Colorant, and masterbatch, colored resin composition, and molded article containing the same

Abstract

[Problem] To provide a colorant that has high heat resistance and thus does not cause discoloration or fading even when exposed for a long period of time under long-term high heat conditions, that has excellent bleed resistance and sublimation resistance and thus does not cause color to migrate to a mold or to other resin components, and that does not cause a thermoplastic resin to lose the physical properties thereof when added thereto. [Solution] This colorant includes at least one compound represented by chemical formula (1a), at least one compound represented by chemical formula (1b), and / or at least one compound represented by chemical formula (1c) (in chemical formulas (1a), (1b), and (1c), each of R1, R2, R4, R5, R7, and R8 is a hydrogen atom or a nitrogen-containing heterocyclic group or an amino group that may have a substituent, each of R3, R6, and R9 is at least one group selected from among an alkoxy group, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamide group, p and r are each 0 to 2 inclusive, and q is 0 to 4 inclusive).

Description

[Technical Field]

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

[0002] Hybrid vehicles (HVs) and electric vehicles (EVs) are powered by motors and are equipped with batteries that generate voltages of 60V or more, much higher than those used in conventional vehicles powered solely by engines. The color of high-voltage wiring harnesses, such as the electrical cables and connectors connected to such high-voltage batteries, is regulated by standards to be orange for the connector housings and wire sheathing, in order to clearly indicate the presence of high-voltage current. For example, in the United States, this is regulated by the SAE J1673 automotive standard. The shades and brightness of orange vary by country, from slightly dark orange to bright orange to even fluorescent orange.

[0003] High-voltage wiring harnesses are exposed for long periods of time to heat generated by components that heat up due to operation of the battery, motor, inverter, engine, etc., and therefore are made from highly heat-resistant thermoplastic resins, such as polyamide resins. Such highly heat-resistant thermoplastic resins are molded at high temperatures of 250 to 350°C. Therefore, the colorant that imparts the orange color to the thermoplastic resin must have high heat resistance that can withstand the high temperatures encountered during molding of the thermoplastic resin and the high heat generated by the battery, etc., and not discolor or fade over the long lifespan of a battery (approximately 10 years), sublimation resistance that does not contaminate the molds and molding machines used to mold the thermoplastic resin, and high bleed resistance that prevents color transfer upon contact with other thermoplastic resin products.

[0004] It is known that orange dyes can be prepared by mixing perinone dyes or naphthalimide dyes with dyes or pigments of other colors. Patent Document 1 describes perinone dyes that color thermoplastic resins orange. Naphthalimide dyes are commercially available, for example, as CI Solvent Yellow 44, 104, 116, and CI Disperse Yellow 11. These naphthalimide dyes have an amino group as a chromophore, and have a lightness L in the CIE-Lab color space coordinates. * It exhibits a bright color with a value of 70 or more, resulting in a vivid orange color. A masterbatch is prepared by kneading this orange dye with a thermoplastic resin raw material, and this masterbatch is mixed with the same or different thermoplastic resin raw material as the thermoplastic resin raw material contained therein and various additives to prepare a colored resin composition, which is then molded into molded products for connectors of high-voltage wire harnesses.

[0005] The dyes mentioned above have relatively simple structures and low molecular weights, making them easy to adjust to obtain an orange color. However, the orange colors prepared using these dyes do not have the heat resistance, bleed resistance, and sublimation resistance required for application to connectors in automotive high-voltage wiring harnesses.

[0006] Meanwhile, Patent Document 2 describes a method for producing a highly heat-resistant orange inorganic pigment for polyamide resin by mixing titanium dioxide, zinc peroxide, and tin oxide powders, calcining the mixture at 850°C, and pulverizing the resulting calcined product. While the pigment has excellent bleeding resistance and sublimation resistance, it lacks clarity and can discolor to brown or dark colors due to thermal history. Furthermore, because the pigment is dispersed in the thermoplastic resin rather than dissolved in it like a dye, it can reduce its physical properties, such as tensile strength and impact resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 54-19012 [Patent Document 2] Korean Patent No. 10-1977321 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made to solve the above-mentioned problems, and aims to provide a colorant which has high heat resistance and therefore does not discolor or fade even when exposed to high temperature conditions for a long period of time, has excellent bleeding resistance and sublimation resistance and therefore does not contaminate molding dies or molding machines or cause color transfer to other resin parts, and does not impair the physical properties of the thermoplastic resin to which it is added, as well as a masterbatch and colored resin composition containing the same, and a molded article obtained from the colored resin composition. [Means for solving the problem]

[0009] The colorant used to achieve the above object is represented by the following chemical formula (1a): [ka] (In chemical formula (1a), R 1 and R 2 are independently hydrogen atoms, Or, amino group 、 or At least one selected from a morpholino group, a piperidinyl group, a pyrrolidinyl group, and a piperazinyl group A nitrogen-containing heterocyclic group and both are not hydrogen atoms at the same time. 、R 3 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamido group, and p is a number of 0 to 2, and / or The following chemical formula (1b) [ka] (In chemical formula (1b), R 4 and R 5 are hydrogen atoms independently of each other Or, amino group、 or a nitrogen-containing heterocyclic group and both are not hydrogen atoms at the same time, R 6 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamido group, and q is a number of 0 to 4. Contains things. and / or the following chemical formula (1c): [ka] (In chemical formula (1c), R 7 and R 8 are each independently a hydrogen atom, an optionally substituted amino group, or a nitrogen-containing heterocyclic group, and R 9 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamido group, and r is a number of 0 to 2.

[0010] The colorant is a compound represented by the chemical formula (1a) in the R 1 or R 2 is the nitrogen-containing heterocyclic group, and 1 and R 2 and a compound in which the rings are linked to each other to form the fused ring.

[0011] Examples of the colorant include those in which the nitrogen-containing heterocyclic group is at least one selected from a morpholino group, a piperidinyl group, a pyrrolidinyl group, and a piperazinyl group.

[0012] In the colorant, the amino group and / or the nitrogen-containing heterocyclic group may have at least one 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 hydroxy group, and a carboxy group.

[0013] The colorant may be, for example, the R 1 and R 2is the fused ring, the chemical formula (1a) is represented by the following chemical formula (1a2): [ka] (In chemical formula (1a2), R 3 and p are the same as those in the chemical formula (1a), and R 10 is a hydrogen atom, a carboxy 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.

[0014] The masterbatch of the present invention contains any of the colorants described above and a thermoplastic resin.

[0015] The masterbatch may contain the colorant in an amount of 5 to 30% by mass.

[0016] The colored resin composition of the present invention contains any of the colorants described above and / or any of the master batches described above, and a thermoplastic resin.

[0017] In the colored resin composition, the thermoplastic resin may contain at least one resin selected from the group consisting of polyamide resin, polyolefin resin, polyester resin, polycarbonate resin, and polyphenylene sulfide resin.

[0018] The molded article of the present invention is molded from any of the above colored resin compositions.

