A colorant, a masterbatch containing the same, a colored resin composition, and a molded article

Abstract

Provided is a colorant which, due to its high heat resistance, does not discolor or fade even when exposed to high temperature conditions for a long time and over a long period, and due to its anti-bleeding property and sublimation resistance, does not contaminate the molding die and molding machine or cause color transfer to other resin parts. Further, it does not deteriorate the physical properties of the added thermoplastic resin. The colorant contains at least one compound represented by the following Chemical Formula 1a, at least one compound represented by the following Chemical Formula 1b, and / or at least one compound represented by the following Chemical Formula 1c. In Chemical Formulas 1a, 1b, and 1c, R 1 , R 2 , R 4 , R 5 , R 7 , and R 8 are a hydrogen atom, an amino group which may have a substituent, or a nitrogen-containing heterocyclic group, and R 3 , R 6 , and R 9 are at least one selected from an alkoxy group, a carboxyl group, a hydroxyl group, a sulfo group, and a sulfonamide group, p and r are 0 to 2, and q is 0 to 4.

Description

Technical Field

[0001] The present invention relates to a colorant containing a compound having a specific structure, a masterbatch containing the colorant, a colored resin composition, and a molded article. Background Art

[0002] The batteries mounted on hybrid vehicles (HV) and electric vehicles (EV) driven by an electric motor generate a voltage of 60 V or more, which is much higher than that of the batteries used in conventional vehicles driven only by an engine. The color of high-voltage wiring harnesses such as cables and connectors connected to such high-voltage batteries is intended to provide a clear visual indication that high-voltage current is flowing, and the outer casing of its connectors and the covering material of the wires are orange according to standards. For example, in the United States, it is specified in the American Automobile Standard SAE J1673. The shade and brightness of orange vary according to the regulations of each country, such as slightly darker orange, bright orange, or even fluorescent orange.

[0003] High-voltage wiring harnesses are exposed to heat generated by components such as batteries, electric motors, inverters, and engines that have an elevated operating temperature for a long time. Therefore, when forming high-voltage wiring harnesses, a highly heat-resistant thermoplastic resin such as polyamide resin is used. This highly heat-resistant thermoplastic resin is molded at a high temperature of 250 to 350°C. Therefore, the colorant that imparts orange to the thermoplastic resin is required to have high heat resistance, be able to withstand the high heat emitted by the battery, etc. at the high temperature during the molding of the thermoplastic resin, and not change color or fade during the long-term process of about 10 years of the battery life; sublimation resistance, not contaminating the molds and molding machines used for molding the thermoplastic resin; and high bleeding resistance, not causing color transfer when contacting other thermoplastic resin products.

[0004] Known orange dyes are prepared by mixing piperidone dyes or naphthalimide dyes and dyes or pigments of other colors. Patent Document 1 describes piperidone dyes for coloring thermoplastic resins orange. In addition, naphthalimide dyes are commercially available, for example, in the form of C.I. Solvent Yellow 44, 104, 116, and C.I. Disperse Yellow 11. Among these naphthalimide dyes, an amino group is included as a chromophore, and a bright color with a brightness L* value of 70 or more in the CIE-Lab color space coordinates is exhibited, so that a bright orange can be obtained. A masterbatch prepared by kneading the orange dye and a thermoplastic resin raw material, a colored resin composition prepared by mixing the same type or different types of thermoplastic resin raw materials and various additives contained therein, and a molded article for a connector of a high-voltage wiring harness are manufactured by molding.

[0005] Since the above dyes have a relatively simple structure and low molecular weight, it is easy to perform color adjustment for the purpose of obtaining orange. On the other hand, the orange obtained by these dyes does not have the heat resistance, bleeding resistance, and sublimation resistance suitable for connectors of automotive high-voltage wiring harnesses.

[0006] On the other hand, Patent Document 2 describes a method for manufacturing a high heat-resistant orange inorganic pigment for polyamide resin by pulverizing a fired product obtained by mixing powders of titanium dioxide, zinc peroxide, and tin oxide and firing them at 850°C. The pigment has excellent bleeding resistance and sublimation resistance, but lacks brightness and may turn brown or dark due to the heat history. In addition, unlike dyes, the pigment is dispersed in the thermoplastic resin rather than dissolved in it, so it may reduce physical properties such as its tensile strength or impact strength.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Publication No. 54-19012

[0010] Patent Document 2: Korean Patent No. 10-1977321 Summary of the Invention

[0011] Technical Problem to be Solved

[0012] The present invention is proposed to solve the above technical problems, and the purpose is to provide a colorant, a masterbatch containing the colorant, a colored resin composition, and a molded product obtained from the colored resin composition. By having high heat resistance, even when exposed to high temperature conditions for a long time and for a long period, no discoloration or fading occurs. Due to the bleeding resistance and sublimation resistance, no contamination of the molding die and molding machine or color transfer to other resin parts occurs. Further, the physical properties of the added thermoplastic resin are not damaged.

[0013] Technical Solution for Solving the Problem

[0014] The colorant for achieving the above purpose contains at least one compound represented by the following Chemical Formula 1a, at least one compound represented by the following Chemical Formula 1b, and / or at least one compound represented by the following Chemical Formula 1c.

[0015]

Chemical Formula 1

[0016]

[0017] (In Chemical Formula 1a, R 1 and R 2Each independently is a hydrogen atom, an amino group which may have a substituent, or a nitrogen-containing heterocyclic group, and the two are not simultaneously hydrogen atoms or are not connected to each other to form a fused ring, R 3 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a hydroxyl group, a sulfo group, and a sulfonamide group, and p is a number from 0 to 2.)

[0018]

Chemical Formula 2

[0019]

[0020] (In Chemical Formula 1b, R 4 and R 5 each independently is a hydrogen atom, an amino group which may have a substituent, or a nitrogen-containing heterocyclic group, and the two are not simultaneously hydrogen atoms, R 6 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a hydroxyl group, a sulfo group, and a sulfonamide group, and q is a number from 0 to 4.)

[0021]

Chemical Formula 3

[0022]

[0023] (In Chemical Formula 1c, R 7 and R 8 each independently is a hydrogen atom, an amino group which may have a substituent, or a nitrogen-containing heterocyclic group, R 9 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a hydroxyl group, a sulfo group, and a sulfonamide group, and r is a number from 0 to 2.).

[0024] In the colorant, the compound represented by Chemical Formula 1a may include the compound in which R 1 or R 2 is the nitrogen-containing heterocyclic group and the compound in which R 1 and R 2 are the fused ring formed by their connection to each other.

[0025] In the colorant, for example, the nitrogen-containing heterocyclic group may include at least one selected from a morpholino group, a piperidyl group, a pyrrolidinyl group, and a piperazinyl group.

[0026] In the colorant, the amino group and / or the nitrogen-containing heterocyclic group has at least one of the substituents selected from a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a carboxyl group.

[0027] In the colorant, for example, the Chemical Formula 1a in which R 1 and R 2 are the fused ring may include the compound represented by the following Chemical Formula 1a2,

[0028]

Chemical Formula 4

[0029]

[0030] (In Chemical Formula 1a2, R 3 and p are the same as those in Chemical Formula 1a, R 10 is a hydrogen atom, a carboxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms, and X is a nitrogen atom, an oxygen atom, or a sulfur atom.)

[0031] The masterbatch of the present invention contains the colorant and the thermoplastic resin described in any one of the above items.

[0032] In the masterbatch, the content of the colorant may be 5 to 30% by mass.

[0033] The colored resin composition of the present invention contains the colorant described in any one of the above items and / or the masterbatch described in any one of the above items and the thermoplastic resin.

[0034] In the colored resin composition, the thermoplastic resin may contain at least one selected from polyamide resins, polyolefin resins, polyester resins, polycarbonate resins, and polyphenylene sulfide resins.

[0035] The molded article of the present invention is molded from any one of the above colored resin compositions.

[0036] The molded article may be a connector housing for an automotive wiring harness.

[0037] Advantages of the Invention

[0038] The colorant of the present invention exhibits high heat resistance, high light resistance, anti-color bleeding property, and good compatibility with the thermoplastic resin contained in the masterbatch and the colored resin composition. Therefore, the mechanical strength properties such as the original tensile strength and impact strength of the thermoplastic resin are not damaged.

[0039] In addition, since the compounds represented by Chemical Formulas 1a to 1c above have nitrogen-containing chromogenic group substituents such as amino groups or nitrogen-containing heterocyclic groups, the molded article formed from the masterbatch and the colored resin composition containing the colorant of the present invention has a highly bright hue with excellent visibility.

[0040] The masterbatch and the colored resin composition containing the colorant of the present invention have high heat resistance and high light resistance, and are therefore suitable for the manufacture of molded articles that require no discoloration or fading. Detailed Description of the Invention

[0041] Hereinafter, the embodiments of the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

[0042] (Colorant)

[0043] The compounds that must be included in the colorant of the present invention include at least one compound represented by the following Chemical Formula 1a, at least one compound represented by the following Chemical Formula 1b, and / or at least one compound represented by the following Chemical Formula 1c.

[0044] [Chemical Formula 5]

[0045]

[0046] (In Chemical Formula 1a, R 1 and R 2 are independently a hydrogen atom, an amino group that may have a substituent, or a nitrogen-containing heterocyclic group, and the two are not simultaneously hydrogen atoms, or are connected to each other to form a condensed ring. R 3 is at least one selected from linear or branched alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, hydroxyl groups, sulfo groups, and sulfonamide groups, and p is a number from 0 to 2.)

[0047] [Chemical Formula 6]

[0048]

[0049] (In Chemical Formula 1b, R 4 and R 5 are independently a hydrogen atom, an amino group that may have a substituent, or a nitrogen-containing heterocyclic group, and the two are not simultaneously hydrogen atoms. R 6 is at least one selected from linear or branched alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, hydroxyl groups, sulfo groups, and sulfonamide groups, and q is a number from 0 to 4.)

[0050] [Chemical Formula 7]

[0051]

[0052] (In Chemical Formula 1c, R 7 and R 8 are independently a hydrogen atom, an amino group that may have a substituent, or a nitrogen-containing heterocyclic group. R 9 is at least one selected from linear or branched alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, hydroxyl groups, sulfo groups, and sulfonamide groups, and r is a number from 0 to 2.)

