JP7320907B1 - Liquid coloring composition, polyester resin composition and method for producing polyester resin molding - Google Patents

Abstract

[Problem] To provide a liquid coloring composition excellent in dispersibility and storage stability of a coloring material, which does not hinder the polymerization reaction in the production of a polyester resin, enables uniform bluing without color unevenness, and provides the color of the coloring material. To provide a non-migration polyester resin composition and a polyester resin molding. A liquid coloring composition to be added when polymerizing a polyester resin, comprising a diol component (A), a surfactant (B), and a dye (C), wherein the dye (C) contains 25 The problem is solved by a liquid coloring composition characterized by having a solubility of 0.5 g or less in 100 mL of ethylene glycol at °C. [Selection figure] None

Description

TECHNICAL FIELD The present invention relates to a liquid coloring composition added when polymerizing a polyester resin, a polyester resin composition, and a method for producing a polyester resin molding.

Plastic molded articles are used in a wide range of fields, such as electrical and electronic equipment parts, automobile parts, medical parts, and food containers, because they are easy to mold. In particular, moldings using polyester resin (polyester resin moldings) have excellent chemical and physical properties, so they can be used as food containers such as PET bottles, sanitary containers, polyester fibers, or films and sheets. used for a wide variety of purposes. In addition, the recycling of polyester resins is being promoted in order to reduce the cost and burden on the environment.

In addition, the polyester resin may have a yellowish hue depending on the raw materials used during polymerization and the polymerization conditions. Specifically, antimony catalysts, which are widely used as polymerization catalysts, are highly toxic and are being replaced with titanium catalysts in recent years. The problem is that it is more yellowish than the polyester resin obtained by using it.

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 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.

As a method for solving such problems, Patent Document 1 discloses a technique of adding a phosphoric acid compound or a phosphorous acid compound during polymerization for the purpose of preventing coloration. Patent Document 2 discloses a technique for obtaining a polyester with a low degree of yellowness by a method for producing polyester. Furthermore, for the purpose of improving color tone, etc., cobalt compounds such as cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate and their hydrates, other inorganic and organic pigments, dyes, fluorescent brighteners, etc. As a method of adding these, during the polycondensation reaction, a powder or a method of dissolving in one of the polyester monomers and adding it, or after the completion of the polycondensation reaction, a powder or , a method of adding as a masterbatch is described.

JP 2006-335974 A JP 2005-314515 A

However, in the conventional methods such as these, it is difficult to uniformly disperse the powdery or granular bluing agent coloring material in the polyester resin composition, and the resulting molded article has a color adjustment. is not sufficient, and color unevenness also occurs.
In addition, if the colorant is used by dispersing it in the raw material of the polyester resin, the compatibility is poor and the colorant cannot be uniformly dispersed, so that the molded article obtained using the colorant has color unevenness.
Furthermore, if the masterbatch is added after the polycondensation reaction is complete, it will require separate weighing and mixing equipment. Since it is contained in the body, mechanical properties are degraded.

Therefore, the object of the present invention is to provide a liquid coloring composition that is excellent in dispersibility and storage stability of the coloring material, does not inhibit the polymerization reaction when producing a polyester resin, and can be blued uniformly without color unevenness. An object of the present invention is to provide a polyester resin composition free from color migration of a coloring material, and a polyester resin molding.

The present inventor has completed the present invention as a result of intensive studies to solve the above problems.
That is, the present invention includes the following embodiments. Embodiments of the present invention are not limited to the following.
[1] A liquid coloring composition added when polymerizing a polyester resin,
comprising a diol component (A), a surfactant (B), and a dye (C);
A liquid coloring composition, wherein the dye (C) has 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, alkylbetaine, and alkylamine oxide. The liquid coloring composition according to [2], which is at least one selected from the group.
[4] The liquid coloring composition according to any one of [1] to [3], which contains 0.1 to 50 parts by mass of the surfactant (B) per 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-liquid coloring composition contains 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] A method for producing the polyester resin composition described above.
[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. a process of manufacturing an object;
A step of molding the obtained polyester resin composition,
The liquid coloring composition contains a diol component (A), a surfactant (B), and a dye (C),
A method for producing a polyester resin molding, wherein the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.