[0019] The molded article may be a connector housing for an automobile wiring harness. [Effects of the Invention]

[0020] The colorant of the present invention exhibits high heat resistance, high light resistance, and bleeding resistance, and is highly compatible with the thermoplastic resin contained in the masterbatch or colored resin composition, so that the colorant does not impair the mechanical strength properties such as tensile strength and impact strength that the thermoplastic resin originally has.

[0021] Furthermore, since the compounds represented by the above chemical formulas (1a) to (1c) have a nitrogen-containing chromophore substituent such as an amino group or a nitrogen-containing heterocyclic group, a molded article formed from the masterbatch and colored resin composition containing the colorant of the present invention has a high brightness hue with excellent visibility.

[0022] The masterbatch and colored resin composition containing the colorant of the present invention have high heat resistance and high light resistance, and are therefore suitable for producing molded articles that are required to be free from discoloration and fading. DETAILED DESCRIPTION OF THE INVENTION

[0023] Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these embodiments.

[0024] (coloring agent) The compound essentially contained in the colorant of the present invention is represented by the following chemical formula (1a): [ka] (In chemical formula (1a), R 1 and R 2 are each independently a hydrogen atom, an optionally substituted amino group, or a nitrogen-containing heterocyclic group, and both are not simultaneously hydrogen atoms or are linked to each other to form a condensed ring; R 3 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamido group, and p is a number of 0 to 2), at least one compound represented by the following chemical formula (1b): [ka] (In chemical formula (1b), R 4 and R 5 are each independently a hydrogen atom, an optionally substituted amino group, or a nitrogen-containing heterocyclic group, and both are not simultaneously hydrogen atoms; R 6is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamido group, and q is a number of 0 to 4), and / or at least one compound represented by the following chemical formula (1c): [ka] (In chemical formula (1c), R 7 and R 8 are each independently a hydrogen atom, an optionally substituted amino group, or a nitrogen-containing heterocyclic group, and R 9 is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group and a sulfonamido group, and r is a number of 0 to 2.

[0025] The compounds of chemical formulas (1a) to (1c) have in common the fact that they are fused ring compounds having a benzoisoquinoline ring as a central skeleton. Specifically, the compound of chemical formula (1a) is a fused ring compound containing a benzimidazole ring in which a benzimidazole ring is fused to a central skeleton, the compound of chemical formula (1b) is a fused ring compound containing a perimidine ring in which a perimidine ring is fused to a central skeleton, and the compound of chemical formula (1c) is a fused ring compound containing an isoindolinone ring in which an isoindolinone ring is fused to a central skeleton.

[0026] 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 Nitrogen-containing heterocyclic groups of R include morpholino, piperidinyl, pyrrolidinyl, and piperazinyl groups. 1 and R 2 When both R and R are nitrogen-containing heterocyclic groups, the nitrogen-containing heterocyclic groups may be the same or different. 4 and R 5 , and R 7 and R 8 The same is true.

[0027] R 1 , R 2 , R 4 , R 5 , R 7 , and R 8 When is an amino group, piperidinyl group, pyrrolidinyl group, or piperazinyl group, it may have a substituent. Examples of the substituent include 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 hydroxy group, and a carboxy group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0028] R in chemical formula (1a) 1 and R 2 When these are linked to each other to form a fused ring, the fused ring has a heteroatom X, and examples of X include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0029] R in chemical formula (1a) 3 , R in chemical formula (1b) 6 and R in chemical formula (1c) 9 Examples of the alkoxy group of R include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. 3 , R 6 , and R 9 "-SO2N(R a )2”, a plurality of R aare preferably each independently 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, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. On the other hand, R 3 , R 6 , and R 9 -NH(SO)2R b ", this R b As above, R a These R 3 , R 6 , and R 9 The substitution position of is not particularly limited.

[0030] p in chemical formula (1a) and r in chemical formula (1c) are numbers from 0 to 2, and preferably 1. Furthermore, q in chemical formula (1b) is a number from 0 to 4, specifically including the integers 0, 1, 2, 3, and 4, and preferably 0.

[0031] The benzimidazole ring-containing fused ring compound of chemical formula (1a) exhibits an orange color. A specific example thereof is represented by the following chemical formula (1a1-1).

[0032] [ka]

[0033] This benzimidazole ring-containing fused ring compound can be obtained by reacting a naphthalic anhydride derivative, such as 4-bromonaphthalic anhydride, with morpholine, followed by reaction with 3,4-diaminobenzoic acid. This reaction produces four isomers of the benzimidazole ring-containing fused ring compound. The ratio of the isomers is not limited. Only one of these isomers may be selected and produced, or a mixture of the isomers may be produced and then separated using a column. The isomers collectively represented by chemical formula (1a1-1) are represented by the following chemical formulas (1a1-1-1) to (1a1-1-4).

[0034] [ka]

[0035] In this specification, for convenience, the structures of compounds within the scope of the present invention are represented by a single comprehensive chemical formula, and the chemical formulas of isomeric structures may be omitted. Specifically, for example, chemical formula (1a1-1) also includes isomers that are optionally contained in the production process, such as those represented by chemical formulas (1a1-1-1) to (1a1-1-4).

[0036] Other specific examples of the benzimidazole ring-containing fused ring compound represented by chemical formula (1a) include those represented by the following chemical formulae (1a1-2) to (1a1-8).

[0037] [ka]

[0038] In chemical formula (1a), R 1 and R 2 At least one of R is a nitrogen-containing heterocyclic group, and R 3 When R is a carboxy group, the benzimidazole ring-containing fused ring compound exhibits higher heat resistance and bleeding resistance, is rich in color development, and is excellent in compatibility with the thermoplastic resin described below, which is preferable. 1 and / or R 2The nitrogen-containing heterocyclic group of R acts as a chromophore and improves heat resistance. 3 This is because the carboxyl group in R improves heat resistance and bleeding resistance. In particular, when the thermoplastic resin is a polyamide resin, 3 It is more preferable that the amide group or carboxy group in the polyamide resin molecule is a carboxy group. In this case, the bleeding resistance is significantly improved. This is presumably because the amide group or carboxy group in the polyamide resin molecule and the carboxy group in the benzimidazole ring-containing fused ring compound form intermolecular hydrogen bonds to suppress the occurrence of the bleeding phenomenon.

[0039] Further examples of the benzimidazole ring-containing fused ring compound represented by chemical formula (1a) include R 1 and R 2 are linked to each other to form a fused ring, which is specifically represented by the following chemical formula (1a2).

[0040] [ka] (In chemical formula (1a2), R 3 and p are the same as those in the chemical formula (1a), and R 10 is a hydrogen atom, a carboxy 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.

[0041] R in chemical formula (1a2) 10 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

[0042] A specific example of the benzimidazole ring-containing fused ring compound represented by chemical formula (1a2) is the compound represented by the following chemical formula (1a2-1): This compound exhibits a reddish orange color (reddish orange).