[0053] The common feature of the compounds of Chemical Formulas 1a to 1c is that they are condensed ring compounds with a benzisoquinoline ring as the central skeleton. Specifically, the compound of Chemical Formula 1a is a condensed ring compound containing a benzimidazole ring with a benzimidazole ring fused as the central skeleton, the compound of Chemical Formula 1b is a condensed ring compound containing a phthalazine ring with a phthalazine ring fused as the central skeleton, and the compound of Chemical Formula 1c is a condensed ring compound containing an isatinone ring with an isatinone ring fused as the central skeleton.

[0054] As R in Chemical Formula 1a 1 and R 2 、R in Chemical Formula 1b 4 and R 5 and R in Chemical Formula 1c 7 and R 8 The nitrogen-containing heterocyclic groups include morpholino, piperidino, pyrrolidino and piperazino groups. When R 1 and R 2 are both nitrogen-containing heterocyclic groups, the two nitrogen-containing heterocyclic groups can be of the same type or different types. The same applies to R 4 and R 5 and R 7 and R 8 .

[0055] When R 1 , R 2 , R 4 , R 5 , R 7 and R 8 are amino, piperidino, pyrrolidino or piperazino groups, these can have substituents. Examples of such substituents include linear or branched alkyl groups having 1 to 4 carbon atoms, linear or branched alkoxy groups having 1 to 4 carbon atoms, hydroxyl group and carboxyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. In addition, examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy.

[0056] When R 1 and R 2 in Chemical Formula 1a are connected to form a fused ring, the fused ring has a heteroatom X, and examples of X include nitrogen atom, oxygen atom and sulfur atom.

[0057] As the alkoxy groups of R 3 in Chemical Formula 1a, R 6 in Chemical Formula 1b and R 9 in Chemical Formula 1c, examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy and tert-butoxy. In addition, when R 3 , R 6 and R 9 are sulfonamide groups represented by “-SO2N(R a )2”, multiple R aIndependently of each other, they are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, and a tert-butoxy group. On the other hand, when R 3 、R 6 and R 9 are a sulfonamide group represented by “-NH(SO)2R b ”, examples of the R b include the same groups as those of the above R a . The substitution positions of these R 3 , R 6 and R 9 are not particularly limited.

[0058] In Chemical Formula 1a, p and in Chemical Formula 1c, r are numbers from 0 to 2, preferably 1. In addition, in Chemical Formula 1b, q is a number from 0 to 4, specifically, integers such as 0, 1, 2, 3, and 4, preferably 0.

[0059] The benzimidazole ring-fused polycyclic compound of Chemical Formula 1a is orange. A specific example thereof is represented by the following Chemical Formula 1a1-1.

[0060]

Chemical Formula 8

[0061]

[0062] The benzimidazole ring-fused polycyclic compound is obtained by reacting a naphthalic anhydride derivative such as 4-bromonaphthalic anhydride with morpholine and then reacting with 3,4-diaminobenzoic acid. Four isomers of the benzimidazole ring-fused polycyclic compound are generated in this reaction. The content ratio of the isomers is arbitrary. Any one of the isomers can be selectively generated only, or a mixture of the isomers can be generated and then the different isomers can be separated by column chromatography. The isomers represented by Chemical Formula 1a1-1 are represented by the following Chemical Formulas 1a1-1-1 to 1a1-1-4.

[0063]

Chemical Formula 9

[0064]

[0065] It should be noted that in this specification, for convenience, the structure of the compounds included in the scope of the present invention can be represented by a general formula, and the chemical formulas of the isomer structures are omitted. Specifically, for example, Chemical Formula 1a1-1 also includes any isomers included during the generation process, such as those represented by Chemical Formulas 1a1-1-1 to 1a1-1-4.

[0066] As another specific example of the benzoimidazole ring-fused ring compound represented by Chemical Formula 1a, for example, compounds represented by the following Chemical Formulas 1a1-2 to 1a1-8 can be cited.

[0067]

Chemical Formula 10

[0068]

[0069] In Chemical Formula 1a, at least one of R 1 and R 2 is a nitrogen-containing heterocyclic group and when R 3 is a carboxyl group, the benzoimidazole ring-fused ring compound exhibits higher heat resistance and bleeding resistance, has rich colors, and has excellent compatibility with the thermoplastic resin described later, and is therefore preferred. This is because the nitrogen-containing heterocyclic group of R 1 and / or R 2 functions as a color-developing group while improving heat resistance, and the carboxyl group of R 3 improves heat resistance and bleeding resistance. In particular, when the thermoplastic resin is a polyamide resin, R 3 is further preferably a carboxyl group. At this time, the bleeding resistance is significantly improved. It is speculated that this is because the amide group or carboxyl group in the polyamide resin molecule and the carboxyl group of the benzoimidazole ring-fused ring compound form hydrogen bonds between molecules, thereby suppressing the occurrence of bleeding.

[0070] As still another example of the benzoimidazole ring-fused ring compound represented by Chemical Formula 1a, compounds in which R 1 and R 2 are connected to each other to form a fused ring can be cited. Specifically, this is represented by the following Chemical Formula 1a2.

[0071]

Chemical Formula 11

[0072]

[0073] (In Chemical Formula 1a2, R 3 and p are the same as those in the above Chemical Formula 1a, R 10 is a hydrogen atom, a carboxyl group or a linear or branched alkyl group having 1 to 4 carbon atoms, and X is a nitrogen atom, an oxygen atom or a sulfur atom.)

[0074] As the alkyl group of R 10 in Chemical Formula 1a2, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl can be cited.

[0075] As a specific example of the benzoimidazole ring-fused ring compound represented by Chemical Formula 1a2, for example, a compound represented by the following Chemical Formula 1a2-1 can be cited. This compound is slightly reddish orange (red orange).

[0076] [Chemical Formula 12]

[0077]

[0078] The benzimidazole ring-fused polycyclic compound represented by Chemical Formula 1a2-1 has a thioxanthene structure in part of its structure. This benzimidazole ring-fused polycyclic compound is obtained as follows: o-aminothiophenol is reacted with 4-bromonaphthalic anhydride to obtain a naphthalimide thioether, followed by a ring-closure reaction to form xanthene, and then further reacted with 3,4-diaminobenzoic acid. This reaction produces four isomers of the benzimidazole ring-fused polycyclic compound. The content ratio of the isomers is arbitrary. Any one of the isomers can be selectively produced alone, or a mixture of the isomers can be produced and then the different isomers can be separated by column chromatography. The isomers represented by Chemical Formula 1a2-1 are represented by the following Chemical Formulas 1a2-1-1 to 1a2-1-4.

[0079] [Chemical Formula 13]

[0080]

[0081] As another specific example of the benzimidazole ring-fused polycyclic compound represented by Chemical Formula 1a2, for example, the compound represented by the following Chemical Formula 1a2-2 can be cited. This compound is slightly yellowish orange (orange-yellow).

[0082] [Chemical Formula 14]

[0083]

[0084] The benzimidazole ring-fused polycyclic compound represented by Chemical Formula 1a2-2 has a xanthene structure in part of its structure. This benzimidazole ring-fused polycyclic compound is obtained as follows: 2-nitrophenol is reacted with 4-bromonaphthalic anhydride to obtain a naphthalimide ether, followed by a reduction reaction and a ring-closure reaction to form xanthene, and then further reacted with 3,4-diaminobenzoic acid. This reaction produces four isomers of the benzimidazole ring-fused polycyclic compound. The content ratio of the isomers is arbitrary. Any one of the isomers can be selectively produced alone, or a mixture of the isomers can be produced and then the different isomers can be separated by column chromatography.

[0085] The naphthodiazine ring-fused polycyclic compound of Chemical Formula 1b is red. A specific example of it is represented by the following Chemical Formula 1b-1.

[0086] [Chemical Formula 15]

[0087]

[0088] The naphthodiazabenzene ring-fused compound is obtained as follows: After reacting a naphthalic anhydride derivative with piperidinecarboxylic acid, it is reacted with 1,8-diaminonaphthalene. This reaction produces two isomers of the naphthodiazabenzene ring-fused compound. The content ratio of the isomers is arbitrary. Either one of the isomers can be selectively produced only, or a mixture of the isomers can be produced and then the different isomers can be separated by column. The isomer represented by Chemical Formula 1b-1 is represented by the following Chemical Formulas 1b-1-1 and 1b-1-2.

[0089]

Chemical Formula 16

[0090]

[0091] As another specific example of the naphthodiazabenzene ring-fused compound represented by Chemical Formula 1b, compounds represented by the following Chemical Formulas 1b-2 to 1b-6 can be cited, for example.

[0092]

Chemical Formula 17

[0093]

[0094] In Chemical Formula 1b, when at least one of R 4 and R 5 is a nitrogen-containing heterocyclic group having a carboxyl group, the naphthodiazabenzene ring-fused compound exhibits higher heat resistance and bleeding resistance, and is rich in color, so it is preferred.

[0095] The isoindolinone ring-fused compound represented by Chemical Formula 1c is dark red to red. A specific example thereof is shown by the following Chemical Formula 1c-1.

[0096]

Chemical Formula 18

[0097]

[0098] The isoindolinone ring-fused compound is obtained as follows: After reacting pyromellitic dianhydride with 1,8-diamino-4-bromonaphthalene, it is further reacted with morpholine. This reaction produces four isomers of the isoindolinone ring-fused compound. The content ratio of the isomers is arbitrary. Either one of the isomers can be selectively produced only, or a mixture of the isomers can be produced and then the different isomers can be separated by column.

[0099] In the production reaction of the isoindolinone ring-fused compound represented by Chemical Formula 1c, when R 7 and R 8When it is a compound represented by Chemical Formula 1c-1 and not a hydrogen atom at the same time, there are isomers. One Chemical Formula 1c-1 also includes isomers represented by the following Chemical Formulas 1c-1-1 and 1c-1-2. Thus, for convenience, the structure of the compounds included in the scope of the present invention is represented by a general formula, and the chemical formulas of the isomer structures are omitted.

[0100] [Chemical Formula 19]

[0101]

[0102] As another specific example of the isoindolinone ring-fused ring compound represented by Chemical Formula 1c, compounds represented by the following Chemical Formulas 1c-2 to 1c-6 can be cited, for example.