According to the present invention, a liquid coloring composition excellent in dispersibility and storage stability of a coloring material, by adding during a polymerization reaction for obtaining a polyester resin, does not inhibit the polymerization reaction of the polyester resin raw material, It is possible to provide a polyester resin composition and a polyester resin molded article that bluing uniformly without color unevenness and free from color migration of a coloring material.

The present invention will be described in detail below. It goes without saying that other embodiments are also included in the scope of the present invention as long as they match the gist of the present invention. In addition, in the present specification, the numerical range specified using "-" includes the numerical values described before and after "-" as the range of lower and upper values.
In the present specification, the terms "dicarboxylic acid component (X) containing at least terephthalic acid", "diol component (Y) containing at least ethylene glycol", "polyester resin composition", and "polyester resin molding" are respectively used. They are sometimes referred to as "dicarboxylic acid component (X)", "diol component (Y)", "resin composition", and "resin molding".
Here, "liquid" refers to being liquid at 25°C.
In addition, the term “main component” refers to the component that has the largest compounding amount among the components.
Unless otherwise noted, the various components appearing in this specification may be used singly or in combination of two or more.

<<Liquid coloring composition>>
The liquid coloring composition of the present invention is a liquid coloring composition added when synthesizing a polyester resin, comprising a diol component (A), a surfactant (B), and a dye (C), and a dye ( C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.
By using the dye (C) as a coloring material and further comprising a diol component (A) and a surfactant (B) to form a liquid coloring composition, the dispersibility and storage stability of the coloring material are excellent, and the polyester resin composition is obtained by the polymerization process, the polyester resin composition can be blued without inhibiting the polymerization reaction, without color unevenness, and without color migration of the dye.

<Diol Component (A)>
The diol component (A) of the present invention functions as a dispersion medium for the dye (C). Diol is also called glycol, and functions as one of the main raw materials that constitute the polyester resin.
That is, the diol component (A) in the liquid coloring composition reacts with the dicarboxylic acid component (X) during the polymerization reaction of the dicarboxylic acid component (X) and the diol component (Y) to produce a polyester resin. , forming a polyester resin.
By using the diol component (A), even if it is added during the synthesis of the polyester resin raw material, the polymerization reaction is not inhibited, and the polyester resin can be uniformly blued.

The diol component (A) is not limited as long as it can be used as a starting 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 preferable 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 of polyethylene terephthalate.

The diol component (A) preferably contains ethylene glycol as a main component.

The melting point of the diol component (A) is preferably −30° C. to 50° C. from the viewpoint of uniformity of the mixed solution during polymerization of the polyester resin. This is preferable because bluing can be performed uniformly without color unevenness.
The melting point of the diol component (A) can be measured using a differential scanning calorimeter.

<Surfactant (B)>
Surfactant (B) has a role of a dispersing agent for dispersing dye (C) in diol component (A). A surfactant has a hydrophilic group and a lipophilic group in its molecule, and reduces the interfacial tension by strong adsorption of mutually immiscible substances to the interface and molecular orientation.

Surfactants are classified into surfactants that dissociate into ions when dissolved in an aqueous solution and surfactants that do not dissociate. Dissociating surfactants are further divided into anionic surfactants or cationic surfactants according to the ionic nature of the surface-active portion. There is also a surfactant in which the portion 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) in the present invention is desirably a nonionic surfactant or an amphoteric surfactant, more desirably a nonionic surfactant. By using these surfactants, the dispersibility and storage stability of the dye (C) in the liquid coloring composition are more excellent, the polymerization of the polyester resin is not inhibited more, and bluing can be performed without color unevenness. It becomes a liquid coloring composition.

The amount of the surfactant (B) in the liquid coloring composition is 0 per 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 preferred, 1 to 20 parts by weight is more preferred, and 2 to 10 parts by weight is even more preferred.

[Nonionic surfactant]
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, sorbitan fatty acid esters, poly(12-hydroxystearic acid)-polyethyleneimine copolymers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters. , glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkylalkanolamides, etc., but not particularly limited, poly(12-hydroxystearic acid)-polyethyleneimine copolymer Coalescence, polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, and sorbitan fatty acid esters are preferred, and polyoxyalkylene derivatives are more preferred. The above is preferable because the dispersibility and storage stability of the dye (C) in the liquid coloring composition are excellent and the polymerization reaction of the polyester resin raw material is not inhibited.

