
　ポリオキシアルキレン誘導体は、例えば、ポリオキシアルキレン構造を有するエーテル（但し、ポリオキシエチレンアルキルエーテルに該当する化合物を除く。）であってよい。ポリオキシアルキレン誘導体の具体例として、ポリオキシエチレンアルキレンアルキルエーテル、ポリオキシエチレンジスチレン化フェニルエーテル、ポリオキシエチレントリベンジルフェニルエーテル、ポリオキシエチレンポリオキシプロピレングリコール、ポリオキシエチレングリセリルエーテル、ポリオキシエチレンジグリセリルエーテル等が挙げられるが、特に限定されない。 The polyoxyalkylene derivative may be, for example, an ether having a polyoxyalkylene structure (excluding compounds corresponding to polyoxyethylene alkyl ether). Specific examples of polyoxyalkylene derivatives include polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene glyceryl ether, and polyoxyethylene. Examples include diglyceryl ether, but are not particularly limited.
　ポリオキシアルキレン誘導体の具体例として、エマルゲンＬＳ－１１４（花王社製、２５℃で液体、ＨＬＢ値１４）、エマルゲンＢ－６６（花王社製、２５℃で液体、ＨＬＢ値１３．２）、アデカプルロニックＬ－６１（ＡＤＥＫＡ社製、２５℃で液体、ＨＬＢ値３）、アデカプルロニックＬ－４３（ＡＤＥＫＡ社製、２５℃で液体、ＨＬＢ値１２、アデカプルロニックＬ－３５（ＡＤＥＫＡ社製、２５℃で液体、ＨＬＢ値１８．５）等が挙げられる。 Specific examples of polyoxyalkylene derivatives include Emulgen LS-114 (manufactured by Kao Corporation, liquid at 25°C, HLB value 14), Emulgen B-66 (manufactured by Kao Corporation, liquid at 25°C, HLB value 13.2), Adeka. Pluronic L-61 (manufactured by ADEKA, liquid at 25°C, HLB value 3), Adeka Pluronic L-43 (manufactured by ADEKA, liquid at 25°C, HLB value 12), ADEKA Pluronic L-35 (manufactured by ADEKA, liquid at 25°C) liquid, HLB value 18.5), etc.
　ソルビタン脂肪酸エステルの具体例として、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンジステアレート、ソルビタントリステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンモノオレエート、ポリオキシエチレンモノステアレート等が挙げられるが、特に限定されない。
　ソルビタン脂肪酸エステルの具体例として、レオドールＳＰ－Ｏ３０－Ｖ（花王社製、２５℃で液体、ＨＬＢ値１．８）、レオドールＳＰ－Ｌ１０（花王社製、２５℃で液体、ＨＬＢ値８．６）、エマゾールＬ－１２０Ｖ（花王社製、２５℃で液体、ＨＬＢ値１６．７）等が挙げられる。 Specific examples of sorbitan fatty acid esters include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, Examples include polyoxyethylene monooleate, polyoxyethylene monostearate, etc., but are not particularly limited.
Specific examples of sorbitan fatty acid esters include Rheodol SP-O30-V (manufactured by Kao Corporation, liquid at 25°C, HLB value 1.8), Rheodol SP-L10 (manufactured by Kao Corporation, liquid at 25°C, HLB value 8.6). ), Emazol L-120V (manufactured by Kao Corporation, liquid at 25°C, HLB value 16.7), and the like.
［両性界面活性剤］
　両性界面活性剤は、アルキルベタイン、アルキルアミンオキサイド等が挙げられ、特に制限されない。 [Ampholytic surfactant]
Examples of the amphoteric surfactant include alkyl betaine, alkyl amine oxide, etc., and are not particularly limited.
　アルキルベタインの具体例として、ラウリルベタイン、ステアリルベタイン、２－アルキル－Ｎ－カルボキシメチル－Ｎ－ヒドロキシエチルイミダゾリニウムベタイン等が挙げられるが、特に限定されない。
　アルキルベタインの具体例として、アンヒトール２０ＢＳ（花王社製、２５℃で液体）、アンヒトール２０Ｙ－Ｂ（花王社製、２５℃で液体）等が挙げられる。 Specific examples of alkyl betaines include lauryl betaine, stearyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, and the like, but are not particularly limited.
Specific examples of alkylbetaine include Amhitol 20BS (manufactured by Kao Corporation, liquid at 25° C.), Amhitol 20Y-B (manufactured by Kao Corporation, liquid at 25° C.), and the like.
　アルキルアミンオキサイドの具体例として、ラウリルジメチルアミンオキサイド等が挙げられるが、特に限定されない。
　アルキルアミンオキサイドの具体例として、アンヒトール２０Ｎ（花王社製、２５℃で液体）等が挙げられる。 Specific examples of alkylamine oxide include lauryl dimethylamine oxide, but are not particularly limited.
Specific examples of the alkylamine oxide include Amhitol 20N (manufactured by Kao Corporation, liquid at 25° C.) and the like.
　界面活性剤（Ｂ）は、ジオール成分（Ａ）との相溶性、及び染料（Ｃ）の分散性に優れることから、２５℃で液体であることが好ましい。 The surfactant (B) is preferably liquid at 25°C because it has excellent compatibility with the diol component (A) and dispersibility of the dye (C).
＜染料（Ｃ）＞
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下の染料である。本発明の実施形態においてはポリエステル樹脂の重合反応の際のブルーイングのために用いられる。例えば、染料（Ｃ）として、染料（Ｃ）を使用せずに得たポリエステル樹脂組成物よりも、染料（Ｃ）を使用して得たポリエステル樹脂組成物の方が、ＣＩＥ１９７６Ｌ*ａ*ｂ*表色系で表されるｂ*を低くできる染料を選択して使用できる。
　染料（Ｃ）が、ジオール成分（Ｙ）が含有するエチレングリコールに対して、溶解度が０．５ｇ以下であることにより、ジカルボン酸成分（Ｘ）とジオール成分（Ｙ）を含むポリエステル樹脂原料の重合反応を阻害せず、ポリエステル樹脂を色ムラなく均一にブルーイングし、色材の色移行性も無いポリエステル樹脂組成物とすることができる。 <Dye (C)>
The dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C. In an embodiment of the present invention, it is used for blueing during the polymerization reaction of polyester resin. For example, a polyester resin composition obtained using dye (C) as a dye (C) is better than a polyester resin composition obtained without using dye (C) according to CIE1976L*a*b* It is possible to select and use dyes that can lower b* expressed in the color system.
Since the dye (C) has a solubility of 0.5 g or less in the ethylene glycol contained in the diol component (Y), polymerization of the polyester resin raw material containing the dicarboxylic acid component (X) and the diol component (Y) is possible. It is possible to obtain a polyester resin composition that does not inhibit the reaction, uniformly blues the polyester resin without color unevenness, and has no color migration of the coloring material.
　疎水性であるポリエステル樹脂組成物からの色移行性を抑える観点から、染料（Ｃ）は親水性成分であるエチレングリコールに対する溶解度が低いことが好ましい。そのため、疎水性であることが好ましく、エチレングリコールに対する溶解度が０．５ｇ以下であり、０．４８ｇ以下であることが好ましく、０．４５ｇ以下であることがより好ましい。
　このような、染料（Ｃ）を用いることにより、無機および有機顔料よりも、液状着色組成物の分散性および保存安定性に優れ、色ムラが少ない成形体を得ることができる。
　また、染料（Ｃ）を用いることにより、コバルトブルーを用いる場合に比べて安全性に優れる。また、群青のような無機顔料や、フタロシアニンブルーのような有機顔料を用いる場合に比べて液状着色組成物中での分散性および保存安定性に優れる。
　なお、染料および顔料とは、例えば、Ｃ．Ｉ　Ｎａｍｅ（Ｃｏｌｏｒ　Ｉｎｄｅｘ　Ｇｅｎｅｒｉｃ　Ｎａｍｅ）における分類に則って識別することができる。 From the viewpoint of suppressing color migration from the hydrophobic polyester resin composition, the dye (C) preferably has low solubility in ethylene glycol, which is a hydrophilic component. Therefore, it is preferably hydrophobic and has a solubility in ethylene glycol of 0.5 g or less, preferably 0.48 g or less, and more preferably 0.45 g or less.
By using such a dye (C), it is possible to obtain a molded article with excellent dispersibility and storage stability of the liquid coloring composition and with less color unevenness than inorganic or organic pigments.
Furthermore, the use of dye (C) provides superior safety compared to the case of using cobalt blue. Furthermore, it has excellent dispersibility and storage stability in a liquid coloring composition compared to the case where an inorganic pigment such as ultramarine blue or an organic pigment such as phthalocyanine blue is used.
Note that dyes and pigments include, for example, C.I. It can be identified according to the classification in I Name (Color Index Generic Name).
　また、色材として２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇより高い染料を用い、エチレングリコールに溶解して液状着色組成物として用いた場合に比べて、ポリエステル樹脂原料の重合反応時や成形時の温度でのブリードが抑制され、色移行性が起こらない。 In addition, compared to the case where a dye having a solubility in 100 mL of ethylene glycol at 25°C is higher than 0.5 g as a coloring material is used as a liquid coloring composition by dissolving it in ethylene glycol, it is more effective during the polymerization reaction of polyester resin raw materials or during molding. Bleed is suppressed at temperatures as low as 100 mph, and color migration does not occur.