[0103] [Chemical Formula 20]

[0104]

[0105] As the value for evaluating the heat resistance of the compounds represented by Chemical Formulas 1a to 1c, the 5% thermal weight loss temperature can be used. This value is the temperature at which the weight of the compounds represented by Chemical Formulas 1a to 1c decreases by 5% from the weight at the start of measurement (room temperature) during the temperature increase process in thermogravimetric differential thermal analysis. The 5% thermal weight loss temperature of the compounds represented by Chemical Formulas 1a to 1c is at least 280 °C, more preferably at least 300 °C, and even more preferably at least 330 °C.

[0106] The maximum absorption wavelength of the compounds represented by Chemical Formulas 1a to 1c varies depending on the substituents they have, but is preferably 420 to 550 nm. It should be noted that this maximum absorption wavelength is measured under ordinary conditions using an ultraviolet-visible spectrophotometer.

[0107] As the color of the covering material for the connector or wire used in the high-voltage wiring harness, orange represented by RAL2000, 2001, 2002, 2003, 2004, 2008, 2009, 2010, 2011, and 2012, etc. on the RAL color card is required. At this time, the hue represented in the CIE-Lab color space is preferably L* = 50 to 100 and a* = 20 to 85 and b* = 30 to 120, more preferably L* = 50 to 80 and a* = 35 to 55 and b* = 30 to 85, and even more preferably L* = 50 to 80 and a* = 35 to 55 and b* = 30 to 80.

[0108] In order to obtain a colorant having a hue in this range, the colorant preferably contains 1 to 100% by mass of at least one compound represented by Chemical Formulas 1a to 1c, more preferably contains 2 to 80% by mass, and even more preferably 2 to 50% by mass.

[0109] The orange color required for covering materials such as high-voltage wiring harnesses varies by country or region. On the RAL color chart, RAL2003 (L* = 64.31, a* = 43.85, b* = 62.20), RAL2008 (L* = 60.46, a* = 46.57, b* = 61.00), RAL2010 (L* = 53.38, a* = 42.56, b* = 50.27), and RAL2012 (L* = 56.08, a* = 42.27, b* = 34.37) are applicable to Europe, North America, and Asian regions.

[0110] The compounds represented by Chemical Formulas 1a to 1c are colorants ranging from orange to red. Therefore, to obtain a colorant with the desired orange hue, one can use only one of the compounds represented by Chemical Formulas 1a to 1c, or a mixture of multiple ones. When using a mixture of multiple ones, the benzimidazole ring-fused compound represented by Chemical Formula 1a, the phenanthroline ring-fused compound represented by Chemical Formula 1b, and the isoindolinone ring-fused compound represented by Chemical Formula 1c can be mixed with compounds having the same skeleton but different substituents respectively. Specifically, for example, to obtain the orange colors of RAL2003, 2008, 2010, and 2012, a colorant can be prepared by mixing the benzimidazole ring-fused compound represented by Chemical Formula 1a1-1 and the benzimidazole ring-fused compound represented by Chemical Formula 1a2-1. At this time, the first compound represented by Chemical Formulas 1a to 1c and the second compound also represented by Chemical Formulas 1a to 1c are preferably mixed at a mass ratio of the first compound: the second compound = 1:4 to 4:1, and more preferably at 1:2 to 2:1.

[0111] As needed, a white pigment can be included in the colorant to increase the brightness of the orange colorant, and a black pigment can be included to reduce the brightness of the orange colorant. Examples of such white pigments include inorganic pigments such as CaCO3, 2PbCO3 and Pb(OH)2, ZnO, TiO2, and ZnS. In addition, examples of black pigments include carbonaceous pigments such as carbon black, graphite, and amorphous carbon, or commercially available black pigments such as C.I. Pigment Black 6, 8, 9, 10, 11, and 28. In addition, examples of pigments other than white and black include C.I. Pigment Orange 68 (manufactured by BASF Corporation).

[0112] In order to adjust the orange color, the colorant of the present invention may further contain other dyes and / or pigments in addition to the compounds represented by Chemical Formulas 1a to 1c. Specifically, yellow dyes, orange dyes, and red dyes or yellow pigments, orange pigments, red pigments, white pigments, and black pigments can be cited. By mixing the compounds represented by Chemical Formulas 1a to 1c that exhibit orange to red colors with these dyes or pigments, orange colorants with arbitrary hues and brightnesses can be obtained. Among them, dyes having fluorescence are preferred because they can enhance visibility by increasing the brightness of the obtained orange color.

[0113] As the yellow dye, a naphthalimide compound represented by the following Chemical Formula 2 can be cited

[0114]

Chemical Formula 21

[0115]

[0116] (In Chemical Formula 2, R 11 is a hydrogen atom, an amino group that may have a substituent, or a nitrogen-containing heterocyclic group, R 12 is at least one selected from a halogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, a linear or branched alkoxy group having 1 to 3 carbon atoms, and an amino group that may have a substituent, R 13 is at least one selected from an amino group, an amide group, an alkoxy group, a carboxyl group, a hydroxyl group, a sulfo group, and a sulfonamide group, A is a linear or branched hydrocarbon group having 1 to 3 carbon atoms, a benzene ring, or a naphthalene ring, m is a number from 0 to 2, and n is a number from 1 to 3.).

[0117] In Chemical Formula 2, as the nitrogen-containing heterocyclic group represented by R 11 , a morpholino group, a piperidyl group, a pyrrolidinyl group, and a piperazinyl group can be cited. When R 11 is an amino group, a piperidyl group, a pyrrolidinyl group, or a piperazinyl group, these may have a substituent. As the substituent, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a carboxyl group can be cited. As the alkyl group, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl can be cited, and as the alkoxy group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy can be cited.

[0118] In Chemical Formula 2, as the halogen atom represented by R 12 , F, Cl, Br, and I can be cited, as the alkyl group, methyl, ethyl, n-propyl, and isopropyl can be cited, and as the alkoxy group, methoxy, ethoxy, n-propoxy, and isopropoxy can be cited.

[0119] When R 12When it is an amino group, as the substituent having the amino group, examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms, linear or branched alkoxy groups having 1 to 4 carbon atoms, hydroxyl groups, and carboxyl groups. As the alkyl group, examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. As the alkoxy group, examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy. R 12 The substitution position of is not particularly limited. In addition, as m representing the number of substituents of R 12 , specifically, integers of 0, 1, and 2 can be cited, and 0 is preferred, that is, R 12 is not substituted.

[0120] In Chemical Formula 2, as the linear or branched hydrocarbon group having 1 to 3 carbon atoms represented by A, specifically, examples thereof include alkylene groups such as methylene, ethylene, trimethylene, and propenyl. The benzene ring represented by A is a polyvalent group formed by removing one hydrogen atom from each of 2, 3, or 4 ring carbon atoms, and examples thereof include arylene groups such as phenylene. In addition, the naphthalene ring represented by A is a polyvalent group formed by removing one hydrogen atom from each of 2, 3, or 4 ring carbon atoms, and examples thereof include naphthylene. As the naphthylene, examples thereof include 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, and 2,6-naphthylene.

[0121] As A in Chemical Formula 2, methylene or o-phenylene, m-phenylene, or p-phenylene is more preferred, and p-phenylene is further preferred. The naphthalimide compound in which A is an arylene group has higher heat resistance. When A in Chemical Formula 2 is an aromatic hydrocarbon group such as an arylene group or a naphthylene group, the substitution position of R 12 is not particularly limited.

[0122] In Chemical Formula 2, as the linear or branched alkoxy group having 1 to 4 carbon atoms represented by R 13 , examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy.

[0123] When R 13 is an amide group represented by “-C(=O)N(R 13a )2”, it is preferred that a plurality of R 13aEach independently is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy. On the other hand, when R 13 is an amide group represented by “-NHC(=O)R 13b ”, examples of the R 13b include the same groups as those of the aforementioned R 13a .

[0124] When R13 is a sulfonamide group represented by “-SO2N(R 13c )2”, preferably, a plurality of R 13c each independently is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples of the alkyl group and alkoxy group of R 13c include the same groups as those of the aforementioned R 13a . Further, when R 13 is a sulfonamide group represented by “-NH(SO)2R 13d ”, examples of the R 13d include the same groups as those of the aforementioned R 13a . In addition, n representing the number of substituents of R 13 is a number from 1 to 3, preferably 1 or 2, more preferably 1.

[0125] Among them, a naphthalimide compound in which R11 is a nitrogen-containing heterocyclic group, A is a phenylene group, m = 0 (i.e., R 12 is not substituted), and R 13 is a carboxyl group exhibits higher heat resistance and bleeding resistance, has rich colors, and has excellent compatibility with a thermoplastic resin described later, and thus is preferred. This is because the nitrogen-containing heterocyclic group of R 11 acts as a chromogenic group and improves heat resistance, the phenylene group of A improves heat resistance, and the carboxyl groups of R 13 respectively impart heat resistance and bleeding resistance. In particular, when the thermoplastic resin is a polyamide resin, R 13 is further preferably a carboxyl group. In this case, the bleeding resistance is significantly improved. It is speculated that this is because the amide group or carboxyl group in the polyamide resin molecule and the carboxyl group of the naphthalimide compound form hydrogen bonds between molecules, thereby suppressing the occurrence of bleeding phenomenon.

[0126] The 5% thermal weight loss temperature of the naphthalimide compound represented by Chemical Formula 2 is at least 280 °C, preferably at least 300 °C, more preferably at least 330 °C, and even more preferably at least 350 °C. The 5% thermal weight loss temperature is measured by the same method as described above.

[0127] The maximum absorption wavelength of visible light of the naphthalimide compound represented by Chemical Formula 2 varies depending on the substituents it has, but is preferably 385 to 439 nm. The maximum absorption wavelength is measured by the same method as described above.

[0128] Specific examples of the naphthalimide compound represented by Chemical Formula 2 are represented by the following Chemical Formula 2a.

[0129]

Chemical Formula 22

[0130]

[0131] In Chemical Formula 2a, the substituent Z generally represents -A-(R 13 ) n of Chemical Formula 2. Examples of each substituent R 11 , R 12 and Z in Chemical Formula 2a are shown in Table 1 and Table 2.

