WO2013047492A1

WO2013047492A1 - Coloring agent composition, aromatic polyester resin composition, molded article, and plasticizer for aromatic polyester resins

Info

Publication number: WO2013047492A1
Application number: PCT/JP2012/074506
Authority: WO
Inventors: 博文山口; 芳明安井
Original assignee: Dic株式会社
Priority date: 2011-09-28
Filing date: 2012-09-25
Publication date: 2013-04-04
Also published as: JPWO2013047492A1; KR20140081805A; CN103764758B; TWI555780B; CN103764758A; TW201323498A; MY185447A; KR101867128B1; JP5327413B1

Abstract

The purpose of the present invention is to provide a plasticizer for aromatic polyester resins, which has excellent heat resistance capable of withstanding melt-mixing with an aromatic polyester resin, improves unravelling (deflocculation) of a pigment in a composition that includes the pigment at a high concentration, and is capable of preventing the formation of coarse particles such as materials not deflocculated. Provided is a coloring agent composition that contains, as essential components, an aromatic polyester resin, a pigment, and an ester-based additive. This coloring agent composition is characterized in that the ester-based additive is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl group having 20-26 carbon atoms.

Description

Colorant composition, aromatic polyester resin composition, molded article, and plasticizer for aromatic polyester resin

The present invention relates to a colorant composition containing an aromatic polyester resin, a pigment and an ester-based additive, an aromatic polyester resin composition obtained using the colorant composition, a molded product thereof, and a plasticizer for the aromatic polyester resin. .

Aromatic polyester resins are excellent in mechanical properties, heat resistance, chemical resistance, etc., and are therefore used for molded products such as fibers, films and containers. In general, coloring of plastics such as aromatic polyester resin is performed for the purpose of imparting improved properties such as decorativeness to a molded product, and various types of colorants are used in the stages of injection molding and extrusion molding. The colorant is a color component obtained by adding a dispersion aid to a pigment or dye, or is obtained by simply adding a resin and mixing or melt-kneading. Various changes.

Conventionally, as the colorant, a colorant composition such as a commonly known dry color that is a powdery colorant, a commonly known liquid color that is a liquid colorant, or a commonly known masterbatch color that is a granular colorant has been used. Each of the colorant compositions is obtained by concentrating pigments and dyes required for a resin molded product to a concentration higher than that in the molded product, and kneaded with a carrier resin similar to the resin to be colored. Therefore, it is diluted in accordance with the pigment concentration ratio in the molding stage.

Generally, organic pigments, inorganic pigments and the like are used as pigments used for preparing the colorant composition. Since all of these pigments have a very high content in the colorant composition, the aggregated pigment particles do not unravel well even when melt-kneaded with the carrier resin. Forms coarse particles called. The coarse particles are mixed in the colored resin composition for molding obtained by mixing the colorant composition containing such coarse particles and the aromatic polyester resin. This coarse particle causes poor appearance of the resulting molded product. As described above, since the colorant composition containing coarse particles impairs the commercial value of a molded product and causes a decrease in yield, it is usually attempted to remove coarse particles using a filter provided in a melt kneader. When the particle size of the coarse particles is large or the number is large, the filter is likely to be clogged, resulting in deterioration of the productivity of the molded product.

In order to improve the looseness of the pigment, a method of mixing a mineral wax such as montanic ester wax together with the pigment is generally used. However, natural resources such as montanic acid ester wax have been depleted in recent years due to over-exploitation, and development of alternative materials such as petroleum wax and synthetic wax has been demanded. Thus, a method is known in which an aliphatic surfactant such as a fatty acid, a fatty acid metal salt, a fatty acid ester, or a fatty acid amide is mixed with a pigment (for example, Patent Document 1). However, aliphatic surfactants have a certain effect in preventing the formation of coarse particles. However, since the compounds themselves have the disadvantage of being easily decomposed by the thermal history during extrusion kneading, plastics of aromatic polyesters having a high melting point are used. It was insufficient for use as an agent.

