Liquid master batch for solid phase polymerization acceleration, thermoplastic resin composition for solid phase polymerization, and modified thermoplastic resin and molding manufacturing method

Abstract

To provide a liquid master batch for solid phase polymerization acceleration which enables provision of a molding that is excellent in productivity and quality, and has less variations, a thermoplastic resin composition for solid phase polymerization, and a modified thermoplastic resin, and to provide a method for producing them.SOLUTION: A liquid master batch for solid phase polymerization acceleration of a modification object thermoplastic resin (C), which is at least one selected from the group consisting of a polyester resin, a polyamide resin and a polycarbonate resin, contains a liquid dispersion medium (A) and a solid phase polymerization accelerator (B), viscosity at 25°C of the liquid dispersion medium (A) is 8,000 mPa s or less, the solid phase polymerization accelerator (B) is at least one kind selected from a phosphorus-based catalyst, a titanium-based catalyst and an antimony-based catalyst, and 10 to 80 pts.mass of the solid phase polymerization accelerator (B) is contained with respect to 100 pts.mass of the liquid dispersion medium (A).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid masterbatch for solid-phase polymerization and a thermoplastic resin composition for solid-phase polymerization. It also relates to a modified thermoplastic resin and a method for producing a molded article.

Background Art

[0002] Thermoplastic resins such as polyester resins, polyamide resins, and polycarbonate resins are excellent in heat resistance, strength, etc., and are used in a wide range of fields such as synthetic fibers, films, sheets, mechanical parts, automotive parts, containers, and electronic materials. Resins with even better physical properties are in demand in the market. Furthermore, the problem of plastic waste has become an important issue, and highly productive recycling technologies are eagerly desired. Also, there is a demand for resin molded articles that are excellent in moldability, hue, and mechanical properties even if they are recycled products.

[0003] Solid-phase polymerization is known as a method for modifying polycondensation thermoplastic resins such as polyester resins, polyamide resins, and polycarbonate resins.

[0004] Patent Document 1 discloses a method in which a used PET resin (polyethylene terephthalate resin) material from bottle collections is extruded in a twin-screw extruder under heating together with a sterically hindered hydroxyphenylalkyl phosphonate ester, the extrudate is formed into granules, and then the granules are subjected to solid-phase condensation under vacuum in a tumbling dryer. According to this method, it has been shown that the limiting viscosity after solid-phase polymerization increases significantly.

[0005] Patent Document 2 discloses a method of obtaining a polyethylene terephthalate (A) by mixing terephthalic acid, isophthalic acid, and ethylene glycol to perform an esterification reaction and then a polycondensation reaction, and melt-kneading the obtained polyethylene terephthalate (A) with trimethylolpropane as a polymerization accelerator to obtain a polymerization accelerator-containing masterbatch. Further, a method of adding this masterbatch to the above polyethylene terephthalate (A) to obtain chip-shaped granules of modified polyethylene terephthalate containing 0.1 wt% of a polymerization accelerator, and then performing solid-phase polymerization for 11 hours to obtain a bottle is disclosed.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In the above Patent Document 1, an increase in molecular weight can be confirmed after solid-phase polymerization of the recycled PET resin. However, there are problems with the viscosity reduction of the recycled PET resin before solid-phase polymerization and the mechanical properties after molding. Also, there is a problem with productivity in that the apparatus is contaminated.

[0008] In the above Patent Document 2, although contamination of the apparatus can be suppressed by dispersing a solid-phase polymerization accelerator in the masterbatch, it is difficult to maintain a predetermined concentration between batches or in a continuous process, and there is a problem that the mechanical properties vary between molded articles, which is particularly prominent when solid-phase polymerizing recycled resins including various shapes. Also, there is a problem with productivity in that the energy consumption for melt-kneading is large when producing the masterbatch and mixing it with polyethylene terephthalate.

[0009] The present invention has been made in view of the above problems, and aims to provide a liquid masterbatch for promoting solid-phase polymerization, a thermoplastic resin composition for solid-phase polymerization, and a modified thermoplastic resin, which are excellent in productivity and quality and have little variation. Another object is to provide methods for producing these. An object is to provide a molded article that is excellent in productivity and has high quality even when using recycled resin, by using the liquid masterbatch for promoting solid-phase polymerization of the present invention.

Means for Solving the Problems

[0010] As a result of intensive studies by the present inventors, it has been found that the problems of the present invention can be solved in the following aspects, and the present invention has been completed. [1]: A liquid masterbatch for promoting solid-phase polymerization of a thermoplastic resin (C) to be modified, which is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, containing a liquid dispersion medium (A) and a solid-phase polymerization accelerator (B), wherein the viscosity of the liquid dispersion medium (A) at 25°C is 8,000 mPa·s or less, and the solid-phase polymerization accelerator (B) is at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, and containing 10 to 80 parts by mass of the solid-phase polymerization accelerator (B) with respect to 100 parts by mass of the liquid dispersion medium (A), a liquid masterbatch for promoting solid-phase polymerization. [2]: The liquid masterbatch for promoting solid-phase polymerization according to [1], wherein the liquid dispersion medium (A) is at least one selected from an aliphatic polyester resin, a polyalkylene glycol resin, and a polyether ester resin. [3]: The liquid masterbatch for promoting solid-phase polymerization according to [1] or [2], wherein the thermal decomposition temperature of the liquid dispersion medium (A) is 250°C or higher. [4]: The liquid masterbatch for promoting solid-phase polymerization according to any one of [1] to [3], wherein the solid-phase polymerization accelerator (B) is an alkyl phosphonate. [5]: The solid-phase polymerization accelerator (B) is the liquid masterbatch for solid-phase polymerization described in any one of [1] to [4], which is a sterically hindered hydroxyphenylalkylphosphonic acid ester. [6]: Further containing a thickener (D), and the thickener (D) is at least one selected from the group consisting of metal soaps, hydrogenated castor oil, fatty acid amides, and fatty acid glycerides, the liquid masterbatch for solid-phase polymerization described in any one of [1] to [5]. [7]: A thermoplastic resin composition for solid-phase polymerization containing a liquid dispersion medium (A), a solid-phase polymerization accelerator (B), and a thermoplastic resin (C) to be modified, wherein the viscosity of the liquid dispersion medium (A) at 25 °C is 8,000 mPa·s or less, the solid-phase polymerization accelerator (B) is at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, the thermoplastic resin (C) to be modified is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, containing 15 to 80 parts by mass of the solid-phase polymerization accelerator (B) with respect to 100 parts by mass of the liquid dispersion medium (A), a thermoplastic resin composition for solid-phase polymerization, containing 70% by mass or more of the thermoplastic resin (C) to be modified based on 100% by mass of the thermoplastic resin composition for solid-phase polymerization. [8]: A process for producing a modified thermoplastic resin, comprising a step of obtaining the liquid masterbatch described in any one of [1] to [6], a melting step of melting a thermoplastic resin (C) to be modified, which is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, a mixing step of mixing the melted thermoplastic resin (C) to be modified and the liquid masterbatch to obtain a thermoplastic resin composition for solid-phase polymerization, and a step of subjecting the thermoplastic resin composition for solid-phase polymerization to solid-phase polymerization. [9]: A process for producing a molded article, comprising a step of molding the modified thermoplastic resin obtained by the method described in [8].

[10] : A step of obtaining the liquid masterbatch described in any one of [1] to [6], A polymerization step of obtaining a thermoplastic resin (C) to be modified, which is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, by polymerization; A mixing step of adding and mixing a liquid masterbatch before or after the polymerization step, or simultaneously with the polymerization step; A method for producing a modified thermoplastic resin, comprising a step of solid-phase polymerizing the obtained thermoplastic resin composition for solid-phase polymerization after the polymerization step.

[11] : A method for producing a molded article, comprising a step of molding the modified thermoplastic resin obtained by the method according to

[10] . A method for producing a molded article. [Effect of the Invention]

[0011] According to the present invention, there is an excellent effect that it is possible to provide a liquid masterbatch for promoting solid-phase polymerization, a thermoplastic resin composition for solid-phase polymerization, a modified thermoplastic resin using them, and a molded article, which are excellent in productivity and quality and have little variation between products. [Embodiments for Carrying Out the Invention]

[0012] Hereinafter, an example of an embodiment to which the present disclosure is applied will be described. However, the present disclosure is not limited to this embodiment, and other embodiments may belong to the scope of the present disclosure as long as they conform to the gist of the present disclosure. Also, the numerical range "A to B" specified in this specification means a range that satisfies a value greater than numerical value A and a value less than numerical value B. Note that the numerical values specified in this specification are values obtained by the methods disclosed in the embodiments or examples. Also, the test pieces in this specification are synonymous with sheets, films, and plates. Each of the various components appearing in this specification may be used alone or in combination of two or more, unless otherwise noted. Also, "thermoplastic resin (C) to be modified" may be referred to as "thermoplastic resin (C)" or "resin (C)", "liquid masterbatch for promoting solid-phase polymerization" may be referred to as "liquid masterbatch" or "masterbatch", "liquid dispersion medium (A)" may be referred to as "liquid medium (A)", and "thermoplastic resin composition for solid-phase polymerization" may be referred to as "thermoplastic resin composition".

[0013] 1. Liquid masterbatch The liquid masterbatch of the present disclosure is a liquid masterbatch for promoting solid-phase polymerization (hereinafter also referred to as this liquid masterbatch), which promotes the solid-phase polymerization of a thermoplastic resin (C) to be modified and is used to obtain a modified thermoplastic resin. This liquid masterbatch contains a liquid dispersion medium (A) and a solid-phase polymerization promoter (B). Further, it is preferably included with a thickener (D) and / or an antioxidant (E).

[0014] This liquid masterbatch contains a liquid dispersion medium (A) and a solid-phase polymerization promoter (B). The viscosity of the liquid dispersion medium (A) at 25 °C is 8,000 mPa·s or less, and the solid-phase polymerization promoter (B) is at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst. It contains 10 to 80 parts by mass of the solid-phase polymerization promoter (B) with respect to 100 parts by mass of the liquid dispersion medium (A). Thereby, it is possible to obtain a liquid masterbatch with high dispersibility, viscosity, and storage stability and excellent productivity.

[0015] When this liquid masterbatch is mixed with the thermoplastic resin (C) to be modified, it can be quantitatively added using a liquid pump. Since it has high fluidity and dispersibility, it can suppress the variation in impact strength between molded articles. In particular, it is excellent in that it can suppress the variation even when using recycled thermoplastic resins including various shapes. Also, when this liquid masterbatch is added during the polymerization of the thermoplastic resin to be modified for the purpose of suppressing the variation, it does not inhibit the polymerization reaction and can be polymerized in a short time, so it is excellent in productivity.

[0016] Further, this liquid masterbatch does not require melt kneading during the production of the masterbatch. Due to its high fluidity and dispersibility, it can be mixed with the thermoplastic resin (C) to be modified in a short time, so it can reduce the energy consumption and time. Also, in terms of its high storage stability and easy storage and transportation, it is excellent in productivity.

[0017] By using this liquid masterbatch, the solid-phase polymerization accelerator (B) can be finely dispersed in the thermoplastic resin (C) to be modified, so that the solid-phase polymerization reaction proceeds efficiently and uniformly. Furthermore, since the thermal history of the masterbatch and the thermoplastic resin (C) to be modified can be reduced, the generation of yellowing, outgassing, and a decrease in molecular weight due to resin deterioration, as well as yellowing and a decrease in catalytic ability due to deterioration of the solid-phase polymerization accelerator (B) can be suppressed. As a result, a high-quality molded article can be obtained, which has a high viscosity, excellent moldability, high mechanical strength such as Charpy impact strength, excellent appearance due to reduction of yellowing and silver streaks, and a small amount of outgassing, and is thus suitable for applications where hygiene is required, such as food packaging.

[0018] From the viewpoint of obtaining a higher-quality modified thermoplastic resin and molded article, it is preferable that the liquid masterbatch contains 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more of the liquid dispersion medium (A) and the solid-phase polymerization accelerator (B). The liquid masterbatch may contain 100% by mass of the liquid dispersion medium (A) and the solid-phase polymerization accelerator (B).

[0019] Hereinafter, each component will be described in detail. Each component can be used alone or as a mixture of two or more.