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).

The HLB (Hydrophile-Lipophile Balance) value is one of the parameters representing the hydrophilicity/hydrophobicity of a material. Various methods are known for calculating the HLB value from the chemical structure, and various methods for actual measurement are also known. In the present invention, however, the Griffin method is used to calculate the HLB value. 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 (total molecular weight of hydrophilic portion) ÷ (molecular weight of material)

Specific examples of polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, and the like. is 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). .

Specific examples of polyoxyalkylene derivatives include polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene glyceryl ether, polyoxyethylene Examples include diglyceryl ether, but are not particularly limited.

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), and 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, 25 ° C. liquid, HLB value 18.5), and the like.

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 and polyoxyethylene monostearate, but are not particularly limited.
Specific examples of sorbitan fatty acid esters include Rhodol SP-O30-V (manufactured by Kao Corporation, liquid at 25° C., HLB value 1.8) and Rheodol SP-L10 (manufactured by Kao Corporation, liquid at 25° C., HLB value 8.6. ), Emsol L-120V (manufactured by Kao Corporation, liquid at 25° C., HLB value 16.7), and the like.

[Amphoteric Surfactant]
Amphoteric surfactants include alkylbetaines, alkylamine oxides, etc., and are not particularly limited.

Specific examples of alkylbetaines include acrylbetaine, stearylbetaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like, but are not particularly limited.
Specific examples of alkylbetaines include Amphithol 20BS (manufactured by Kao Corporation, liquid at 25°C) and Amphithol 20Y-B (manufactured by Kao Corporation, liquid at 25°C).

Specific examples of alkylamine oxides include lauryldimethylamine oxide and the like, but are not particularly limited.
Specific examples of alkylamine oxides include Amphitol 20N (manufactured by Kao Corporation, liquid at 25°C).

Surfactant (B) is preferably liquid at 25° C., since it has excellent compatibility with diol component (A) and dispersibility of dye (C).

<Dye (C)>
Dye (C) is a dye having a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C. In the present invention, it is used for bluing during the polymerization reaction of the polyester resin.
The solubility of the dye (C) in the ethylene glycol contained in the diol component (Y) is 0.5 g or less, so that the polyester resin raw material containing the dicarboxylic acid component (X) and the diol component (Y) can be polymerized. It is possible to obtain a polyester resin composition that does not hinder the reaction, uniformly blues the polyester resin without color unevenness, and does not cause color migration of the coloring material.

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 of 0.5 g or less, preferably 0.48 g or less, more preferably 0.45 or less.
By using such a dye (C), it is possible to obtain a molded article having excellent dispersibility and storage stability of the liquid coloring composition and less color unevenness than inorganic and organic pigments.
Moreover, by using the dye (C), the safety is superior to the case of using cobalt blue. Moreover, compared with the case of using an inorganic pigment such as ultramarine blue or an organic pigment such as phthalocyanine blue, the dispersibility and storage stability in the liquid coloring composition are excellent.
Dyes and pigments include, for example, C.I. It can be identified according to the classification in I Name (Color Index Generic Name).

In addition, as a coloring material, a dye having a solubility in 100 mL of ethylene glycol at 25 ° C. is higher than 0.5 g, and compared with the case where it is dissolved in ethylene glycol and used as a liquid coloring composition, during the polymerization reaction of the polyester resin raw material and during molding Bleeding at room temperature is suppressed, and color migration does not occur.

Incidentally, bluing means that the hue of the obtained polyester resin composition or polyester resin molded article changes to a bluish tone when visually observed. For example, b * represented by the CIE1976 L * a * b * color system is a polyester resin obtained by adding a dye (C) than a polyester resin composition obtained without adding a dye (C) It can be described as lower for the composition.

The solubility of the dye in 100 mL of ethylene glycol at 25°C is the upper limit of the amount of dye that can be dissolved in 100 mL of ethylene glycol at 25°C. This is the upper weight limit of the dye when no solids or crystals are observed after filtering above.