As a colorant composition used for coloring an aromatic polyester resin, for example, a terminal of a reaction product of a dihydric alcohol having 2 to 25 carbon atoms and an aromatic acid having 8 to 18 carbon atoms is terminated with a monovalent compound having 4 to 18 carbon atoms. A colorant composition containing an aromatic polyester resin obtained by sealing with alcohol and a pigment is disclosed (for example, Patent Document 2). However, even the aromatic polyester resin used in obtaining the colorant composition disclosed in Patent Document 2 does not have sufficient looseness (peptization) of the pigment. Therefore, coarse particles are mixed in the colorant composition. As a result, the filter provided in the melt kneader is clogged, and the productivity of the molded product is deteriorated.

Japanese Patent Laid-Open No. 11-148020 JP-A-9-310008

The problem to be solved by the present invention is to have excellent heat resistance that can withstand melt kneading with an aromatic polyester resin, and to improve the looseness (peptization) of the pigment in a composition containing a high concentration of pigment. An object of the present invention is to provide a plasticizer for an aromatic polyester resin which can be improved and can prevent the formation of coarse particles such as unpeptized material. Another object of the present invention is to provide a colorant composition using the plasticizer, an aromatic polyester resin composition obtained by diluting the colorant composition with an aromatic polyester resin, and a molded product thereof.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the aromatic polycarboxylic acid alkyl ester has an alkyl chain of the alkyl ester as compared to the alkyl group of the monoalcohol used in Patent Document 2. By adding a compound (ester-based additive) having a long-chain alkyl group together with the aromatic polyester resin and the pigment, the looseness (peptization) of the pigment in the aromatic polyester resin is improved, and the aromatic polyester The formation of coarse particles such as unpeptized material in the resin can be prevented, and the ester-based additive is excellent in heat resistance and hardly decomposes even when added to an aromatic polyester having a high melting point. The present inventors have found out that the formation of coarse particles such as unpeptized material can be satisfactorily prevented, thereby completing the present invention.

That is, the present invention is a colorant composition containing, as essential components, an aromatic polyester resin, a pigment, and an ester additive, and the ester additive is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl ester The present invention provides a colorant composition, wherein the alkyl chain is a linear alkyl group having 20 to 26 carbon atoms.

The present invention also provides an aromatic polyester resin composition obtained by melt-kneading the colorant composition and the aromatic polyester resin for dilution.

Also, the present invention provides a molded product characterized by molding the aromatic polyester resin composition.

Further, the present invention provides a plasticizer for an aromatic polyester resin, which is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl chain having 20 to 26 carbon atoms. It is to provide.

According to the present invention, the composition has excellent heat resistance that can withstand melt kneading with an aromatic polyester resin, and improves the looseness (peptization) of the pigment in a composition containing a high concentration of pigment. A plasticizer for an aromatic polyester resin capable of preventing the formation of coarse particles such as a product can be provided. Moreover, the coloring agent composition using the said plasticizer, the aromatic polyester resin composition obtained by diluting this coloring agent composition with an aromatic polyester resin, and its molded article can also be provided.

14 is an optical microscope observation photograph inside the molded product obtained in Example 13. FIG. 6 is an optical microscope observation photograph inside the molded product obtained in Comparative Example 11.

The colorant composition of the present invention is a colorant composition containing an aromatic polyester resin, a pigment, and an ester-based additive as essential components, wherein the ester-based additive is an alkyl ester of an aromatic polycarboxylic acid. The alkyl chain of the alkyl ester is a linear alkyl group having 20 to 26 carbon atoms.

Examples of the aromatic polyester resin used in the colorant composition of the present invention include polyethylene terephthalate resin, polyethylene terephthalate-isophthalate copolymer resin, polyethylene-1,4-cyclohexanedimethylene-terephthalate copolymer resin, polyethylene-2, 6-naphthalene dicarboxylate resin, polyethylene-2,6-naphthalene dicarboxylate-terephthalate copolymer resin, polyethylene-terephthalate-4,4′-biphenyl dicarboxylate resin, poly-1,3-propylene-terephthalate resin, Examples include polybutylene terephthalate resin, polybutylene-2,6-naphthalenedicarboxylate resin, polyethylene naphthalate resin, and polybutylene naphthalate resin. Of these, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin and polybutylene naphthalate resin are preferred. The aromatic polyester can be used alone or in combination of two or more.