[0020] 1-1. Liquid dispersion medium (A) The liquid dispersion medium (A) functions as a dispersion medium for dispersing the solid-phase polymerization accelerator (B) in the liquid masterbatch. The liquid dispersion medium (A) plays a role of efficiently homogenizing the solid-phase polymerization accelerator (B) when mixed with the thermoplastic resin (C) to be modified. The liquid dispersion medium (A) may be used alone or in combination of two or more. The liquid dispersion medium (A) is preferably at least one selected from aliphatic polyester resins, polyalkylene glycol resins, polyether ester resins, and glycols.

[0021] The liquid dispersion medium (A) is characterized in that its viscosity at 25°C is 8,000 mPa·s or less. Thereby, a liquid masterbatch excellent in the dispersibility of the solid-phase polymerization accelerator (B) can be obtained, and a high-quality modified thermoplastic resin and molded article excellent in productivity, moldability, and physical properties can be obtained.

[0022] From the viewpoint of dispersibility, the viscosity of the liquid dispersion medium (A) at 25°C is 8,000 mPa·s or less, more preferably 5,000 mPa·s or less, and even more preferably 3,000 mPa·s or less. From the viewpoint of moldability, it is more preferably 10 mPa·s or more, and even more preferably 20 mPa·s or more. The viscosity in this specification is a value measured at 25°C and a rotor rotation speed of 10 min using a B-type viscometer in accordance with JIS K7117-1:1999. -1 It is the value measured at.

[0023] The thermal decomposition start temperature of the liquid dispersion medium (A) is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 240°C or higher, and particularly preferably 260°C or higher. Also, it is preferably 1000°C or lower. By being within this range, when obtaining a molded article from the modified thermoplastic resin, the decomposition of the liquid dispersion medium (A) is small, so the generation of outgas can be reduced, and the occurrence of molding defects such as silver streaks can be reduced, and thus a molded article can be stably obtained. The thermal decomposition start temperature is the temperature at which the weight loss during heating is measured using a differential thermal thermogravimetry simultaneous measurement device (TG / DTA), and the weight loss rate is 10%.

[0024] The content of the liquid dispersion medium (A) is preferably 10% by mass or more, more preferably 20 - 90% by mass, and even more preferably 30 - 80% by mass in 100% by mass of the liquid masterbatch. By being within the above range, the fluidity of the liquid masterbatch can be maintained in the stirring and mixing processes during production, and a molded article with even better moldability and mechanical properties can be obtained.

[0025] In addition, the liquid dispersion medium (A) preferably has a number average molecular weight (Mn) of 100 to 10,000. When Mn is 100 or more, it is preferable in terms of moldability, and more preferably 300 or more. When Mn is 10,000 or less, it is preferable in terms of dispersibility, and more preferably 5,000 or less. The number average molecular weight is a value in terms of standard polystyrene molecular weight determined by gel permeation chromatography (GPC) measurement.

[0026] Examples of the liquid dispersion medium (A) include liquid polymers, polyvalent carboxylic acid esters, glycols, epoxidized oils, etc. These may be used alone or in combination of two or more. A liquid polymer or glycol is preferable in that it suppresses the viscosity reduction before solid-phase polymerization and is excellent in the moldability of the modified thermoplastic resin after solid-phase polymerization. From the viewpoint of the solid-phase polymerization promoting effect, a liquid polymer is more preferable.

[0027] [Liquid polymer] The liquid polymer is not particularly limited as long as it has a viscosity at 25 °C of 8,000 mPa·s or less. Examples include polyester resins, polyether resins, polyolefin resins, acrylic resins, vinyl resins, silicones, etc. When the thermoplastic resin (C) requires a high molding temperature such as polyethylene terephthalate (PET) or polyamide-based resins, it has high heat resistance, so outgassing can be reduced, and it is excellent in mechanical properties such as Charpy impact strength due to its excellent compatibility. Therefore, aliphatic polyester resins, polyalkylene glycol resins, and polyether ester resins are preferable. From the viewpoint of hydrolysis resistance, polyalkylene glycol resins are particularly preferable.

[0028] (Aliphatic polyester resin) Examples of the aliphatic polyester resin include polyester resins derived from the reaction of aliphatic polyvalent carboxylic acids or their ester-forming derivatives with polyhydric alcohols, polyester resins derived from aliphatic hydroxycarboxylic acids or their ester-forming derivatives, or mixtures and copolymers thereof.

[0029] The aliphatic polycarboxylic acid constituting the aliphatic polyester resin is not particularly limited as long as it is an aliphatic carboxylic acid having two or more carboxyl groups. Examples thereof include aliphatic polycarboxylic acids such as succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3,6-hexanetricarboxylic acid, and 1,3,5-hexanetricarboxylic acid. These aliphatic carboxylic acids may be used alone or in combination of two or more.

[0030] The polyhydric alcohol constituting the aliphatic polyester resin is not particularly limited as long as it is an alcohol having two or more hydroxyl groups. Examples thereof include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, and polyalkylene glycols such as diethylene glycol and dipropylene glycol, and trihydric or higher alcohols such as glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, and sorbitol. These may be used alone or in combination of two or more.

[0031] The freezing point of the aliphatic polyester resin is preferably -5°C or lower, more preferably -60°C to -10°C.

[0032] Specific examples of the aliphatic polyester resin include Adeka Sizer PN-170 (manufactured by ADEKA, viscosity at 25°C: 800 mPa·s, freezing point: -15°C, adipic acid polyester resin), Adeka Sizer P-200 (manufactured by ADEKA, viscosity at 25°C: 2,600 mPa·s, freezing point: -20°C, adipic acid polyester resin), Adeka Sizer PN-250 (manufactured by ADEKA, viscosity at 25°C: 4,500 mPa·s, freezing point: -20°C, adipic acid polyester resin), and the like.

[0033] (Polyalkylene glycol resin) The polyalkylene glycol resin generally consists of alkylene glycols having repeating units with 1 to 6 carbon atoms. However, from the viewpoints of compatibility, water absorption, and screw slipperiness, a polyalkylene glycol resin having repeating units with 2 to 4 carbon atoms is preferred.

[0034] Specific examples of the polyalkylene glycol resin include, for example, polyethylene glycol in which the number of carbon atoms in the repeating unit is 2 in each case, polytrimethylene glycol and polypropylene glycol in which the number of carbon atoms in the repeating unit is 3 in each case, polytetramethylene glycol and polybutylene glycol in which the number of carbon atoms in the repeating unit is 4 in each case, polyether polyols obtained by addition polymerization of alkylene oxide to dihydric or higher alcohols, and the like. Polypropylene glycol is particularly preferred from the viewpoints of compatibility and water absorption.

[0035] (Polyether ester resin) The polyether ester resin is obtained by esterifying the above-mentioned aliphatic polyvalent carboxylic acid described for the aliphatic polyester resin and the above-mentioned alkylene glycol.

[0036] Specific examples of the polyether ester resin include Adeka Sizer RS-107 (manufactured by ADEKA, viscosity at 25°C is 20 mPa·s, freezing point is -47°C, adipic acid ether ester resin), Adeka Sizer RS-700 (manufactured by ADEKA, viscosity at 25°C is 30 mPa·s, freezing point is -53°C, polyether ester resin), and the like.

[0037] [Polyvalent carboxylic acid ester] The polyvalent carboxylic acid ester has a structure in which two or more alcohols are ester-bonded to the polyvalent carboxylic acid. Examples of the polyvalent carboxylic acid ester include aliphatic polyvalent carboxylic acid esters, aromatic polyvalent carboxylic acid esters, or mixtures thereof. From the viewpoint of heat resistance, aromatic polyvalent carboxylic acid esters are preferred.

[0038] (Aliphatic polyvalent carboxylic acid ester) The aliphatic polyvalent carboxylic acid constituting the aliphatic polyvalent carboxylic acid ester is not particularly limited as long as it is an aliphatic carboxylic acid having two or more carboxyl groups. For example, dicarboxylic acids such as succinic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid; tricarboxylic acids such as citric acid, acetylcitric acid, propanetricarboxylic acid, hexanetricarboxylic acid; and tetracarboxylic acids such as cyclohexanetetracarboxylic acid can be mentioned. From the viewpoint of viscosity, dicarboxylic acids and tricarboxylic acids are preferred, and the number of carbon atoms is preferably 4 or more and 8 or less. More preferably, it is acetylcitric acid. The alcohol constituting the aliphatic polyvalent carboxylic acid ester is not particularly limited, but from the viewpoint of viscosity, monohydric alcohol is preferred, and the number of carbon atoms is preferably 1 or more and 5 or less. For example, methanol, ethanol, propanol, butanol, etc. can be mentioned. Particularly preferred aliphatic polyvalent carboxylic acid esters are tributyl acetylcitrate and triethyl acetylcitrate.

[0039] (Aromatic polyvalent carboxylic acid ester) The aromatic polyvalent carboxylic acid constituting the aromatic polyvalent carboxylic acid ester is not particularly limited as long as it is an aromatic carboxylic acid having two or more carboxyl groups. Examples thereof include phthalic acid, trimellitic acid, pyromellitic acid and the like. The alcohol constituting the aromatic polyvalent carboxylic acid ester is not particularly limited, but from the viewpoint of viscosity, a monohydric alcohol is preferable, and the number of carbon atoms is preferably 5 or less. Examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like. As the aliphatic polyvalent carboxylic acid ester, 2-ethylhexyl trimellitate and 2-ethylhexyl pyromellitate are preferable.

[0040] [Glycol] The glycol is not particularly limited as long as it is an alcohol having two hydroxyl groups, but from the viewpoints of productivity and physical properties, aliphatic glycols exemplified by ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,4-cyclohexanedimethanol and the like are preferable. Among them, ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol and 1,4-cyclohexanedimethanol are preferable, and ethylene glycol is more preferable from the viewpoint of dispersibility.

[0041] From the viewpoint of the uniformity of the mixed solution, the melting point of the glycol is preferably -30°C to 50°C. The melting point of the glycol can be measured using a differential scanning calorimeter.

[0042] [Epoxidized oil and fat] The epoxidized oil and fat has a structure in which an epoxy group is introduced into the carbon-carbon unsaturated bond of the oil and fat. Here, the oil and fat means an ester compound of a fatty acid and glycerin. Examples of the epoxidized oil and fat include epoxidized soybean oil, epoxidized linseed oil, epoxidized palm oil and the like.

[0043] 1-2. Solid-phase polymerization accelerator (B) The solid-phase polymerization accelerator (B) is a catalyst for accelerating the solid-phase polymerization of the thermoplastic resin (C) to be modified, and is at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst.

[0044] The liquid masterbatch of the present invention contains 10 to 80 parts by mass of the solid-phase polymerization accelerator (B) with respect to 100 parts by mass of the liquid dispersion medium (A). And by using at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, it has been found that the molecular weight of the thermoplastic resin (C) to be modified can be increased to a high molecular weight uniformly in a short time. From the viewpoint of uniformly dispersing the solid-phase polymerization accelerator (B) in the liquid masterbatch to promote the solid-phase polymerization reaction, the content of the solid-phase polymerization accelerator (B) is preferably 65 parts by mass or less, more preferably 50 parts by mass or less, with respect to 100 parts by mass of the liquid dispersion medium (A). Also, from the viewpoint of reducing the addition amount of the liquid dispersion medium (A) and increasing the strength of the molded body, it is preferably 15 parts by mass or more, more preferably 25 parts by mass or more.

[0045] The content rate of the solid-phase polymerization accelerator (B) in 100% by mass of this liquid masterbatch is preferably 10 to 45% by mass. From the viewpoint of making the processability more excellent, the solid-phase polymerization accelerator (B) in 100% by mass of the liquid masterbatch is more preferably 40% by mass or less, and still more preferably 35% by mass or less. Also, from the viewpoint of enhancing the polymerization accelerating effect of the liquid masterbatch during solid-phase polymerization, the lower limit is more preferably 15% by mass, and still more preferably 20% by mass.

[0046] As a preferred example of the solid-phase polymerization accelerator (B), it is preferably an acid catalyst. The acid catalyst is selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, and can promote the reaction by showing Bronsted acidity or Lewis acidity in the solid-phase polymerization step. As the solid-phase polymerization accelerator (B), a phosphorus-based catalyst is preferable from the viewpoints of dispersibility and solid-phase polymerization accelerating effect. Also, it preferably has an aromatic ring skeleton and / or an alicyclic skeleton. By having an aromatic ring skeleton and / or an alicyclic skeleton in the solid-phase polymerization accelerator (B), the compatibility with the thermoplastic resin (C) to be modified can be further enhanced.