　なお、ブルーイングとは、得られたポリエステル樹脂組成物またはポリエステル樹脂成形体を目視で見た際の色相が、青味色調に変化していることをいう。例えば、ＣＩＥ１９７６Ｌ*ａ*ｂ*表色系で表されるｂ*が、染料（Ｃ）を添加せずに得たポリエステル樹脂組成物よりも、染料（Ｃ）を添加して得られたポリエステル樹脂組成物の方が低いことと表すことができる。 Note that bluing refers to a change in the hue of the obtained polyester resin composition or polyester resin molded article to a bluish tone when visually observed. For example, b* expressed in the CIE1976L*a*b* color system is higher in a polyester resin composition obtained by adding dye (C) than in a polyester resin composition obtained without adding dye (C). It can be expressed that the composition is lower.
　染料の２５℃におけるエチレングリコール１００ｍＬに対する溶解度とは、２５℃のエチレングリコール１００ｍＬに溶ける染料の量の上限の限度であって、２５℃のエチレングリコール１００ｍＬに染料を加えて１分間撹拌し、目開き５μｍの木綿布上で濾過し、固体や結晶の認められないときの染料の上限の質量である。 The solubility of a dye in 100 mL of ethylene glycol at 25 °C is the upper limit of the amount of dye that can dissolve in 100 mL of ethylene glycol at 25 °C.The dye is added to 100 mL of ethylene glycol at 25 °C, stirred for 1 minute, This is the upper limit of the mass of the dye when no solids or crystals are observed when filtered on a 5 μm cotton cloth.
　液状着色組成物における染料（Ｃ）の配合量は、染料（Ｃ）の分散性の観点から、ジオール成分（Ａ）１００質量部に対し、１～１５０質量部が好ましく、２～１３０質量部がより好ましく、５～１２０質量部が更に好ましい。更に染料（Ｃ）の保存安定性の観点から、染料（Ｃ）の配合量はジオール成分（Ａ）１００質量部に対し、５～１００質量部が好ましく、５～６０質量部が更に好ましい。
　このような液状着色組成物であることにより、ポリエステル樹脂を重合する際に添加される濃厚染料組成物として、よりブルーイング剤含有組成物としての機能を有効に発揮することができる。 From the viewpoint of dispersibility of the dye (C), the blending amount of the dye (C) in the liquid coloring composition is preferably 1 to 150 parts by weight, and 2 to 130 parts by weight, based on 100 parts by weight of the diol component (A). More preferably, 5 to 120 parts by mass is even more preferred. Furthermore, from the viewpoint of storage stability of the dye (C), the amount of the dye (C) to be blended is preferably 5 to 100 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the diol component (A).
By using such a liquid coloring composition, it is possible to more effectively exhibit its function as a bluing agent-containing composition as a concentrated dye composition added when polymerizing a polyester resin.
　染料（Ｃ）としては、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下であれば特に制限されず、ポリエステル樹脂の色調にあわせて選択することができる。染料（Ｃ）としては、アンスラキノン系染料、ペリノン系染料、アゾ系染料、チアゾール系染料、オキサジン系染料、フタロシアニン系染料、キサンテン系染料、フタロシアニン系染料、キノリン系染料、アジン系染料、インジゴイド系染料、キサンテン系染料、アジン系染料、アクリジン系染料、メチン系染料、チアゾール系染料、チアジン系染料、ローダミン系染料、トリアリールメタン系染料等が挙げられる。
　なかでも、ブルーイング効果が高く、液状着色組成物中での分散性に優れることから、アンスラキノン系染料またはペリノン系染料が好ましい。 The dye (C) is not particularly limited as long as it has a solubility in 100 mL of ethylene glycol at 25° C. of 0.5 g or less, and can be selected according to the color tone of the polyester resin. Dyes (C) include anthraquinone dyes, perinone dyes, azo dyes, thiazole dyes, oxazine dyes, phthalocyanine dyes, xanthene dyes, phthalocyanine dyes, quinoline dyes, azine dyes, and indigoid dyes. Examples include dyes, xanthene dyes, azine dyes, acridine dyes, methine dyes, thiazole dyes, thiazine dyes, rhodamine dyes, and triarylmethane dyes.
Among these, anthraquinone dyes or perinone dyes are preferred because they have a high bluing effect and excellent dispersibility in liquid coloring compositions.
　アンスラキノン系またはペリノン系染料として具体的には、Ｓｏｌｖｅｎｔ　Ｒｅｄ５２、１１７、１３５、１６９、１７６、Ｄｉｓｐｅｒｓｅ　Ｒｅｄ５、Ｓｏｌｖｅｎｔ　Ｏｒａｎｇｅ６３、６７、６８、７２、７８、　Ｓｏｌｖｅｎｔ　Ｙｅｌｌｏｗ９８、１０３、１０５、１１３、１１６、Ｄｉｓｐｅｒｓｅ　Ｙｅｌｌｏｗ５４、６４、１６０、Ｓｏｌｖｅｎｔ　Ｇｒｅｅｎ３、２０、２６、Ｓｏｌｖｅｎｔ　Ｂｌｕｅ３５、３６、４５、５９、６３、７８、８３、９４、９７、１０４、１２２、１３２、Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ１３、３１、３３、３６、などが挙げられる。
　なかでも、ブルーイングの効果の観点より、Ｓｏｌｖｅｎｔ　Ｒｅｄ５２、１１７、１３５、１６９、１７６、Ｓｏｌｖｅｎｔ　Ｇｒｅｅｎ３、２０、２６、Ｓｏｌｖｅｎｔ　Ｂｌｕｅ３５、３６、４５、５９、６３、７８、８３、９４、９７、１０４、１２２、１３２、Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ１３、３１、３３、３６が好ましく、Ｓｏｌｖｅｎｔ　Ｒｅｄ１３５、Ｓｏｌｖｅｎｔ　Ｂｌｕｅ３５、３６、４５、５９、６３、７８、８３、９４、９７、１０４、１２２、１３２、Ｓｏｌｖｅｎｔ　Ｖｉｏｌｅｔ１３、３１、３３、３６がより好ましい。 Specifically, the anthraquinone or perinone dyes include Solvent Red52, 117, 135, 169, 176, Disperse Red5, Solvent Orange63, 67, 68, 72, 78, Solvent Yellow98, 103, 105, 113, 116, Di sparse Yellow 54, 64, 160, Solvent Green 3, 20, 26, Solvent Blue 35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 33, 36, etc. It will be done.
Among them, from the viewpoint of bluing effect, Solvent Red52, 117, 135, 169, 176, Solvent Green3, 20, 26, Solvent Blue35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 33, 36 are preferred, Solvent Red 135, Solvent Blue 35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 3 3, 36 is more preferred.
＜その他添加剤＞
　本発明の実施形態によれば、液状着色組成物は、他の任意の重合体や制電剤、消泡剤、染色性改良剤、艶消剤、蛍光増白剤、安定剤、酸化防止剤、粘度調整剤、その他の添加剤が含有されていてもよい。酸化防止剤としては、芳香族アミン系、フェノール系等の酸化防止剤が使用可能であり、安定剤としては、リン酸やリン酸エステル系等のリン系、硫黄系、アミン系等の安定剤が使用可能である。 <Other additives>
According to embodiments of the present invention, the liquid coloring composition may contain other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, matting agents, optical brighteners, stabilizers, antioxidants. , a viscosity modifier, and other additives may also be contained. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphorus-based, sulfur-based, and amine-based stabilizers such as phosphoric acid and phosphoric acid esters can be used. is available.
　なお、液状着色組成物は、ジオール成分（Ａ）以外の有機溶剤を含まないことが好ましい。これは、意図的に添加された状態を除く概念であり、実質的に含まないことを表し、液状着色組成物の全質量に対し、他の有機溶剤は１質量％以下、０．５質量％以下、または０．１質量％以下であればよく、あるいは０質量％であってよい。 Note that the liquid coloring composition preferably does not contain any organic solvent other than the diol component (A). This is a concept that excludes intentional addition, and means that it is substantially free, and the content of other organic solvents is 1% by mass or less, 0.5% by mass based on the total mass of the liquid coloring composition. or less, or 0.1% by mass or less, or 0% by mass.
　ジオール成分（Ａ）と界面活性剤（Ｂ）と染料（Ｃ）以外の他の任意の成分の合計の配合量は、液状着色組成物の全質量に対し、１０質量％以下、５質量％以下、または１質量％以下であってよく、あるいは０質量％であってよい。 The total amount of any other components other than the diol component (A), surfactant (B), and dye (C) is 10% by mass or less and 5% by mass or less based on the total mass of the liquid coloring composition. , or 1% by weight or less, or 0% by weight.
＜液状着色組成物の製造方法＞
　本発明の実施形態における液状着色組成物の製造方法は、特に限定されるものではなく、例えば、ジオール成分（Ａ）と、界面活性剤（Ｂ）と、染料（Ｃ）と、更に必要に応じてその他添加剤とを加え、ヘンシェルミキサーやタンブラー、ディスパー等で混合し、シルバーソンミキサー（シルバーソン社製）等を用いて分散することで、液状着色組成物を得ることができる。分散装置は、上記以外にもニーダー、ロールミル、ボールミル、サンドミル等、任意の装置を使用することができる。分散性に優れるといった理由からビーズミル、シルバーソンミキサー、またはロールミルを用いることが好ましい。
　液状着色組成物は、染料（Ｃ）が分散された染料分散液であり、ブルーイング剤含有組成物として用いることができる。 <Method for producing liquid coloring composition>
The method for producing the liquid coloring composition in the embodiment of the present invention is not particularly limited, and includes, for example, a diol component (A), a surfactant (B), a dye (C), and, if necessary, a method for producing a liquid coloring composition. A liquid coloring composition can be obtained by adding other additives and mixing with a Henschel mixer, tumbler, disper, etc., and dispersing using a Silverson mixer (manufactured by Silverson). As the dispersing device, any device other than the above-mentioned devices such as a kneader, roll mill, ball mill, sand mill, etc. can be used. It is preferable to use a bead mill, a Silverson mixer, or a roll mill because of their excellent dispersibility.