The aromatic polyester resin used in the present invention is preferably an aromatic polyester resin having an intrinsic viscosity (IV) of 0.5 to 1.5, more preferably 0.6 to 1.3, and preferably 0.63 to 1.2. Further preferred. In the present invention, the intrinsic viscosity (IV) is a value determined by a method based on JIS K 7367-5.

The pigment used in the present invention is not particularly limited as long as it is used as a pigment. For example, heretofore known pigments can be mentioned. Specific examples include azo, phthalocyanine, quinacridone, dioxazine, perylene, and isoindolinone organic pigments; carbon black; titanium oxide, oxidation Examples thereof include inorganic pigments such as iron-based, chromium oxide-based, and yellow lead-based pigments. Of these, carbon black is preferred. These pigments can be used alone or in combination of two or more.

The content of the pigment in the colorant composition is preferably in the range of 0.1 to 235 parts by weight, more preferably in the range of 0.1 to 150 parts by weight, with respect to 100 parts by weight of the aromatic polyester. A range of parts is more preferred. If it is in the said range, it is excellent in heat resistance and can express the better kneading | mixing effect with respect to affinity with carrier resin.

The ester-based additive used in the present invention is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl chain having 20 to 26 carbon atoms. Here, an ester-based additive in which an alkyl chain having 20 to 24 carbon atoms is excellent in heat resistance and exhibits a better kneading effect with respect to affinity to an aromatic polyester resin as a carrier resin. Therefore, an alkyl chain having 20 to 23 carbon atoms is more preferable.

The ester-based additive (ester compound) used in the present invention includes, for example, an aromatic polycarboxylic acid or an acid anhydride (A) thereof and a monoalcohol (B) having a linear alkyl chain having 20 to 26 carbon atoms. ) And an esterification reaction. In the present invention, the valence of the aromatic polyvalent carboxylic acid refers to the number of carboxyl groups in one molecule, and the acid anhydride refers to the number of carboxyl groups before dehydration condensation.

The aromatic polyvalent carboxylic acid is not particularly limited as long as it is an aromatic compound having two or more carboxyl groups. For example, phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophane Examples include acids, planitic acid, pyromellitic acid, and merit acid. Examples of the aromatic polyvalent carboxylic acid anhydride include acid anhydrides of the aromatic polycarboxylic acid. Among these, an aromatic compound having three or more carboxyl groups is preferable from the viewpoint that a better kneading effect can be expressed with respect to the affinity to the aromatic polyester resin as the carrier resin. Of these, trimellitic acid, pyromellitic acid and acid anhydrides thereof are preferable. The aromatic polyvalent carboxylic acid or its acid anhydride (A) can be used alone or in combination of two or more.

The monoalcohol (B) used in the present invention is a monoalcohol having a linear alkyl chain having 20 to 26 carbon atoms. Examples of such alcohol include eicosanol (C20), heneicosanol (C21), docosanol (C22), tricosanol (C23), tetracosanol (C24), pentacosanol (C25), hexacosanol ( C26) and the like. Among them, a straight chain having 20 to 24 carbon atoms from the viewpoint of excellent heat resistance and exhibiting a better kneading effect with respect to affinity for the carrier resin. A monoalcohol having an alkyl chain is preferable, and a monoalcohol having an alkyl chain having 20 to 23 carbon atoms is more preferable. Specifically, eicosanol (C20), heneicosanol (C21), docosanol (C22), tricosanol (C23), and tetracosanol (C24) are preferable.

In the present invention, a monoalcohol other than the monoalcohol (B) may be used in combination with the monoalcohol (B) as long as the effects of the present invention are not impaired. Examples of monoalcohols other than monoalcohol (B) include octanol (C8), decanol (C10), dodecanol (C12), tetradecanol (C14), hexadecanol (C16), octadecanol (C18), Heptacosanol (C27), Octacosanol (C28), Nonacosanol (C29), Triancontanol (C30), Hentrianantanol (C31), Dotriacontanol (C32), Cellomerisyl alcohol (C33), Tetratriacontanol (C34), heptatriacontanol (C35), hexatriacontanol (C36) and the like.

The substitution position of the hydroxyl group in the monoalcohol (B) or monoalcohol other than the monoalcohol (B) used in the present invention may be either the 1-position or the 2-position, but the 1-position is preferred.