The amount of the dye (C) in the liquid coloring composition is preferably 1 to 150 parts by mass, and 2 to 130 parts by mass with respect to 100 parts by mass of the diol component (A) from the viewpoint of dispersibility of the dye (C). More preferably, 2 to 120 parts by mass is even more preferable.
By being such a liquid colored composition, the function as a composition containing a bluing agent can be more effectively exhibited as a concentrated dye composition added when polymerizing a polyester resin.

The dye (C) is not particularly limited as long as it has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25° C., 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. Dyes, xanthene dyes, azine dyes, acridine dyes, methine dyes, thiazole dyes, thiazine dyes, rhodamine dyes, triarylmethane dyes, and the like.
Among these, anthraquinone dyes and perinone dyes are preferred because of their high bluing effect and excellent dispersibility in the liquid coloring composition.

Specific examples of anthraquinone or perinone dyes include Solvent Red 52, 117, 135, 169, 176, Disperse Red 5, Solvent Orange 63, 67, 68, 72, 78, Solvent Yellow 98, 103, 105, 113, 116, Disperse 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. be done.
Among them, from the viewpoint of bluing effect, Solvent Red 52, 117, 135, 169, 176, 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 are preferred;
Solvent Red 135, Solvent Blue 35, 36, 45, 59, 63, 78, 83, 94, 97, 104, 122, 132, Solvent Violet 13, 31, 33, 36 are more preferred.

<Other additives>
The liquid coloring composition of the present invention contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, matting agents, fluorescent whitening agents, stabilizers, antioxidants, viscosity modifiers, and other Additives may be contained. As antioxidants, antioxidants such as aromatic amines and phenols can be used. is available.

In addition, it is preferable that the liquid coloring composition does not contain an organic solvent other than the diol component (A). This is a concept excluding the intentionally added state, represents that it does not substantially contain, relative to the total weight of the liquid coloring composition, the other organic solvent is 1% by weight or less, 0.5% by weight or less, or 0.1% by mass or less, or may be 0% by mass.

<Method for producing liquid colored composition>
The method for producing the liquid coloring composition in the present invention is not particularly limited, and for example, a diol component (A), a surfactant (B), a dye (C), and if necessary other additions agent, mixed with a Henschel mixer, tumbler, disper or the like, and dispersed with a Silverson mixer (manufactured by Silverson) or the like to obtain a liquid colored composition. As the dispersing device, any device such as a kneader, a roll mill, a ball mill, a sand mill, etc. can be used in addition to the above. A bead mill, a Silverson mixer, or a roll mill is preferably used for the reasons that molding is easy and dispersibility is excellent.
The liquid coloring composition can be used as a bluing agent-containing composition with a dye dispersion in which the dye (C) is dispersed.

<<Polyester resin composition>>
A polyester resin composition is obtained by adding a liquid coloring composition when a polyester resin raw material is polymerized to produce a polyester resin.
By using the liquid coloring composition of the present invention, the polymerization reaction of the polyester resin raw material containing the dicarboxylic acid component (X) and the diol component (Y) is not inhibited, and the polyester resin is uniformly blued without color unevenness. A polyester resin composition free from color migration of the material can be obtained.
At this time, the diol component (A) in the liquid coloring composition is also polymerized as a diol component with the dicarboxylic acid component (X) to form a polyester resin, so that it also functions as a raw material for the polyester resin.
Therefore, the diol component (A) is also preferably ethylene glycol, which is the component contained in the diol component (Y).
The step of adding the liquid coloring composition may be performed before the initiation of polymerization or during the polymerization reaction.

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), a surfactant agent (B), as well as dye (C).

<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 resins. 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), terephthalic acid is preferably the main component.
The main component means that the component having the highest content among the components constituting the dicarboxylic acid component (X) is terephthalic acid.

As the dicarboxylic acid component (X), one synthesized 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 of the present invention has a high effect of bluing the polyester resin without color unevenness, so even when using a dicarboxylic acid component obtained by depolymerizing the polyester resin by recycling, the color tone is good. A resin molded product can be obtained.