[0047] Examples of the aromatic ring skeleton include a carbocyclic skeleton, a heterocyclic skeleton, and combinations thereof. The number of ring-constituting carbons in the aromatic ring skeleton is preferably 3 to 20, more preferably 4 to 16, 5 to 14, or 6 to 10. Examples of the aromatic ring skeleton include a benzene ring skeleton, a naphthalene ring skeleton, and an anthracene ring skeleton. Examples of the alicyclic skeleton include an alicyclic hydrocarbon skeleton having 5 to 20 carbon atoms, such as a cyclopentane skeleton, a cyclohexane skeleton, a cyclooctane skeleton, a cyclodecane skeleton, an adamantane skeleton, a norbornane skeleton, a dicyclopentane skeleton, and a tricyclodecane skeleton. Further, it may be a heterocyclic ring such as morpholine.

[0048] From the viewpoint of avoiding aggregation of the solid-phase polymerization accelerator (B), it is preferable that the substituents of the aromatic ring skeleton and / or the alicyclic skeleton have an isobutyl group, a sec-butyl group, a tert-butyl group, etc.

[0049] [Phosphorus-based catalyst] Examples of the phosphorus-based catalyst include phosphoric acid such as phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and acidic methyl phosphate, and their alkyl esters and phenyl esters, methylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, and alkyl esters and phenyl esters of phosphonic acid such as methyl methylphosphonate, ethyl phenylphosphonate, and phenyl benzylphosphonate. The esters of phosphoric acid or phosphonic acid include diesters and monoesters. From the viewpoint of the molecular weight increasing effect, an alkyl phosphonate ester is preferable, and a sterically hindered hydroxyphenylalkyl phosphonate ester is more preferable.

[0050] As a preferred example of the sterically hindered hydroxyphenylalkyl phosphonate ester, the general formula (1) can be exemplified. Here, the ester as used herein includes salts containing an ester group as described later.

Chemical formula

Chemical formula

[0051] In general formula (1), the alkyl group having 1 to 20 carbon atoms is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc., and may be linear or branched. Among these, an alkyl group having 2 to 4 carbon atoms is more preferable. Further, the alkyl group having 1 to 4 carbon atoms that substitutes the cyclohexyl group preferably has 1 to 3 substituents, particularly preferably 1 or 2 substituents, and is a branched or unbranched alkyl radical. Examples of the alkyl group having 1 to 4 carbon atoms that substitutes the cyclohexyl group include cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, or tert-butylcyclohexyl. Also, the phenyl group or naphthyl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent preferably has 1 to 3 substituents, particularly preferably 1 or 2. Further, as the preferred examples, o-methylphenyl, m-methylphenyl or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl or 4-tert-butylnaphthyl can be exemplified. Also, the 1- to 3-valent metal cation is preferably an alkali metal cation, an alkaline earth metal cation, a heavy metal cation or an aluminum cation. As a preferred example, Na + , K + , Mg 2+ , Ca 2+ , Ba 2+ , Zn 2+ , Al 3+ can be mentioned. Among these, Ca 2+ is particularly preferred. R 1 or R 2 preferably has at least one tert-butyl group. Particularly preferably, R 1 and R 2 are tert-butyl groups. n is preferably 1 or 2, particularly preferably 1. R 3 or R 4 preferably has at least one alkyl group having 2 to 4 carbon atoms. More preferably, R 3 and R 4 are alkyl groups having 2 to 4 carbon atoms, particularly preferably an ethyl group.

[0052] As preferred examples of the general formula (1) above, the following compounds can be exemplified. In the following compounds, t-Bu means a tertiary butyl group and Et means an ethyl group.

Chemical formula

[0053] [Titanium-based catalyst] Examples of the titanium-based catalyst include titanium complexes, titanium alkoxides such as tetra-i-propyl titanate, tetra-n-butyl titanate, and tetra-n-butyl titanate tetramer, titanium oxide, and titanium acetylacetonate.

[0054] [Antimony-based catalyst] Examples of the antimony-based catalyst include antimony oxides such as antimony trioxide and antimony pentoxide, antimony carboxylates such as antimony acetate, antimony oxalate, and potassium antimony tartrate, and antimony alkoxides such as antimony tri-n-butoxide and antimony triethoxide.

[0055] 1-3. Thickener (D) This liquid masterbatch preferably contains a thickener (D) in order to improve the dispersion stability and to be uniformly mixed with the thermoplastic resin (C). When the thickener (D) is dissolved or dispersed in a liquid medium, it has a function of reducing the fluidity of the liquid even with a small amount of addition by forming a three-dimensional structure such as a network through interactions such as hydrogen bonds between molecules or particles. By using this, the dispersion stability of the liquid masterbatch and the uniformity of the mechanical properties of the molded body can be further improved.

[0056] When containing the thickener (D), the addition amount is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 2.5% by mass based on 100% by mass of the liquid masterbatch. When it is 0.1% by mass or more, the dispersion stability is more excellent. When it is 10% by mass or less, the mechanical properties of the molded body are more excellent.

[0057] From the viewpoint of the thickening effect, the thickener (D) is preferably a solid or a liquid having a viscosity exceeding 8,000 mPa·s at 25°C. Among them, from the viewpoint of storage stability, it is preferable that it is solid at 25°C. At this time, the melting point is more preferably 30 to 1000°C. The melting point is a value measured using a differential scanning calorimeter under the condition of a heating rate of 10°C / min.

[0058] The thickener (D) is classified into an inorganic thickener and an organic thickener, and an organic thickener is preferably used from the viewpoints of the mechanical properties and uniformity of the molded body. As the inorganic thickener, fine particles that are dispersed as a colloid in a liquid medium are used. Specifically, examples include fine silica, fine aluminum oxide, fine calcium carbonate, bentonite, etc. These may be complexed with an organic substance.

[0059] Examples of the organic thickener include low molecular weight thickeners such as fatty acid esters, fatty acid amides, fatty acid metal salts, amino acid derivatives, and urea derivatives; and polymer thickeners such as polyethylene oxide and polymerized oil. The low molecular weight thickener has the property of forming a three-dimensional structure by intermolecular interaction in a liquid medium, and can impart pseudoplasticity even with a small amount of addition, so it is preferable from the viewpoint of dispersion stability. From the viewpoint of reducing the addition amount, the molecular weight of the low molecular weight thickener is preferably 900 or less. As the low molecular weight thickener, from the viewpoint of the impact strength of the molded body, a fatty acid ester, a fatty acid amide, or a fatty acid metal salt is preferable, and a fatty acid ester and a fatty acid amide are more preferable. The polymer thickener is considered to be dispersed in a liquid medium and interact with itself between particles, and when other particles are present in the liquid medium, it adsorbs to the particles and imparts an interaction. The thickener (D) may be used alone or in combination of two or more.

[0060] [Fatty acid ester] The fatty acid ester has a structure in which one or more fatty acids are ester-bonded to an alcohol. Examples of the alcohol include monohydric or polyhydric alcohols. Preferably, the number of oxygen atoms is 8 or less. The monohydric alcohol is preferably a higher alcohol having 6 or more carbon atoms, more preferably a higher alcohol having 10 or more carbon atoms. For example, myristyl alcohol, stearyl alcohol, and oleyl alcohol can be mentioned. Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol; polyhydric alcohols having 3 or more valences such as glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, and sorbitol. Among them, glycerin, propylene glycol, pentaerythritol, and dipentaerythritol are preferable, and glycerin and dipentaerythritol are more preferable.

[0061] The fatty acid is a monovalent carboxylic acid having a carboxy group in the hydrocarbon chain. For example, saturated fatty acids such as caproic acid, caprylic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid; unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, linolenic acid, arachidonic acid, brassidic acid, erucic acid, and ricinoleic acid; hydroxy fatty acids such as 12-hydroxystearic acid; aliphatic dicarboxylic acids such as adipic acid. Preferably, it is a fatty acid having 6 or more carbon atoms, more preferably a fatty acid having 13 or more carbon atoms. Among them, myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid, and 12-hydroxystearic acid are particularly preferable, and stearic acid and 12-hydroxystearic acid are especially preferable. As the fatty acid ester, triglyceride of 12-hydroxystearic acid is particularly preferable.

[0062] [Fatty acid amide] The fatty acid amide has a structure in which one or more fatty acids are amide-bonded to an amine. Examples of the amine include monovalent or polyvalent amines. The monovalent amine is preferably ammonia and an amine having 10 or more carbon atoms. For example, oleylamine and stearylamine can be mentioned. The polyvalent amine preferably has 3 or less nitrogen atoms. Among them, diamines having 6 or less carbon atoms such as ethylenediamine and hexamethylenediamine are preferable.

[0063] Examples of the fatty acid include the above-mentioned fatty acids. Preferably, it is a long-chain fatty acid having 13 or more carbon atoms, more preferably stearic acid, 12-hydroxystearic acid, and erucic acid.

[0064] Examples of the fatty acid amide include aliphatic monocarboxylic acid amides such as lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, behenic acid amide, ricinoleic acid amide, and hydroxystearic acid amide; N-substituted aliphatic monocarboxylic acid amides such as N-oleyloleic acid amide, N-oleylstearic acid amide, and N-stearyloleic acid amide; aliphatic biscarboxylic acid amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide; N,N'-ethylene-bis-oleylamide; N,N'-ethylenebisstearic acid amide; N,N'-methylenebisstearic acid amide. Preferably, they are stearic acid amide, erucic acid amide, and N,N'-ethylenebisstearic acid amide.

[0065] [Fatty acid metal salt] Examples of the fatty acid constituting the fatty acid metal salt include the above-mentioned fatty acids. Preferably, they are myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, and oleic acid.

[0066] The metal constituting the fatty acid metal salt is preferably a divalent or trivalent metal and lithium. For example, magnesium, aluminum, calcium, barium, zinc, etc. can be mentioned. Examples of the fatty acid metal salts include calcium stearate, magnesium stearate, barium stearate, zinc stearate, aluminum stearate, lithium stearate, calcium laurate, magnesium laurate, barium laurate, zinc laurate, aluminum laurate, and lithium laurate. Preferably, they are magnesium stearate and magnesium 12-hydroxystearate.

[0067] 1-4. Antioxidant (E) In order to maintain the high catalytic activity of the solid-phase polymerization accelerator (B), the combined use with the antioxidant (E) is very effective for this liquid masterbatch. Examples of the antioxidant (E) include phenolic antioxidants, phosphorus antioxidants, amine antioxidants, sulfur antioxidants, and the like.

[0068] When the antioxidant (E) is contained, from the viewpoint of the heat resistance of the final molded article, the effective content of the antioxidant (E) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the liquid masterbatch. The antioxidant may be used alone or in combination of two or more.

[0069] [Phosphorus antioxidant] Examples of phosphorus-based antioxidants include, for example, phosphite-based antioxidants. Specific examples thereof include triphenyl phosphite, tris(nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono(tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra(tridecyl) pentaerythritol tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenyl di(tridecyl) phosphite), tetra(tridecyl) 4,4'-isopropylidenediphenyl diphosphite, bis(tridecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris(4-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, and the like.

[0070] Among them, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, and bis(2,4-dicumylphenyl) pentaerythritol diphosphite are preferred. From the viewpoint of heat resistance, tris(2,4-di-tert-butylphenyl) phosphite is particularly preferred. Examples of commercially available products of such phosphite-based antioxidants include "Irgafos 168" and "Irganox B225" manufactured by BASF, and "Adekastab 2112" manufactured by ADEKA, etc.

[0071] [Phenolic antioxidant] Examples of phenolic antioxidants include hindered phenolic antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol and the like. Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred.

[0072] Examples of commercially available products of such phenolic antioxidants include "Irganox1010" and "Irganox1076" manufactured by BASF, and "Adekastab AO-60" and "Adekastab AO-50" manufactured by ADEKA.

[0073] 1-5. Other components This liquid masterbatch may contain, in addition to the liquid dispersion medium (A), the solid-phase polymerization accelerator (B), the thickener (D), and the antioxidant (E), optional components. For example, resins, pigments, dyes, ultraviolet absorbers, flame retardants, etc. other than the above can be exemplified.

[0074] 1-6. Characteristics of the liquid masterbatch The viscosity of the liquid masterbatch at 25°C is preferably 50 to 100,000 mPa·s, more preferably 100 to 10,000 mPa·s, and even more preferably 200 to 5,000 mPa·s. From the viewpoint of dispersion stability, 50 mPa·s or more is preferable, and from the viewpoint of the discharge stability of the liquid supply machine, 100,000 mPa·s or less is preferable. From the viewpoint of shortening the mixing time with the thermoplastic resin (C) to be modified, 10,000 mPa·s or less is preferable. The viscosity can be measured at 25°C and a rotor rotation speed of 10 min using a B-type viscometer in accordance with JIS K7117-1:1999 -1 and can be measured.