[0132]

Table 1

[0133] Table 1

[0134]

[0135]

Table 2

[0136] Table 2

[0137]

[0138] Colorants can be prepared by combining at least one of the compounds represented by Chemical Formulas 1a to 1c with other dyes or pigments other than the compounds described above. Thus, colorants of various colors can be obtained. For example, orange (for example, a combination of any one of the compounds represented by Chemical Formulas 1a to 1c and a yellow to red dye or pigment), green (for example, a combination of any one of the compounds represented by Chemical Formulas 1a to 1c and a blue dye or pigment), purple (for example, a combination of any one of the compounds represented by Chemical Formulas 1a to 1c and a blue dye or pigment), and black (for example, a combination of any one of the compounds represented by Chemical Formulas 1a to 1c and a blue dye or pigment and a yellow dye or pigment, or for example, a combination of any one of the compounds represented by Chemical Formulas 1a to 1c and a blue dye or pigment). In industry, colorants of orange and black are often used in particular.

[0139] As the dyes and pigments for preparing colorants, dyes and pigments that do not impair the effects of the present invention are selected. As preferred dyes and pigments, at least one organic dye and pigment selected from the group consisting of azo dyes and pigments, azo metal dyes and pigments, naphthol azo dyes and pigments, azo lake dyes and pigments, azo hypo dyes and pigments, anthraquinone dyes and pigments, quinacridone dyes and pigments, dioxazine dyes and pigments, pyrrolopyrrole dione dyes and pigments, anthrapyridone dyes and pigments, isoindolinone dyes and pigments, indanthrone dyes and pigments, pyrene ketone dyes and pigments, perylene dyes and pigments, indigo dyes and pigments, thioindigo dyes and pigments, quinoline dyes and pigments, benzimidazolone dyes and pigments, and triphenylmethane dyes and pigments can be cited. These are yellow, red, blue, green or black.

[0140] In addition, as a red dye, an azine dye ORIENTLPI-1 (maximum absorption wavelength 560 nm) manufactured by Orient Chemical Industries, Ltd. can be cited.

[0141] When the colorant contains the above-mentioned pigments and / or dyes, relative to 1 part by mass of the compound 1 represented by Chemical Formulas 1a to 1c, these are preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and even more preferably 0.5 to 20 parts by mass.

[0142] (Masterbatch)

[0143] The masterbatch of the present invention contains at least one compound represented by Chemical Formulas 1a to 1c and optional dyes and / or pigments and a thermoplastic resin as required. The masterbatch can contain a mixed colorant formed by mixing at least one compound represented by Chemical Formulas 1a to 1c and optional dyes and / or pigments and a thermoplastic resin. The type of this thermoplastic resin can be the same as or different from the main component resin (uncolored resin) used for coloring the resin composition. As the colorant, specifically, a colorant containing the dye represented by Chemical Formula 2 or the above-mentioned pigments can be cited.

[0144] In the masterbatch, the content of the colorant is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass.

[0145] As a process for manufacturing the masterbatch, high-temperature extrusion treatment etc. can be cited. The colorants containing at least one compound represented by Chemical Formulas 1a to 1c and optional dyes and / or pigments of the present invention are hardly decomposed, sublimated, and discolored due to high temperature. Therefore, the colorants composed of at least one compound represented by Chemical Formulas 1a to 1c and the colorants containing the same and optional dyes and / or pigments can be applied to masterbatches (high-concentration colored resin compositions).

[0146] Such masterbatch can be obtained by the following hot melt method. Powders or granules of a thermoplastic resin serving as a masterbatch base, the colorant of the present invention, and additives as required are mixed in a roller or a super mixer, etc., and then put into an extruder, a batch kneader, a roll kneader, etc. to form granules or coarse grains. Thereby, the masterbatch can be obtained. In addition, the masterbatch can be obtained, for example, by adding the colorant of the present invention and other additives as required to a thermoplastic resin still in a solution state after synthesis and then removing the solvent. It should be noted that, through the same treatment, the coloring resin composition with a conventional concentration described later can be obtained.

[0147] As the thermoplastic resin, known resins or commercially available resins can be used. For example, polyamide resins, polyolefin resins such as polyethylene or polypropylene, polyester resins, polycarbonate resins, and polyphenylene sulfide resins can be cited.

[0148] The polyamide resin refers to a polyamide polymer having an acid amide group (-CONH-) in its molecule and capable of being melted by heating. Preferably, a polyamide resin containing at least one selected from the salts composed of aliphatic diamines and aromatic dicarboxylic acids and the salts composed of aromatic diamines and aliphatic dicarboxylic acids as a constituent unit is used. As the polyamide resin, polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 69, polyamide 610, polyamide 612, polyamide 96, amorphous polyamide, high melting point polyamide, polyamide RIM, polyamide 4, polyamide 6I, polyamide 56, polyamide 6T, polyamide 9T, polyamide MXD6, polyamide MP6, polyamide MP10, and copolymers of two or more of these can be cited. As the copolymer, specifically, polyamide 6 / 66 copolymer, polyamide 6 / 66 / 610 copolymer, polyamide 6 / 66 / 11 / 12 copolymer, crystalline polyamide / amorphous polyamide copolymer, etc. can be cited. In addition, the polyamide resin can be a mixed polymer of a polyamide resin and other synthetic resins. As an example of such a mixed polymer, polyamide / polyester mixed polymer, polyamide / polyphenylene ether mixed polymer, polyamide / polycarbonate mixed polymer, polyamide / polyolefin mixed polymer, polyamide / styrene / acrylonitrile mixed polymer, polyamide / acrylate mixed polymer, and polyamide / silicone mixed polymer, etc. can be cited. These polyamide resins can be used alone or in combination of two or more.

[0149] As polyolefin resins, for example, homopolymers of α-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, etc., copolymers thereof, and copolymers of these with other copolymerizable unsaturated monomers can be cited. (As copolymers, block copolymers, random copolymers, and graft copolymers can be cited.) etc. More specifically, examples can include polyethylene resins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer; polypropylene resins such as propylene homopolymer, propylene-ethylene block copolymer or random copolymer, and propylene-ethylene-1-butene copolymer; polybutene-1, poly-4-methyl-1-pentene, etc. These polyolefin resins can be used alone or in combination of two or more. Among these, polyethylene resin and / or polypropylene resin is preferably used. More preferably, polypropylene resin. The molecular weight of this polypropylene resin is not particularly limited, and a wide range of molecular weights can be used.

[0150] As polyester resins, for example, polyethylene terephthalate resin obtained by polycondensation reaction of terephthalic acid and ethylene glycol, and polybutylene terephthalate resin obtained by polycondensation reaction of terephthalic acid and butanediol can be cited. As examples of other polyester resins, copolymers in which a part of the terephthalic acid component or diol component is substituted with a substituent such as an alkyl group having 1 to 4 carbon atoms, etc., such as in the terephthalic acid component, 15 mol% or less (for example, 0.5 to 15 mol%), preferably 5 mol% or less (for example, 0.5 to 5 mol%) and / or in the diol components such as ethylene glycol and butanediol, 15 mol% or less (for example, 0.5 to 15 mol%), preferably 5 mol% or less (for example, 0.5 to 5 mol%). In addition, the polyester resin can be single or a mixture of multiple.

[0151] Polycarbonate resin is a thermoplastic resin that has a carbonate bond in the main chain and in a linear molecule formed by connecting a large number of carbonates of aromatic hydrocarbons, the molecular main chain has a bulky benzene nucleus and a flexible carbonate. As polycarbonate resins produced industrially in large quantities, aromatic polycarbonates obtained from bisphenol A can be cited and can be used.

[0152] Polyphenylene sulfide resin is a polymer mainly composed of repeating units represented by (-φ-S-)[φ is a substituted or unsubstituted phenylene group]. As polyphenylene sulfide resin, a resin obtained by polymerizing a monomer synthesized by reacting p-dichlorobenzene and alkali sulfide under high temperature and high pressure can be used.

[0153] (Colored resin composition)

[0154] The colored resin composition of the present invention is a mixture of the above masterbatch and an uncolored resin. The content of the masterbatch in the colored resin composition is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass. The colored resin composition can be obtained by mixing the colorant and / or the masterbatch of the present invention, the uncolored resin, and, if necessary, the additives described below in a roller or a super mixer, etc., and using an extruder, a batch kneader, a roll kneader, etc., by the hot melt method to form pellets or coarse grains. Such a colored resin composition is also called a compound and is a raw material for molding articles of resin. By molding and processing the colored resin composition by a conventional method, a resin molded article with uniform coloring can be obtained.

[0155] As the uncolored resin, the same resins as those used for the above masterbatch can be cited. In addition to the colorant and the uncolored resin as the masterbatch, additives can be contained in the colored resin composition, if necessary. As such additives, for example, reinforcing materials, ultraviolet absorbers, light stabilizers, flame retardants, flame retardant aids, antioxidants, brightness regulators, lubricants, and mold release agents can be cited.

[0156] The reinforcing material is not particularly limited as long as it can be used to reinforce a thermoplastic resin. For example, inorganic fibers such as glass fibers, carbon fibers, metal fibers, potassium titanate fibers, calcium silicate fibers, sepiolite, wollastonite, and asbestos, and organic fibers such as aramid, polyphenylene sulfide resin fibers, polyamide resin fibers, polyester resin fibers, and liquid crystal polymer resin fibers can be cited. Among them, glass fibers can be preferably used. The fiber length of such glass fibers is 2 to 15 mm, and the fiber diameter is 1 to 20 μm. There is no particular limitation on the form of the glass fibers. For example, roving or milled fibers can be cited. These glass fibers can be used alone or in combination of two or more. For example, the content is preferably 5 to 120 parts by mass with respect to a total of 100 parts by mass of the colorant and the uncolored resin. When it is less than 5 parts by mass, a sufficient glass fiber reinforcement effect cannot be obtained, and when it exceeds 120 parts by mass, the moldability is reduced. It is preferably 10 to 60 parts by mass, and particularly preferably 20 to 50 parts by mass. A commercially available glass fiber-containing uncolored resin can be used, or glass fibers can be added to the uncolored resin each time the colored resin composition is prepared.

[0157] As the ultraviolet absorber and the light stabilizer, benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, benzoate compounds, oxanilide compounds, hindered amine compounds, and nickel complexes, etc. can be cited.

[0158] The flame retardant is suitable for preventing the molded articles exposed to high temperatures from catching fire, such as the connector housing of the wire harness for automobiles. As such flame retardants, chlorine-based flame retardants, bromine-based flame retardants, antimony-based flame retardants, phosphorus-based flame retardants, silicon-based flame retardants, and nitrogen-based flame retardants can be cited.