As a method for producing an ester-based additive (ester compound) used in the present invention, a method in which the aromatic polycarboxylic acid (A) and the monoalcohol (B) are charged into a reactor and subjected to a normal esterification reaction. Etc. Moreover, it is preferable to use an esterification catalyst for the purpose of promoting this esterification reaction.

A metal or an organometallic compound can be used as the esterification catalyst. Specific examples include at least one metal or organometallic compound selected from the group consisting of Group 2, Group 4, Group 12, Group 13, Group 14 of the Periodic Table. More specifically, for example, metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, tin octoate, 2-ethyl Examples thereof include metal compounds such as hexanetin, acetylacetonate zinc, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride, hafnium tetrachloride complex, germanium oxide, and tetraethoxygermanium. Of these, titanium alcohols such as titanium tetraisopropoxide, titanium tetrabutoxide, and titanium oxyacetylacetonate have good reactivity, ease of handling, and storage stability of the ester compound obtained by the esterification reaction. Coxide is preferred.

Further, the amount of the esterification catalyst used may be an amount that can control the esterification reaction and suppress the coloring of the resulting ester compound, and the total amount of the polyhydric alcohol and the monodicarboxylic acid. On the other hand, the range of 10 to 2,000 ppm is preferable, and the range of 20 to 1,000 ppm is more preferable.

When the ester additive is produced, the esterification catalyst is added at the same time when the aromatic polycarboxylic acid (A) and the aliphatic linear monoalcohol (B) are charged into a reactor. You may add, you may add in the middle of temperature rising, and may divide | segment and add an esterification catalyst.

In the esterification reaction, the charge ratio between the polyvalent carboxylic acid (A) and the aliphatic linear monoalcohol (B) is a polyvalent carboxylic acid with respect to the alcoholic hydroxyl group of the aliphatic linear monoalcohol (B). The acid (A) is not particularly limited, but, for example, the carboxyl group of the polyvalent carboxylic acid (A) is 0.10 equivalent to 1.00 equivalent of the alcoholic hydroxyl group of the aliphatic linear monoalcohol (B). It is preferable to adjust so as to be in the range of 80 to 1.20 equivalents, more preferably in the range of 0.90 to 1.10 equivalents.

The reaction temperature in producing the ester-based additive is 60 to 300 because the reaction can be promoted while suppressing the evaporation and sublimation of each raw material, and the thermal decomposition and coloring of the ester compound produced by the reaction can be suppressed. The range of ° C is preferred, and the range of 100 to 250 ° C is more preferred.

The ester-based additive obtained by the above production method is stable and resistant to hydrolysis even under high temperature and high humidity, and is less likely to cause bleeding because of its good compatibility with the aromatic polyester resin. In addition, by adjusting the acid value and adjusting the affinity according to the surface treatment state of the pigment, it is possible to improve the looseness of the target colorant. And having an acid value of 15 or less, preferably having a hydroxyl value of 20 or less, and more preferably having an acid value of 10 or less, particularly preferably having a hydroxyl value of 15 or less, And having an acid value of 5 or less.

The number average molecular weight of the ester additive used in the present invention is preferably 800 to 3,000, more preferably 1,000 to 2,500. The weight average molecular weight is preferably 900 to 2,700, more preferably 1,100 to 2,500.

In the present invention, the weight average molecular weight and the number average molecular weight were measured according to the following conditions.
[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK- GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids was filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

The form of the ester-based additive thus obtained is not particularly limited, and examples thereof include powder, granule, pellet, plate, and flake. The production method thereof is not particularly limited, but the molten ester compound is taken out to a stainless steel vat or a belt conveyor with a cooling device, and then a powder, plate, flakes, etc. are crushed by a pulverizer or the like, and the solidified and pulverized product is compressed or heated. The method of granulating by the method etc., the method of taking out directly from a molten state to particle | grains and a pellet form, the method of knead | mixing with a base polyester resin in a fixed ratio, and taking out by masterbatch etc. are mentioned.