[0043] [ka]

[0044] The benzimidazole ring-containing fused ring compound represented by chemical formula (1a2-1) has a thioxanthene structure as part of its structure. This benzimidazole ring-containing fused ring compound can be obtained by reacting 2-aminobenzenethiol with 4-bromonaphthalic anhydride to obtain a naphthalimide thioether, followed by a ring-closure reaction to form a xanthene derivative, and then further reacting with 3,4-diaminobenzoic acid. This reaction produces four isomers of the benzimidazole ring-containing fused ring compound. The ratio of the isomers is not limited. Only one of these isomers may be produced, or a mixture of the isomers may be produced and then separated using a column. The isomers collectively represented by chemical formula (1a2-1) are represented by the following chemical formulas (1a2-1-1) to (1a2-1-4).

[0045] [ka]

[0046] Another specific example of the benzimidazole ring-containing fused ring compound represented by chemical formula (1a2) is the compound represented by the following chemical formula (1a2-2): This compound exhibits a yellowish orange color (orange yellow).

[0047] [ka]

[0048] The benzimidazole ring-containing fused ring compound represented by chemical formula (1a2-2) has a xanthene structure as part of its structure. This benzimidazole ring-containing fused ring compound can be obtained by reacting 2-nitrophenol with 4-bromonaphthalic anhydride to obtain a naphthalimide ether, followed by reduction and ring-closure to form a xanthene derivative, and then further reacting with 3,4-diaminobenzoic acid. This reaction produces four isomers of the benzimidazole ring-containing fused ring compound. The ratio of the isomers is not critical. It is possible to selectively produce one of these isomers, or to produce a mixture of isomers and then separate the isomers using a column.

[0049] The perimidine ring-containing fused ring compound of chemical formula (1b) exhibits a red color. A specific example thereof is represented by the following chemical formula (1b-1).

[0050] [ka]

[0051] This perimidine ring-containing fused ring compound can be obtained by reacting a naphthalic anhydride derivative with 4-piperidinecarboxylic acid, followed by a reaction with 1,8-diaminonaphthalene. This reaction produces two isomers of the perimidine ring-containing fused ring compound. The ratio of the isomers is not limited. Either one of these isomers can be selected and produced, or a mixture of the isomers can be produced and then separated using a column. The isomers collectively represented by chemical formula (1b-1) are represented by the following chemical formulas (1b-1-1) and (1b-1-2).

[0052] [ka]

[0053] Other specific examples of the perimidine ring-containing fused ring compound represented by chemical formula (1b) include those represented by the following chemical formulas (1b-2) to (1b-6). [ka]

[0054] In chemical formula (1b), R 4 and R 5 When at least one of the groups is a nitrogen-containing heterocyclic group having a carboxy group, the perimidine ring-containing fused ring compound exhibits higher heat resistance and bleeding resistance, and is also excellent in color development, which is preferable.

[0055] The isoindolinone ring-containing fused ring compound represented by chemical formula (1c) exhibits a dark red to red color. A specific example thereof is represented by the following chemical formula (1c-1).

[0056] [ka]

[0057] This isoindolinone ring-containing fused ring compound can be obtained by reacting pyromellitic anhydride with 1,8-diamino-4-bromonaphthalene, followed by further reaction with morpholine. This reaction produces four isomeric isomers of the isoindolinone ring-containing fused ring compound. The ratio of the isomers is not limited. Only one of these isomers can be produced, or a mixture of the isomers can be produced and then separated using a column.

[0058] In the reaction for producing the isoindolinone ring-containing fused ring compound represented by chemical formula (1c), R 7 and R 8 When a compound in which the hydrogen atom is not present is simultaneously produced, an isomer exists. 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 structures of compounds included in the scope of the present invention are represented by one comprehensive chemical formula, and the chemical formulas of the isomeric structures are omitted.

[0059] [ka]

[0060] Other specific examples of the isoindolinone ring-containing fused ring compound represented by chemical formula (1c) include those represented by the following chemical formulae (1c-2) to (1c-6).

[0061] [ka]

[0062] The 5% thermal weight loss temperature can be used as a value for evaluating the heat resistance of the compounds represented by chemical formulas (1a) to (1c). This value is the temperature at which the weight of the compound represented by chemical formulas (1a) to (1c) is measured to have lost 5% of its weight from the weight at the start of the measurement (room temperature) during the temperature rise process of thermogravimetric differential thermal analysis. The 5% thermal weight loss temperature of the compound 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.

[0063] 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. This maximum absorption wavelength is measured using an ultraviolet-visible spectrophotometer under general conditions.

[0064] The color required for the connectors and wire sheathing of high-voltage wire harnesses is orange, which is expressed as RAL2000, 2001, 2002, 2003, 2004, 2008, 2009, 2010, 2011, and 2012 on the RAL color chart. In this case, the hue expressed in the CIE-Lab color space is L * =50~100 and a * =20~85 and b * = 30 to 120, and L * =50~80 and a * =35~55 and b * More preferably, L = 30 to 85. * =50~80 and a * =35~55 and b *It is even more preferable that the ratio is 30 to 80.

[0065] To obtain a colorant exhibiting a hue within this range, the content of at least one compound represented by chemical formulas (1a) to (1c) in the colorant is preferably 1 to 100 mass %, more preferably 2 to 80 mass %, and even more preferably 2 to 50 mass %.

[0066] The orange color required for covering materials such as high-voltage wire harnesses varies depending on the country or region. * =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) is preferred in Europe, North America, and Asia.

[0067] The compounds represented by chemical formulas (1a) to (1c) are colorants that exhibit orange to red colors. Therefore, to obtain a colorant exhibiting an orange color with a desired hue, only one of the compounds represented by chemical formulas (1a) to (1c) may be used, or multiple types may be mixed and used. When multiple types are used in combination, the benzimidazole ring-containing fused ring compound represented by chemical formula (1a), the perimidine ring-containing fused ring compound represented by chemical formula (1b), and the isoindolinone ring-containing fused ring compound represented by chemical formula (1c) may be mixed with compounds that share a common skeleton but differ only in substituents. Specifically, for example, to obtain the orange colors RAL2003, 2008, 2010, and 2012, a colorant can be prepared by mixing a benzimidazole ring-containing fused ring compound represented by chemical formula (1a1-1) with a benzimidazole ring-containing fused ring compound represented by chemical formula (1a2-1). In this case, 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 in a mass ratio of first compound:second compound = 1:4 to 4:1, more preferably 1:2 to 2:1.

[0068] The colorant can optionally contain a white pigment to increase the brightness of the orange colorant, or a black pigment to decrease it. Examples of white pigments include inorganic pigments such as CaCO3, 2PbCO3·Pb(OH)2, ZnO, TiO2, and ZnS. Examples of black pigments include carbon-based pigments such as carbon black, graphite, and amorphous carbon, as well as commercially available black pigments such as CI Pigment Black 6, 8, 9, 10, 11, and 28. Examples of pigments other than white and black include CI Pigment Orange 68 and Sicopal® Orange K2430 (manufactured by BASF).

[0069] 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). Specific examples include yellow dyes, orange dyes, and red dyes, as well as yellow pigments, orange pigments, red pigments, white pigments, and black pigments. By mixing the compounds represented by chemical formulas (1a) to (1c) that exhibit orange or red colors with these dyes or pigments, orange colorants exhibiting any hue and brightness can be obtained. Of these, fluorescent dyes are preferred because they increase the brightness of the resulting orange color, thereby improving visibility.