<Diol Component (Y)>
The diol component (Y) is a diol component containing at least ethylene glycol, and is a raw material for the polyester resin. The diol component (Y) may contain ethylene glycol and diol components other than the ethylene glycol described for the diol component (A), such as diethylene glycol, triethylene glycol and polyethylene glycol.
As the diol component (Y), ethylene glycol is preferably the main component.
However, the diol component (A) contained in the liquid coloring composition is excluded as the diol component (Y).
In addition, the main component means that the component having the highest content among the components constituting the diol component (Y) is ethylene glycol.

As the diol component (Y), one synthesized from raw materials may be used, or a component obtained by depolymerizing a polyester resin by recycling may be used.
The liquid coloring composition of the present invention has a high effect of bluing the polyester resin without color unevenness, so even when using a component obtained by depolymerizing the polyester resin by recycling or the like, the color tone is good. A resin molding is obtained.

<Polymerization catalyst (Z)>
The polymerization catalyst (Z) is a catalyst that accelerates the polymerization reaction of the polyester resin raw material, and is not particularly limited in the polymerization of the polyester resin. 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 of the present invention has a high effect of uniformly bluing the polyester resin without color unevenness during the polymerization reaction of the polyester resin raw material, so even when using a titanium catalyst with a high reaction rate, It becomes possible to obtain a resin molding with good color tone.

<Other ingredients>
The polyester resin composition of the present invention 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 bluing of the polyester resin.
As other ingredients, any polymer, antistatic agent, antifoaming agent, dyeability improver, matting agent, fluorescent whitening agent, stabilizer, antioxidant, and other additives may be contained. good. As antioxidants, antioxidants such as aromatic amines and phenols can be used. is available.

<Method for producing polyester resin composition>
The polyester resin composition of the present invention can be produced using the dicarboxylic acid component (X), the diol component (Y), the polymerization catalyst (Z), and the liquid coloring composition of the present invention.
The polymerization method for obtaining the polyester resin is not particularly limited. A method in which a polymerization catalyst (Z) is introduced, 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. is mentioned. In the present specification, these reactions are collectively referred to as polymerization reactions.

As for the polymerization reaction ratio of the polyester resin raw material, the molar ratio of the dicarboxylic acid component (X): the diol component (Y) is preferably in the range of 1:1.03 to 1:2.5, preferably 1:1.05. More preferably, the ratio is in the range of ~1:1.2. Within the above range, a polyester resin molded article having excellent mechanical properties can be obtained.

From the viewpoint of bleeding 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 still more preferably 3 ppm, based on 100% by mass of the polyester resin composition. It is below.

Although the reaction temperature for polymerization is not particularly limited, it 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, decomposition of the resin and by-production of volatile matter that causes odor tend to be suppressed. It is in. The lower limit of the reaction temperature for polymerization is more preferably 200°C, particularly preferably 220°C. The upper limit of the reaction temperature for polymerization is more preferably 270°C. The degree of vacuum for polymerization is preferably 0.5 kPa or more. When it is 0.5 kPa or more, the reactivity tends to be good, and the productivity is improved.

The obtained polyester resin composition can be in the form of pellets (cylindrical chips, etc.), powder, granules or beads. Pellets produced by a single-screw extruder or a twin-screw extruder are preferable because they have a strong kneading force and can be easily molded later.

《Polyester resin molding》
A polyester resin molded article is a molded article using a polyester resin, and is obtained by molding the polyester resin composition described above.
Specifically, for example, it can be produced by melt-kneading a polyester resin composition and molding it with a conventionally known molding machine. The molding machine includes, but is not limited to, an injection molding machine, an extrusion molding machine, a rotary molding machine, and the like.

Examples of polyester resin moldings include films, laminates, coatings, fibers, injection moldings for foods and daily miscellaneous goods, compression injection moldings, rotational moldings, extrusion moldings, and the like.
Since the polyester resin molded article of the present invention is uniformly blued without color unevenness, it is suitable for use in applications that are required to be visible to consumers and particularly good in appearance. can be used.

EXAMPLES The present invention will be described in more detail below 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.
In addition, the compounding amounts in the table are in parts by mass and converted to non-volatile content. A blank column in the table indicates that it was not blended.

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)
A2: 1,3-propylene glycol (manufactured by Mitsubishi Chemical Corporation, melting point 19.5°C)
A3: 1,4-butylene glycol (manufactured by Mitsubishi Chemical Corporation, melting point 19°C)
A4: 1,4-cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., melting point 31.5 ° C.)