The content of the ester-based additive thus obtained in the colorant composition is in the range of 0.5 to 120 parts by mass, more preferably 0.8 to 100 parts by mass with respect to 100 parts of the aromatic polyester. Range. Within the above range, it is excellent in heat resistance and can exhibit a good kneading effect due to its affinity for the carrier resin, and as a result, formation of coarse particles such as unpeptized material can be prevented. .

Although it is not clear at the present time about the mechanism of action that the ester-based additive exhibits excellent pigment loosening (peptization), it has an aromatic skeleton, making it more heat resistant than those of conventional aliphatic skeletons. Excellent, hardly decomposed even at high temperatures during melt kneading, can continue to exhibit the original plasticizing effect and surface active effect, and as a result, it can reduce the melt viscosity even in colorant compositions containing pigments at high concentrations It is thought that was made. Moreover, it is considered that the structure has a high affinity with the aromatic polyester resin as the carrier resin, and the ester additive effectively acts on the carrier resin and the pigment to enhance the kneading effect. As a result, the looseness of the pigment in the colorant composition is improved and the formation of coarse particles such as unpeptized material is reduced, leading to a reduction in the filtration pressure of the filter installed in the melt kneader. It is thought that. Thus, the ester additive can be suitably used as a plasticizer for an aromatic polyester resin and as a pigment dispersant.

The colorant composition of the present invention is obtained by mixing the above aromatic polyester resin, pigment and ester-based additive, but the order of mixing is not particularly limited. For example, (Method 1) the aromatic polyester resin, the pigment and the ester-based additive may be kneaded simultaneously, or (Method 2) the kneaded product of the pigment and the ester-based additive is obtained in advance, and then the aromatic polyester resin and It can also be kneaded. More specifically, for example, in the case of Method 1, the aromatic polyester resin, the pigment and the ester-based additive are mixed in advance so that the materials are well mixed, and then at a temperature in the range of 220 to 300 ° C., Melting and kneading may be performed using a single screw or twin screw extruder, and in the case of method 2, the pigment and the ester-based additive are mixed at a temperature in the range of 80 to 150 ° C. The kneaded material obtained may be melt-kneaded using an axial extruder, and then the obtained kneaded material may be melt-kneaded with an aromatic polyester resin using an extruder or the like.

The colorant composition thus obtained is used as a masterbatch color, and the form thereof is not particularly limited, and examples thereof include pellets, plates, and flakes.

The colorant composition of the present invention may contain other optional components in addition to the above components, for example, additives such as a lubricant, an antistatic agent, an ultraviolet absorber, and an antioxidant as necessary. Good.

The colorant composition of the present invention thus obtained is mixed with an aromatic polyester resin for dilution (referred to as an aromatic polyester resin for dilution in the present invention) to obtain an aromatic polyester resin composition that is colored. Then, it can be molded into a colored resin molded product. More specifically, the range of 100 to 1,000,000 parts by weight of the aromatic polyester resin for dilution, preferably 200 to 100,000 parts by weight of the aromatic polyester resin for dilution is 100 parts by weight of the colorant composition of the present invention. After an aromatic polyester resin composition is obtained by melting and kneading at a temperature higher than the melting point, for example, in the range of 220 to 300 ° C., an injection molding or T Molded products of various shapes can be obtained by performing die film molding or the like. Examples of the aromatic polyester resin for dilution include the same carrier resins used in the colorant composition, and it is preferable to use a combination of the same types of carrier resins. In addition to the molding method as described above, the colorant composition and the aromatic polyester resin for dilution are mixed in advance by a mixer, blender, etc., and then injected into an injection molding machine and melt-kneaded and directly molded. can give.

As content of the ester-type additive in the aromatic polyester resin composition obtained at this time, for example, with respect to a total of 100 parts by mass of the aromatic polyester resin and the aromatic polyester resin for dilution in the colorant composition The amount is preferably 0.00001 parts by weight to 0.14 parts by weight, and more preferably 0.00008 parts by weight to 0.10 parts by weight.

Hereinafter, examples of the present invention will be given, and the present invention will be described in detail while comparing with comparative examples. In the examples, “part” and “%” are based on mass unless otherwise specified.