[0075] 1-7. Method for producing the liquid masterbatch The method for producing the liquid masterbatch in the present invention is not particularly limited. For example, the liquid dispersion medium (A), the solid-phase polymerization accelerator (B), and, if necessary, the thickener (D), the antioxidant (E), and other components are added, and mixed with a Henschel mixer, tumbler, disper, etc., and dispersed using a Silverstone mixer (manufactured by Silverstone Co., Ltd.) etc. to obtain the liquid masterbatch. As the dispersion device, in addition to the above, a kneader, roll mill, ball mill, sand mill, etc., any device can be used. For reasons such as easy molding processing and excellent dispersibility, it is preferable to use a Silverstone mixer or a roll mill.

[0076] 2. Molded article The molded article according to this embodiment is obtained through a process of polymerizing a mixture containing the thermoplastic resin (C) to be modified and at least the liquid masterbatch for solid-phase polymerization by solid-phase polymerization to produce a modified thermoplastic resin, and molding the modified thermoplastic resin. That is, the modified thermoplastic resin is a thermoplastic resin (C) to be modified, the molecular weight of which is increased by solid-phase polymerization to obtain a high-molecular-weight thermoplastic resin. The thermoplastic resin composition before solid-phase polymerization may be used in the form of pellets, powder, granules, beads, or the like. In addition, the modified thermoplastic resin after solid-phase polymerization may be directly used for forming a molded article after production, or a molded article may be produced after once forming it into pellets, powder, granules, beads, or the like.

[0077] This molded article is an arbitrary molded product formed according to the application, and examples include films, sheets, plates, net-like bodies, containers, cylindrical bodies, filamentous bodies such as filaments, non-woven fabrics, and woven fabrics. The surface of the molded article may be smooth or may have uneven or complex shapes.

[0078] Note that the liquid masterbatch for promoting solid-phase polymerization and the thermoplastic resin composition for solid-phase polymerization may contain any components other than the thermoplastic resin (C), the liquid dispersion medium (A), and the solid-phase polymerization promoter (B) within the scope not departing from the gist of the present disclosure.

[0079] Examples of the optional additive include resins and / or catalysts, chain extenders, antioxidants, antistatic agents, surfactants, flame retardants, ultraviolet absorbers, fillers, and lubricants other than the liquid dispersion medium (A) or the thermoplastic resin (C) within the scope not departing from the gist of the present disclosure.

[0080] A thermoplastic resin composition for solid-phase polymerization can be produced from a mixture of only the thermoplastic resin (C) and this masterbatch, and a molded article can be obtained through the modified thermoplastic resin by solid-phase polymerization. Further, the thermoplastic resin composition for solid-phase polymerization may be a mixture to which any components are added. In this case, the molded article is formed of a modified thermoplastic resin composition containing the modified thermoplastic resin and any components.

[0081] The liquid masterbatch for promoting solid-phase polymerization is a liquid composition containing a solid-phase polymerization accelerator (B) for solid-phase polymerization dispersed at a high concentration, and plays a role of modifying the thermoplastic resin (C) as the main component at a specified ratio by mixing the liquid masterbatch with the thermoplastic resin (C).

[0082] The thermoplastic resin composition for solid-phase polymerization is a thermoplastic resin composition before solid-phase polymerization, which is formed by mixing at least the liquid masterbatch for promoting solid-phase polymerization with the thermoplastic resin (C) to be modified, and the thermoplastic resin (C) becomes a modified thermoplastic resin by solid-phase polymerization.

[0083] The molded article, which is a thermoplastic resin product, is formed by various molding methods including uniaxial molding and biaxial molding. However, since the physical properties of recycled thermoplastic resin are inferior to those of virgin thermoplastic resin, the productivity is significantly reduced. In addition, since the quality of recycled thermoplastic resin deteriorates, its range of use is limited.

[0084] On the other hand, according to the modified thermoplastic resin and the molded article of the present invention, even when a recycled thermoplastic resin is used as the thermoplastic resin (C) to be modified, a modified thermoplastic resin and a molded article with high quality and high productivity can be obtained. The main reason is by using the liquid masterbatch of the present disclosure. Hereinafter, each component will be described in detail.

[0085] 2-1. Thermoplastic resin (C) to be modified The thermoplastic resin (C) to be modified is a thermoplastic resin to be modified, and the modified thermoplastic resin modified by the liquid masterbatch is the main component of the molded article. In this specification, the main component means the component with the largest blending amount in the component. From the viewpoint of mechanical properties, based on 100% by mass of the thermoplastic resin composition for solid-phase polymerization, it is preferable to contain 70% by mass or more of the thermoplastic resin (C) to be modified, preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. From the viewpoints of outgas amount and uniformity, 99.5% by mass or less is preferable, and 99% by mass or less is more preferable.

[0086] The thermoplastic resin (C) is at least one selected from the group consisting of a polyester resin, a polycarbonate resin, and a polyamide resin, and may be amorphous or crystalline. Further, the thermoplastic resin (C) may be linear or branched. Further, the thermoplastic resin (C) may be a virgin resin or a recycled resin. The thermoplastic resin (C) may be of one kind or a mixture of two or more kinds.

[0087] With this liquid masterbatch, the thermoplastic resin (C) can be modified to increase its molecular weight and uniformly increase the melt viscosity. Therefore, it is particularly suitable for the modification of recycled thermoplastic resins with reduced molecular weight. Further, for polyester resins, polycarbonate resins, or polyamide resins, regardless of the type of thermoplastic resin, it is suitable for the modification of thermoplastic resins according to needs. From the viewpoint of obtaining a higher-quality molded article, the thermoplastic resin (C) is preferably a linear thermoplastic resin.

[0088] From the viewpoints of the distributability and heat resistance of the liquid masterbatch, the flow start temperature of the thermoplastic resin (C) is preferably 150°C or higher and 300°C or lower, and more preferably 160°C or higher and 280°C or lower. The flow start temperature can be determined using a flow tester. Specifically, for example, using "CFT-EX series" manufactured by Shimadzu Corporation, etc., when passing through a capillary with a die hole diameter of φ1 mm and a die length of 1 mm under a pressure of 9.8 MPa, the minimum temperature at which the melt viscosity of the thermoplastic resin (C) becomes 4800 Pa·s or less can be measured.

[0089] [Polyester resin] The polyester resin is not particularly limited, and typically, a polyester resin obtained by polycondensing a polyhydric alcohol such as a diol and a polyvalent carboxylic acid such as a dicarboxylic acid or its ester-forming derivative, a polyester resin obtained by polycondensing a hydroxycarboxylic acid or its ester-forming derivative, or a mixture and copolymer of these can be exemplified.

[0090] The ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids are lower alkyl esters of carboxylic acids, acid halides, etc. Examples of the lower alkyl esters of carboxylic acids include methyl ester, ethyl ester, hydroxyethyl ester, hydroxybutyl ester, etc. Specific examples of the halides of carboxylic acids include acid chlorides, acid bromides, and acid iodides. Also, polyhydric alcohols are alcohols having two or more hydroxyl groups in the molecule, and alcohols having a structure in which hydroxyl groups are substituted one by one on two or more carbon atoms of a chain aliphatic hydrocarbon, a cyclic aliphatic hydrocarbon, an aromatic hydrocarbon, or a hydrocarbon compound combining these can be exemplified.

[0091] As the diol component, various diols can be exemplified. For example, aliphatic diols such as ethylene glycol, diethylene glycol, propanediol, butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hexanediol, etc., saturated alicyclic primary diols such as 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, decahydronaphthalenedimethanol, decahydronaphthalenediethano, norbornanedimethanol, norbornanediethano, tricyclodecanedimethanol, tricyclodecaneethanol, tetracyclododecanedimethanol, tetracyclododecanediethanol, decalindimethanol, decalindietanol, etc., saturated heterocyclic primary diols containing cyclic ethers such as 2,6-dihydroxy-9-oxabicyclo[3,3,1]nonane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (spiroglycol), 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, isosorbide, etc., alicyclic diols such as other cyclohexanediol, bicyclohexyl-4,4'-diol, 2,2-bis(4-hydroxycyclohexylpropane), 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)propane, cyclopentanediol, 3-methyl-1,2-cyclopentadiene diol, 4-cyclopentene-1,3-diol, adamantadiol, etc., aromatic diols such as bisphenol A, bisphenol S, styrene glycol, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9'-bis(4-hydroxyphenyl)fluorene can be exemplified. As the polyhydric alcohol having three or more functional groups, glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol, sorbitol, etc. can be mentioned.

[0092] Examples of the dicarboxylic acid or its ester-forming derivative include fatty acid dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, glutaric acid, and succinic acid; aromatic dicarboxylic acids such as terephthalic acid, naphthalenedicarboxylic acid, and isophthalic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; or ester-forming derivatives thereof. Examples of polyvalent carboxylic acids having three or more functional groups include trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, and monopotassium trimellitate.

[0093] Examples of the hydroxycarboxylic acid include lactic acid, hydroxybutyric acid, and polycaprolactone.

[0094] Specific examples of the polyester resin include polyethylene terephthalate resin (PET resin), polyethylene (terephthalate / isophthalate) resin (I-PET resin), glycol-modified polyethylene terephthalate resin (PET-G resin), polybutylene terephthalate resin (PBT resin), polycyclohexylene dimethylene terephthalate resin (PCT resin), polytrimethylene terephthalate resin (PTT resin), polyethylene naphthalate (PEN resin), polybutylene naphthalate resin (PBN resin), polybutylene adipate terephthalate resin (PBAT resin), polybutylene succinate resin (PBS resin), polyethylene adipate resin (PEA resin), polylactic acid resin (PLA resin), polyglycolic acid resin (PGA resin), polyhydroxyalkanoate resin (PHA resin), and the like.

[0095] From the viewpoints of the productivity and quality of the molded article, the polyester resin to be modified is preferably polyethylene terephthalate resin, polyethylene (terephthalate / isophthalate) resin (I-PET resin), glycol-modified polyethylene terephthalate resin (PET-G resin), polybutylene terephthalate resin (PBT resin), polycyclohexylene dimethylene terephthalate resin (PCT resin), polybutylene phthalate resin, or polycyclohexylene dimethylene terephthalate resin. Further, polyethylene terephthalate resin, polyethylene (terephthalate / isophthalate) resin (I-PET resin), glycol-modified polyethylene terephthalate resin (PET-G resin), or a mixture thereof is more preferable because of excellent transparency and easy moldability.

[0096] The intrinsic viscosity (IV) of the polyester resin is not particularly limited. However, the lower the intrinsic viscosity (IV), the longer the polymerization time needs to be set. Considering the cost and the like in view of the production time, a resin having an intrinsic viscosity of 0.4 dl / g or more is preferable, more preferably 0.6 dl / g or more, and still more preferably 0.7 dl / g or more. The upper limit is not limited, but from the viewpoint of improving the properties of the polyester resin, it is preferably 1.2 dl / g or less. The intrinsic viscosity and the melt viscosity in this specification refer to the values obtained by the examples described later.

[0097] [Polycarbonate resin] Examples of the polycarbonate resin (PC resin) include, but are not particularly limited to, aliphatic polycarbonates and aromatic polycarbonates. From the viewpoints of impact resistance, heat resistance, etc., aromatic polycarbonate resins are preferred. The aromatic polycarbonate resin is a thermoplastic polymer or copolymer, which may be branched, and is obtained by reacting an aromatic dihydroxy compound or a small amount of polyhydroxy compound thereof with phosgene or a carbonic acid diester. The production method of the aromatic polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used. Further, when the melting method is used, an aromatic polycarbonate resin with the amount of OH groups at the terminal groups adjusted can be used.

[0098] Examples of the raw material aromatic dihydroxy compound include 2,2-bis(4-hydroxyphenyl)propane (=bisphenol A), tetramethyl bisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, etc., and bisphenol A is preferably mentioned. Further, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

[0099] To obtain a branched aromatic polycarbonate resin, a part of the above-described aromatic dihydroxy compound is replaced with the following branching agents, namely, polyhydroxy compounds such as phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-2, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 2,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptene-3, 1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, or compounds such as 3,3-bis(4-hydroxyaryl)oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin. The amount of these substituting compounds used is usually 0.01-10 mol%, preferably 0.1-2 mol%, based on the aromatic dihydroxy compound.