The liquid colored composition is a dye dispersion in which the dye (C) is dispersed, and can be used as a bluing agent-containing composition.
《ポリエステル樹脂組成物》
　ポリエステル樹脂組成物は、ポリエステル樹脂原料を重合してポリエステル樹脂を製造する際に、液状着色組成物を使用して得られる。
　本発明の実施形態による液状着色組成物を用いることで、ジカルボン酸成分（Ｘ）とジオール成分（Ｙ）を含むポリエステル樹脂原料の重合反応を阻害せず、ポリエステル樹脂を色ムラなく均一にブルーイングし、色材の色移行性も無いポリエステル樹脂組成物とできる。
　なお、このとき、液状着色組成物中のジオール成分（Ａ）もジオール成分としてジカルボン酸成分（Ｘ）と重合反応し、ポリエステル樹脂となるため、ポリエステル樹脂原料としても機能する。
　そのため、ジオール成分（Ａ）も、ジオール成分（Ｙ）が含有する成分である、エチレングリコールであることが好ましい。
　液状着色組成物は、重合のための反応容器に添加して使用できる。液状着色組成物を添加する工程は、重合開始前でもよいし、重合反応中であってもよい。 《Polyester resin composition》
A polyester resin composition is obtained by using a liquid coloring composition when producing a polyester resin by polymerizing a polyester resin raw material.
By using the liquid coloring composition according to the embodiment of the present invention, the polyester resin can be uniformly blued without uneven coloring without inhibiting the polymerization reaction of the polyester resin raw material containing the dicarboxylic acid component (X) and the diol component (Y). In addition, a polyester resin composition can be obtained that does not have the color migration property of the coloring material.
At this time, the diol component (A) in the liquid coloring composition also undergoes a polymerization reaction as a diol component with the dicarboxylic acid component (X) to become a polyester resin, and thus also functions as a polyester resin raw material.
Therefore, the diol component (A) is also preferably ethylene glycol, which is a component contained in the diol component (Y).
The liquid colored composition can be used by being added to a reaction vessel for polymerization. The step of adding the liquid coloring composition may be performed before the start of polymerization or during the polymerization reaction.
　すなわち、ポリエステル樹脂組成物は、重合触媒（Ｚ）の存在下でジカルボン酸成分（Ｘ）と、ジオール成分（Ａ）およびジオール成分（Ｙ）とが重合反応して得られたポリエステル樹脂、界面活性剤（Ｂ）、ならびに染料（Ｃ）を含む。 That is, the polyester resin composition is a polyester resin obtained by a polymerization reaction of a dicarboxylic acid component (X), a diol component (A), and a diol component (Y) in the presence of a polymerization catalyst (Z), and a surfactant. agent (B) and dye (C).
　＜ジカルボン酸成分（Ｘ）＞
　ジカルボン酸成分（Ｘ）は、少なくともテレフタル酸を含むジカルボン酸成分であり、ポリエステル樹脂の原料である。ジカルボン酸成分（Ｘ）は、テレフタル酸と、例えば、テレフタル酸、テレフタル酸ジメチル、テレフタル酸ジエチル、テレフタル酸ジブチル等を含んでもよい。
　ジカルボン酸成分（Ｘ）としては、テレフタル酸が主成分であることが好ましい。
　なお、主成分とは、ジカルボン酸成分（Ｘ）を構成する成分中、最も含有率が高い成分がテレフタル酸であることをいう。 <Dicarboxylic acid component (X)>
The dicarboxylic acid component (X) is a dicarboxylic acid component containing at least terephthalic acid, and is a raw material for polyester resin. The dicarboxylic acid component (X) may include terephthalic acid and, for example, terephthalic acid, dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, and the like.
As the dicarboxylic acid component (X), it is preferable that terephthalic acid is the main component.
In addition, the main component means that the component with the highest content rate among the components constituting the dicarboxylic acid component (X) is terephthalic acid.
　ジカルボン酸成分（Ｘ）は、素原料から合成して得られた成分を用いてもよいし、リサイクル等によりポリエステル樹脂を解重合して得られた成分を用いてもよい。
　本発明の実施形態において、液状着色組成物は、ポリエステル樹脂を色ムラなくブルーイングする効果が高いため、リサイクルによりポリエステル樹脂を解重合して得られたジカルボン酸成分を用いた場合であっても、色調が良好な樹脂成形体が得られる。 As the dicarboxylic acid component (X), a component obtained by synthesis from raw materials may be used, or a component obtained by depolymerizing a polyester resin by recycling or the like may be used.
In the embodiment of the present invention, the liquid coloring composition has a high effect of blueing the polyester resin without color unevenness, so even when a dicarboxylic acid component obtained by depolymerizing the polyester resin by recycling is used. , a resin molded article with good color tone can be obtained.
　＜ジオール成分（Ｙ）＞
　ジオール成分（Ｙ）は、少なくともエチレングリコールを含むジオール成分であり、ポリエステル樹脂の原料である。ジオール成分（Ｙ）は、エチレングリコールと、例えばジエチレングリコール、トリエチレングリコール、ポリエチレングリコール等、ジオール成分（Ａ）で説明したエチレングリコール以外のジオール成分を含んでもよい。
　ジオール成分（Ｙ）としては、エチレングリコールが主成分であることが好ましい。
　ただし、ジオール成分（Ｙ）として、液状着色組成物が含有するジオール成分（Ａ）は除く。すなわち、ポリエステル樹脂の製造には、ジオール成分（Ａ）を含有する液状着色組成物と、液状着色組成物とは別にジオール成分（Ｙ）とを使用し、ポリエステル樹脂の原料は、ジオール成分（Ａ）と、ジオール成分（Ａ）とは別にジオール成分（Ｙ）とを含む。ジオール成分（Ｙ）は、ジオール成分（Ａ）に含まれるジオールと同一のジオールを含んでいてもよいし、ジオール成分（Ａ）に含まれるジオールとは異なるジオールを含んでいてもよく、さらに、同一のジオールと異なるジオールとの両方を含んでいてもよい。
　なお、主成分とは、ジオール成分（Ｙ）を構成する成分中、最も含有率が高い成分がエチレングリコールであることをいう。 <Diol component (Y)>
The diol component (Y) is a diol component containing at least ethylene glycol, and is a raw material for polyester resin. The diol component (Y) may contain ethylene glycol and a diol component other than ethylene glycol explained in the diol component (A), such as diethylene glycol, triethylene glycol, polyethylene glycol, etc.
As the diol component (Y), it is preferable that ethylene glycol is the main component.
However, the diol component (A) contained in the liquid coloring composition is excluded as the diol component (Y). That is, in the production of polyester resin, a liquid coloring composition containing a diol component (A) and a diol component (Y) are used separately from the liquid coloring composition, and the raw material for the polyester resin is a diol component (A). ) and a diol component (Y) separately from the diol component (A). The diol component (Y) may contain the same diol as the diol contained in the diol component (A), or may contain a diol different from the diol contained in the diol component (A), and further, It may contain both the same diol and different diols.
In addition, the main component means that the component with the highest content rate among the components constituting the diol component (Y) is ethylene glycol.
　ジオール成分（Ｙ）は、素原料から合成して得られた成分を用いてもよいし、リサイクルによりポリエステル樹脂を解重合して得られた成分を用いてもよい。
　本発明の実施形態において、液状着色組成物は、ポリエステル樹脂を色ムラなくブルーイングする効果が高いため、リサイクル等によりポリエステル樹脂を解重合して得られた成分を用いた場合であっても、色調が良好な樹脂成形体が得られる。 As the diol component (Y), a component obtained by synthesis from raw materials may be used, or a component obtained by depolymerizing a polyester resin by recycling may be used.
In the embodiment of the present invention, the liquid coloring composition has a high effect of blueing the polyester resin evenly, so even when using a component obtained by depolymerizing the polyester resin by recycling etc. A resin molded article with good color tone can be obtained.
　＜重合触媒（Ｚ）＞
　重合触媒（Ｚ）は、ポリエステル樹脂原料の重合反応を促進させる触媒であり、ポリエステル樹脂の重合に際しては、特に制限はなく、例えば、チタンテトラアルコキシド、テトラブトキシチタン、酸化チタン等のチタン系触媒、ジブチルスズオキシド、酢酸スズ、酢酸亜鉛、二硫化スズ等のスズ系触媒、三酸化アンチモン等のアンチモン系触媒、二酸化ゲルマニウム、酢酸マグネシウム等の重合触媒を用いることができる。 <Polymerization catalyst (Z)>
The polymerization catalyst (Z) is a catalyst that accelerates the polymerization reaction of the polyester resin raw material, and there are no particular restrictions on the polymerization of the polyester resin. Examples include titanium-based catalysts such as titanium tetraalkoxide, tetrabutoxytitanium, and titanium oxide; Tin-based catalysts such as dibutyltin oxide, tin acetate, zinc acetate, and tin disulfide, antimony-based catalysts such as antimony trioxide, and polymerization catalysts such as germanium dioxide and magnesium acetate can be used.