[0070] As a yellow dye, the following chemical formula (2) [ka] (In chemical formula (2), R 11 is a hydrogen atom, an amino group or a nitrogen-containing heterocyclic group which may have a substituent, and 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 which may have a substituent; R 13 is at least one selected from an amino group, an amido group, an alkoxy group, a carboxy group, a hydroxy 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.

[0071] In chemical formula (2), R 11 Examples of the nitrogen-containing heterocyclic group represented by the formula (R) include a morpholino group, a piperidinyl group, a pyrrolidinyl group, and a piperazinyl group. 11When is an amino group, piperidinyl group, pyrrolidinyl group, or piperazinyl group, it may have a substituent. Examples of the substituent include 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 hydroxy group, and a carboxy group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0072] In chemical formula (2), R 12 Examples of the halogen atom represented by the formula (I) include F, Cl, Br, and I; examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; and examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group.

[0073] R 12 When R is an amino group, the substituents on this amino group include 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 hydroxy group, and a carboxy group. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. 12 The substitution position of R is not particularly limited. 12 Specific examples of m, which indicates the number of substituents as R 12 is unsubstituted.

[0074] In chemical formula (2), examples of the linear or branched hydrocarbon group having 1 to 3 carbon atoms represented by A include alkylene groups such as methylene, ethylene, trimethylene, and propylene. The benzene ring represented by A is a polyvalent group formed by removing one hydrogen atom from each of two, three, or four ring carbon atoms, such as an arylene group such as a phenylene group. The naphthalene ring represented by A is a polyvalent group formed by removing one hydrogen atom from each of two, three, or four ring carbon atoms, such as a naphthylene group. Examples of this naphthylene group 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.

[0075] A in the chemical formula (2) is preferably a methylene group, or an o-phenylene group, m-phenylene group, or p-phenylene group, and more preferably a p-phenylene group. A naphthalimide compound in which A is an arylene group has higher heat resistance. When A in the chemical formula (2) is an aromatic hydrocarbon group such as an arylene group or a naphthylene group, R 12 The substitution position of is not particularly limited.

[0076] In chemical formula (2), R 13 Examples of the linear or branched alkoxy group having 1 to 4 carbon atoms and represented by the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0077] R 13 is "-C(=O)N(R 13a )2”, a plurality of R 13aare preferably each independently 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, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. On the other hand, R 13 -NHC(=O)R 13b ", this R 13b As above, R 13a The same can be mentioned.

[0078] R 13 "-SO2N(R 13c When the sulfonamide group is represented by "R 13c are preferably each independently 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. 13c As the alkyl group and alkoxy group of the above R 13a Furthermore, R 13 -NH(SO)2R 13d ", this R 13d As above R 13a The same as R 13 n, which indicates the number of substituents as the group, is a number of 1 to 3, preferably 1 or 2, and more preferably 1.

[0079] Among them, R 11 is a nitrogen-containing heterocyclic group, A is a phenylene group, and m=0 (i.e., R 12 is unsubstituted), and R 13 Naphthalimide compounds in which R is a carboxy group are preferred because they exhibit higher heat resistance and bleeding resistance, are rich in color development, and are also excellent in compatibility with the thermoplastic resins described below. 11The nitrogen-containing heterocyclic group of A acts as a chromophore and improves heat resistance, the phenylene group of A improves heat resistance, and R 13 This is because the carboxyl group of R provides heat resistance and bleeding resistance. 13 It is more preferable that the amide group or carboxy group in the polyamide resin molecule is a carboxy group. In this case, the bleeding resistance is significantly improved. This is because the amide group or carboxy group in the polyamide resin molecule and the carboxy group in the naphthalimide compound form intermolecular hydrogen bonds, thereby suppressing the occurrence of the bleeding phenomenon.

[0080] 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 in the same manner as above.

[0081] The maximum absorption wavelength of the naphthalimide compound represented by chemical formula (2) for visible light varies depending on the substituents it has, but is preferably 385 to 439 nm. The maximum absorption wavelength is measured in the same manner as above.

[0082] A specific example of the naphthalimide compound represented by chemical formula (2) is represented by the following chemical formula (2a).

[0083] [ka]

[0084] In the chemical formula (2a), the substituent Z is -A-(R 13 ) n Each substituent R in chemical formula (2a) 11 , R 12 Examples of Z and Z are shown in Tables 1 and 2.

[0085] [Table 1]

[0086] [Table 2]

[0087] A colorant may be prepared by combining at least one of the compounds represented by chemical formulas (1a) to (1c) with a dye or pigment other than the above compounds. This allows colorants of various colors to be obtained. Examples include orange (e.g., a combination of any of the compounds represented by chemical formulas (1a) to (1c) with a yellow or red dye or pigment), green (e.g., a combination of any of the compounds represented by chemical formulas (1a) to (1c) with a blue dye or pigment), purple (e.g., a combination of any of the compounds represented by chemical formulas (1a) to (1c) with a blue dye or pigment), and black (e.g., a combination of any of the compounds represented by chemical formulas (1a) to (1c) with a blue dye or pigment and a yellow dye or pigment, or a combination of any of the compounds represented by chemical formulas (1a) to (1c) with a blue dye or pigment). Orange and black colorants are particularly widely used industrially.

[0088] The dyes and pigments used in preparing the colorant are selected from those that do not impair the effects of the present invention. Preferred dyes and pigments include at least one organic dye or pigment selected from the group consisting of azo dyes and pigments, azo metal-containing dyes and pigments, naphthol azo dyes and pigments, azo lake dyes and pigments, azomethine dyes and pigments, anthraquinone dyes and pigments, quinacridone dyes and pigments, dioxazine dyes and pigments, diketopyrrolopyrrole dyes and pigments, anthopyridone dyes and pigments, isoindolinone dyes and pigments, indanthrone dyes and pigments, perinone 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. These dyes and pigments exhibit yellow, red, blue, green, or black.

[0089] An example of a red dye is ORIENT LPI-1 (maximum absorption wavelength: 560 nm), an azine dye manufactured by Orient Chemical Industries Co., Ltd.

[0090] When the colorant contains the above-mentioned pigment and / or dye, the amount of the pigment and / or dye is 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, per part by mass of the compound represented by chemical formulas (1a) to (1c).

[0091] (Masterbatch) The masterbatch of the present invention contains at least one compound represented by chemical formulas (1a) to (1c), and, if necessary, an optional dye and / or pigment, and a thermoplastic resin. The masterbatch may contain a mixed colorant, which is a mixture of at least one compound represented by chemical formulas (1a) to (1c) and an optional dye and / or pigment, and a thermoplastic resin. This thermoplastic resin may be the same or different from the main component resin (uncolored resin) used in the colored resin composition. Specific examples of colorants include those containing the dye represented by chemical formula (2) and the above-mentioned pigments.

[0092] The content of the colorant in the masterbatch is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass.