[0159] As chlorine-based flame retardants, for example, chlorinated paraffin, chlorinated polyethylene, chlorinated polyolefins such as chlorinated polyethylene, dodecachloropentacyclooctadec-7,15-diene, and chlorendic anhydride can be cited.

[0160] As bromine-based flame retardants, for example, tetrabromobisphenol A (TBBA), tetrabromobisphenol S (TBBS), hexabromocyclododecane, decabromodiphenyl ether, decabromodiphenyl ether, 2,6-dibromophenol, 2,4-dibromophenol, 2,4,6-tribromophenol, ethylenebis(tetrabromophthalimide), TBBA-carbonate oligomer, TBBA-epoxy oligomer, bis(pentabromophenoxy)ethane, 1,2-bis(2,4,6-pentabromophenoxy)ethane, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, bis(pentabromophenyl)ethane, octabromodiphenyl ether, ethylenebis(pentabromodiphenyl), TBBA-bis(dibromopropyl ether), TBBA-bis(aryl ether), poly(dibromophenol), hexabromobenzene, polybromotrimethylphenylindane, ethylenebis(tetrabromophthalimide), tris(2,4,6-tribromophenyl) cyanurate, TBBA-bis(dibromopropyl), TBBS-bis(dibromopropyl), brominated polystyrene resin, brominated epoxy resin, brominated phenoxy resin, brominated styrene-maleic anhydride polymer, brominated polyphenylene ether, tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate, and pentabromobenzyl acrylate can be cited.

[0161] As antimony-based flame retardants, for example, antimony trioxide, antimony pentoxide, sodium antimonate, and antimony phosphate can be cited.

[0162] As phosphorus-based flame retardants, for example, red phosphorus, polyphosphoric acid, ammonium polyphosphate, phenoxyphosphazene having a phosphorus-nitrogen bond in the main chain, aminophosphazene, triphenyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tolyl phosphate, tolyldiphenyl phosphate, xylenyldiphenyl phosphate, tricresyl phosphate, tritolyl phosphate, tris(tert-butylated phenyl) phosphate, tris(isobutylated phenyl) phosphate, 2-ethylhexyl diphenyl phosphate, 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylyl phosphate), TBBA-bis(diphenyl phosphate), tris(butoxyethyl) phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate, tris(β-chloropropyl) phosphate, 2,2-bis(chloromethyl)trimethylene bis(bis(2-chloroethyl) phosphate), bis(nonylphenyl)phenyl phosphate, tolyl bis(di-2,6-xylyl) phosphate, and polyoxyalkylene bis(dichloralkyl) phosphate can be cited.

[0163] As silicone-based flame retardants, for example, silicone oil, silane, and aluminum silicate can be listed.

[0164] As nitrogen-based flame retardants, for example, melamine, cyanuric acid, melamine cyanurate, urea, and guanidine can be listed.

[0165] The above-mentioned flame retardants can be used alone or in combination. The content of the flame retardant is preferably 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and particularly preferably 10 to 20 parts by mass, for example, relative to a total of 100 parts by mass of the colorant and the uncolored resin.

[0166] Halogen-based flame retardants such as chlorine-based or bromine-based flame retardants generate harmful gases during combustion when incinerating thermoplastic resin products containing them. Therefore, non-halogen-based flame retardants such as phosphorus-based or nitrogen-based flame retardants are often used. The benzimidazole ring-fused polycyclic compound, quinoxaline ring-fused polycyclic compound, and / or isoindolinone ring-fused polycyclic compound contained in the colorant of the present invention do not cause color change and fading that occur in ordinary dyes or pigments contained in conventional colorants, and also do not cause color change and fading due to non-halogen-based flame retardants in a high-temperature environment. Therefore, the colorant of the present invention is suitable as a colorant for non-halogen-based flame retardant grade resins containing non-halogen-based flame retardants.

[0167] As flame retardant aids, for example, antimony compounds such as antimony trioxide and sodium antimonate, or zinc borate, barium metaborate, hydrated alumina, zirconia, ammonium polyphosphate, and tin oxide can be listed.

[0168] As antioxidants, phenolic compounds having phenolic hydroxyl groups, phosphorus-based compounds having phosphorus atoms, sulfur-based compounds having sulfur atoms, and thioether-based compounds can be listed.

[0169] As phosphorus-based compounds, triphenyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite can be listed.

[0170] As sulfur-based compounds and thioether-based compounds, dilauryl thiodipropionate, ditetradecyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), thio-bis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, and trilauryl trithiophosphite can be listed.

[0171] The brightness regulator is used to reduce the transparency of the molded article made of the resin composition, so that the metal electrical contacts built in the high-voltage wire harness connector and the wires in the wire covering material cannot be seen from the outside. As the brightness regulator, for example, titanium oxide, zinc oxide, zinc sulfide, barium sulfate, lithopone (a mixture of zinc sulfide and barium sulfate), calcium carbonate, silica, carbon black, titanium black, carmine, ultramarine, cobalt aluminate, and chromium green can be cited.

[0172] As the lubricant, for example, hydrocarbon lubricants such as polyethylene wax and polypropylene wax, fatty acid lubricants such as stearic acid, higher alcohol lubricants such as stearyl alcohol, aliphatic amide lubricants such as stearamide; metal soaps such as calcium stearate, zinc stearate, and magnesium stearate, etc. can be cited.

[0173] As the mold release agent, for example, long-chain fatty acids or their esters or metal salts, aliphatic carboxylic acids, polyethylene wax, and silicone can be cited.

[0174] (Molded article)

[0175] The molded article of the present invention is composed of the above-mentioned colored resin composition. The molded article is, for example, the housing of an automotive high-voltage wire harness connector such as HV or EV. The connector housing is a housing that covers metal components and is used to connect wires to each other or connect wires to electrical devices such as batteries. The molded article can be manufactured by various common procedures. For example, the above-mentioned colored resin composition is melted, and molding methods such as injection molding, extrusion molding, compression molding, foam molding, blow molding, vacuum molding, injection blow molding, rotational molding, calendering, and solution casting can be adopted. Through such molding, molded articles of various shapes can be obtained.

[0176] As an example of the molded article, a connector of a high-voltage wire harness can be cited, but the molded article is not limited thereto. For example, as a component for a wire harness, a wire covering material can be cited. As other molded articles, laser-welded components manufactured by laser-welding a plurality of components, such as an intake manifold or an engine hood of an internal combustion engine, can be cited. In addition to heat resistance and bleeding resistance, the colorant of the present invention also has excellent light resistance, so it is also applicable to molded articles used outdoors. As the molded article, medical tubes used during infusion of infusions or nutritional agents, food packaging materials such as suction nozzle bags containing liquid foods or beverage compositions, and bottle caps and labels can be further cited.

[0177]

Examples

[0178] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

[0179] (Synthesis Example 1)

[0180] In a 100 ml four-necked flask, 14.79 g of 4-bromonaphthalic anhydride (0.053 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 ml of N-methyl-2-pyrrolidone (NMP) were charged and stirred. 9.76 g of morpholine (0.112 mol, manufactured by Fujifilm Wako Pure Chemical Corporation) was added to this solution, and the mixture was stirred at 120 °C for 2 hours. 8.12 g of 3,4-diaminobenzoic acid (0.053 mol, manufactured by Fujifilm Wako Pure Chemical Corporation) was added to this solution, and the mixture was further stirred at 120 °C for 20 hours. After cooling to room temperature, 50 ml of methanol was added dropwise and dispersed for 1 hour. The obtained dispersion was transferred to a 500 ml beaker, 200 ml of methanol was added, and the mixture was dispersed for 12 hours. Then, the precipitate of the dispersion was filtered and washed with 150 ml of methanol and 200 ml of deionized water. In an atmospheric dryer, the obtained wet filter cake was dried at 80 °C for 20 hours, and 19.06 g of an orange solid (yield 90.0%) was obtained as a benzimidazole ring-fused polycyclic compound represented by the following Chemical Formula 1a1-1.

[0181] The obtained orange solid was measured using an elemental analyzer (manufactured by PerkinElmer Japan Co., Ltd., trade name: EA2400II fully automatic elemental analyzer). The results are shown below. From these results, it was confirmed that the obtained benzimidazole ring-fused polycyclic compound had the structure of the following Chemical Formula 1a1-1.

[0182]

Chemical Formula 23

[0183]

[0184] Elemental analysis values

[0185] Measured value C: 68.98%, H: 4.20%, N: 10.45%

[0186] Theoretical value C: 69.17%, H: 4.29%, N: 10.52%

[0187] (Synthesis Example 2)

[0188] 13.27 g of potassium carbonate (0.096 mol, manufactured by Fujifilm Wako Pure Chemical Corporation), 53.2 g of 4-bromonaphthalic anhydride (0.192 mol, manufactured by Fujifilm Wako Pure Chemical Corporation), 96 g of isopropyl alcohol, and 144 g of sulfolane were placed in a 500-ml four-necked flask and stirred at room temperature for a while until completely dissolved. Then, the temperature was raised to 50°C, and 26.44 g of o-aminothiophenol (0.211 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the addition was complete, the temperature was raised to 90°C and the reaction was carried out for 12 hours. After cooling to below 15°C, filtration was performed to obtain 81 g of a wet filter cake. The wet filter cake was added to 120 ml of deionized water, the temperature was raised to 40°C, and it was dispersed for 2 hours. After cooling to room temperature, filtration was performed and it was washed with 1000 ml of deionized water. In a vacuum dryer, the obtained 63.8 g of wet filter cake was dried at 80°C for 16 hours, and 43.15 g of a loess-colored solid was obtained as a naphthylthioether compound represented by the following Chemical Formula 1a2-1'.

[0189]

Chemical Formula 24

[0190]

[0191] 38.6 g of the naphthalimide thioether compound represented by Chemical Formula 1a2-1' (0.12 mol) and 579 g of DMF were placed in a 1000-ml separatory funnel and cooled to below 15°C while stirring. Then, while maintaining below 15°C, 96 g (0.92 mol) of 35 mass% hydrochloric acid was slowly added dropwise thereto. After the addition was complete, it was further cooled to below 5°C in an ice bath. Next, while maintaining below 5°C, 21 g (0.12 mol) of a 40 mass% aqueous sodium nitrite solution was added dropwise thereto and stirred for 2 hours. Then, the temperature was raised to 100°C, and after reacting for 2 hours, it was cooled to room temperature and filtered to obtain a wet filter cake. The wet filter cake was placed in a 300-ml beaker, 150 ml of deionized water was added thereto, and it was dispersed for 30 minutes. After dispersion, filtration was performed and it was washed with 2000 ml of deionized water. In a vacuum dryer, the wet filter cake was dried at 80°C for 16 hours, and 30.12 g of an orange solid was obtained as a thioxanthene ring-fused polycyclic compound represented by the following Chemical Formula 1a2-1".