[0100] Among the above-described aromatic polycarbonate resins, a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane or a polycarbonate copolymer derived from 2,2-bis(4-hydroxyphenyl)propane and another aromatic dihydroxy compound is preferred. Also, a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure, may be used.

[0101] The above-described aromatic polycarbonate resin may be used alone or in combination of two or more.

[0102] To adjust the molecular weight of the aromatic polycarbonate resin, a monohydric aromatic hydroxy compound may be used. Examples of this monohydric aromatic hydroxy compound include m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p-long-chain alkyl-substituted phenol, and the like.

[0103] It should be noted that there is an error in the original text you provided. The correct usage amount range of the substituting compounds should be "usually 0.01-10 mol%, preferably 0.1-2 mol%", not "usually 0.0110 mol%, preferably 0.12 mol%". The translation has been adjusted accordingly.The intrinsic viscosity (IV) of the polycarbonate resin is not limited, but is preferably 0.3 dl / g or more, and more preferably 0.4 dl / g or more. The upper limit is not particularly limited, but from the viewpoint of handleability during molding processing considering the melt viscosity, it is usually 1.2 dl / g. By setting the intrinsic viscosity to 0.4 dl / g or more, a more excellent effect can be obtained in terms of moldability. The intrinsic viscosity of the polycarbonate resin is a value measured by dissolving polycarbonate resin pellets in a methylene chloride solution and using an automatic viscosity measuring device "SS-600-L2" manufactured by Shibayama Scientific Instruments Co., Ltd.

[0104] [Polyamide resin] The polyamide resin (PA resin) is a polyamide polymer having an acid amide group (-CONH-) in its molecule and capable of being melted by heating. Specifically, it is various polyamide resins such as polycondensates of lactams, polycondensates of diamine compounds and dicarboxylic acid compounds, polycondensates of ω-aminocarboxylic acids, or copolyamide resins or blends thereof.

[0105] Examples of the lactam that is a raw material for polycondensation of the polyamide resin include ε-caprolactam, ω-laurolactam, etc.

[0106] Examples of the diamine compound include aliphatic, alicyclic, and aromatic diamines such as tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine, (2,2,4- or 2,4,4-) trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine (MXDA), paraxylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine, etc.

[0107] Examples of the dicarboxylic acid compound include aliphatic, alicyclic, and aromatic dicarboxylic acids such as adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.

[0108] Examples of the ω-aminocarboxylic acid include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid.

[0109] Specific examples of the polyamide resin obtained by polycondensation from these raw materials include PA4, PA6, PA11, PA12, PA46, PA66, PA610, PA612, polyhexamethylene terephthalamide (PA6T), polyhexamethylene isophthalamide (PA6I), polymetaxylylene adipamide (PAMXD6), polymetaxylylene dodecamide (PAMXD12), PA9T, PA9MT, etc. In the present invention, these polyamide homopolymers or copolymers can be used alone or in the form of a mixture, respectively. Among the polyamide resins as described above, from the viewpoint of moldability, polyamide 6, polyamide 66, polyamide 11, polyamide 12, or a xylylenediamine-based polyamide resin (MX nylon) obtained by polycondensation of an α,ω-linear aliphatic dibasic acid and xylylenediamine is more preferable.

[0110] The relative viscosity (RV) of the polyamide resin is not limited, but is preferably 1.5 dl / g or more, more preferably 1.6 dl / g or more. The upper limit is not particularly limited, but from the viewpoint of handleability during molding considering the melt viscosity, it is usually 5.0 dl / g. By setting the relative viscosity to 1.6 dl / g or more, a more excellent effect can be obtained in terms of moldability. The intrinsic viscosity of the polyamide resin is a value measured using an automatic viscosity measuring device "SS-600-L2" manufactured by Shibayama Scientific Instruments Co., Ltd. by dissolving polyamide resin pellets in a 96 mass% sulfuric acid solution at a concentration of 1 g / dl.

[0111] 2-2. Method for manufacturing the molded body The molded body of the present embodiment is obtained by molding a modified thermoplastic resin. The modified thermoplastic resin for forming the molded body is obtained by subjecting a thermoplastic resin for solid-phase polymerization, which is a mixture of the present liquid masterbatch and the thermoplastic resin (C), to solid-phase polymerization. The thermoplastic resin for solid-phase polymerization may be produced by mixing the molten thermoplastic resin (C) and the present masterbatch, or may be produced by adding the masterbatch in the polymerization step of obtaining the thermoplastic resin (C) by polymerization.

[0112] Note that each step does not necessarily need to be performed continuously, and the thermoplastic resin composition and the modified thermoplastic resin may be used after being formed into pellets, powder, granules, etc. by a single-screw extruder, twin-screw extruder, kneader-ruder, etc.

[0113] The addition amount of the present liquid masterbatch is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass%, and further preferably 0.5 to 2 mass% based on 100 mass% of the obtained thermoplastic resin composition for solid-phase polymerization. When the addition amount is 0.1 mass% or more, the uniformity of the molded body is further improved. Also, when it is 10 mass% or less, the mechanical properties of the molded body are likely to be improved.

[0114] In addition, the content of the solid-phase polymerization accelerator (B) in the thermoplastic resin composition for solid-phase polymerization is preferably 0.01 to 10% by mass based on 100% by mass of the thermoplastic resin composition for solid-phase polymerization. From the viewpoints of IV and RV, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. From the viewpoints of outgas and yellowing, 5% by mass or less is preferable, and 1% by mass or less is more preferable.

[0115] When a liquid masterbatch is added before or after the polymerization step of the thermoplastic resin (C) to be modified, or simultaneously with the polymerization step, as in the production method (ii) described later, based on 100% by mass of the thermoplastic resin composition for solid-phase polymerization, the liquid masterbatch or the content ratio of the solid-phase polymerization accelerator (B) may be within the above range.

[0116] Furthermore, according to the method for producing the modified thermoplastic resin and the molded article of the present invention, the amount of outgas generated in the production process of the molded article can be significantly improved. The reason is that the molecular weight of the thermoplastic resin increases, and decomposition products of the thermoplastic resin with a low molecular weight that generate outgas do not occur.

[0117] In addition, by using the liquid dispersion medium (A), it is not necessary to perform melt kneading during the production of the masterbatch, and mixing can be performed in a short time even during mixing with the thermoplastic resin (C) to be modified. Therefore, the energy consumption and time can be reduced, and the productivity is improved. In addition, since the thermal history of the masterbatch and the thermoplastic resin (C) to be modified can be reduced, a decrease in melt viscosity, yellowing, and generation of outgas due to deterioration of the thermoplastic resin (C) can be suppressed, and yellowing, reduction in transparency, and reduction in catalytic ability due to deterioration of the solid-phase polymerization accelerator (B) can also be suppressed. By these actions, a high-quality modified thermoplastic resin and molded article with high productivity and excellent moldability and physical properties can be obtained.

[0118] Moreover, even when a recycled thermoplastic resin is used as the thermoplastic resin (C) to be modified, since the quantitative supply property by the liquid supply machine is high, the variation in mechanical properties between molded articles can be reduced. Alternatively, even when the solid-phase polymerization accelerating catalyst is added during the polymerization of the thermoplastic resin to be modified, quantitative continuous supply is possible and the polymerization reaction is not inhibited, so the productivity can be improved.

[0119] When the thermoplastic resin (C) to be modified is a polyester resin or a polycarbonate resin, the ratio IV y / IV x of the intrinsic viscosity IV value (IV y ) of the modified thermoplastic resin after solid-phase polymerization to the IV value (IV x ) of the thermoplastic resin for solid-phase polymerization described above is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio IV y / IV x is not particularly limited, but is usually about 1.20. y ) and the IV value (IV x ) of the thermoplastic resin for solid-phase polymerization described above is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio IV y / IV x is not particularly limited, but is usually about 1.20. x ) of the thermoplastic resin for solid-phase polymerization described above is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio IV y / IV x is not particularly limited, but is usually about 1.20. y / IV x is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio IV y / IV x is not particularly limited, but is usually about 1.20. y / IV x is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio IV y / IV x is not particularly limited, but is usually about 1.20.

[0120] When the thermoplastic resin (C) to be modified is a polyamide resin, the ratio RV y / RV x of the relative viscosity RV value (RV y ) of the modified thermoplastic resin after solid-phase polymerization to the RV value (RV x) ) of the thermoplastic resin for solid-phase polymerization described above is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio RV y / RV x is not particularly limited, but is usually about 1.20. y ) and the RV value (RV x) ) of the thermoplastic resin for solid-phase polymerization described above is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio RV y / RV x is not particularly limited, but is usually about 1.20. x) of the thermoplastic resin for solid-phase polymerization described above is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio RV y / RV x is not particularly limited, but is usually about 1.20. y / RV x is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio RV y / RV x is not particularly limited, but is usually about 1.20. y / RV x is preferably 1.05 or more, more preferably 1.10 or more, and even more preferably 1.15 or more. The upper limit value of the ratio RV y / RV x is not particularly limited, but is usually about 1.20.

[0121] As a method for manufacturing a molded article, specifically, for example, [Manufacturing method (i)] a step of obtaining the present liquid masterbatch (step (i-1)), a melting step of melting the thermoplastic resin (C) to be modified (step (i-2)), a mixing step of mixing the melted thermoplastic resin (C) to be modified and the liquid masterbatch to obtain a thermoplastic resin composition for solid-phase polymerization (step (i-3)), and a step of solid-phase polymerizing the thermoplastic resin composition simultaneously with or after the mixing step (step (i-4)) to manufacture a modified thermoplastic resin, and a step of molding the obtained modified thermoplastic resin to form a molded article (step (i-5)).

[0122] Also, for example, [Manufacturing method (ii)] a step of obtaining the present liquid masterbatch (step (ii-1)), a polymerization step of obtaining the thermoplastic resin (C) to be modified by polymerization (step (ii-2)), a mixing step of adding and mixing the liquid masterbatch before, after, or simultaneously with the polymerization step to obtain a thermoplastic resin composition for solid-phase polymerization (step (ii-3)), and a step of solid-phase polymerizing the thermoplastic resin for solid-phase polymerization after the polymerization step (step (ii-4)) to manufacture a modified thermoplastic resin, and a step of molding the obtained modified thermoplastic resin to form a molded article (step (ii-5)).

[0123] [Manufacturing method (i)] The manufacturing method (i) of the molded article includes the following steps (i-1) to (i-5). Step (i-1); A step of obtaining a liquid masterbatch Step (i-2); A melting step of melting the thermoplastic resin (C) to be modified Step (i-3); A mixing step of mixing the melted thermoplastic resin (C) to be modified and the liquid masterbatch to obtain a thermoplastic resin composition for solid-phase polymerization Step (i-4); A step of solid-phase polymerizing the thermoplastic resin composition for solid-phase polymerization Step (i-5); A step of molding the modified thermoplastic resin

[0124] (Step (i-1)) Step (i-1) is a step of obtaining a liquid masterbatch, and the liquid masterbatch can be obtained by the method described in the above-mentioned "1-7. Method for Producing Liquid Masterbatch".

[0125] (Steps (i-2) and (i-3)) Step (i-2) is a melting step of melting the thermoplastic resin (C) to be modified, and step (i-3) is a mixing step of mixing the melted thermoplastic resin (C) to be modified with the liquid masterbatch.

[0126] When mixing the thermoplastic resin (C) and the masterbatch, for example, after melting the thermoplastic resin (C), the masterbatch can be added and mixed, or after adding the masterbatch to the non-molten thermoplastic resin (C), melt mixing can be performed. In order to maintain a predetermined concentration between batches or in a continuous process, it is preferable to add the masterbatch after melting the thermoplastic resin (C). In particular, when using a recycled thermoplastic resin as the thermoplastic resin (C), since the resin to be modified is often a mixture of various shapes, by quantitatively adding the liquid masterbatch after melting, the concentration of the solid-phase polymerization accelerator (B) can be kept uniform in terms of time and space.

[0127] In the mixing step, mixing can be performed at a temperature 0 to 30 °C higher than the flow start temperature of the thermoplastic resin (C) so that the masterbatch becomes homogeneous. The mixing time is not particularly limited as long as homogeneous mixing can be achieved. For example, it is 1 to 20 minutes.