[0093] Examples of processes for producing a masterbatch include high-temperature extrusion. The colorant of the present invention, which contains at least one compound represented by chemical formulas (1a) to (1c) and an optional dye and / or pigment, is resistant to decomposition, sublimation, and discoloration at high temperatures. Therefore, the colorant consisting of at least one compound represented by chemical formulas (1a) to (1c) and the colorant containing the same and an optional dye and / or pigment can be suitably used in a masterbatch (high-concentration colored resin composition).

[0094] Such a masterbatch can be obtained by the following heat-melting method. Powder or pellets of a thermoplastic resin serving as the base of the masterbatch, the colorant of the present invention, and optional additives are mixed in a tumbler or super mixer, and the mixture is then fed into an extruder, batch mixer, roll mixer, or the like to pelletize or coarsely granulate. This allows the masterbatch to be obtained. Alternatively, the masterbatch can be obtained by, for example, adding the colorant of the present invention and optional other additives to a thermoplastic resin that is still in solution after synthesis, followed by removing the solvent. A colored resin composition of normal concentration, as described below, can be obtained by similar processing.

[0095] Known or commercially available thermoplastic resins can be used, including, for example, polyamide resins, polyolefin resins such as polyethylene and polypropylene, polyester resins, polycarbonate resins, and polyphenylene sulfide resins.

[0096] Polyamide resins are polyamide polymers that contain acid amide groups (—CONH—) in their molecules and can be melted by heating. Preferred polyamide resins include those containing at least one structural unit selected from the group consisting of a salt of an aliphatic diamine and an aromatic dicarboxylic acid and a salt of an aromatic diamine and an aliphatic dicarboxylic acid. Examples of polyamide resins include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 69, polyamide 610, polyamide 612, polyamide 96, amorphous polyamides, high-melting-point polyamides, 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. Specific examples of such copolymers include polyamide 6 / 66 copolymer, polyamide 6 / 66 / 610 copolymer, polyamide 6 / 66 / 11 / 12 copolymer, and crystalline / amorphous polyamide copolymer. The polyamide resin may also be a blend of a polyamide resin and another synthetic resin. Examples of such blends include polyamide / polyester blends, polyamide / polyphenylene oxide blends, polyamide / polycarbonate blends, polyamide / polyolefin blends, polyamide / styrene / acrylonitrile blends, polyamide / acrylic ester blends, and polyamide / silicone blends. These polyamide resins may be used alone or in combination.

[0097] Examples of polyolefin resins include homopolymers and copolymers of α-olefins such as ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and octene-1, as well as copolymers of these with other copolymerizable unsaturated monomers (such copolymers include block copolymers, random copolymers, and graft copolymers). More specific examples include polyethylene-based 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-based resins such as propylene homopolymer, propylene-ethylene block copolymer or random copolymer, and propylene-ethylene-butene-1 copolymer; polybutene-1, poly-4-methylpentene-1, and the like. These polyolefin-based resins may be used alone or in combination. Among these, polyethylene resins and / or polypropylene resins are preferred. Polypropylene-based resins are more preferred. The molecular weight of the polypropylene-based resin is not particularly limited, and resins of a wide range of molecular weights can be used.

[0098] Examples of polyester resins include polyethylene terephthalate resin obtained by polycondensation of terephthalic acid and ethylene glycol, and polybutylene terephthalate resin obtained by polycondensation of terephthalic acid and butylene glycol. Other examples of polyester resins include copolymers in which a portion of the terephthalic acid component or glycol component is substituted with a substituent, such as an alkyl group having 1 to 4 carbon atoms, in an amount of 15 mol% or less (e.g., 0.5 to 15 mol%), preferably 5 mol% or less (e.g., 0.5 to 5 mol%) of the terephthalic acid component, and / or 15 mol% or less (e.g., 0.5 to 15 mol%), preferably 5 mol% or less (e.g., 0.5 to 5 mol%) of the glycol component, such as ethylene glycol or butylene glycol. The polyester resin may be a single resin or a mixture of multiple types.

[0099] Polycarbonate resin is a thermoplastic resin with carbonate ester bonds in the main chain, and has a bulky benzene nucleus and flexible carbonate in the molecular main chain in a linear molecule of many linked carbonate esters of aromatic hydrocarbons. An example of an industrially mass-produced polycarbonate resin is aromatic polycarbonate obtained from bisphenol A, which can be used.

[0100] Polyphenylene sulfide resin is a polymer primarily composed of repeating units consisting of thiophenylene groups represented by (-φ-S-) [φ is a substituted or unsubstituted phenylene group]. Polyphenylene sulfide resin can be obtained by polymerizing a monomer synthesized by reacting paradichlorobenzene with an alkali sulfide under high temperature and pressure.

[0101] (Colored resin composition) The colored resin composition of the present invention is a mixture of the 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 even 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, an uncolored resin, and, if necessary, additives described below, in a tumbler or super mixer, and then pelletizing or coarsening the mixture by a heat-melting method using an extruder, a batch mixer, a roll mixer, or the like. Such a colored resin composition is also called a compound and is a raw material for molding a resin molded article. A uniformly colored resin molded article can be obtained by molding the colored resin composition using a conventional method.

[0102] The uncolored resin may be the same as the thermoplastic resin used in the masterbatch. The colored resin composition may contain additives, if necessary, in addition to the colorant and uncolored resin used as the masterbatch. Examples of such additives include reinforcing materials, ultraviolet absorbers, light stabilizers, flame retardants, flame retardant assistants, antioxidants, brightness adjusters, lubricants, and mold release agents.

[0103] The reinforcing material may be any material that can be used to reinforce thermoplastic resins, and is not particularly limited. Examples include inorganic fibers such as glass fiber, carbon fiber, metal fiber, potassium titanate fiber, calcium silicate fiber, sepiolite, wollastonite, and rock wool, as well as organic fibers such as aramid, polyphenylene sulfide resin fiber, polyamide resin fiber, polyester resin fiber, and liquid crystal polymer resin fiber. Glass fiber is particularly preferred. The fiber length of such glass fiber is 2 to 15 mm, and the fiber diameter is 1 to 20 μm. The form of the glass fiber is not particularly limited, and examples include roving and milled fiber. These glass fibers may be used alone or in combination of two or more. The content is preferably 5 to 120 parts by mass per 100 parts by mass of the total of the colorant and uncolored resin. Less than 5 parts by mass of the glass fiber does not provide sufficient glass fiber reinforcing effect, while more than 120 parts by mass reduces moldability. The content is preferably 10 to 60 parts by mass, and particularly preferably 20 to 50 parts by mass. A commercially available uncolored resin containing glass fiber may be used, or glass fiber may be added to the uncolored resin each time a colored resin composition is prepared.

[0104] Examples of ultraviolet absorbers and light stabilizers include benzotriazole-based compounds, benzophenone-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, benzoate-based compounds, oxalide-based compounds, hindered amine-based compounds, and nickel complex salts.

[0105] Flame retardants are suitably used to prevent ignition of molded articles exposed to high heat, such as connector housings for automotive wiring harnesses. Examples of such flame retardants include 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.