[0192]

Chemical Formula 25

[0193]

[0194] In a 500 ml four-necked flask, 27.4 g (0.09 mol) of the thioxanthene ring-fused polycyclic compound represented by Chemical Formula 1a2-1 and 195 g of N-methyl-2-pyrrolidone were charged, and the temperature was raised to 120 °C. 13.7 g of 3,4-diaminobenzoic acid (0.09 mol, manufactured by Fujifilm Wako Pure Chemical Corporation) was added thereto, and the mixture was stirred for 24 hours. The reaction solution was hot-filtered and washed in the order of 800 ml of DMF at 100 °C, 500 ml of methanol, and 100 ml of deionized water. In a vacuum dryer, the obtained 101 g of wet filter cake was dried at 80 °C for 15 hours, and 32.05 g of a red solid (yield 84.7%) was obtained as a benzimidazole ring-fused polycyclic compound represented by the following Chemical Formula 1a2-1 and containing a thioxanthene ring.

[0195]

Chemical Formula 26

[0196]

[0197] (Synthesis Example 3)

[0198] In a 100 ml four-necked flask, 13.3 g of 4-bromonaphthalic anhydride (0.048 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 ml of NMP were charged and stirred. 6.51 g of 4-pyridinecarboxylic acid (0.050 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 9.34 of tributylamine (0.05 mol, manufactured by Fujifilm Wako Pure Chemical Corporation) were added to this solution, and the temperature was raised to 120 °C. The reaction was carried out at 120 °C for 5 hours. 8.35 g of 1,8-diaminonaphthalene (0.053 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution, and the reaction was carried out at 120 °C for 6 hours. After 6 hours, when the liquid temperature reached 65 °C, 50 ml of methanol was dropped into the reaction solution and dispersed for 1 hour. The obtained dispersion was transferred to a 500 ml beaker, 200 ml of methanol was added thereto, and further dispersed overnight. Then, the precipitate of the dispersion was filtered and washed with 200 ml of methanol and 200 ml of deionized water. In an atmospheric dryer, the obtained wet filter cake was dried at 80 °C for 40 hours, and 17.72 g of a dark red solid (yield 82.5%) was obtained as a naphthodiazine ring-fused polycyclic compound represented by the following Formula 1b-1.

[0199]

Chemical Formula 27

[0200]

[0201] (Synthesis Example 4)

[0202] Into a 300 ml four-necked flask, 9.49 g of 1,8-diaminonaphthalene (0.06 mol, manufactured by Fujifilm Wako Pure Chemical Corporation) and 11.53 g of trimellitic anhydride (0.06 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were charged. 75 ml of NMP was added thereto, and the temperature was raised to 120 °C and stirred for 4 hours. After 4 hours, it was cooled to room temperature. The obtained dispersion was transferred to a 500 ml beaker, and 200 ml

[0203] of methanol was added and dispersed for 12 hours. Then, the precipitate of the dispersion was filtered and washed with 150 ml of methanol and 300 ml of deionized water heated to 60 °C. In an atmospheric dryer, the obtained wet filter cake was dried at 80 °C for 20 hours, and 15.33 g of a dark red solid (yield 81.3%) was obtained as a polycyclic compound containing an isatinone ring represented by the following formula 1c-2.

[0204]

Chemical formula 28

[0205]

[0206] (Heat resistance evaluation)

[0207] The compounds obtained in Synthesis Examples 1 to 4 were measured using a thermogravimetric differential thermal simultaneous analyzer (TG-DTA6200EXSTAR6000 manufactured by Hitachi High-Technologies Science Corporation) under the temperature rising conditions from 30 °C to 550 °C and a temperature rising rate of 10 °C / min. The temperature at which the weight decreased by 5% from the initial sample weight was read from the chart. For comparison, the 5% weight loss temperature of commercially available C.I. Solvent Orange 60 represented by the following chemical formula was also measured. The results are shown in Table 3.

[0208]

Chemical formula 29

[0209] C.I. Solvent Orange 60

[0210]

Table 3

[0211] Table 3

[0212]

[0213] As can be seen from Table 3, any of the compounds of the synthesis examples contained in the colorants of the present invention exhibited a higher 5% weight loss temperature compared to C.I. Solvent Orange 60. From this, it can be understood that any of the compounds represented by Chemical formulas 1a, 1b, and 1c has high heat resistance and does not change color or fade even when exposed to high temperature conditions.

[0214] (Example 1-1)

[0215] 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: 70G33L) and 0.5 g of the benzimidazole ring-fused compound obtained in Synthesis Example 1 were placed in a stainless-steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. This was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 290°C and a mold temperature of 80°C. Thus, a molded article having a 1-mm-thick portion was produced. The appearance and surface gloss of this molded article were good, and it exhibited a uniform orange color without color unevenness.

[0216] (Example 1-2)

[0217] Except that after the colored resin composition prepared in Example 1-1 was put into the injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the operation was carried out in the same manner as in Example 1-1, and a molded article of Example 1-2 was produced.

[0218] (Evaluation of heat resistance retention of molded article)

[0219] The hues of the molded articles of Example 1-1 and Example 1-2 were measured using a spectral colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: SD7000). The measurement position of the molded article was the 1-mm-thick portion. In addition, the measurement conditions were: light source: D65·φ25.4 mm, viewing angle: 10 degrees, excluding specular reflection light, pressing object: standard white board (manufactured by Suka Testing Machine Co., Ltd.). By obtaining the L value, a value, and b value obtained by measuring the molded article of Example 1-1, the change amounts of the respective values of the L value, a value, and b value obtained by measuring the molded article of Example 1-2 were obtained, and ΔL*, Δa*, and Δb* were calculated. These values were substituted into the following formula to obtain the color difference ΔE.

[0220] ΔE = [(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 1 / 2

[0221] As a result, ΔE = 2.23.

[0222] (Evaluation of hiding power)

[0223] ​Using two types of pressing objects such as a standard blackboard and a standard whiteboard (both manufactured by Suka Testing Machine Co., Ltd.), the operation was carried out in the same manner as in the above color tone evaluation, and the concealment was measured using the same board as the molded product of Example 1-1. For the white board, L* = 73.68, and for the black board, L* = 73.31. The L* value obtained in the above color tone evaluation was used as the L* of the white board, and this value and the L* of the black board were substituted into the following formula to calculate the concealment rate.

[0224] Concealment rate [%] = [(L* of black board) / (L* of white board)] × 100

[0225] The concealment rate was 99.5%.

[0226] (Anti-color bleeding evaluation)

[0227] The molded product of Example 1-1 and a white contact sheet made of the same resin were overlapped, and the two were further fixed with clips to prepare an evaluation sample. The evaluation sample was placed in a heating bath maintained at a constant temperature of 100 °C in a tank. After 24 hours from the start of standing, the evaluation sample was taken out of the heating bath, the clip was removed, and the white contact sheet was observed with the naked eye. According to the degree of color transfer (color bleeding) from the molded product to the white contact sheet, the evaluation was carried out as follows.

[0228] 〇: No color bleeding was observed.

[0229] △: Color bleeding was observed only at the contact part.

[0230] ×: Contamination (sublimation) was observed not only at the contact part but also in the non-contact part.

[0231] As a result, there was no color transfer to the white contact sheet, and the evaluation was 〇.

[0232] (Example 1-3)

[0233] 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: 70G33L) and 0.5 g of the benzimidazole ring-fused compound obtained in Synthesis Example 1 were placed in a stainless steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50), and a molded product for tensile evaluation and a molded product for impact characteristics were produced at a cylinder temperature of 290 °C and a mold temperature of 80 °C. These molded products were processed into a tensile evaluation test piece having a shape conforming to JIS K7162 (2014) type 1A and a Charpy impact evaluation test piece having a type 1 · notch shape A conforming to JIS K7111-1 (2012).

[0234] (Production of test reference plate)

[0235] Except for not using a colorant, the operation was carried out in the same manner as in Examples 1-3 to produce a test piece for tensile evaluation and a test piece for Charpy impact evaluation.

[0236] (Tensile property evaluation)

[0237] In accordance with JIS K7161-1 (2014), using a universal tensile testing machine (manufactured by Orientec Co., Ltd., trade name: RTC-1310A), the test pieces for tensile evaluation of Examples 1-3 were pulled at a tensile speed of 5 mm / min. The tensile strength obtained thereby was 196.03 MPa. Similarly, the test pieces for tensile evaluation of the test reference plate were pulled. The tensile strength obtained thereby was 196.26 MPa. It can be seen that the tensile strength of the test pieces for tensile evaluation of Examples 1-3 is almost the same as that of the test reference plate of the same resin molded plate without a colorant, but due to the inclusion of a colorant, the mechanical strength has not decreased.

[0238] (Impact property evaluation)

[0239] In accordance with JIS K7111-2 (2006), using a digital impact testing machine (manufactured by Toyo Seiki Seisaku-sho, Ltd., trade name: DG-UB), an impact was applied to the test pieces for Charpy impact evaluation of Examples 1-3 with a hammer force of 1 J and an impact speed of 2.9 m / s. The fracture energy was 0.483 J and the impact strength was 15.50 kJ / m 2 . Similarly, an impact was applied to the test pieces for Charpy impact evaluation of the test reference plate. The fracture energy was 0.481 J and the impact strength was 14.88 kJ / m 2 . It can be seen that the impact strength of the test pieces for Charpy impact evaluation of Examples 1-3 is almost the same as that of the test reference plate of the same resin molded plate without a colorant, but due to the inclusion of a colorant, the mechanical strength has not decreased.

[0240] (Example 2-1)

[0241] 499.95 g of polyamide 66 resin (manufactured by DuPont, trade name: 70G33L) and 0.05 g of the benzimidazole ring-fused compound obtained in Synthesis Example 2 were placed in a stainless steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine & Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 290 °C and a mold temperature of 80 °C. Thus, a molded article having a 1-mm-thick portion was produced. The appearance and surface gloss of the molded article were good, and it exhibited a uniform orange color without color unevenness.