<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: Amphitol 20BS (manufactured by Kao Corporation)
B8: Amphithol 20N (manufactured by Kao Corporation)
B9: Ramtel PD-105 (manufactured by Kao Corporation)
B10: Cortamine 24P (manufactured by Kao Corporation)

The structure and physical properties of surfactant (B) are shown below.

<Dye (C)>
C1: Macrolex Blue RR (dye: anthraquinone dye, SolventBlue 97, 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: Diaresin Red HS (dye: perinone dye, SolventRed135, 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)

<Pigment (D)>
D1: Ultramarine blue No1500 (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 Toyocolor Co., Ltd., solubility in 100 mL of ethylene glycol at 25° C. is 0.2 g)

<Dicarboxylic acid component (X)>
X1: Terephthalic acid obtained by synthesis from raw materials X2: Terephthalic acid obtained by depolymerizing a polyester resin

<Diol Component (Y)>
Y1: Ethylene glycol obtained by synthesizing from raw materials Y2: Ethylene glycol obtained by depolymerizing a polyester resin

<Polymerization catalyst (Z)>
Z1: titanium oxide Z2: antimony trioxide

[Example 1]
(Production 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 colored liquid composition (T1).

[Examples 2 to 26, Comparative Examples 1 and 2]
(Production of liquid colored composition (T2-28))
Liquid coloring compositions (T2 to 28) were produced in the same manner as the liquid coloring composition (T1), except that the materials and amounts (parts by mass) shown in Tables 2 to 4 were changed.

[Comparative Examples 3 and 4]
(Production of liquid colored composition (T29, 30))
Liquid coloring compositions (T29, 30) were produced in the same manner as the liquid coloring composition (T1) except that they were changed to the materials and blending amounts (parts by mass) shown in Table 4, but the liquid coloring composition Dispersibility and storage stability in the liquid were poor, and a good liquid coloring composition could not be obtained.

<<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 2-4.

(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 according to 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, practical ×: _D90 is 50 μm or more, impractical

(Storage stability evaluation)
The obtained liquid colored composition was allowed to stand still for 30 days, and separation and sedimentation of the dye (C) in the liquid colored composition were visually confirmed and evaluated according to the following criteria.
[Evaluation criteria]
◎: No separation or sedimentation, very good ○: Some separation or sedimentation, but it becomes uniform when stirred, good △: Some separation or sedimentation, but it becomes uniform when stirred, and practically usable ×: Separation or sedimentation occurs , Not uniform even if stirred, impractical

[Example 27]
(Production of polyester resin composition)
69 parts by mass of dicarboxylic acid component (X1) (terephthalic acid synthesized from raw materials) and 30 parts by mass of diol component (Y1) (ethylene glycol synthesized from raw materials) were placed in a reaction vessel equipped with a distillation column. .5 parts by mass are added, and then 0.0002 parts of the liquid coloring composition (T1) is added so that the content of the dye (C) is 1 ppm based on 100 parts by mass of the polyester resin composition, Further, 0.5 parts by mass of the polymerization catalyst (Z1) was added.
Next, the rotation speed of the stirring blade in the reaction vessel was kept at 200 rpm, and the temperature was started to rise. After the esterification reaction was completed and water was no longer distilled 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 to a degree of vacuum of 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 a predetermined level, the stirring is stopped, the reaction system is returned to normal pressure, extruded from the nozzle in strand form, 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 28 to 55, Comparative Examples 3 to 6]
A polyester resin composition was produced in the same manner as the polyester resin composition of Example 24, except that the materials and blending amounts (parts by mass) shown in Table 4 were changed.

<<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. Table 5 shows the results.

(Polymerization time evaluation)
The ratio of the polymerization time (b) required for the obtained polyester resin composition to the polymerization time (b) required for the polyester resin composition produced without adding the liquid colored resin composition of the present invention is shown below. It was calculated and evaluated by the formula.
Polymerization time ratio (%) = (b) / (a) x 100
[Evaluation criteria]
O: Polymerization time ratio is less than 120%, good △: Polymerization time ratio is 120% or more and less than 150%, practically possible ×: Polymerization time ratio is 150% or more, not practical

(hue evaluation)
The obtained polyester resin composition and the polyester resin obtained without adding the liquid coloring composition were each molded into a 1 mm thick plate at 280 ° C. using an injection molding machine, and CIE 1976 L * a * b * color specification The color difference Δb* in the system was obtained from the following formula and evaluated.