[0106] Examples of chlorine-based flame retardants include chlorinated paraffin, chlorinated polyethylene, chlorinated polyolefins such as chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene, and chlorendic anhydride.

[0107] Examples of brominated flame retardants include tetrabromobisphenol A (TBBA), tetrabromobisphenol S (TBBS), hexabromocyclododecane, decabromodiphenyl ether, decabromodiphenyl oxide, 2,6-dibromophenol, 2,4-dibromophenol, 2,4,6-tribromophenol, ethylene bis(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, and octabromodiphenyl. nyloxide, ethylene bispentabromodiphenyl, TBBA-bis(dibromopropyl ether), TBBA-bis(aryl ether), poly(dibromophenol), hexabromobenzene, polybromotrimethylphenylindane, ethylene bistetrabromophthalimide, 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.

[0108] Antimony-based flame retardants include, for example, antimony trioxide, antimony pentoxide, sodium antimonate, and antimony phosphate.

[0109] Examples of phosphorus-based flame retardants include red phosphorus, polyphosphoric acid, ammonium polyphosphate, phenoxyphosphazenes having a bond between a phosphorus atom and a nitrogen atom in the main chain, aminophosphazenes, triphenyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, cresyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(tert-butylated phenyl)phosphate, tris(isobutylated phenyl)phosphate, 2-ethylhexyl diphenyl phosphate, 1,3- phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), TBBA-bis(diphenyl phosphate), tris(butoxyethyl)phosphate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(β-chloropropyl)phosphate, 2,2-bis(chloromethyl)trimethylenebis(bis(2-chloroethyl)phosphate), bis(nonylphenyl)phenyl phosphate, cresyl bis(di-2,6-xylenyl)phosphate, and polyoxyalkylene bisdichloroalkyl phosphates.

[0110] Silicon-based flame retardants include, for example, silicone oil, organosilanes, and aluminum silicates.

[0111] Nitrogen-based flame retardants include, for example, melamine, cyanuric acid, melamine cyanurate, urea, and guanidine.

[0112] The flame retardant may be used singly 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, per 100 parts by mass of the total of the colorant and uncolored resin.

[0113] Because halogen-based flame retardants, such as chlorine-based and bromine-based flame retardants, can produce harmful gases during combustion when incinerating thermoplastic resin products containing these flame retardants, non-halogen flame retardants, such as phosphorus-based and nitrogen-based flame retardants, are often used. The benzimidazole ring-containing fused ring compound, perimidine ring-containing fused ring compound, and / or isoindolinone ring-containing fused ring compound contained in the colorant of the present invention do not undergo the discoloration or fading that occurs with typical dyes and pigments contained in conventional colorants, and they also do not undergo the discoloration or fading in high-temperature environments that are associated with halogen-free flame retardants. Therefore, the colorant of the present invention is suitable as a colorant for halogen-free flame-retardant grade resins containing halogen-free flame retardants.

[0114] Examples of the flame retardant aid include antimony compounds such as diantimony trioxide and sodium antimonate, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, ammonium polyphosphate, and tin oxide.

[0115] Examples of antioxidants include phenolic compounds having a phenolic hydroxyl group, phosphorus compounds having a phosphorus atom, and sulfur compounds and thioether compounds having a sulfur atom.

[0116] Phosphorus-based compounds include triphenyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tri(nonylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.

[0117] Sulfur-based compounds and thioether-based compounds include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate, and trilauryl trithiophosphite.

[0118] Brightness adjusters are used to reduce the transparency of molded articles made from resin compositions so that the metal electrical contacts built into connectors of high-voltage wire harnesses and the wires inside the wire coating cannot be seen from the outside. Examples of brightness adjusters include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, lithopone (a mixture of zinc sulfide and barium sulfate), calcium carbonate, silica, carbon black, titanium black, red iron oxide, ultramarine, cobalt aluminate, and chrome green.

[0119] Examples of lubricants include hydrocarbon-based lubricants such as polyethylene wax and polypropylene wax, fatty acid-based lubricants such as stearic acid, higher alcohol-based lubricants such as stearyl alcohol, and aliphatic amide-based lubricants such as stearic acid amide; and metal soaps such as calcium stearate, zinc stearate, and magnesium stearate.

[0120] Examples of the release agent include long-chain fatty acids or their esters and metal salts, aliphatic carboxylic acids, polyethylene wax, and silicones.

[0121] (molded product) The molded article of the present invention is made from the above-described colored resin composition. The molded article is, for example, a connector housing for a high-voltage wire harness for an automobile such as an HV or EV. The connector housing is a case that covers a metal part for connecting electric wires to each other or to an electric device such as a battery. The molded article can be produced by various commonly used procedures. For example, the above-described colored resin composition can be melted and molded using a molding method such as injection molding, extrusion molding, compression molding, foam molding, blow molding, vacuum molding, injection blow molding, rotational molding, calendar molding, or solution casting. Molded articles of various shapes can be obtained by such molding.

[0122] Although a connector for a high-voltage wire harness has been cited as an example of a molded article, the molded article is not limited thereto. For example, a wire harness component can be a wire coating material. Other molded articles include laser-welded parts, such as an intake manifold or engine cover for an internal combustion engine, which are manufactured by laser welding multiple components. The colorant of the present invention has excellent heat resistance, bleed resistance, and light resistance, and is therefore suitable for use in molded articles used outdoors. Further molded articles include medical tubing used for intravenous infusion of infusion fluids or nutrients, food packaging such as spout pouches containing liquid food or beverage compositions, and caps and labels for PET bottles. [Example]

[0123] The present invention will be explained in more detail below by way of examples, but the present invention is not limited to these examples.

[0124] Synthesis Example 1 14.79 g (0.053 mol, Tokyo Chemical Industry Co., Ltd.) of 4-bromonaphthalic anhydride and 30 ml of N-methyl-2-pyrrolidone (NMP) were added to a 100 ml four-neck flask and stirred. 9.76 g (0.112 mol, Fujifilm Wako Pure Chemical Industries, Ltd.) of morpholine was added to this solution and stirred at 120 °C for 2 hours. 8.12 g (0.053 mol, Fujifilm Wako Pure Chemical Industries, Ltd.) of 3,4-diaminobenzoic acid was added to this solution and stirred at 120 °C for an additional 20 hours. After cooling to room temperature, 50 ml of methanol was added dropwise and the mixture was dispersed for 1 hour. The resulting dispersion was transferred to a 500 ml beaker, 200 ml of methanol was added, and the mixture was dispersed for 12 hours. The precipitate from the dispersion was then filtered and washed with 150 ml of methanol and 200 ml of ion-exchanged water. The obtained wet cake was dried in a normal pressure dryer at 80° C. for 20 hours to obtain 19.06 g (yield 90.0%) of an orange solid as a benzimidazole ring-containing fused ring compound represented by the following chemical formula (1a1-1).