　本発明の実施形態によれば、液状着色組成物は、ポリエステル樹脂原料の重合反応の際に、ポリエステル樹脂を色ムラ無く均一にブルーイングする効果が高いため、反応速度が速いチタン触媒を用いた場合であっても、色調が良好な樹脂成形体を得ることが可能となる。本発明の実施形態において、例えば、重合触媒（Ｚ）は、チタン系触媒である。 According to an embodiment of the present invention, the liquid coloring composition uses a titanium catalyst that has a high reaction rate because it has a high effect of uniformly blueing the polyester resin without color unevenness during the polymerization reaction of the polyester resin raw material. Even in the case where the resin molded article has a good color tone, it is possible to obtain a resin molded article with good color tone. In an embodiment of the present invention, for example, the polymerization catalyst (Z) is a titanium-based catalyst.
　重合触媒（Ｚ）の配合量は、得られるポリエステル樹脂の物性の観点から、ジカルボン酸成分（Ｘ）及びジオール成分（Ｙ）の合計１００質量％に対して、好ましくは０．５質量％以下であり、０．２質量％以下が更に好ましい。重合触媒（Ｚ）の配合量は、ジカルボン酸成分（Ｘ）及びジオール成分（Ｙ）の合計１００質量％に対して、好ましくは０．００１質量％以上であり、０．０５質量％以上が更に好ましい。 The amount of the polymerization catalyst (Z) is preferably 0.5% by mass or less based on the total of 100% by mass of the dicarboxylic acid component (X) and the diol component (Y) from the viewpoint of the physical properties of the resulting polyester resin. Yes, and more preferably 0.2% by mass or less. The blending amount of the polymerization catalyst (Z) is preferably 0.001% by mass or more, and 0.05% by mass or more based on the total of 100% by mass of the dicarboxylic acid component (X) and diol component (Y). preferable.
　＜その他成分＞
　本発明の実施形態において、ポリエステル樹脂組成物は、ポリエステル樹脂原料の重合反応とポリエステル樹脂のブルーイングを阻害しない限り、上記以外の成分を含んでいてもよい。
　その他の成分としては、任意の重合体や制電剤、消泡剤、染色性改良剤、艶消剤、蛍光増白剤、安定剤、酸化防止剤、その他の添加剤が含有されていてもよい。酸化防止剤としては、芳香族アミン系、フェノール系等の酸化防止剤が使用可能であり、安定剤としては、リン酸やリン酸エステル系等のリン系、硫黄系、アミン系等の安定剤が使用可能である。 <Other ingredients>
In an embodiment of the present invention, the polyester resin composition may contain components other than those described above, as long as they do not inhibit the polymerization reaction of the polyester resin raw material and the blueing of the polyester resin.
Other ingredients may include arbitrary polymers, antistatic agents, antifoaming agents, dyeability improvers, matting agents, optical brighteners, stabilizers, antioxidants, and other additives. good. As antioxidants, aromatic amine-based and phenol-based antioxidants can be used, and as stabilizers, phosphorus-based, sulfur-based, and amine-based stabilizers such as phosphoric acid and phosphoric acid esters can be used. is available.
＜ポリエステル樹脂組成物の製造方法＞
　本発明の実施形態において、ポリエステル樹脂組成物は、ジカルボン酸成分（Ｘ）と、ジオール成分（Ｙ）と重合触媒（Ｚ）と、本発明の実施形態による液状着色組成物を用いて製造できる。ポリエステル樹脂組成物の製造方法は、例えば、重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂組成物を製造する工程を含む。この工程は、反応容器に、ジカルボン酸成分（Ｘ）、ジオール成分（Ｙ）、重合触媒（Ｚ）、および液状着色組成物をそれぞれ加えることを含んでよい。ジカルボン酸成分（Ｘ）、ジオール成分（Ｙ）、重合触媒（Ｚ）、および液状着色組成物を加える順番は特に限定されない。これらの２種以上を同時に加えてもよい。またこの工程では、ジオール成分（Ａ）もジカルボン酸成分（Ｘ）と重合反応する。液状着色組成物は、重合開始前に加えても、重合反応中に加えてもよい。重合反応には、更に任意の成分を使用してもよい。 <Method for producing polyester resin composition>
In an embodiment of the present invention, a polyester resin composition can be manufactured using a dicarboxylic acid component (X), a diol component (Y), a polymerization catalyst (Z), and a liquid colored composition according to an embodiment of the present invention. The method for producing a polyester resin composition includes, for example, adding a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol in the presence of a polymerization catalyst (Z) and a liquid coloring composition. It includes a step of producing a polyester resin composition by conducting a polymerization reaction. This step may include respectively adding a dicarboxylic acid component (X), a diol component (Y), a polymerization catalyst (Z), and a liquid coloring composition to a reaction vessel. The order in which the dicarboxylic acid component (X), diol component (Y), polymerization catalyst (Z), and liquid coloring composition are added is not particularly limited. Two or more of these may be added at the same time. Further, in this step, the diol component (A) also undergoes a polymerization reaction with the dicarboxylic acid component (X). The liquid coloring composition may be added before the start of polymerization or during the polymerization reaction. Further optional components may be used in the polymerization reaction.
　ポリエステル樹脂を得るための重合方法は、特に制限はされないが、例えば、ジカルボン酸成分（Ｘ）と、ジオール成分（Ｙ）を反応容器に投入し、更に本発明の実施形態による液状着色組成物を投入した後、重合触媒（Ｚ）を投入し、ジカルボン酸成分（Ｘ）と、ジオール成分（Ｙ）のエステル化反応またはエステル交換反応により得られた生成物を、重縮合反応してポリエステル樹脂を製造する方法が挙げられる。本明細書では、これらの反応を含めて重合反応という場合がある。 The polymerization method for obtaining the polyester resin is not particularly limited, but for example, the dicarboxylic acid component (X) and the diol component (Y) are charged into a reaction container, and then the liquid colored composition according to the embodiment of the present invention is added. After that, a polymerization catalyst (Z) is added, and the product obtained by the esterification reaction or transesterification reaction of the dicarboxylic acid component (X) and the diol component (Y) is subjected to a polycondensation reaction to produce a polyester resin. A manufacturing method is mentioned. In this specification, these reactions may be referred to as polymerization reactions.
　ポリエステル樹脂原料の重合反応の比率は、ジカルボン酸成分（Ｘ）：ジオール成分（Ｙ）のモル比が１：１．０３～１：２．５の範囲であることが好ましく、１：１．０５～１：１．２の範囲であることがより好ましい。上記範囲にあることで、機械物性に優れたポリエステル樹脂成形体を得ることができる。 The ratio of the polymerization reaction of the polyester resin raw material is preferably such that the molar ratio of dicarboxylic acid component (X) to diol component (Y) is in the range of 1:1.03 to 1:2.5, and 1:1.05. More preferably, the ratio is in the range of 1:1.2. By being within the above range, a polyester resin molded article with excellent mechanical properties can be obtained.
　本発明の実施形態において、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）、および少なくともエチレングリコールを含むジオール成分（Ｙ）の少なくともいずれかが、ポリエステル樹脂を解重合して得られた成分であってよい。 In an embodiment of the present invention, at least one of the dicarboxylic acid component (X) containing at least terephthalic acid and the diol component (Y) containing at least ethylene glycol is a component obtained by depolymerizing a polyester resin. good.
　液状着色組成物の配合量は、得られるポリエステルの物性と色の均一性の観点から、ジカルボン酸成分（Ｘ）及びジオール成分（Ｙ）の合計１００質量％に対して、好ましくは０．０００１～１質量％であり、より好ましくは０．０００１５～０．５質量％であり、更に好ましくは０．０００２～０．５質量％である。 From the viewpoint of the physical properties and color uniformity of the resulting polyester, the amount of the liquid coloring composition to be blended is preferably 0.0001 to 100% based on the total of 100% by mass of the dicarboxylic acid component (X) and the diol component (Y). 1% by mass, more preferably 0.00015 to 0.5% by mass, still more preferably 0.0002 to 0.5% by mass.
　得られるポリエステル樹脂の物性と色の均一性の観点から、重合反応に使用するジオール成分（Ｙ）と、重合反応に使用する液状着色組成物に含まれているジオール成分（Ａ）との比率は、ジオール成分（Ｙ）１００質量％に対して、ジオール成分（Ａ）が０．０００１～２質量％であることが好ましく、より好ましくは０．０００２～１．５質量％であり、更に好ましくは０．０００５～１質量％である。 From the viewpoint of physical properties and color uniformity of the resulting polyester resin, the ratio of the diol component (Y) used in the polymerization reaction and the diol component (A) contained in the liquid coloring composition used in the polymerization reaction is , the diol component (A) is preferably 0.0001 to 2% by mass, more preferably 0.0002 to 1.5% by mass, and even more preferably It is 0.0005 to 1% by mass.
　染料（Ｃ）の分散性及び得られるポリエステル樹脂の物性の観点から、重合反応に使用するジオール成分（Ｙ）と、重合反応に使用する液状着色組成物に含まれている界面活性剤（Ｂ）との比率は、ジオール成分（Ｙ）１００質量％に対して、界面活性剤（Ｂ）が０．０００００１～０．８質量％であることが好ましく、より好ましくは０．０００００５～０．５質量％であり、更に好ましくは０．００００１～０．３質量％である。 From the viewpoint of the dispersibility of the dye (C) and the physical properties of the resulting polyester resin, the diol component (Y) used in the polymerization reaction and the surfactant (B) contained in the liquid coloring composition used in the polymerization reaction. The ratio of the surfactant (B) to 100% by mass of the diol component (Y) is preferably 0.000001 to 0.8% by mass, more preferably 0.000005 to 0.5% by mass. %, more preferably 0.00001 to 0.3% by mass.