Example 1 (Preparation of plasticizer for aromatic polyester resin)
In a 3 L four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube and fractional distillation tube, 176.8 g of phthalic anhydride, 847.6 g of docosanol (containing 98% docosanol), 51 g of toluene and titanium After charging 0.31 g of tetraisopropoxide (hereinafter abbreviated as “TiPT”), the temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Warm up. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.25 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, the pressure was reduced to 0.67 kPa or less at 230 ° C., and toluene and unreacted alcohol were removed. Removed. After the outflow of toluene and unreacted alcohol ceased, the reduced pressure was released, the temperature was lowered, and the reaction product was filtered out through diatomaceous earth to obtain a plasticizer (1) for aromatic polyester resin. The plasticizer (1) had a number average molecular weight (Mn) of 1090, a weight average molecular weight (Mw) of 1160, an acid value of 2.2, a hydroxyl value of 3.3 and a white solid.

Example 2 (same as above)
In a 3 L four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and fractional distillation tube, trimellitic anhydride 220.8 g, docosanol (containing 98% docosanol) 534.2 g, octadecanol (Product containing 98% octadecanol) After charging 442.5 g, toluene 60 g and TiPT 0.36 g, nitrogen gas was blown in a range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. The temperature was raised to 230 ° C. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.29 g of 85% phosphoric acid aqueous solution was charged, and pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After toluene did not flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a stainless steel vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (2) for aromatic polyester resin. The appearance of the plasticizer (2) was a white solid, the number average molecular weight (Mn) was 1850, the weight average molecular weight (Mw) was 1930, the acid value was 3.3, and the hydroxyl value was 4.5.

Example 3 (same as above)
In a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a trough tube, 192.0 g of trimellitic anhydride, 929.1 g of docosanol (containing 98% docosanol), 56 g of toluene, After charging 0.33 g of TiPT, the temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.27 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After toluene did not flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a stainless steel vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (3) for aromatic polyester resin. The appearance of the plasticizer (3) was a white solid, the number average molecular weight (Mn) was 1670, the weight average molecular weight (Mw) was 1750, the acid value was 2.0, and the hydroxyl value was 7.3.

Example 4 (same as above)
In a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a trough tube, 190.5 g of pyromellitic acid, 929.1 g of docosanol (containing 98% docosanol), 56 g of toluene, After charging 0.34 g of TiPT, the temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.27 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After the toluene flow out, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a stainless steel vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (4) for aromatic polyester resin. The appearance of the plasticizer (4) was a white solid, the number average molecular weight (Mn) was 2260, the weight average molecular weight (Mw) was 2390, the acid value was 4.1, and the hydroxyl value was 8.1.

Comparative Example 1 (Preparation of plasticizer for aromatic polyester resin for comparison)
In a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a trough for fractionation, pyromellitic acid 218.4 g, octadecanol (containing 98% octadecanol) 882.4 g, After charging 55 g of toluene and 0.33 g of TiPT, the temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.26 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After the toluene outflow ceased, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a stainless steel vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (1 ′) for comparison control aromatic polyester resin . The appearance of the plasticizer (1 ′) was a white solid, the number average molecular weight (Mn) was 1900, the weight average molecular weight (Mw) was 1970, the acid value was 5.5, and the hydroxyl value was 4.1.

Comparative Example 2 (same as above)
After charging 108.8 g of pentaerythritol, 908.8 g of stearic acid, 51 g of toluene and 0.31 g of TiPT into a 3 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a trough tube for fractional distillation. The temperature was raised to 230 ° C. while blowing nitrogen gas in the range of 100 to 500 ml / min so as to maintain the tower top temperature at 100 ° C. or lower. Next, a dehydration esterification reaction was performed while removing water generated at 230 ° C. When the acid value of the reaction product became 2 or less, 0.24 g of 85% phosphoric acid aqueous solution was charged, pressure reduction was started, and the pressure was reduced to 0.67 kPa or less at 230 ° C. to remove toluene. After the outflow of toluene disappeared, the reduced pressure was released, the temperature was lowered, and the solution was taken out into a stainless steel vat while maintaining the liquid temperature at 100 ° C. to obtain a plasticizer (2 ′) for comparison control aromatic polyester resin. . The appearance of the plasticizer (2 ′) was a white solid, the number average molecular weight (Mn) was 1620, the weight average molecular weight (Mw) was 1680, the acid value was 1.9, and the hydroxyl value was 15.0.