[0125] The obtained orange solid was analyzed using an elemental analyzer (manufactured by PerkinElmer Japan Co., Ltd., trade name: EA 2400II fully automatic elemental analyzer). The results are shown below. From these results, it was confirmed that the obtained benzimidazole ring-containing fused ring compound had a structure represented by the following chemical formula (1a1-1).

[0126] [ka]

[0127] Elemental analysis values Actual measurements: C: 68.98%, H: 4.20%, N: 10.45% Theoretical values: C: 69.17%, H: 4.29%, N: 10.52%

[0128] Synthesis Example 2 A 500 ml four-neck flask was charged with 13.27 g (0.096 mol, Fujifilm Wako Pure Chemical Industries, Ltd.), 53.2 g (0.192 mol, Fujifilm Wako Pure Chemical Industries, Ltd.), 96 g of isopropanol, and 144 g of sulfolane, and the mixture was stirred at room temperature until completely dissolved. The mixture was then heated to 50°C, and 26.44 g (0.211 mol, Tokyo Chemical Industry Co., Ltd.) of 2-aminobenzenethiol was added dropwise. After the dropwise addition, the mixture was heated to 90°C and reacted for 12 hours. The mixture was cooled to below 15°C and filtered to obtain 81 g of a wet cake. This wet cake was added to 120 ml of ion-exchanged water, heated to 40°C, and dispersed for 2 hours. The mixture was cooled to room temperature, filtered, and washed with 1000 ml of ion-exchanged water. The obtained wet cake (63.8 g) was dried in a vacuum dryer at 80° C. for 16 hours to obtain 43.15 g of a ochre solid as a naphthalic thioether compound represented by the following chemical formula (1a2-1′).

[0129] [ka]

[0130] A 1000 ml separable flask was charged with 38.6 g (0.12 mol) of a naphthalimide thioether compound represented by chemical formula (1a2-1') and 579 g of DMF, and the mixture was cooled to below 15°C while stirring. Then, while maintaining the temperature below 15°C, 96 g (0.92 mol) of 35% by mass hydrochloric acid was slowly added dropwise. After the addition, the mixture was further cooled to below 5°C in an ice bath. Next, while maintaining the temperature below 5°C, 21 g (0.12 mol) of a 40% by mass aqueous sodium nitrite solution was added dropwise and stirred for 2 hours. The mixture was then heated to 100°C and reacted for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a wet cake. This wet cake was placed in a 300 ml beaker, 150 ml of ion-exchanged water was added, and the mixture was dispersed for 30 minutes. After dispersion, the mixture was filtered and washed with 2000 ml of ion-exchanged water. This wet cake was dried in a vacuum dryer at 80° C. for 16 hours to obtain 30.12 g of an orange solid as a thioxanthene ring-containing fused ring compound represented by the following chemical formula (1a2-1″).

[0131] [ka]

[0132] A 500 ml four-neck flask was charged with 27.4 g (0.09 mol) of a thioxanthene ring-containing fused ring compound represented by chemical formula (1a2-1") and 195 g of N-methyl-2-pyrrolidone, and the temperature was raised to 120°C. 13.7 g (0.09 mol) of 3,4-diaminobenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred for 24 hours. The reaction solution was filtered while hot and washed successively with 800 ml of 100°C DMF, 500 ml of methanol, and 100 ml of ion-exchanged water. 101 g of the resulting wet cake was dried in a vacuum dryer at 80°C for 15 hours, yielding 32.05 g of a red solid (yield 84.7%) as a benzimidazole ring-containing fused ring compound having a thioxanthene ring, represented by the following chemical formula (1a2-1).

[0133] [ka]

[0134] Synthesis Example 3 13.3 g (0.048 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of 4-bromonaphthalic anhydride and 30 ml of NMP were placed in a 100 ml four-neck flask and stirred. 6.51 g (0.050 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of 4-piperidinecarboxylic acid and 9.34 g (0.05 mol, manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) of tributylamine were added to this solution, and the mixture was heated to 120°C. The mixture was allowed to react at 120°C for 5 hours. 8.35 g (0.053 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of 1,8-diaminonaphthalene was added to this solution, and the mixture was allowed to react at 120°C for 6 hours. After 6 hours, the mixture was cooled to 65°C, and then 50 ml of methanol was added dropwise to the reaction mixture, followed by dispersion for 1 hour. The resulting dispersion was transferred to a 500 ml beaker, 200 ml of methanol was added, and the mixture was further dispersed overnight. The precipitate in the dispersion was then filtered and washed with 200 ml of methanol and 200 ml of ion-exchanged water. The resulting wet cake was dried in a normal pressure dryer at 80°C for 40 hours to obtain 17.72 g of a dark red solid (yield 82.5%) as a perimidine ring-containing fused ring compound represented by the following formula (1b-1).

[0135] [ka]

[0136] Synthesis Example 4 9.49 g (0.06 mol, Fujifilm Wako Pure Chemical Industries, Ltd.) of 1,8-diaminonaphthalene and 11.53 g (0.06 mol, Tokyo Chemical Industry Co., Ltd.) of trimellitic anhydride were placed in a 300 ml four-neck flask, and 75 ml of NMP was added. The mixture was heated to 120 °C and stirred for 4 hours. After 4 hours, it was cooled to room temperature. The resulting dispersion was transferred to a 500 ml beaker, 200 ml of methanol was added, and the mixture was dispersed for 12 hours. The precipitate from the dispersion was then filtered and washed with 150 ml of methanol and 300 ml of ion-exchanged water heated to 60 °C. The resulting wet cake was dried in a normal pressure dryer at 80 °C for 20 hours to obtain 15.33 g of a dark red solid (yield 81.3%) as an isoindolinone ring-containing fused ring compound represented by the following formula (1c-2).

[0137] [ka]

[0138] (Heat resistance evaluation) The compounds obtained in Synthesis Examples 1 to 4 were measured using a simultaneous thermogravimetry and differential scanning calorimetry analyzer (TG-DTA6200 EXSTAR6000, manufactured by Hitachi High-Tech Science Corporation) under heating conditions of 30°C to 550°C at a heating rate of 10°C / min. The temperature at which the sample weight had decreased by 5% from the initial weight was read from the chart. For comparison, the 5% weight loss temperature of commercially available CI Solvent Orange 60, shown in the chemical formula below, was also measured. The results are shown in Table 3.

[0139] [ka]

[0140] [Table 3]

[0141] As can be seen from Table 3, all of the compounds of the synthesis examples included in the colorant of the present invention exhibited a higher 5% weight loss temperature than CI Solvent Orange 60. This demonstrates that the compounds represented by chemical formulas (1a), (1b), and (1c) all have high heat resistance and do not discolor or fade even when exposed to high temperature conditions.

[0142] (Example 1-1) A colored resin composition was prepared by placing 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: Zytel® 70G33L) and 0.5 g of the benzimidazole ring-containing fused ring compound obtained in Synthesis Example 1 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 290°C and a mold temperature of 80°C. This resulted in the production of one molded article with a 1 mm thick section. The appearance and surface gloss of this molded article were good, and it exhibited a uniform orange color with no color unevenness.

[0143] (Example 1-2) The colored resin composition prepared in Example 1-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 1-1 was repeated except that one molded article of Example 1-2 was produced.