[0128] In the mixing step, it is preferable to supply the liquid masterbatch using a liquid feeder. As the liquid feeder, a rotary positive displacement pump with less pulsation is preferable because quantitative supplyability is required. Examples of the rotary positive displacement pump include a tube pump, a gear pump, and a mono pump, and a gear pump or a mono pump is preferable from the viewpoint of the transport stability of high-viscosity liquids. This masterbatch can be added continuously and quantitatively through a supply line connected to a liquid feeder. Various known valves can be used in the liquid addition section, but a globe valve, a Y-type valve, or an injection valve capable of adjusting the flow rate is preferred, and an injection valve is most preferred from the viewpoint of preventing the retention and backflow of the liquid masterbatch.

[0129] (Step (i-4)) Step (i-4) is a step of solid-phase polymerization either simultaneously with or after the mixing step of step (i-3). In the solid-phase polymerization step, under vacuum conditions, by performing a polycondensation step in the solid phase, the molecular weight of the thermoplastic resin (C) to be modified increases, and a modified thermoplastic resin can be obtained.

[0130] When the thermoplastic resin (C) to be modified is a polyester resin or a polycarbonate resin, the ratio IV of the intrinsic viscosity IV value (IV x ) of the thermoplastic resin for solid-phase polymerization to the IV value (IV0) of the thermoplastic resin (C) before processing used as a raw material is preferably 0.8 or more, more preferably 0.85 or more, and even more preferably 0.90 or more. The upper limit value of the ratio IV x / IV0 is not particularly limited, but is usually 1.00. x When the thermoplastic resin (C) to be modified is a polyamide resin, the ratio RV of the relative viscosity RV value (RV

[0131] (RV x ) of the thermoplastic resin for solid-phase polymerization to the RV value (RV0) of the thermoplastic resin (C) before processing used as a raw material is preferably 0.8 or more, more preferably 0.85 or more, and even more preferably 0.90 or more. The upper limit value of the ratio RV x / RV0 is not particularly limited, but is usually 1.00. x The upper limit value of the ratio RV

[0132] In the solid-phase polymerization step, the polycondensation step is carried out in the solid phase under vacuum conditions or with a flow of high-temperature nitrogen at a temperature 5 to 50 °C lower than the flow start temperature of the thermoplastic resin (C) usually. Further, when it is desired to obtain a lower molecular weight dispersity, the polycondensation step can be carried out in the solid phase at a temperature lower than the flow start temperature, for example, 30 to 70 °C lower, within a range not lower than the glass transition temperature. For example, a method can be exemplified in which a recycled thermoplastic resin and a liquid masterbatch are pelletized at 280 °C using a twin-screw extruder and then solid-phase polymerized at 220 °C in a tumbling dryer under a vacuum of about 1 mbar for, for example, 5 to 10 hours. By solid-phase polymerization, the molecular weight of the thermoplastic resin (C) increases and the viscosity increases.

[0133] The solid-phase polymerization time can achieve an increase in the molecular weight of the thermoplastic resin (C) in a short time compared to the method of directly adding the solid-phase polymerization accelerator (B) in powder or pellet form to the thermoplastic resin (C) without using this liquid masterbatch. The reason is considered to be that the solid-phase polymerization accelerator (B) is uniformly dispersed in the thermoplastic resin (C), and local thickening can be suppressed. For this reason, the reaction between the solid-phase polymerization accelerator (B) and the thermoplastic resin (C) is promoted in the solid-phase polymerization step, and the thickening of the thermoplastic resin (C) is promoted. As a result, a high-quality thermoplastic resin can be obtained. Also, productivity can be significantly increased.

[0134] The degree of increase in the melt viscosity of the thermoplastic resin (C) is preferably 5 to 40%, more preferably 7 to 30%, and still more preferably 10 to 25% with respect to the melt viscosity of the thermoplastic resin (C) before processing. By having the increase rate of the melt viscosity within the above range, the physical properties of the thermoplastic resin (C) can be improved without affecting the moldability.

[0135] (Step (i-5)) Step (i-5) is a step of molding the modified thermoplastic resin. The molding of the modified thermoplastic resin can be molded into various shapes by a usual method using various known molding machines. For example, single-screw extrusion molding, twin-screw extrusion molding, injection molding, blow molding, etc. can be mentioned.

[0136] [Manufacturing method (ii)] The manufacturing method (ii) of the molded body includes the following steps (ii-1) to (ii-5). Step (ii-1); Step of obtaining a liquid masterbatch Step (ii-2); Polymerization step of obtaining the thermoplastic resin (C) to be modified by polymerization Step (ii-3); Mixing step of adding and mixing the liquid masterbatch before or after the polymerization step, or simultaneously with the polymerization step Step (ii-4); Step of solid-phase polymerizing the thermoplastic resin composition for solid-phase polymerization obtained by the polymerization step Step (ii-5); Step of molding the modified thermoplastic resin

[0137] (Step (ii-1)) Step (ii-1) is a step of obtaining a liquid masterbatch, and the liquid masterbatch can be obtained by the method described in the above-mentioned "1-7. Manufacturing method of liquid masterbatch".

[0138] (Steps (ii-2) and (ii-3)) Step (ii-2) is a polymerization step of obtaining the thermoplastic resin (C) to be modified by polymerization, and step (ii-3) is a mixing step of adding and mixing the liquid masterbatch before or after the polymerization step, or simultaneously with the polymerization step.

[0139] In the polymerization step, for example, when the resin (C) is a polyester resin, a dicarboxylic acid component, a diol component, and a polymerization catalyst are charged into a reaction vessel, and the product obtained by the esterification reaction or transesterification reaction of the dicarboxylic acid component and the diol component is subjected to a polycondensation reaction to produce a polyester resin. In this specification, these steps for obtaining the resin (C) from the monomers are collectively referred to as the polymerization step.

[0140] For example, the present masterbatch can be added to the raw materials of the thermoplastic resin (C) before, during, or after the polymerization reaction. From the viewpoints of preventing inhibition of the polymerization reaction and preventing catalyst deterioration, it is preferable to add the liquid masterbatch after the polymerization step. When adding before the polymerization step, if the liquid dispersion medium (A) is glycol, it is preferable because it functions as a monomer. Also, in order to prevent inhibition of the polymerization reaction, the contents of calcium element and aluminum element in the liquid masterbatch are preferably 100 ppm or less. That is, the solid-phase polymerization accelerator (B) preferably has a content of calcium element and aluminum element of 1000 ppm or less. Generally, in the polymerization step of the thermoplastic resin (C), a plurality of continuous reaction tanks are used, and the reactants are transferred between the reaction tanks via pipes. Here, by using a liquid feeder, the liquid masterbatch can be continuously supplied to the pipes between the reaction tanks, which is preferable from the viewpoints of productivity and uniform mixing. From the viewpoints of preventing inhibition of the polymerization reaction and preventing catalyst deterioration, it is preferable to add the liquid masterbatch immediately before or immediately after the final stage polycondensation reaction tank.

[0141] In the mixing step of adding and mixing the liquid masterbatch before or after, or simultaneously with the polymerization step in step (ii-3), the thermoplastic resin for solid-phase polymerization can be obtained by the same method as the method described in the above-mentioned production method (i) "step (i-3)".

[0142] (Step (ii-4)) Step (ii-4) is a step of subjecting the thermoplastic resin composition for solid-phase polymerization obtained by the polymerization step to solid-phase polymerization. The step of step (ii-4) can obtain a modified thermoplastic resin by the same method as the method described in the above-mentioned production method (i) "step (i-4)".

[0143] (Step (ii-5)) Step (ii-5) is a step of molding the modified thermoplastic resin. The step of step (ii-5) can obtain a molded body by the same method as the method described in the above-mentioned manufacturing method (i) "step (i-5)".

Example

[0144] Hereinafter, the present disclosure will be described in more detail based on examples, but the present disclosure is not limited to the examples. Unless otherwise specified, in the examples, "parts" and "%" represent "parts by mass" and "mass%", respectively.

[0145] <Measurement of number average molecular weight> The number average molecular weight is the number average molecular weight in terms of standard polystyrene molecular weight, and is measured by using two columns of TSKgel SuperMultipore HZ-M (exclusion limit molecular weight: 2×106, theoretical plate number: 16,000 plates / book, filler material: styrene-divinylbenzene copolymer, filler particle size: 4μm, column temperature 40°C) in series in a high performance liquid chromatography (manufactured by Tosoh Corporation, "HLC-8320GPC"). GPC is a liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) according to the difference in their molecular sizes.

[0146] <Measurement of viscosity> The viscosity was measured using a B-type viscometer at a rotor rotation speed of 10 min in accordance with JIS K7117-1:1999. -1 The measurement was carried out immediately after the liquid dispersion medium (A) or the liquid masterbatch was allowed to stand in a constant temperature bath at 25°C for 1 hour or more and then sufficiently stirred.

[0147] <Measurement of thermal decomposition start temperature> The thermal decomposition start temperature is the temperature at which the weight loss during heating at a constant rate is measured using a differential thermal thermogravimetric simultaneous measurement device (TG / DTA) under the following conditions, and the weight loss rate becomes 10%. Measuring instrument: TG / DTA 6200 manufactured by Seiko Instruments Inc. Measurement range: RT~400°C Heating rate: 10°C / min Atmosphere: Nitrogen

[0148] <Measurement of Flow Initiation Temperature> The flow initiation temperature was determined by measuring the minimum temperature at which the melt viscosity of the thermoplastic resin becomes 4800 Pa·s or less when passing through a capillary with a die hole diameter of φ1 mm and a die length of 1 mm under a pressure of 9.8 MPa using a "CFT-EX series" flow tester manufactured by Shimadzu Corporation.

[0149] <Measurement of Melting Point> The melting point was measured using a differential thermal thermogravimetric simultaneous measurement device (TG / DTA) under the following conditions. Measuring instrument: TG / DTA 6300 manufactured by Seiko Instruments Inc. Measurement range: RT~1000 °C Heating rate: 10 °C / min Atmosphere: Nitrogen

[0150] <Measurement of Intrinsic Viscosity (IV) or Relative Viscosity (RV)> The resin pellets were dissolved under the following conditions respectively, and measured and determined using an automatic viscosity measuring device "SS-600-L2" manufactured by Shibayama Scientific Instruments Co., Ltd. · Polyester resin The polyester resin pellets were dissolved in phenol / 1,1,2,2-tetrachloroethane = 1 / 1 to calculate the intrinsic viscosity (IV). · Polycarbonate resin The polycarbonate resin pellets were dissolved in a methylene chloride solution to calculate the intrinsic viscosity (IV). · Polyamide resin The polyamide resin pellets were dissolved in a 96 mass% sulfuric acid solution at a concentration of 1 g / dl to calculate the relative viscosity (RV).

[0151] The materials used in the examples and comparative examples are shown below. ≪Liquid Dispersion Medium (A), etc.≫ A-1: Sansozer E-9000H (manufactured by ADEKA, epoxidized linseed oil) A-2: Adeka Sizer PN-150 (manufactured by ADEKA, adipic acid polyester) A-3: Adeka Sizer PN-250 (manufactured by ADEKA, adipic acid polyester) A-4: PEG-400 (manufactured by Sanyo Chemical Industries, polyethylene glycol) A-5: Unionol D-1200 (manufactured by Sanyo Chemical Industries, polypropylene glycol) A-6: Sunnex PP-3000 (manufactured by Sanyo Chemical Industries, polypropylene glycol) A-7: Sunnex GP-600 (manufactured by Sanyo Chemical Industries, polyether polyol) A-8: Adeka Stazer RS-700 (manufactured by ADEKA, polyether ester) A-9: Adeka Stazer UL-80 (manufactured by ADEKA, 2-ethylhexyl pyromellitate) A-10: Adeka Stazer PN-6810 (manufactured by ADEKA, tributyl acetylcitrate) A-11: Ethylene glycol (manufactured by Maruzen Petrochemical Co., Ltd.) A'-1: Adeka Stazer PN-350 (manufactured by ADEKA, adipic acid polyester)

[0152] Table 1 shows the types, structures, viscosities, number average molecular weights (Mn), and thermal decomposition temperatures of the liquid dispersion medium (A).