　染料（Ｃ）の含有率は、ブルーイング効果の観点から、ポリエステル樹脂組成物１００質量％を基準として、０ｐｐｍを超え１０ｐｐｍ以下であることが好ましく、より好ましくは５ｐｐｍ以下であり、さらに好ましくは３ｐｐｍ以下である。 From the viewpoint of the bluing effect, the content of the dye (C) is preferably more than 0 ppm and 10 ppm or less, more preferably 5 ppm or less, and even more preferably 3 ppm, based on 100% by mass of the polyester resin composition. It is as follows.
　重合の反応温度は、特に制限されないが、１８０℃～２８０℃の範囲であることが好ましい。重合の反応温度が１８０℃以上の場合には、生産性が良好となる傾向にあり、２８０℃以下の場合には、樹脂の分解や、臭気の要因となる揮発分の副生成を抑制できる傾向にある。重合の反応温度の下限値は２００℃がより好ましく、２２０℃が特に好ましい。重合の反応温度の上限値は２７０℃がより好ましい。重合の真空度は、０．５ｋＰａ以上が好ましい。０．５ｋＰａ以上の場合、反応性が良好となる傾向にあり、生産性が向上する。 The reaction temperature for polymerization is not particularly limited, but is preferably in the range of 180°C to 280°C. When the polymerization reaction temperature is 180°C or higher, productivity tends to be good, and when it is 280°C or lower, it tends to suppress resin decomposition and volatile by-products that cause odor. It is in. The lower limit of the polymerization reaction temperature is more preferably 200°C, particularly preferably 220°C. The upper limit of the polymerization reaction temperature is more preferably 270°C. The degree of vacuum during polymerization is preferably 0.5 kPa or more. When it is 0.5 kPa or more, reactivity tends to be good and productivity is improved.
　得られたポリエステル樹脂組成物は、ペレット状（円柱状チップ等）、粉体状、顆粒状あるいはビーズ状の形状とすることができる。混練力が強く、その後の成形加工が容易なことから、単軸押出機または二軸押出機にて製造したペレット状であることが好ましい。 The obtained polyester resin composition can be in the form of pellets (such as cylindrical chips), powder, granules, or beads. It is preferable to use a pellet form produced by a single-screw extruder or a twin-screw extruder because the kneading force is strong and the subsequent molding process is easy.
《ポリエステル樹脂成形体》
　ポリエステル樹脂成形体は、ポリエステル樹脂を用いた成形体であって、前述のポリエステル樹脂組成物を成形して得られる。
　具体的には、例えば、ポリエステル樹脂組成物を溶融混錬し、従来公知の成形機により成形することにより製造できる。成形機としては、射出成形機、押出成形機、回転成形機等が挙げられるがこれに限定されない。 《Polyester resin molded body》
The polyester resin molded article is a molded article using a polyester resin, and is obtained by molding the above-mentioned polyester resin composition.
Specifically, it can be manufactured, for example, by melt-kneading a polyester resin composition and molding it using a conventionally known molding machine. Examples of the molding machine include, but are not limited to, injection molding machines, extrusion molding machines, rotary molding machines, and the like.
　ポリエステル樹脂成形体は、フィルム、ラミネート、コーティング、繊維、食品用及び日用雑貨用等の射出成形体、圧縮射出成形体、回転成形体又は押出成形体等が挙げられる。
　本発明の実施形態によれば、ポリエステル樹脂成形体は、色ムラ無く均一にブルーイングされていることから、使用時において、消費者が目にし、とくに外観が良好であることが求められる用途であっても、好適に用いることができる。 Examples of the polyester resin molded product include films, laminates, coatings, fibers, injection molded products for foods and daily necessities, compression injection molded products, rotary molded products, extrusion molded products, and the like.
According to the embodiment of the present invention, the polyester resin molded product is uniformly blued without any color unevenness, so that it can be seen by consumers during use, and is particularly suitable for applications that require a good appearance. Even if there is, it can be used suitably.
《本発明の実施形態》
　本発明は、例えば、以下の実施形態を含む。本発明の実施形態は、以下に限定されない。
　〔１〕ポリエステル樹脂を重合により得る際に使用される液状着色組成物であって、
　ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、液状着色組成物。
　〔２〕界面活性剤（Ｂ）は、ノニオン系界面活性剤および両性界面活性剤の少なくともいずれかである、〔１〕記載の液状着色組成物。
　〔３〕界面活性剤（Ｂ）は、ポリ（１２－ヒドロキシステアリン酸）－ポリエチレンイミン共重合体、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレン誘導体、ソルビタン脂肪酸エステル、アルキルベタイン、及びアルキルアミンオキサイドからなる群より選ばれる少なくともいずれかである、〔１〕又は〔２〕記載の液状着色組成物。
　〔４〕ジオール成分（Ａ）１００質量部に対して、界面活性剤（Ｂ）を０．１～５０質量部含む、〔１〕～〔３〕いずれか記載の液状着色組成物。
　〔５〕染料（Ｃ）は、アンスラキノン系染料またはペリノン系染料である、〔１〕～〔４〕いずれか記載の液状着色組成物。
　〔６〕重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂を製造する工程を備え、
　前記液液状着色組成物は、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、ポリエステル樹脂組成物の製造方法。
　〔７〕重合触媒（Ｚ）はチタン系触媒である、〔６〕記載のポリエステル樹脂組成物の製造方法。
　〔８〕少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）、および少なくともエチレングリコールを含むジオール成分（Ｙ）の少なくともいずれかが、ポリエステル樹脂を解重合して得られた成分である、〔６〕又は〔７〕記載のポリエステル樹脂組成物の製造方法。
　〔９〕重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂組成物を製造する工程と、
　得られたポリエステル樹脂組成物を成形する工程とを備え、
　前記液状着色組成物は、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、ポリエステル樹脂成形体の製造方法。 《Embodiments of the present invention》
The present invention includes, for example, the following embodiments. Embodiments of the invention are not limited to the following.
[1] A liquid coloring composition used when obtaining a polyester resin by polymerization,
Contains a diol component (A), a surfactant (B), and a dye (C),
The dye (C) is a liquid coloring composition having a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
[2] The liquid coloring composition according to [1], wherein the surfactant (B) is at least one of a nonionic surfactant and an amphoteric surfactant.
[3] Surfactant (B) consists of poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, alkyl betaine, and alkyl amine oxide. The liquid coloring composition according to [1] or [2], which is at least one selected from the group.
[4] The liquid colored composition according to any one of [1] to [3], which contains 0.1 to 50 parts by mass of the surfactant (B) based on 100 parts by mass of the diol component (A).
[5] The liquid coloring composition according to any one of [1] to [4], wherein the dye (C) is an anthraquinone dye or a perinone dye.
[6] In the presence of a polymerization catalyst (Z) and a liquid coloring composition, a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol are polymerized to form a polyester resin. Equipped with a manufacturing process,
The liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
A method for producing a polyester resin composition, wherein the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
[7] The method for producing a polyester resin composition according to [6], wherein the polymerization catalyst (Z) is a titanium-based catalyst.
[8] At least one of the dicarboxylic acid component (X) containing at least terephthalic acid and the diol component (Y) containing at least ethylene glycol is a component obtained by depolymerizing a polyester resin, [6] or [7] The method for producing the polyester resin composition described in [7].
[9] In the presence of a polymerization catalyst (Z) and a liquid coloring composition, a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol are polymerized to form a polyester resin composition. The process of manufacturing things,
and a step of molding the obtained polyester resin composition,
The liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
A method for producing a polyester resin molded article, in which the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
　本願の開示は、２０２２年７月１９日に出願された特願２０２２－１１４６８０号および２０２３年３月７日に出願された特願２０２３－０３４２５３号に記載の主題と関連しており、それらの全ての開示内容は参照によりここに援用される。 The disclosure of this application is related to the subject matter described in Japanese Patent Application No. 2022-114680 filed on July 19, 2022 and Japanese Patent Application No. 2023-034253 filed on March 7, 2023, and The entire disclosure is incorporated herein by reference.
　以下、実施例に基づき本発明を更に詳しく説明するが、本発明は実施例に限定されるものではない。実施例中、部および％は、特に断りがない場合は、それぞれ、質量部および質量％を表す。
　また、表中の配合量は、質量部であり、不揮発分換算値である。尚、表中の空欄は配合していないことを表す。 Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to the Examples. In the examples, parts and % represent parts by mass and % by mass, respectively, unless otherwise specified.
Moreover, the blending amounts in the table are parts by mass and are nonvolatile content equivalent values. In addition, a blank column in the table indicates that it is not blended.
　実施例および比較例で使用した材料を以下に示す。
　＜ジオール成分（Ａ）＞
　Ａ１：エチレングリコール（丸善石油化学社製、融点－１３℃、分子量６２）
　Ａ２：１，３－プロパンジオール（東京化成工業社製、融点-２７℃、分子量７６）
　Ａ３：１，４－ブタンジオール（三菱ケミカル社製、融点２０℃、分子量９０）
　Ａ４：１，４－シクロヘキサンジメタノール（東京化成工業社製、融点５２℃、分子量１４４）
　Ａ５：ポリエチレングリコール４００（三洋化成社製、融点７℃、分子量４００）
　融点は、示差走査熱量計「ＤＳＣ６２００」（セイコーインスツルメンツ社製）を用いて温度範囲：－３０～１００℃、昇温速度：１０℃／分の条件で測定した値である。 The materials used in Examples and Comparative Examples are shown below.