Example 5 (Preparation of colorant composition)
58 parts of polybutylene terephthalate (inherent viscosity (IV) according to JIS K 7367-5 is 0.69), 40 parts of carbon black (circle equivalent diameter by electron microscope observation, average particle diameter 15 to 25 nm), and aromatic polyester resin The colorant composition (1) of the present invention was obtained by charging the plasticizer (1) for use into a twin-screw extruder and melt-kneading them. A twin screw extruder having a screw diameter of 25 mm and an L / D value of 45 was used, and the jacket temperature was set to 260 to 270 ° C. In the preparation of the colorant composition (1), the torque value when kneaded under the condition that the rotational speed of the screw is 200 rpm is measured, and the value (average torque value) when the torque value is stabilized is evaluated according to the following criteria. did. The lower the value, the lower the melt viscosity of the melt-kneaded product, which means that the kneadability is excellent and the productivity is also excellent. The evaluation results are shown in Table 1.

<Evaluation criteria for average torque value>
A: Average torque value is less than 29.0 N · m ○: Average torque value is more than 29.0 N · m and less than 30.0 N · m Δ: Average torque value is more than 30.0 N · m and less than 31.0 N · m ×: Average torque value is 31.0 N · m or more

Examples 6 to 9 and Comparative Examples 3 to 5
Colorant compositions (2) to (4) and comparative colorant compositions (1 ′) to (5) were used in the same manner as in Example 5 except that the plasticizers shown in Tables 1 and 2 were used. ') Was obtained. The average torque value was measured and evaluated in the same manner as in Example 5. The evaluation results are shown in Tables 1 and 2.

Footnotes in Table 2 Montan wax: Montanate ester wax “Licolub WE4” manufactured by Clariant Co., Ltd.
PE wax: Modified polyethylene wax “TEGOMER E 525” manufactured by EVONIK INDUSTRIES

Example 9 (Preparation of aromatic polyester resin composition)
The colorant composition (1) obtained in Example 5 and the aromatic polyester resin for dilution were melt-kneaded by a single screw extruder to prepare a colored aromatic polyester resin composition (1). When preparing this composition, the peptization (disintegration) of the colorant composition was evaluated according to the following method. In addition, as the aromatic polyester resin for dilution, polybutylene terephthalate used when obtaining the colorant composition (1) was used.

<Evaluation method of peptizability>
Mass ratio of the colorant composition (1) and the aromatic polyester resin for dilution to a testing machine in which a filtration tester is attached to the outlet side of a single screw extruder having a screw diameter of 30 mm and an L / D value of 30 16.7 / 83.3, and the mixture of the colorant composition (1) and the aromatic polyester resin for dilution is extruded from the filtration tester, and the aromatic polyester resin composition (1). Got. Here, the temperature of the jacket of the single screw extruder was set to 280 ° C. The configuration of the filter attached to the filtration pressure tester was # 80 μm × baked 40 μm × # 80 μm, and the screw rotation speed was 80 rpm.

When extruding the aromatic polyester resin composition from the filtration pressure tester, the pressure when the aromatic polyester resin composition (1) flows into the filter inlet side (resin pressure) and the pressure when the aromatic polyester resin composition is discharged from the filter outlet side Was measured, and the difference (filtration pressure, MPa) was determined. This was used as a filtration pressure test value, and evaluated according to the following criteria. It means that the lower the filtration pressure test value, the smaller the formation of coarse particles such as unpeptized material and the better the looseness. The evaluation results are shown in Table 3.

◎: Less than 2 MPa ○: 2 MPa or more, less than 4 MPa Δ: 4 MPa or more, less than 6 MPa ×: 6 MPa or more

Examples 10 to 12 and Comparative Examples 7 to 9
Aromatic polyester resin compositions (2) to (4) and an aromatic polyester resin composition for comparison (in the same manner as in Example 9 except that the colorant compositions shown in Tables 3 and 4 were used) 1 ′) to (4 ′) were obtained. In the same manner as in Example 9, the looseness and aggregates were evaluated. The evaluation results are shown in Tables 3 and 4.