[0153]

Table 1

[0154] ≪Solid-phase polymerization accelerator (B)≫ B-1: Irganox 1222 (manufactured by BASF, phosphorus-based catalyst, sterically hindered hydroxyphenylalkyl phosphonate, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate) B-2: Irganox 1425 (manufactured by BASF, phosphorus-based catalyst, sterically hindered hydroxyphenylalkyl phosphonate, calcium diethyl bis[[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate] B-3: Phosphorus-based catalyst, alkyl phosphonate, diethyl 4-hydroxybenzylphosphonate B-4: Antimony-based catalyst, antimony trioxide (manufactured by Nippon Seiko K.K.) B-5: SPC-124 (manufactured by Sakai Chemical Industry Co., Ltd., titanium-based catalyst)

[0155] ≪Thermoplastic resin (C)≫ (Polyester resin) C-1: Bottle-derived recycled PET C-2: MA-2101M (manufactured by Unitika Ltd., PET) C-3: Clapet KS710-BS (manufactured by Kuraray Co., Ltd., PET) C-4: PIFG-5 (manufactured by Bell Polyester Products Co., Ltd., I-PET) C-5: GN401 (manufactured by Eastman Chemical Company, PET-G) C-6: Novaduran 5010 (manufactured by Mitsubishi Engineering Plastics Corporation, PBT resin) C-7: EASTER DN011 (manufactured by Eastman Chemical Company, PCT resin) (Polycarbonate resin) C-8: Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation, PC resin) (Polyamide resin) C-9: Amilan CM3001-N (manufactured by Toray Industries, Inc., PA66)

[0156] Table 2 shows the intrinsic viscosity (IV) or relative viscosity (RV) and the flow start temperature (°C) of the thermoplastic resin (C).

[0157]

Table 2

[0158] ≪Thickening agent (D)≫ D-1: K-3 Wax 500 (manufactured by Kawaken Fine Chemicals Co., Ltd., triglyceride 12-hydroxystearate, melting point 85°C) D-2: SAK-MS-P (manufactured by San Ace Co., Ltd., magnesium stearate, melting point 88°C) D-3: Alflo H-50TF (manufactured by NOF Corporation, ethylene bisstearamide, melting point 140°C) D-4: Kunibis 110 (manufactured by Kunimine Industries Co., montmorillonite, melting point > 1000 °C)

[0159] ≪Antioxidant (E)≫ E-1: Irgafos 168 (manufactured by BASF, phosphorus-based antioxidant, tris(2,4-di-tert-butylphenyl) phosphite) E-2: Irganox B225 (manufactured by BASF, phosphorus-based / phenolic antioxidant, tris(2,4-di-tert-butylphenyl) phosphite / pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate])

[0160] ≪Manufacture of Liquid Masterbatch and Solid Masterbatch≫ (Example 1-1) [Manufacture of Liquid Masterbatch (L-1)] Weighed 69 parts by mass of liquid dispersion medium (A-1) "Sanso Sizer E-9000H" (manufactured by ADEKA, epoxidized linseed oil), 30 parts by mass of solid-phase polymerization accelerator (B-1), and 1 part by mass of thickener (D-1), and mixed and dispersed them with a bead mill to obtain liquid masterbatch (L-1).

[0161] (Examples 1-2 to 30, Comparative Examples 1-1 to 3) [Manufacture of Liquid Masterbatches (L-2 to 30, L'-1 to 3)] Liquid masterbatches (L-2 to 30, L'-1 to 3) according to the examples and comparative examples were obtained in the same manner as in Example 1-1, except that the materials and compounding amounts (parts by mass) shown in Table 3 were changed respectively. When containing antioxidant (E), weighed liquid dispersion medium (A), solid-phase polymerization accelerator (B), thickener (D), and antioxidant (E), and obtained the masterbatch in the same manner as in Example 1-1.

[0162] (Comparative Example 1-4) [Manufacture of Solid Masterbatch (S-1)] Weigh 79 parts by mass of a thermoplastic resin (C-1) (recycled PET derived from bottles), 20 parts by mass of a solid-phase polymerization accelerator (B-1), and 1 part by mass of a thickening agent (D-1), and melt-knead them at 270 °C using a twin-screw extruder (manufactured by Japan Steel Works, Ltd., L / D = 52.5) to obtain a solid masterbatch (S-1).

[0163] ≪Evaluation of Liquid Masterbatch≫ The dispersibility, viscosity, and storage stability of the obtained liquid masterbatch were evaluated by the following methods. The results are shown in Table 3. Note that "(content of (B)) / (100 parts of (A))" is the content of the solid-phase polymerization accelerator (B) with respect to 100 parts by mass of the liquid dispersion medium (A).

[0164] (Dispersibility Evaluation) The particle size (D 90 ) at a cumulative volume percentage of 90% was measured using a dynamic light scattering particle size distribution measuring device LB-550 (manufactured by Horiba, Ltd.). Evaluation was performed according to the following criteria. [Evaluation Criteria] ++: D 90 is less than 50 μm, and it is good + : D 90 is 50 μm or more and less than 100 μm, and it is practical NG: D 90 is 100 μm or more, and it is not acceptable

[0165] (Viscosity Evaluation) The viscosity at 25 °C was measured, and evaluation was performed according to the following criteria. [Evaluation Criteria] +++: The viscosity is less than 5,000 mPa·s, and it is excellent ++ : The viscosity is 5,000 mPa·s or more and less than 10,000 mPa·s, and it is good + : The viscosity is 10,000 mPa·s or more and less than 100,000 mPa·s, and it is practical NG : The viscosity is 100,000 mPa·s or more, and it is not acceptable

[0166] (Storage Stability Evaluation) The fluidity at 25 °C was confirmed one month after production, and evaluation was performed according to the following criteria. [Evaluation Criteria] ++: Flows, has the same fluidity as immediately after production, good + : Flows, has lower fluidity than immediately after production, practical NG: Does not flow, not practical

[0167]

Table 3-1

[0168]

Table 3-2

[0169]

Table 3-3

[0170] ≪Manufacture of Thermoplastic Resin Composition for Solid Phase Polymerization≫ (Example 2-1) The thermoplastic resin (C-1) was charged into a single-screw extruder (manufactured by Nippon Placon Co., Ltd.), and 1 part by mass of the liquid masterbatch (L-1) was added to 100 parts by mass of the thermoplastic resin (C-1) by a tube pump. Extrusion processing (damage screw, screw diameter 40 mm, screw rotation speed 90 rpm, processing temperature 280 °C, discharge 20 kg / h, residence time in the extruder 1 minute) was carried out at 280 °C using a single-screw extruder to obtain a pellet-shaped (diameter about 2.5 mm, length about 2.5 mm) thermoplastic resin composition for solid phase polymerization (PE-1).

[0171] (Examples 2-2 to 41, Comparative Examples 2-1 to 3) Pellet-shaped thermoplastic resin compositions for solid phase polymerization (PE-2 to 41, PE'-1 to 3) were obtained in the same manner as in Example 2-1, except that the materials and compounding amounts (parts by mass) shown in Table 4 and the extrusion temperature were each changed to a temperature 20 °C higher than the flow start temperature of the thermoplastic resin (C).

[0172] (Comparative Example 2-5) A polyester resin composition (PE’-5) was obtained in the same manner as in Example 2-1, except that the liquid masterbatch (L-1) was changed to 0.3 part of a powdery solid-phase polymerization accelerator (B-1).

[0173] (Example 2-42) 69 parts by mass of terephthalic acid and 30.5 parts by mass of ethylene glycol were charged into a first reaction vessel equipped with a distillation column. Next, the rotation speed of the stirring blade in the reaction vessel was maintained at 200 rpm, and the reaction system was heated so that the temperature in the reaction system reached 265°C, and this temperature was maintained. After the esterification reaction was completed and the distillation of water from the reaction system ceased, the reaction mixture was transferred to a second reaction vessel, and 0.05 part by mass of titanium dioxide was added. After raising the temperature to 250°C at a rotation speed of 200 rpm of the stirring blade and holding for 60 minutes, the pressure in the reaction system was reduced over about 40 minutes to a vacuum degree of 0.5 kPa. When transferring the obtained reaction mixture to a third reaction vessel, 1 part by mass of a liquid masterbatch (L-8) was added per 100 parts by mass of the reaction mixture using a tube pump. In the third reaction vessel, a condensation reaction was carried out while maintaining 250°C, 0.5 kPa, and a rotation speed of 200 rpm of the stirring blade. As the reaction proceeded, the viscosity of the reaction system increased, and when the torque of the stirring blade showed a predetermined torque, the stirring was stopped, and the reaction system was returned to normal pressure to obtain a thermoplastic resin composition. The obtained thermoplastic resin composition was extruded in a strand shape from a nozzle, cooled with water, and then cut to obtain a thermoplastic resin composition for solid-phase polymerization in pellet form (diameter: about 2.5 mm, length: about 2.5 mm) (PE-42).

[0174] (Example 2-43) Into a reaction vessel equipped with a distillation column, 69 parts by mass of terephthalic acid, 30.5 parts by mass of ethylene glycol, and 0.87 parts by mass of a liquid masterbatch (L-30) were charged. Next, the rotation speed of the stirring blade in the reaction vessel was maintained at 200 rpm, heating was started, and the reaction system was heated so that the temperature in the reaction system reached 265 °C and this temperature was maintained. After the esterification reaction was completed and the distillation of water from the reaction system ceased, 0.05 parts by mass of germanium dioxide was added, the temperature in the reaction system was set to 250 °C, the pressure in the reaction system was reduced over about 40 minutes, and a condensation reaction was carried out while maintaining the degree of vacuum at 0.5 kPa. As the reaction proceeded, the viscosity of the reaction system increased, and when the torque of the stirring blade showed a predetermined torque, stirring was stopped, the reaction system was returned to normal pressure, and then it was extruded in a strand shape from a nozzle, cooled with water, and then cut to obtain a thermoplastic resin composition for solid-phase polymerization (PE-43) in the form of pellets (diameter about 2.5 mm, length about 2.5 mm).

[0175] (Comparative Example 2-4) 100 parts by mass of a thermoplastic resin (C-1) and 1 part by mass of a solid masterbatch (S-1) were tumbled and then subjected to extrusion processing using a single-screw extruder (manufactured by Nippon Placon Co., Ltd.) to obtain a thermoplastic resin composition for solid-phase polymerization (PE'-4) in the form of pellets.

[0176] (Comparative Example 2-6) A polyester resin composition (PE'-6) was obtained in the same manner as in Example 2-43, except that the liquid masterbatch (L-30) was changed to 0.26 part of a powdery solid-phase polymerization accelerator (B-1).

[0177] ≪Evaluation of Thermoplastic Resin Composition for Solid-Phase Polymerization, Modified Thermoplastic Resin, and Molded Body≫ The thermoplastic resin composition for solid-phase polymerization, the modified thermoplastic resin, and the molded body were evaluated by the methods shown below. The results are shown in Table 4. Note that for all evaluation criteria, "NG" means "not practical", "+" means "practical", "++" means "good", and "+++" means "excellent". Note that for Examples 2-42 and 43, as the thermoplastic resin (C) without the addition of a solid-phase polymerization accelerator, a thermoplastic resin produced without the addition of a liquid masterbatch was used as a comparative target.

[0178] <Production of Modified Thermoplastic Resin> Solid-phase polymerization was carried out using the thermoplastic resin composition pellets for solid-phase polymerization of each example and comparative example to obtain modified thermoplastic resin pellets. The solid-phase polymerization conditions were a temperature 40 °C lower than the flow start temperature of the thermoplastic resin (C), a vacuum degree of 0.3 Torr, and 10 hours.

[0179] <Method for Measuring Intrinsic Viscosity (IV) and Relative Viscosity (RV) of Thermoplastic Resin Composition> The intrinsic viscosity and relative viscosity of the thermoplastic resin composition pellets of each example and comparative example were measured by the following method according to the type of the thermoplastic resin (C). · In the case of polyester resin; intrinsic viscosity (IV) The polyester resin composition pellets were dissolved in phenol / 1,1,2,2-tetrachloroethane = 1 / 1 and measured using an automatic viscosity measuring device "SS-600-L2" manufactured by Shibayama Scientific Instrument Co., Ltd. · In the case of polycarbonate resin; intrinsic viscosity (IV) The polycarbonate resin composition pellets were dissolved in a methylene chloride solution and measured using an automatic viscosity measuring device "SS-600-L2" manufactured by Shibayama Scientific Instrument Co., Ltd. · In the case of polyamide resin; relative viscosity (RV) The polyamide resin composition pellets were dissolved in a 96 mass% sulfuric acid solution at a concentration of 1 g / dl and measured using an automatic viscosity measuring device "SS-600-L2" manufactured by Shibayama Scientific Instrument Co., Ltd.