<Diol component (A)>
A1: Ethylene glycol (manufactured by Maruzen Petrochemical Co., Ltd., melting point -13°C, molecular weight 62)
A2: 1,3-propanediol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point -27°C, molecular weight 76)
A3: 1,4-butanediol (manufactured by Mitsubishi Chemical, melting point 20°C, molecular weight 90)
A4: 1,4-cyclohexanedimethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point 52°C, molecular weight 144)
A5: Polyethylene glycol 400 (manufactured by Sanyo Chemical Co., Ltd., melting point 7°C, molecular weight 400)
The melting point is a value measured using a differential scanning calorimeter "DSC6200" (manufactured by Seiko Instruments) under conditions of a temperature range of -30 to 100°C and a heating rate of 10°C/min.
　＜界面活性剤（Ｂ）＞
　Ｂ１：アデカプルロニックＬ－６１（ＡＤＥＫＡ社製）
　Ｂ２：アデカプルロニックＬ－４３（ＡＤＥＫＡ社製）
　Ｂ３：アデカプルロニックＬ－３５（ＡＤＥＫＡ社製）
　Ｂ４：ポリ（１２－ヒドロキシステアリン酸）－ポリエチレンイミン共重合体
　Ｂ５：エマルゲン１０９Ｐ（花王社製）
　Ｂ６：レオドールＳＰ－Ｏ３０－Ｖ（花王社製）
　Ｂ７：アンヒトール２０ＢＳ（花王社製）
　Ｂ８：アンヒトール２０Ｎ（花王社製）
　Ｂ９：ラムテルＰＤ－１０５（花王社製）
　Ｂ１０：コータミン２４Ｐ（花王社製） <Surfactant (B)>
B1: ADEKA Pluronic L-61 (manufactured by ADEKA)
B2: ADEKA Pluronic L-43 (manufactured by ADEKA)
B3: ADEKA Pluronic L-35 (manufactured by ADEKA)
B4: Poly(12-hydroxystearic acid)-polyethyleneimine copolymer B5: Emulgen 109P (manufactured by Kao Corporation)
B6: Rheodor SP-O30-V (manufactured by Kao Corporation)
B7: Anhitor 20BS (manufactured by Kao Corporation)
B8: Amhitol 20N (manufactured by Kao Corporation)
B9: Ramtel PD-105 (manufactured by Kao Corporation)
B10: Cortamine 24P (manufactured by Kao Corporation)
　界面活性剤（Ｂ）の構造と物性値を下記に示した。
The structure and physical properties of surfactant (B) are shown below.
　＜染料（Ｃ）＞
　Ｃ１：マクロレックスブルーＲＲ（染料：アンスラキノン系染料、ＳｏｌｖｅｎｔＢｌｕｅ９７、ランクセス社製、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．２ｇ）
　Ｃ２：スミプラストバイオレットＢ（染料：アンスラキノン系染料、ＳｏｌｖｅｎｔＶｉｏｌｅｔ１３、住化ケムテックス社製、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．４５ｇ）
　Ｃ３：ダイヤレジンレッドＨＳ（染料：ペリノン系染料、ＳｏｌｖｅｎｔＲｅｄ１３５、三菱化学社製、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．２ｇ）
　Ｃ’１：カヤラスターコイズブルーＧＬ（染料、ダイレクトブルー８６、日本化薬社製、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が７ｇ） <Dye (C)>
C1: Macrolex Blue RR (Dye: Anthraquinone dye, Solvent Blue 97, manufactured by Lanxess, solubility in 100 mL of ethylene glycol at 25°C is 0.2 g)
C2: Sumiplast Violet B (Dye: Anthraquinone dye, SolventViolet 13, manufactured by Sumika Chemtex Co., Ltd., solubility in 100 mL of ethylene glycol at 25 ° C. is 0.45 g)
C3: Diamond Resin Red HS (Dye: perinone dye, Solvent Red 135, manufactured by Mitsubishi Chemical Corporation, solubility in 100 mL of ethylene glycol at 25 ° C. is 0.2 g)
C'1: Kayara Turquoise Blue GL (dye, Direct Blue 86, manufactured by Nippon Kayaku Co., Ltd., solubility in 100 mL of ethylene glycol at 25 ° C. is 7 g)
　＜顔料（Ｄ）＞
　Ｄ１：群青Ｎｏ１５００（無機顔料、群青、第一化成工業社製、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．４ｇ）
　Ｄ２：リオノールブルーＦＧ７３３０（有機顔料、フタロシアニンブルー、トーヨーカラー社製、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．２ｇ） <Pigment (D)>
D1: Ultramarine No. 1500 (inorganic pigment, ultramarine blue, manufactured by Daiichi Kasei Kogyo Co., Ltd., solubility in 100 mL of ethylene glycol at 25°C is 0.4 g)
D2: Lionol Blue FG7330 (organic pigment, phthalocyanine blue, manufactured by Toyo Color Co., Ltd., solubility in 100 mL of ethylene glycol at 25°C is 0.2 g)
＜可塑剤＞
　ＤＯＰ：フタル酸ビス（２－エチルヘキシル） <Plasticizer>
DOP: Bis(2-ethylhexyl) phthalate
＜ジカルボン酸成分（Ｘ）＞
　Ｘ１：素原料から合成して得られたテレフタル酸
　Ｘ２：ポリエステル樹脂を解重合して得られたテレフタル酸 <Dicarboxylic acid component (X)>
X1: Terephthalic acid obtained by synthesis from raw materials X2: Terephthalic acid obtained by depolymerizing polyester resin
＜ジオール成分（Ｙ）＞
　Ｙ１：素原料から合成して得られたエチレングリコール
　Ｙ２：ポリエステル樹脂を解重合して得られたエチレングリコール <Diol component (Y)>
Y1: Ethylene glycol obtained by synthesis from raw materials Y2: Ethylene glycol obtained by depolymerizing polyester resin
＜重合触媒（Ｚ）＞
　Ｚ１：酸化チタン
　Ｚ２：三酸化アンチモン <Polymerization catalyst (Z)>
Z1: Titanium oxide Z2: Antimony trioxide
　［実施例１］
　（液状着色組成物（Ｔ１）の製造）
　ジオール成分（Ａ）１００質量部、界面活性剤（Ｂ１）１５質量部、染料（Ｃ１）１２０質量部をビーズミルにて混合及び分散し液状着色組成物（Ｔ１）を得た。 [Example 1]
(Manufacture of liquid colored composition (T1))
100 parts by mass of diol component (A), 15 parts by mass of surfactant (B1), and 120 parts by mass of dye (C1) were mixed and dispersed in a bead mill to obtain a liquid colored composition (T1).
　［実施例２～３３、比較例１、２］
　（液状着色組成物（Ｔ２～３５）の製造）
　表２～５に示す材料と配合量（質量部）にそれぞれ変更した以外は、液状着色組成物（Ｔ１）と同様の方法で液状着色組成物（Ｔ２～３５）をそれぞれ製造した。 [Examples 2 to 33, Comparative Examples 1 and 2]
(Manufacture of liquid coloring composition (T2-35))
Liquid coloring compositions (T2 to 35) were produced in the same manner as liquid coloring composition (T1), except that the materials and blending amounts (parts by mass) shown in Tables 2 to 5 were changed.
　［比較例３、４］
（液状着色組成物（Ｔ３６、３７）の製造）
　表５に示す材料と配合量（質量部）にそれぞれ変更した以外は、液状着色組成物（Ｔ１）と同様の方法で液状着色組成物（Ｔ３６、３７）をそれぞれ製造したものの、液状着色組成物中での分散性と保存安定性が悪く、良好な液状着色組成物を得ることができなかった。 [Comparative Examples 3 and 4]
(Manufacture of liquid coloring composition (T36, 37))
Liquid coloring compositions (T36, 37) were manufactured in the same manner as liquid coloring composition (T1), except that the materials and blending amounts (parts by mass) shown in Table 5 were changed. It was not possible to obtain a good liquid coloring composition due to poor dispersibility and storage stability.
《液状着色組成物の評価》
　得られた液状着色組成物の分散性と保存安定性を下記の方法で評価した。結果を表２～５に示す。 《Evaluation of liquid coloring composition》
The dispersibility and storage stability of the obtained liquid coloring composition were evaluated by the following methods. The results are shown in Tables 2 to 5.
（分散性評価）
　累積体積百分率が９０％のときの粒径（Ｄ９０）を、動的光散乱式粒径分布測定装置ＬＢ－５５０（堀場製作所社製）を用いて測定した。下記基準で評価を行った。
　［評価基準］
　　　◎：Ｄ９０が１０μｍ未満であり、非常に良好
　　　〇：Ｄ９０が１０μｍ以上３０μｍ未満であり、良好
　　　△：Ｄ９０が３０μｍ以上５０μｍ未満であり、実用可能
　　　×：Ｄ９０が５０μｍ以上であり、実用不可 (Dispersibility evaluation)
The particle size (D 90 ) at a cumulative volume percentage of 90% was measured using a dynamic light scattering particle size distribution analyzer LB-550 (manufactured by Horiba, Ltd.). Evaluation was performed based on the following criteria.