[0242] (Example 2-2)

[0243] Except that the colored resin composition prepared in Example 2-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes before injection molding, the same operations as in Example 2-1 were carried out to produce a molded article of Example 2-2.

[0244] (Evaluation of heat resistance retention of molded article)

[0245] The hues of the molded articles of Example 2-1 and Example 2-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 3.03.

[0246] By the same operation as in Example 1-1, the anti-color bleeding property of the molded article of Example 2-1 was evaluated. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0247] (Example 3-1)

[0248] 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: 70G33L) and 0.5 g of the naphthalene-fused phthalazine ring-containing compound obtained in Synthesis Example 3 were placed in a stainless steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 290 °C and a mold temperature of 80 °C. Thus, a molded article having a 1-mm thick portion was produced. The appearance and surface gloss of the molded article were good, and it showed a uniform red color without color unevenness.

[0249] (Example 3-2)

[0250] Except that the colored resin composition prepared in Example 3-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes before injection molding, the same operations as in Example 3-1 were carried out to produce a molded article of Example 3-2.

[0251] (Evaluation of heat resistance retention of molded article)

[0252] The hues of the molded articles of Example 3-1 and Example 3-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 1.40.

[0253] (Evaluation of anti-color bleeding property)

[0254] By the same operation as in Example 1-1, the molded article of Example 3-1 was evaluated for color bleeding resistance. As a result, there was no color transfer to the contacted white sheet at all, and the evaluation was ○.

[0255] (Example 4-1)

[0256] 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: 70G33L) and 0.5 g of the isoindolinone ring-fused compound obtained in Synthesis Example 4 were placed in a stainless steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 290 °C and a mold temperature of 80 °C. Thus, a molded article having a 1-mm thick portion was produced. The appearance and surface gloss of the molded article were good, and it exhibited a uniform red color without color unevenness.

[0257] (Example 4-2)

[0258] Except that after the colored resin composition prepared in Example 4-1 was put into the injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the operation was carried out in the same manner as in Example 4-1 to produce a molded article of Example 4-2.

[0259] (Evaluation of heat retention resistance of molded article)

[0260] The hues of the molded article of Example 4-1 and the molded article of Example 4-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 2.27.

[0261] (Evaluation of color bleeding resistance)

[0262] By the same operation as in Example 1-1, the molded article of Example 4-1 was evaluated for color bleeding resistance. As a result, there was no color transfer to the contacted white sheet at all, and the evaluation was ○.

[0263] (Comparative Example 1-1)

[0264] 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: 70 g of 33L) and 0.5 g of C.I. Pigment Orange 43 (manufactured by Clariant Corporation, trade name: PV Fast Orange GRL) as a colorant were placed in a stainless-steel drum and stirred and mixed for 1 hour. The obtained mixture was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 290 °C and a mold temperature of 80 °C. Thus, a molded article having a 1-mm-thick portion was produced. The appearance and surface gloss of the molded article were good, and it exhibited a uniform orange color without color unevenness.

[0265] (Comparative Example 1-2)

[0266] Except that after the mixture prepared in Comparative Example 1-1 was put into the injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the same operations as in Comparative Example 1-1 were carried out to produce a molded article of Comparative Example 1-2.

[0267] (Evaluation of heat resistance retention of molded article)

[0268] The hues of the molded articles of Comparative Example 1-1 and Comparative Example 1-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 4.48.

[0269] (Evaluation of bleeding resistance)

[0270] By the same operation as in Example 1-1, the bleeding resistance of the molded article of Comparative Example 1-1 was evaluated. As a result, it was confirmed that the color of the colorant was transferred to the color of the contacted white sheet, and the evaluation was Δ.

[0271] Table 4 summarizes and shows the color difference ΔE of the molded articles of Example 1-1, 2-1, 3-1, and 4-1 and Comparative Example 1-1 and the results of the bleeding resistance test at a tank temperature of 100 °C.

[0272]

Table 4

[0273] Table 4

[0274]

[0275] ※PA = Polyamide

[0276] It can be known that the colorants of the examples of the present invention have extremely small color changes even when kept at a high temperature in the injection molding machine, and no color transfer occurs even when in contact with the contacted white sheet, so the bleeding resistance is high.

[0277] (Colorant Example 1)

[0278] 100 g of the orange dye-containing benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 1, 7.5 g of the red dye-containing phenanthroline ring-fused polycyclic compound obtained in Synthesis Example 3, and 100 g of titanium oxide as a white pigment (manufactured by Ishihara Sangyo Co., Ltd., CR62), were placed in a stainless-steel drum and stirred and mixed for 1 hour to prepare Colorant Example 1.

[0279] (Colorant Example 2)

[0280] 20 g of the orange dye-containing benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 1, 20 g of another orange dye-containing benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 2, 10 g of the red dye-containing phenanthroline ring-fused polycyclic compound obtained in Synthesis Example 3, and 200 g of titanium oxide as a white pigment (manufactured by Ishihara Sangyo Co., Ltd., CR62), were placed in a stainless-steel drum and stirred and mixed for 1 hour to prepare Colorant Example 2.

[0281] (Masterbatch Example 1)

[0282] 900 g of polyamide 66 resin (manufactured by DuPont, trade name: 101NC010) and 100 g of the colorant obtained in Example 1 were placed in a stainless-steel drum and stirred and mixed for 1 hour. The obtained mixture was melt-mixed using a single-screw extruder (manufactured by Empresa Industrial S.A., trade name: E30SV) at a cylinder temperature of 290°C. The mixture was cooled in a water bath and cut using a granulator to obtain colored pellets. Thereafter, through a drying process, an orange masterbatch with a colorant concentration of 10% by mass was obtained.

[0283] (Masterbatch Example 2)

[0284] 900 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genesta ) G1300A) and 100 g of the colorant obtained in Colorant Example 2 were placed in a stainless-steel drum and stirred and mixed for 1 hour. The obtained mixture was melt-mixed using a single-screw extruder (manufactured by Empresa Industrial S.A., trade name: E30SV) at a cylinder temperature of 290°C. The mixture was cooled in a water bath and cut using a granulator to obtain colored pellets. Thereafter, through a drying process, an orange masterbatch with a colorant concentration of 10% by mass was obtained.

[0285] (Masterbatch Example 3)

[0286] 900 g of polyamide 66 resin (manufactured by DuPont, trade name: 101 NC010) and 100 g of the benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 1 were placed in a stainless steel drum and stirred and mixed for 1 hour. The obtained mixture was melt-mixed at a cylinder temperature of 290°C using a single-screw extruder (manufactured by Empresa Nacional de Participaciones, S.A., trade name: E30SV). The mixture was cooled in a water bath and cut with a granulator to obtain colored granules. Thereafter, through a drying process, an orange masterbatch with a colorant concentration of 10% by mass was obtained.

[0287] (Masterbatch Example 4)

[0288] 900 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar G1300A) and 100 g of the benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 1 were placed in a stainless steel drum and stirred and mixed for 1 hour. The obtained mixture was melt-mixed at a cylinder temperature of 290°C using a single-screw extruder (manufactured by Empresa Nacional de Participaciones, S.A., trade name: E30SV). The mixture was cooled in a water bath and cut with a granulator to obtain colored granules. Thereafter, through a drying process, an orange masterbatch with a colorant concentration of 10% by mass was obtained.

[0289] (Example 5-1)

[0290] 840 g of polyamide 66 resin (manufactured by Asahi Kasei Corporation, trade name: Leona FH772) and 10 g of the masterbatch of Masterbatch Example 1 were placed in a stainless steel drum, and a colored resin composition was prepared by stirring and mixing for 1 hour. It was put into an injection molding machine (manufactured by Toyo Machine & Metal Co., Ltd., trade name: SI-50) set at a cylinder temperature of 290°C (nozzle tip temperature 290°C) and a mold temperature of 85°C, and a rectangular molded article of Example 5-1 having a vertical dimension of 80 mm × a horizontal dimension of 50 mm, with a 1 mm thick portion and a 3 mm thick portion, and being orange in color was produced by molding in a conventional manner.

[0291] (Hue Measurement)

[0292] The hue of the molded article of Example 5-1 was measured in the same manner as the hue measurement in the "Evaluation of Heat Resistance Retention of Molded Article" of the molded article of Example 1-1. As a result, a deep orange hue of L* = 65.49 a* = 38.49 b* = 83.55 was exhibited.

[0293] (Example 5-2)

[0294] Except that after the colored resin composition prepared in Example 5-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the operation was carried out in the same manner as in Example 5-1 to produce a molded article of Example 5-2.

[0295] (Evaluation of heat resistance retention of molded article)

[0296] The hue of the molded article of Example 5-2 was measured in the same manner as in Example 1-2. The L value, a value, and b value obtained here and those of Example 5-1 obtained in the above "hue measurement" were calculated in the same manner as in the "evaluation of heat resistance retention of molded article" of the molded article of Example 1-1 to obtain the color difference ΔE between the two. The result was ΔE = 2.05.

[0297] (Evaluation of bleeding resistance)

[0298] By the same operation as in Example 1-1, the bleeding resistance of the molded article of Example 5-1 was evaluated. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0299] (Example 6-1)

[0300] 840 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar G1300A) and 10 g of the masterbatch of Example 3 were put into a stainless steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50) set at a cylinder temperature of 320 °C (nozzle tip temperature 290 °C) and a mold temperature of 135 °C, and a planar view rectangular orange molded article of Example 6-1 with a vertical dimension of 80 mm × a horizontal dimension of 50 mm and having a 1 mm thick part and a 3 mm thick part was produced by molding in a conventional manner.

[0301] (Example 6-2)

[0302] Except that after the colored resin composition prepared in Example 6-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the operation was carried out in the same manner as in Example 6-1 to produce a molded article of Example 6-2.

[0303] (Evaluation of heat resistance retention of molded article)

[0304] The hues of the molded article of Example 6-1 and the molded article of Example 6-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 4.36.