[0180] <Evaluation of Intrinsic Viscosity (IV) and Relative Viscosity (RV) before Solid-phase Polymerization> The intrinsic viscosity (IV x ) or relative viscosity (RV x ) of the thermoplastic resin composition pellets before solid-phase polymerization of each example and comparative example, and the ratio IV of the intrinsic viscosity (IV0) or relative viscosity (RV0) of the thermoplastic resin (C) without adding the solid-phase polymerization accelerator used for each x / IV0 or RV x / RV0 was evaluated according to the following criteria in accordance with the type of the thermoplastic resin (C) to be modified used in each example and comparative example. [Evaluation Criteria for Polyester Resin and Polycarbonate Resin] +++: 0.95 ≤ IV x / IV0 ++ : 0.90 ≤ IV x / IV0 < 0.95 + : 0.85 ≤ IV x / IV0 < 0.90 NG : IV x / IV0 < 0.85 [Evaluation Criteria for Polyamide Resin] +++: 0.95 ≤ RV x / RV0 ++ : 0.90 ≤ RV x / RV0 < 0.95 + : 0.85 ≤ RV x / RV0 < 0.90 NG : RV x / RV0 < 0.85

[0181] <Evaluation of Intrinsic Viscosity (IV) and Relative Viscosity (RV) after Solid Phase Polymerization> Using the thermoplastic resin composition pellets before solid phase polymerization of each example and comparative example, the intrinsic viscosity (IV x ) or relative viscosity (RV x ), and the intrinsic viscosity (IV y ) measured using the modified thermoplastic resin pellets, or the relative viscosity (RV y ), the following criteria were used for evaluation in accordance with the type of the thermoplastic resin (C) to be modified used in each example and comparative example. [Evaluation Criteria for Polyester Resin and Polycarbonate Resin] +++: 1.10 ≤ IV y / IV x ++ : 1.08 ≤ IV y / IV x < 1.10 + : 1.05 ≤ IV y / IV x < 1.08 NG : IV y / IV x<1.05 [Evaluation Criteria for Polyamide Resin] +++: 1.10 ≤ RV y / RV x ++: 1.08 ≤ RV y / RV x <1.10 +: 1.05 ≤ RV y / RV x <1.08 NG: RV y / RV x <1.05

[0182] <Outgas Amount> For each example and comparative example, about 10 mg of the modified thermoplastic resin pellets after solid-phase polymerization were held under nitrogen in STA7200 manufactured by Hitachi High-Tech Sciences Corporation at a temperature 20 °C higher than the flow start temperature of the thermoplastic resin (C) for 1 hour, and the weight loss rate was measured. The weight loss rate after solid-phase polymerization of the thermoplastic resin composition pellets of the examples and comparative examples was designated as TG1, and the weight loss rate after solid-phase polymerization of the thermoplastic resin composition pellets without adding a solid-phase polymerization accelerator to the thermoplastic resin (C) used respectively was designated as TG0, and the evaluation was carried out according to the following criteria. [Evaluation Criteria] ++: TG1 / TG0 < 0.9 +: 0.9 ≤ TG1 / TG0 < 1.0 NG: 1.0 ≤ TG1 / TG0

[0183] <Silver Streak> Using the thermoplastic resin composition pellets after solid-phase polymerization of each example and comparative example, 10 test pieces of 80 × 80 × 4 mm were prepared. Each test piece was observed, and the number of test pieces with appearance abnormalities due to silver streaks was designated as n, and the evaluation was carried out according to the following criteria. [Evaluation Criteria] ++: 0 ≤ n ≤ 1 +: 2 ≤ n ≤ 4 NG: 5 ≤ n ≤ 10

[0184] <Charpy Impact Strength> Using the thermoplastic resin composition pellets after solid-phase polymerization of each example and comparative example, Charpy impact test specimens (with notches) were prepared. Using the prepared plate specimens, the Charpy impact strength (with notches) was measured at 23°C. The Charpy impact strength (with notches) of the thermoplastic resin composition after solid-phase polymerization of each example and comparative example was designated as S1, and the Charpy impact strength (with notches) of the thermoplastic resin (C) to which no solid-phase polymerization accelerator was added was designated as S0, and evaluation was performed according to the following criteria. [Evaluation Criteria] +++: 1.10 ≦ S1 / S0 ++ : 1.05 ≦ S1 / S0 < 1.10 + : 1.00 ≦ S1 / S0 < 1.05 NG : S1 / S0 < 1.00

[0185] <Strength Uniformity> The variation between products was evaluated based on the uniformity of the Charpy impact strength. Using the thermoplastic resin composition pellets after solid-phase polymerization of each example and comparative example, 10 Charpy impact test specimens (with notches) were prepared. Using the prepared plate specimens, the Charpy impact strength (with notches) was measured at 23°C. With the standard deviation being σ and the average value being μ, evaluation was performed according to the following criteria. [Evaluation Criteria] ++: σ / μ ≦ 0.1 + : 0.1 < σ / μ ≦ 0.2 NG: 0.2 < σ / μ

[0186] [Table 4-1]

[0187] [Table 4-2]

[0188] [Table 4-3]

[0189] [Table 4-4]

[0190]

Table 4-5

[0191] From the results of Tables 3 and 4, it was confirmed that the liquid masterbatch for promoting solid-phase polymerization of the present invention is highly productive and of high quality, and can provide a molded article with little variation between products. That is, this liquid masterbatch does not contaminate the apparatus due to scattering or outgassing, and has high dispersibility, viscosity, and storage stability. Therefore, the energy consumption and time required for mixing can be reduced, and it is excellent in productivity. In addition, when this liquid masterbatch is used, the modified thermoplastic resin after solid-phase polymerization has a high viscosity and excellent moldability, and also has excellent impact strength of the molded article. This is considered to be because the solid-phase polymerization accelerator (B) can be finely dispersed in the thermoplastic resin (C) to be modified, and the solid-phase polymerization reaction proceeds efficiently. In addition, the molded article using the liquid masterbatch is not only excellent in appearance and mechanical strength, but also excellent in the uniformity of impact strength, and can suppress the variation between products. It can be quantitatively added using a liquid pump, and since the fluidity and dispersibility are high, the solid-phase polymerization accelerator (B) is uniformly diffused, so it is considered that the variation in impact strength between molded articles can be suppressed. In addition, it was confirmed that even when the thermoplastic resin (C) to be modified is a recycled resin or when it is added in the polymerization step of the thermoplastic resin (C) to be modified, the quality and uniformity of the molded article are excellent.

[0192] In addition, according to the comparison between the examples, when the viscosity of the liquid medium (A) of this liquid masterbatch is within a suitable range, the solid-phase polymerization accelerator (B) is a phosphorus-based catalyst, and the thickener (D) is an organic thickener, it is particularly excellent in dispersibility. In addition, by containing a suitable amount of the thickener (D), it is more excellent in viscosity and storage stability.

[0193] The thermoplastic resin composition for solid-phase polymerization using this liquid masterbatch has a suppressed decrease in viscosity (IV with respect to IV0 x or RV with respect to RV0 x ). In particular, when the content of the solid-phase polymerization accelerator (B) is 15 parts by mass or more with respect to 100 parts by mass of the liquid dispersion medium (A), the viscosity before solid-phase polymerization is even more excellent at ++ or higher. It is considered that the heat history in the manufacturing process of the masterbatch was reduced, and the decrease in viscosity was suppressed due to the small addition amount of the liquid dispersion medium (A) in the liquid masterbatch.

[0194] In the modified thermoplastic resin obtained by solid-phase polymerization, the increase in viscosity after solid-phase polymerization (IV x with respect to IV y or RV x with respect to RV y ) was good, and the outgas generation was also suppressed. When a phosphorus-based catalyst was used as the solid-phase polymerization accelerator (B), the increase in viscosity after solid-phase polymerization was better than that of titanium-based and antimony-based catalysts, and was ++ or higher.

[0195] Since the decrease in viscosity before solid-phase polymerization is more suppressed and the viscosity increases more after solid-phase polymerization, the moldability of the modified thermoplastic resin is improved, so it can be suitably applied to various applications such as fibers, films, sheets, foams, and containers. Also, the Charpy impact strength is high, and it is more excellent in terms of physical properties.

[0196] By using a liquid medium (A) with a high thermal decomposition temperature, outgas and silver streaks were reduced, and the appearance of the molded body was better. Also, when Examples 2-1 to 29 were compared, the Charpy impact strength was particularly good when the dispersibility of the liquid masterbatch was high by using a liquid polymer and glycol.

[0197] [Industrial Applicability] According to the present liquid masterbatch and the present thermoplastic resin composition, since they are excellent in molding processability and can provide high-quality molded articles by general-purpose processing methods, they are suitable for reuse applications of plastic products mainly composed of, for example, polybutylene terephthalate resin, polycarbonate resin, or polyamide resin, which are used or generated in the production process, such as containers, cards, films, sheets, and fibers. In addition, since the present molded article is excellent in quality, it can be suitably applied to a wide variety of uses as a high-functional resin material, such as fibers, films, sheets, foams, containers, electronic materials, building materials, automotive parts, and various industrial parts / products.

Claims

1. A liquid masterbatch for promoting solid-phase polymerization of a thermoplastic resin (C) to be modified, which is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, containing a liquid dispersion medium (A) and a solid-phase polymerization promoter (B), wherein the viscosity of the liquid dispersion medium (A) at 25 °C is 8,000 mPa·s or less, the solid-phase polymerization promoter (B) is at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, and containing 10 to 80 parts by mass of the solid-phase polymerization promoter (B) with respect to 100 parts by mass of the liquid dispersion medium (A), a liquid masterbatch for promoting solid-phase polymerization.

2. The liquid masterbatch for promoting solid-phase polymerization according to Claim 1, wherein the liquid dispersion medium (A) is at least one selected from an aliphatic polyester resin, a polyalkylene glycol resin, a polyether ester resin, and a glycol.

3. The liquid masterbatch for promoting solid-phase polymerization according to Claim 1, wherein the thermal decomposition temperature of the liquid dispersion medium (A) is 250 °C or higher.

4. The liquid masterbatch for promoting solid-phase polymerization according to Claim 1, wherein the solid-phase polymerization promoter (B) is an alkyl phosphonate ester.

5. The liquid masterbatch for promoting solid-phase polymerization according to Claim 1, wherein the solid-phase polymerization promoter (B) is a sterically hindered hydroxyphenylalkyl phosphonate ester.

6. The liquid masterbatch for promoting solid-phase polymerization according to Claim 1, further comprising a thickener (D), wherein the thickener (D) is at least one selected from the group consisting of a metal soap, a hydrogenated castor oil, a fatty acid amide, and a fatty acid glyceride.

7. A thermoplastic resin composition for solid-phase polymerization containing a liquid dispersion medium (A), a solid-phase polymerization promoter (B), and a thermoplastic resin (C) to be modified, wherein the viscosity of the liquid dispersion medium (A) at 25 °C is 8,000 mPa·s or less, the solid-phase polymerization promoter (B) is at least one selected from a phosphorus-based catalyst, a titanium-based catalyst, and an antimony-based catalyst, the thermoplastic resin (C) to be modified is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, containing 15 to 80 parts by mass of the solid-phase polymerization promoter (B) with respect to 100 parts by mass of the liquid dispersion medium (A), and containing 70% by mass or more of the thermoplastic resin (C) to be modified based on 100% by mass of the thermoplastic resin composition for solid-phase polymerization.

8. A step of obtaining the liquid masterbatch according to any one of claims 1 to 6; A melting step of melting a thermoplastic resin (C) to be modified, which is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin; A mixing step of mixing the melted thermoplastic resin (C) to be modified with the liquid masterbatch to obtain a thermoplastic resin composition for solid-phase polymerization; A method for producing a modified thermoplastic resin, comprising a step of subjecting the thermoplastic resin composition for solid-phase polymerization to solid-phase polymerization.

9. A method for producing a molded article, comprising a step of molding the modified thermoplastic resin obtained by the method according to claim 8.

10. A step of obtaining the liquid masterbatch according to any one of claims 1 to 6; A polymerization step of obtaining a thermoplastic resin (C) to be modified, which is at least one selected from the group consisting of a polyester resin, a polyamide resin, and a polycarbonate resin, by polymerization; A mixing step of adding and mixing the liquid masterbatch before or after the polymerization step, or simultaneously with the polymerization step; A method for producing a modified thermoplastic resin, comprising a step of subjecting the obtained thermoplastic resin composition for solid-phase polymerization to solid-phase polymerization after the polymerization step.

11. A method for producing a molded article, comprising a step of molding the modified thermoplastic resin obtained by the method according to claim 10.

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