[Evaluation criteria]
◎: D90 is less than 10 μm, very good ○: D90 is 10 μm or more and less than 30 μm, good △: D90 is 30 μm or more and less than 50 μm, suitable for practical use ×: D90 is 50 μm or more, Impractical
（保存安定性評価）
　得られた液状着色組成物を３０日間静置し、液状着色組成物中での染料（Ｃ）の分離、沈降を目視で確認し、下記基準で評価を行った。
　［評価基準］
　　　◎：分離、沈降が無く、非常に良好
　　　〇：分離、沈降が若干あるが撹拌すると均一になり、良好
　　　△：分離、沈降があるが撹拌すると均一になり、実用可能
　　　×：分離、沈降があり、撹拌しても均一にならず、実用不可 (Storage stability evaluation)
The obtained liquid coloring composition was allowed to stand for 30 days, and the separation and precipitation of the dye (C) in the liquid coloring composition was visually confirmed and evaluated according to the following criteria.
[Evaluation criteria]
◎: There is no separation or sedimentation, very good 〇: There is some separation or sedimentation, but it becomes uniform when stirred and is good. △: There is separation or sedimentation, but it becomes uniform when stirring, and it is practical. ×: There is separation or sedimentation. , even if stirred, it will not become uniform, making it impractical.
　［実施例３４］
　（ポリエステル樹脂組成物の製造）
　蒸留塔備え付けの反応容器に、ジカルボン酸成分（Ｘ１）（素原料から合成して得られたテレフタル酸）６９質量部とジオール成分（Ｙ１）（素原料から合成して得られたエチレングリコール）３０．５質量部を投入し、その後、液状着色組成物（Ｔ１）をポリエステル樹脂組成物１００質量部を基準として、染料（Ｃ）の含有率が１ｐｐｍとなるように、０．０００２質量部投入し、更に重合触媒（Ｚ１）を０．５質量部投入した。
　次いで、反応容器中の攪拌翼の回転数を２００ｒｐｍに保ち、昇温を開始し、反応系内の温度が２６５℃になるように加熱し、この温度を保持した。エステル化反応が終了し、反応系内からの水の留出がなくなった後、反応系内の温度を２５０℃にし、反応系内を約４０分かけて減圧し、真空度を０．５ｋＰａとし、反応系からジオール成分を留出させながら縮合反応を行った。反応とともに反応系の粘度が上昇し、攪拌翼のトルクが所定のトルクを示した時点で攪拌を停止し、反応系を常圧に戻し、ノズルからストランド状に押出し、水冷した後、切断して、ペレット状（直径約２．５ｍｍ、長さ約２．５ｍｍ）のポリエステル樹脂組成物を得た。 [Example 34]
(Manufacture of polyester resin composition)
In a reaction vessel equipped with a distillation column, 69 parts by mass of dicarboxylic acid component (X1) (terephthalic acid obtained by synthesis from raw materials) and 30 parts by mass of diol component (Y1) (ethylene glycol obtained by synthesis from raw materials). Then, 0.0002 parts by mass of the liquid coloring composition (T1) was added so that the dye (C) content was 1 ppm based on 100 parts by mass of the polyester resin composition. Furthermore, 0.5 parts by mass of a polymerization catalyst (Z1) was added.
Next, the rotational speed of the stirring blade in the reaction vessel was maintained at 200 rpm, and the temperature was started to increase to bring the temperature inside the reaction system to 265° C., and this temperature was maintained. After the esterification reaction was completed and no water was distilled out from the reaction system, the temperature in the reaction system was raised to 250°C, and the pressure in the reaction system was reduced over about 40 minutes, and the degree of vacuum was set to 0.5 kPa. The condensation reaction was carried out while distilling the diol component from the reaction system. The viscosity of the reaction system increases with the reaction, and when the torque of the stirring blade reaches the specified torque, the stirring is stopped, the reaction system is returned to normal pressure, and the strand is extruded from the nozzle, cooled with water, and then cut. A polyester resin composition in the form of pellets (about 2.5 mm in diameter and about 2.5 mm in length) was obtained.
　［実施例３５～６９、比較例６、７］
　表６に示す材料と配合量（質量部）にそれぞれ変更した以外は、実施例３４のポリエステル樹脂組成物と同様の方法で、ポリエステル樹脂組成物をそれぞれ製造した。 [Examples 35 to 69, Comparative Examples 6 and 7]
Polyester resin compositions were produced in the same manner as for the polyester resin composition of Example 34, except that the materials and blending amounts (parts by mass) shown in Table 6 were changed.
《ポリエステル樹脂組成物の評価》
　得られたポリエステル樹脂組成物の重合時間、色相、色ムラ、色移行性を下記の方法で評価した。結果を表６に示す。 《Evaluation of polyester resin composition》
The polymerization time, hue, color unevenness, and color migration of the obtained polyester resin composition were evaluated by the following methods. The results are shown in Table 6.
（重合時間評価）
　液状着色組成物を添加せずに製造したポリエステル樹脂組成物が要した重合時間（イ）に対して、得られたポリエステル樹脂組成物が要した重合時間（ロ）の比を下記式にて算出し評価した。
　重合時間比（％）＝（ロ）／（イ）×１００
　［評価基準］
　　　〇：重合時間比が１２０％未満であり、良好
　　　△：重合時間比が１２０％以上１５０％未満であり、実用可能
　　　×：重合時間比が１５０％以上であり、実用不可 (Polymerization time evaluation)
Calculate the ratio of the polymerization time (b) required for the obtained polyester resin composition to the polymerization time (a) required for the polyester resin composition produced without adding a liquid coloring composition using the following formula. and evaluated.
Polymerization time ratio (%) = (b) / (a) x 100
[Evaluation criteria]
○: Polymerization time ratio is less than 120%, good. △: Polymerization time ratio is 120% or more and less than 150%, practical. ×: Polymerization time ratio is 150% or more, not practical.
（色相評価）
　得られたポリエステル樹脂組成物と、液状着色組成物を添加せずに得たポリエステル樹脂を、それぞれ射出成形機を用いて２８０℃で１ｍｍ厚のプレートに成形し、ＣＩＥ１９７６Ｌ*ａ*ｂ*表色系での色差Δｂ*を下記式より求め、評価した。
 
Δｂ*＝（液状着色組成物を添加せずに得たポリエステル樹脂組成物の色度ｂ*）
　　－（実施例または比較例で得られたポリエステル樹脂組成物の色度ｂ*）
　［評価基準］
　　　〇：　Δｂ*＜０、ブルーイングされており良好
　　　×：　Δｂ*≧０、ブルーイングされておらず不良 (Hue evaluation)
The obtained polyester resin composition and the polyester resin obtained without adding a liquid coloring composition were each molded into a 1 mm thick plate at 280°C using an injection molding machine, and the CIE1976L*a*b* color system was The color difference Δb* in the system was determined and evaluated using the following formula.

Δb*=(Chromaticity b* of polyester resin composition obtained without adding liquid coloring composition)
- (Chromaticity b* of polyester resin composition obtained in Examples or Comparative Examples)
[Evaluation criteria]
〇: Δb*<0, blued and good ×: Δb*≧0, not blued and bad
（色ムラ評価）
　得られたポリエステル樹脂組成物を、射出成形機を用いて２８０℃で１ｍｍ厚のプレート１０枚に成形し、それぞれの色相をＣＩＥ１９７６Ｌ*ａ*ｂ*表色系で測色し、Ｌ*、ａ*、ｂ*の標準偏差および目視から下記の通り評価した。
　［評価基準］
　　　〇：Ｌ*、ａ*、ｂ*それぞれの標準偏差が０．５以下であり、
各プレート毎に色ムラが無く、良好
　　　△：Ｌ*、ａ*、ｂ*それぞれの標準偏差が０．５を超え、０．６以下であり、
各プレート毎に色ムラが無く、実用可能
　　　×：Ｌ*、ａ*、ｂ*それぞれの標準偏差が０．６を超え、０．７以下であり、
各プレート毎に色ムラがあり、実用不可 (color unevenness evaluation)
The obtained polyester resin composition was molded into 10 plates with a thickness of 1 mm at 280°C using an injection molding machine, and the hue of each was measured using the CIE1976L*a*b* color system, and L*, a Evaluation was made as follows based on the standard deviation of * and b* and visual observation.
[Evaluation criteria]
〇: The standard deviation of each of L*, a*, b* is 0.5 or less,
There is no color unevenness for each plate, which is good. △: The standard deviation of each of L*, a*, b* is more than 0.5 and less than 0.6,
There is no color unevenness for each plate, and it is practical.
Each plate has uneven color and is not practical.
（色移行性評価）
　得られたポリエステル樹脂組成物を、射出成形機を用いて２８０℃で１ｍｍ厚のプレートに成形し、得られたプレートを８０℃に加温して綿布でふき取り、綿布の着色を目視で確認した。
　［評価基準］
　　　〇：綿布の着色が無く、良好
　　　×：綿布が着色し、実用不可 (Color migration evaluation)
The obtained polyester resin composition was molded into a 1 mm thick plate at 280°C using an injection molding machine, the obtained plate was heated to 80°C and wiped with a cotton cloth, and the coloring of the cotton cloth was visually confirmed. .
[Evaluation criteria]
〇: Cotton fabric is not colored and is in good condition ×: Cotton fabric is colored and is not practical
（機械物性）
　得られたポリエステル樹脂ペレットを、ブロー成形機を用いて２８０℃でブロー成形し、厚み１ｍｍのペットボトルを５０本作製した。得られたペットボトルのうち、任意の１０本で衝撃試験を行った。具体的には、ペットボトルの８割に水を充填し、高さ１ｍから落下させた。評価基準は以下の通りとした。
　［評価基準］
　　　◎：１０本全てのボトルに穴あきは見られず、変形が見られるボトルが５本未満であった。
　　　〇：１０本全てのボトルに穴あきは見られなかったが、変形が見られるボトルが５本以上１０本未満であった。 
　　　△：１０本全てのボトルに変形が見られ、穴が開いたボトルが２本未満であった。
　　　×：１０本全てのボトルに変形が見られ、穴が開いたボトルが２本以上あった。
(mechanical properties)
The obtained polyester resin pellets were blow molded at 280° C. using a blow molding machine to produce 50 PET bottles each having a thickness of 1 mm. An impact test was conducted on 10 of the obtained PET bottles. Specifically, a plastic bottle was filled 80% with water and dropped from a height of 1 m. The evaluation criteria were as follows.