[0305] (Evaluation of bleeding resistance)

[0306] Except for setting the temperature in the tank to 130 °C, the molded product of Example 7-1 was evaluated for bleeding resistance by the same operation as in Example 1-1. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0307] (Example 7-1)

[0308] 840 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar G1300A) and 10 g of the masterbatch of Example 2 were put into a stainless-steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50) set at a cylinder temperature of 320 °C (nozzle tip temperature of 290 °C) and a mold temperature of 135 °C, and a plane-view rectangular orange molded product of Example 7-1 with a vertical dimension of 80 mm × a horizontal dimension of 50 mm and having a 1-mm-thick part and a 3-mm-thick part was produced by molding in a conventional manner.

[0309] (Measurement of hue)

[0310] The hue of the molded product of Example 7-1 was measured in the same manner as the hue measurement in the "Evaluation of heat retention resistance of the molded product" of the molded product of Example 1-1. As a result, a hue equivalent to RAL2003 of L* = 65.90 a* = 42.70 b* = 65.72 was exhibited.

[0311] (Example 7-2)

[0312] Except that after the colored resin composition prepared in Example 7-1 was put into the injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the same operation as in Example 7-1 was performed to produce a molded product of Example 7-2.

[0313] (Evaluation of heat retention resistance of the molded product)

[0314] The hues of the molded product of Example 7-1 and the molded product of Example 7-2 were measured by the same method as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 6.64.

[0315] (Evaluation of bleeding resistance)

[0316] The molded product of Example 7-1 was evaluated for bleeding resistance by the same operation as in Example 6-1. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0317] (Example 8-1)

[0318] 499.5 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar G1300A) and 0.5 g of the naphthalene-fused phthalazine ring-containing polycyclic compound obtained in Synthesis Example 3 were placed in a stainless-steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine & Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 320 °C and a mold temperature of 135 °C. Thus, a molded article having a 1-mm-thick portion was produced. The appearance and surface gloss of the molded article were good, and it exhibited a uniform red color without color unevenness.

[0319] (Example 8-2)

[0320] Except that after the colored resin composition prepared in Example 8-1 was put into the injection molding machine and left in the cylinder of the injection molding machine for 3 minutes, injection molding was carried out, the same operations as in Example 8-1 were performed to produce a molded article of Example 8-2.

[0321] (Evaluation of heat resistance retention of molded article)

[0322] The hues of the molded articles of Example 8-1 and Example 8-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 1.40.

[0323] (Evaluation of bleeding resistance)

[0324] By the same operation as in Example 6-1, the bleeding resistance of the molded article of Example 8-1 was evaluated. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0325] (Example 9-1)

[0326] 499.5 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar G1300A) and 0.5 g of the isoindolinone ring-fused polycyclic compound obtained in Synthesis Example 4 were placed in a stainless-steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine & Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in the conventional manner at a cylinder temperature of 320 °C and a mold temperature of 135 °C. Thus, a molded article having a 1-mm-thick portion was produced. The appearance and surface gloss of the molded article were good, and it exhibited a uniform red color without color unevenness.

[0327] (Example 9-2)

[0328] Except that the colored resin composition prepared in Example 9-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes before injection molding, the operation was carried out in the same manner as in Example 9-1 to produce a molded article of Example 9-2.

[0329] (Evaluation of heat resistance retention of molded article)

[0330] The hues of the molded articles of Example 9-1 and Example 9-2 were measured in the same manner as in Example 1-1 and Example 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 0.83.

[0331] (Evaluation of bleeding resistance)

[0332] By the same operation as in Example 6-1, the bleeding resistance of the molded article of Example 9-1 was evaluated. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0333] (Example 10-1)

[0334] 399.6 g of polyphenylene sulfide resin (manufactured by Polyplastics Co., Ltd., trade name: Durafide ) 1130A6), 0.32 g of the orange dye-containing benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 1, and 0.08 g of the same orange dye-containing benzimidazole ring-fused polycyclic compound obtained in Synthesis Example 2 were placed in a stainless steel drum and mixed by stirring for 1 hour to prepare a colored resin composition. It was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50-6S), and injection molding was carried out in a conventional manner at a cylinder temperature of 310 °C and a mold temperature of 140 °C. Thus, a molded article having a 1-mm thick portion was produced. The appearance and surface gloss of the molded article were good, and it showed a uniform orange color without color unevenness.

[0335] (Hue measurement)

[0336] The hue of the molded article of Example 10-1 was measured in the same manner as the hue measurement in the "Evaluation of heat resistance retention of molded article" of the molded article of Example 1-1. As a result, it showed a deep orange hue of L* = 66.24 a* = 39.64 b* = 62.68.

[0337] (Example 10-2)

[0338] Except that the colored resin composition prepared in Example 10-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes before injection molding, the operation was carried out in the same manner as in Example 10-1 to produce a molded article of Example 10-2.

[0339] (Evaluation of heat resistance retention of molded article)

[0340] The hues of the molded articles of Example 10-1 and Example 10-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 4.54.

[0341] (Evaluation of bleeding resistance)

[0342] By the same operation as in Example 6-1, the bleeding resistance of the molded article of Example 10-1 was evaluated. As a result, there was no color transfer to the color of the contacted white sheet, and the evaluation was ○.

[0343] (Comparative Example 2-1)

[0344] 499.5 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar G1300A) and 0.5 g of C.I. Pigment Orange 43 (manufactured by Clariant, trade name: PV Fast Orange GRL) as a colorant were put into a stainless steel drum and stirred and mixed for 1 hour. The obtained mixture was put into an injection molding machine (manufactured by Toyo Machine Metal Co., Ltd., trade name: SI-50), and injection molding was carried out in a conventional manner at a cylinder temperature of 320 °C and a mold temperature of 135 °C. Thus, a molded article having a 1 mm thick portion was produced. The appearance and surface gloss of the molded article were good, and it showed a uniform orange color without color unevenness.

[0345] (Comparative Example 2-2)

[0346] Except that the mixture prepared in Comparative Example 2-1 was put into an injection molding machine and left in the cylinder of the injection molding machine for 3 minutes before injection molding, the operation was carried out in the same manner as in Comparative Example 1-1 to produce a molded article of Comparative Example 2-2.

[0347] (Evaluation of heat resistance retention of molded article)

[0348] The hues of the molded articles of Comparative Example 2-1 and Comparative Example 2-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was obtained from the results. The result was ΔE = 7.50.

[0349] (Evaluation of bleeding resistance)

[0350] By the same operation as in Example 6-1, the molded article of Comparative Example 1-1 was evaluated for anti-color bleeding property. As a result, it was confirmed that the colorant transferred to the color of the contacted white sheet, and the evaluation was Δ.

[0351] Table 5 summarizes and shows the color difference ΔE of the molded articles of Example 6-1, 7-1, 8-1, 9-1, and 10-1 and Comparative Example 2-1 and the results of the color bleeding test at a tank temperature of 130°C.

[0352]

Table 5

[0353] Table 5

[0354]

[0355] ※PA = polyamide, PPS = polyphenylene sulfide

[0356] It can be seen that the colorant of the embodiment of the present invention has extremely small color change even when held at a high temperature in an injection molding machine, and does not cause color transfer even when in contact with a contacted white sheet, so the anti-color bleeding property is high.

[0357] (Example 11)

[0358] Using the colored resin composition prepared in Example 1-1, a connector housing for an automotive wire harness was produced by insert molding with a metal component for electrical connection fixed in a mold. The connector housing exhibited a bright orange color.

[0359]

Industrial Applicability

[0360] The colorant of the present invention, the masterbatch containing the colorant, and the colored resin composition are used for manufacturing a colored molded article, which can be used as a connector housing for a high-voltage wire harness for automobiles, a wire covering material, an intake manifold of an internal combustion engine, an engine hood, etc., a laser-welded component manufactured by laser-welding a plurality of components, a medical tube used in infusion or nutritional agent infusion, a food packaging material such as a spouted pouch containing a liquid food or beverage composition, and a bottle cap and a label.

Claims

1. A masterbatch, comprising: a colorant for coloring a thermoplastic resin and a thermoplastic resin; wherein the colorant comprises at least one compound represented by the following Chemical Formula 1a and / or at least one compound represented by the following Chemical Formula 1b, [Chemical Formula 1] In Chemical Formula 1a, R 1 and R 2 are each independently a hydrogen atom, a substituted amino group, or a nitrogen-containing heterocyclic group, where The nitrogen-containing heterocyclic group is selected from at least one of morpholinyl, piperidinyl, pyrrolidinyl and piperazinyl, and the substituted amino group or nitrogen-containing heterocyclic group is optionally substituted with a substituent selected from linear or branched alkyl groups having 1 to 4 carbon atoms, linear or branched alkoxy groups having 1 to 4 carbon atoms, hydroxyl groups and carboxyl groups; and R 1 and R 2 are not simultaneously hydrogen atoms; R 3 is at least one selected from straight-chain or branched alkoxy groups, carboxyl groups, hydroxyl groups, sulfo groups, and sulfonamide groups having 1 to 4 carbon atoms, and p is a number from 0 to 2, [Chemical Formula 2] In Chemical Formula 1b, R 4 and R 5 are each independently a hydrogen atom or a substituted nitrogen-containing heterocyclic group, where the nitrogen-containing heterocyclic group is selected from at least one of morpholinyl, piperidinyl, pyrrolidinyl, and piperazinyl, and the substituted nitrogen-containing heterocyclic group is optionally substituted with a substituent selected from a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and a carboxyl group; and R 4 and R 5 are not simultaneously hydrogen atoms; R 6 is at least one selected from linear or branched alkoxy groups, carboxyl groups, hydroxyl groups, sulfo groups, and sulfonamide groups having 1 to 4 carbon atoms, and q is a number from 0 to 4; wherein, The compound represented by the chemical formula 1a includes those in which R 1 or R 2 is the compound of the nitrogen-containing heterocyclic group.

2. The masterbatch according to claim 1, wherein the content of the colorant is 5 to 30% by mass.

3. A colored resin composition, comprising: the masterbatch according to claim 1 or claim 2 and a thermoplastic resin.

4. The colored resin composition according to claim 3, wherein the thermoplastic resin comprises at least one selected from the group consisting of a polyamide resin, a polyolefin resin, a polyester resin, a polycarbonate resin, and a polyphenylene sulfide resin.

5. A molded article, wherein it is molded from the colored resin composition according to claim 3 or claim 4.

6. The molded article according to claim 5, wherein the molded article is a connector housing for an automotive wiring harness.

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