Example 13 (Preparation of aromatic polyester resin composition)
The colorant composition (1) obtained in Example 5 and the aromatic polyester resin for dilution were melt-kneaded by a single-screw extruder according to the following method, and a pellet-shaped molded product of a colored aromatic polyester resin composition ( 1) was prepared. The aggregates in this molded product were evaluated by the following method. The evaluation results are shown in Table 5. In addition, as the aromatic polyester resin for dilution, polybutylene terephthalate used when obtaining the colorant composition (1) was used.

<Preparation method of pellet-shaped molding>
The colorant composition (1) and the aromatic polyester resin for dilution were mixed so that the concentration of carbon black was 2.5% to obtain a mixture. This mixture was melt-kneaded using a single screw extruder having a screw diameter of 30 mm and an L / D value of 30 to prepare a pellet-shaped molded product (1). Here, the temperature of the jacket of the single screw extruder was set to 280 ° C.

<Evaluation method of aggregates present in molded product>
A 0.5 mg tiny piece was cut from the pellet-shaped molding, arranged on a slide glass, and sandwiched between different slide glasses. Next, it was pressed with a 250 ° C. hot press so that the glass was not broken, and formed into a button shape having a thickness of about 0.01 mm and a diameter of 8 mm to obtain a specimen. Ten test pieces were prepared, and the surface of the test piece was observed with a 100 × optical micrograph. The presence of coarse particles on the surface of the specimen was observed. The total number of 10 test pieces was determined by counting the number of coarse particles having an equivalent circle diameter of 31 to 40 μm, the number of coarse particles of 41 to 60 μm, and the number of coarse particles of 61 μm or more. The evaluation results are shown in Table 5. Moreover, the microscope picture of the test piece obtained from the molded article obtained in Example 13 and the comparative example 11 mentioned later is shown to FIG.

Examples 13 to 16 and Comparative Examples 10 to 12
Except using the colorant composition shown in Table 5 and Table 6, in the same manner as in Example 13, pellets (1) to (4) and comparative pellets (1 ') to (4 ′) was obtained. Aggregates were evaluated in the same manner as in Example 13. The evaluation results are shown in Tables 5 and 6.

Footnotes in Table 6-: Not evaluated

1 ... Unpeptized material

Claims

A colorant composition comprising an aromatic polyester resin, a pigment and an ester additive as essential components, wherein the ester additive is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a carbon atom A colorant composition characterized by being a linear alkyl group of several 20 to 26.
The ester additive is obtained by esterifying an aromatic polyvalent carboxylic acid or acid anhydride (A) thereof and a monoalcohol (B) having a linear alkyl chain having 20 to 24 carbon atoms. The colorant composition according to claim 1, which has been obtained.
The colorant composition according to claim 1, wherein the monoalcohol (B) is at least one monoalcohol selected from the group consisting of eicosanol, heneicosanol, docosanol, tricosanol and carnerville alcohol.
The colorant composition according to any one of claims 1 to 3, wherein the aromatic polyvalent carboxylic acid or acid anhydride (A) thereof is trivalent or higher.
The aromatic polycarboxylic acid or acid anhydride (A) thereof is one or more selected from the group consisting of trimellitic acid, pyromellitic acid and acid anhydrides thereof. A colorant composition according to claim 1.
The aromatic polyester resin is at least one aromatic polyester resin selected from the group consisting of polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin and polybutylene naphthalate resin. The colorant composition according to any one of 1 to 5.
The colorant composition according to any one of claims 1 to 6, wherein the pigment is carbon black.
The pigment is in the range of 0.1 to 150 parts by mass and the ester-based additive is included in an amount of 0.8 to 100 parts by mass with respect to 100 parts by mass of the aromatic polyester resin. The described colorant composition.
An aromatic polyester resin composition obtained by melt-kneading the colorant composition according to any one of claims 1 to 8 and an aromatic polyester resin for dilution.
A molded product obtained by molding the aromatic polyester resin composition according to claim 9.
A plasticizer for an aromatic polyester resin, which is an alkyl ester of an aromatic polycarboxylic acid, and the alkyl chain of the alkyl ester is a linear alkyl chain having 20 to 26 carbon atoms.