[Evaluation criteria]
◎: No holes were observed in any of the 10 bottles, and less than 5 bottles were found to be deformed.
○: No holes were observed in any of the 10 bottles, but deformation was observed in 5 or more but less than 10 bottles.
Δ: Deformation was observed in all 10 bottles, and less than 2 bottles had holes.
×: Deformation was observed in all 10 bottles, and two or more bottles had holes.
　表６に示す通り、本発明の実施形態による液状着色組成物により、色材の分散性と保存安定性に優れており、さらに該液状着色組成物を用いることで、ポリエステル樹脂を製造する際の、ポリエステル樹脂原料の重合反応を阻害せず、色ムラなく均一にブルーイングすることができ、色材の色移行性が無いポリエステル樹脂成形体が得られることが確認できた。
　重合触媒（Ｚ）としては、チタン触媒を用いた場合であっても、色調が良好なポリエステル樹脂成形体を形成できることが確認できた。
　また、ジカルボン酸成分（Ｘ）と、ジオール成分（Ｙ）の少なくともいずれかが、ポリエステル樹脂を解重合して得られた化合物であっても、重合時間評価、色相、色ムラ、および色移行性に優れており、ポリエステル樹脂の再利用の場合にも、有効に適用できることが確認できた。 As shown in Table 6, the liquid coloring composition according to the embodiment of the present invention has excellent dispersibility and storage stability of the coloring material, and furthermore, by using the liquid coloring composition, it is possible to improve the coloring composition when producing polyester resin. It was confirmed that the polymerization reaction of the polyester resin raw material was not inhibited, uniform bluing was possible without color unevenness, and a polyester resin molded article without color migration of the coloring material was obtained.
It was confirmed that even when a titanium catalyst was used as the polymerization catalyst (Z), a polyester resin molded article with good color tone could be formed.
In addition, even if at least one of the dicarboxylic acid component (X) and the diol component (Y) is a compound obtained by depolymerizing a polyester resin, evaluation of polymerization time, hue, color unevenness, and color migration property It was confirmed that this method has excellent properties and can be effectively applied to the reuse of polyester resin.
　これに対して、可塑剤に染料（Ｃ）を分散して用いた比較例１の液状着色組成物は、分散性、保存安定性については実用可能なものではあるが、ポリエステル樹脂組成物の重合時間が長くなってしまい、また、色ムラがあり、実用できるものではない結果であった。
　また、ポリエステル樹脂の原料に溶解する色材、すなわち親水性色材を用いた比較例２の液状着色組成物は、成形体からの染料の色移行が起こり、多様な用途、特に飲料容器としても用いられることのあるポリエステル樹脂組成物およびその成形体として実用することはできない結果であった。 On the other hand, the liquid coloring composition of Comparative Example 1, in which the dye (C) was dispersed in a plasticizer, was practical in terms of dispersibility and storage stability, but the polymerization of the polyester resin composition It took a long time, and the color was uneven, so the result was not practical.
In addition, the liquid coloring composition of Comparative Example 2, which uses a coloring material that dissolves in the raw material of polyester resin, that is, a hydrophilic coloring material, causes color migration of the dye from the molded product, and can be used for various purposes, especially as a beverage container. The result was that it could not be put to practical use as a polyester resin composition or a molded article thereof that may be used.

Claims (9)

  1. 　ポリエステル樹脂を重合により得る際に使用される液状着色組成物であって、
    　ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
    　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、液状着色組成物。     A liquid coloring composition used when obtaining a polyester resin by polymerization,
    Contains a diol component (A), a surfactant (B), and a dye (C),
    The dye (C) is a liquid coloring composition having a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
  2. 　界面活性剤（Ｂ）は、ノニオン系界面活性剤および両性界面活性剤の少なくともいずれかである、請求項１記載の液状着色組成物。 The liquid coloring composition according to claim 1, wherein the surfactant (B) is at least one of a nonionic surfactant and an amphoteric surfactant.
  3. 　界面活性剤（Ｂ）は、ポリ（１２－ヒドロキシステアリン酸）－ポリエチレンイミン共重合体、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレン誘導体、ソルビタン脂肪酸エステル、アルキルベタイン、及びアルキルアミンオキサイドからなる群より選ばれる少なくともいずれかである、請求項１又は２記載の液状着色組成物。 The surfactant (B) is selected from the group consisting of poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, alkyl betaine, and alkyl amine oxide. The liquid coloring composition according to claim 1 or 2, which is at least one of:
  4. 　ジオール成分（Ａ）１００質量部に対して、界面活性剤（Ｂ）を０．１～５０質量部含む、請求項１～３のいずれか記載の液状着色組成物。 The liquid colored composition according to any one of claims 1 to 3, comprising 0.1 to 50 parts by mass of the surfactant (B) based on 100 parts by mass of the diol component (A).
  5. 　染料（Ｃ）は、アンスラキノン系染料またはペリノン系染料である、請求項１～４のいずれか記載の液状着色組成物。 The liquid coloring composition according to any one of claims 1 to 4, wherein the dye (C) is an anthraquinone dye or a perinone dye.
  6. 　重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂組成物を製造する工程を備え、
    　前記液状着色組成物は、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
    　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、ポリエステル樹脂組成物の製造方法。     In the presence of a polymerization catalyst (Z) and a liquid coloring composition, a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol are polymerized to produce a polyester resin composition. Equipped with a process to
    The liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
    A method for producing a polyester resin composition, wherein the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
  7. 　重合触媒（Ｚ）は、チタン系触媒である、請求項６記載のポリエステル樹脂組成物の製造方法。 The method for producing a polyester resin composition according to claim 6, wherein the polymerization catalyst (Z) is a titanium-based catalyst.
  8. 　少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）、および少なくともエチレングリコールを含むジオール成分（Ｙ）の少なくともいずれかが、ポリエステル樹脂を解重合して得られた成分である、請求項６又は７記載のポリエステル樹脂組成物の製造方法。 8. At least one of the dicarboxylic acid component (X) containing at least terephthalic acid and the diol component (Y) containing at least ethylene glycol is a component obtained by depolymerizing a polyester resin. A method for producing a polyester resin composition.
  9. 　重合触媒（Ｚ）と液状着色組成物の存在下で、少なくともテレフタル酸を含むジカルボン酸成分（Ｘ）と少なくともエチレングリコールを含むジオール成分（Ｙ）とを重合反応させて、ポリエステル樹脂組成物を製造する工程と、
    　得られたポリエステル樹脂組成物を成形する工程とを備え、
    　前記液状着色組成物は、ジオール成分（Ａ）、界面活性剤（Ｂ）、及び染料（Ｃ）を含み、
    　染料（Ｃ）は、２５℃におけるエチレングリコール１００ｍＬに対する溶解度が０．５ｇ以下である、ポリエステル樹脂成形体の製造方法。     In the presence of a polymerization catalyst (Z) and a liquid coloring composition, a dicarboxylic acid component (X) containing at least terephthalic acid and a diol component (Y) containing at least ethylene glycol are polymerized to produce a polyester resin composition. The process of
    and a step of molding the obtained polyester resin composition,
    The liquid coloring composition includes a diol component (A), a surfactant (B), and a dye (C),
    A method for producing a polyester resin molded article, in which the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
PCT/JP2023/026277 2022-07-19 2023-07-18 Liquid coloring composition, and method for manufacturing polyester resin composition and polyester resin molding body WO2024019052A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4918917A (en) * 1972-06-15 1974-02-19
JPS5034061B1 (en) * 1973-07-23 1975-11-05
JPS55149344A (en) * 1980-05-02 1980-11-20 Dainippon Ink & Chem Inc Colored polyester composition
JP2003105236A (en) * 2001-09-28 2003-04-09 Ricoh Co Ltd Ink for ink-jet printing, ink set, recording method and recording device
JP2003183531A (en) * 2001-10-19 2003-07-03 Eastman Chem Co Reactive anthraquinone coloring compound and polymer material reacting with the same
JP2006241286A (en) * 2005-03-02 2006-09-14 Ricoh Co Ltd Aqueous ink, recording method, and image-forming apparatus
JP2018131615A (en) * 2017-02-15 2018-08-23 東洋インキＳｃホールディングス株式会社 Coloring resin composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4918917A (en) * 1972-06-15 1974-02-19
JPS5034061B1 (en) * 1973-07-23 1975-11-05
JPS55149344A (en) * 1980-05-02 1980-11-20 Dainippon Ink & Chem Inc Colored polyester composition
JP2003105236A (en) * 2001-09-28 2003-04-09 Ricoh Co Ltd Ink for ink-jet printing, ink set, recording method and recording device
JP2003183531A (en) * 2001-10-19 2003-07-03 Eastman Chem Co Reactive anthraquinone coloring compound and polymer material reacting with the same
JP2006241286A (en) * 2005-03-02 2006-09-14 Ricoh Co Ltd Aqueous ink, recording method, and image-forming apparatus
JP2018131615A (en) * 2017-02-15 2018-08-23 東洋インキＳｃホールディングス株式会社 Coloring resin composition

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