Δb* = (chromaticity b* of the polyester resin composition obtained without adding the liquid coloring composition)
- (Chromaticity b* of the polyester resin composition obtained in Examples or Comparative Examples)
[Evaluation criteria]
○: Δb*<0, blued and good ×: Δb*≧0, blued and not defective

(Color unevenness evaluation)
The obtained polyester resin composition was molded into 10 plates having a thickness of 1 mm at 280 ° C. using an injection molding machine, and the hue of each was measured according to the CIE 1976 L * a * b * color system. Evaluation was made as follows from the standard deviation of * and b* and visual observation.
[Evaluation criteria]
○: L *, a *, b * each standard deviation is 0.5 or less,
Good with no color unevenness on each plate △: Standard deviation of each of L*, a*, and b* exceeds 0.5 and is 0.6 or less,
There is no color unevenness on each plate, and it is practically usable.
Color unevenness on each plate, impractical

(Color migration evaluation)
The resulting polyester resin composition was molded into a plate having a thickness of 1 mm at 280°C using an injection molding machine, the obtained plate was heated to 50°C and wiped off with a cotton cloth, and the coloration of the cotton cloth was visually confirmed. .
[Evaluation criteria]
○: No coloration of cotton cloth, good ×: Coloring of cotton cloth, impractical

As shown in Table 5, the liquid coloring composition of the present invention is excellent in dispersibility and storage stability of the coloring material, and further by using the liquid coloring composition, when producing a polyester resin, the polyester resin It was confirmed that the polymerization reaction of the raw material was not inhibited, the bluing could be performed uniformly without color unevenness, and a polyester resin molded article free from 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-based resin molded article having a good color tone could be formed.
Further, 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 It was confirmed that it can be effectively applied even when the polyester resin is reused.

On the other hand, the liquid coloring composition of Comparative Example 1, in which the dye (C) is dispersed in the plasticizer, is practical in terms of dispersibility and storage stability, but the polymerization of the polyester resin composition It took a long time, and the results were not practical.
In addition, the liquid coloring composition of Comparative Example 2 using a coloring material that dissolves in the raw material of the polyester resin, that is, a hydrophilic coloring material, causes color migration of the dye from the molded body, and can be used for various purposes, especially as a beverage container. The result was that the polyester resin composition and its molded product could not be put to practical use.

Claims (9)

A liquid coloring composition added when polymerizing a polyester resin,
comprising a diol component (A), a surfactant (B), and a dye (C);
A liquid coloring composition, wherein the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C. 2. The liquid coloring composition according to claim 1, wherein the surfactant (B) is at least one of a nonionic surfactant and an amphoteric surfactant. Surfactant (B) is selected from the group consisting of poly(12-hydroxystearic acid)-polyethyleneimine copolymer, polyoxyethylene alkyl ether, polyoxyalkylene derivative, sorbitan fatty acid ester, alkylbetaine, and alkylamine oxide. The liquid coloring composition according to claim 2, which is at least one. The liquid coloring composition according to claim 1 or 2, comprising 0.1 to 50 parts by mass of the surfactant (B) with respect to 100 parts by mass of the diol component (A). 3. The liquid coloring composition according to claim 1, wherein the dye (C) is an anthraquinone dye or a perinone dye. 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. with a process to
The liquid coloring composition contains 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 claim 6, wherein the polymerization catalyst (Z) is a titanium-based catalyst. The dicarboxylic acid component (X) containing at least terephthalic acid and at least one of the diol component (Y) containing at least ethylene glycol according to claim 6 or 7, which is a component obtained by depolymerizing a polyester resin. A method for producing a polyester resin composition. 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. and
A step of molding the obtained polyester resin composition,
The liquid coloring composition contains a diol component (A), a surfactant (B), and a dye (C),
A method for producing a polyester resin molding, wherein the dye (C) has a solubility of 0.5 g or less in 100 mL of ethylene glycol at 25°C.