[0144] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 1-1 and 1-2 were measured using a spectrophotometer (product name: SD7000, manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement points on the molded articles were 1 mm thick. The measurement conditions were: light source: D65, φ25.4 mm, viewing angle: 10 degrees, specular reflection excluded, and holder: standard white board (manufactured by Suga Test Instruments Co., Ltd.). The molded article of Example 1-1 was measured, and the change in the L value, a value, and b value obtained by measuring the molded article of Example 1-2 was calculated as ΔL. * , Δa * , and Δb * These values ​​were substituted into the following formula to determine the color difference ΔE. ΔE=[(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2 ] 1 / 2 The result was ΔE=2.23.

[0145] (Concealment evaluation) Two types of presser plates, a standard black plate and a standard white plate (both manufactured by Suga Test Instruments Co., Ltd.), were used, and the same operation as in the above-mentioned hue evaluation was carried out to measure the hiding power using the same plate as the molded product of Example 1-1. * = 73.68, and the black board is L * =73.31. * Values ​​on the white plate L * and this value and the black plate L * The hiding rate was calculated by substituting the above into the following formula: Concealment rate [%] = [(black plate L * ) / (white board L * )] × 100 The concealment rate was 99.5%.

[0146] (Bleeding resistance evaluation) An evaluation sample was prepared by overlapping the molded article of Example 1-1 with a contacted white piece made of the same resin and then securing them together with clips. This evaluation sample was placed in a heating chamber with a constant temperature of 100°C. After 24 hours of standing, the evaluation sample was removed from the heating chamber, the clips were removed, and the contacted white piece was visually observed. The degree of color transfer (bleed) from the molded article to the contacted white piece was evaluated as follows: ○: No bleeding was observed. △: Bleeding was observed only at the contact area. ×: Contamination was observed not only in the contact area but also in the non-contact area (sublimation). As a result, there was absolutely no color transfer to the contacted white piece, and it was evaluated as good.

[0147] (Examples 1-3) A colored resin composition was prepared by mixing 499.5 g of polyamide 66 resin (DuPont, trade name: Zytel® 70G33L) and 0.5 g of the benzimidazole ring-containing fused compound obtained in Synthesis Example 1 in a stainless steel tumbler and stirring for 1 hour. This mixture was then placed in an injection molding machine (Toyo Machinery & Metal Co., Ltd., trade name: Si-50) at a cylinder temperature of 290°C and a mold temperature of 80°C to produce molded articles for tensile evaluation and impact properties evaluation. These molded articles were processed into tensile evaluation test specimens having the shape of a Type 1A test specimen in accordance with JIS K7162 (2014) and Charpy impact evaluation test specimens having a Type 1 notch shape A in accordance with JIS K7111-1 (2012).

[0148] (Preparation of test reference plate) Test pieces for tensile evaluation and test pieces for Charpy impact evaluation were prepared in the same manner as in Example 1-3, except that no coloring agent was used.

[0149] (Tensile property evaluation) In accordance with JIS K7161-1 (2014), the test piece for tensile evaluation of Example 1-3 was pulled at a pulling rate of 5 mm / min using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., product name: RTC-1310A). The tensile strength obtained was 196.03 MPa. Similarly, the test piece for tensile evaluation of the reference test plate was pulled. The tensile strength obtained was 196.26 MPa. The tensile strength of the test piece for tensile evaluation of Example 1-3 was approximately the same as that of the reference test plate, which was the same resin molded plate but did not contain a colorant, demonstrating that the inclusion of a colorant did not reduce mechanical strength.

[0150] (Impact property evaluation) In accordance with JIS K7111-2 (2006), a digital impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name: DG-UB) was used to apply impact to the Charpy impact evaluation specimen of Example 1-3 at a hammer capacity 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. 2Similarly, an impact was applied to a test specimen for Charpy impact evaluation of the test standard plate. The fracture energy was 0.481 J and the impact strength was 14.88 kJ / m 2 The impact strength of the Charpy impact evaluation test specimen of Example 1-3 was almost the same as that of the reference test plate, which was a resin-molded plate containing no colorant, and it was found that the inclusion of a colorant did not reduce the mechanical strength.

[0151] Example 2-1 A colored resin composition was prepared by placing 499.95 g of polyamide 66 resin (manufactured by DuPont, trade name: Zytel® 70G33L) and 0.05 g of the benzimidazole ring-containing fused ring compound obtained in Synthesis Example 2 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 290°C and a mold temperature of 80°C. This resulted in the production of one molded article with a 1 mm thick section. The appearance and surface gloss of this molded article were good, and it exhibited a uniform orange color with no color unevenness.

[0152] (Example 2-2) The colored resin composition prepared in Example 2-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 2-1 was repeated except that one molded article of Example 2-2 was produced.

[0153] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 2-1 and 2-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=3.03.

[0154] The molded product of Example 2-1 was evaluated for bleeding resistance in the same manner as in Example 1-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0155] Example 3-1 A colored resin composition was prepared by placing 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: Zytel® 70G33L) and 0.5 g of the perimidine ring-containing fused ring compound obtained in Synthesis Example 3 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 290°C and a mold temperature of 80°C. This resulted in the production of one molded article with a 1 mm thick section. The appearance and surface gloss of this molded article were good, and it exhibited a uniform red color without color unevenness.

[0156] (Example 3-2) The colored resin composition prepared in Example 3-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 3-1 was carried out, except that one molded article of Example 3-2 was produced.

[0157] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 3-1 and 3-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=1.40.

[0158] (Bleeding resistance evaluation) The molded article of Example 3-1 was evaluated for bleeding resistance in the same manner as in Example 1-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0159] Example 4-1 A colored resin composition was prepared by placing 499.5 g of polyamide 66 resin (manufactured by DuPont, trade name: Zytel® 70G33L) and 0.5 g of the isoindolinone ring-containing fused ring compound obtained in Synthesis Example 4 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 290°C and a mold temperature of 80°C. This resulted in the production of one molded article with a 1 mm thick section. The appearance and surface gloss of this molded article were good, and it exhibited a uniform red color without any color unevenness.

[0160] (Example 4-2) The colored resin composition prepared in Example 4-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 4-1 was carried out, except that one molded article of Example 4-2 was produced.

[0161] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 4-1 and 4-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=2.27.

[0162] (Bleeding resistance evaluation) The molded article of Example 4-1 was evaluated for bleeding resistance in the same manner as in Example 1-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0163] (Comparative Example 1-1) 499.5 g of polyamide 66 resin (DuPont, trade name: Zytel® 70G33L) and 0.5 g of CI Pigment Orange 43 (Clariant, trade name: PV Fast Orange GRL) as a colorant were placed in a stainless steel tumbler and mixed with stirring for 1 hour. The resulting mixture was placed in an injection molding machine (Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 290°C and a mold temperature of 80°C. This resulted in the production of a molded product with a 1 mm thick section. The molded product had good appearance and surface gloss, and exhibited a uniform orange color with no color unevenness.

[0164] (Comparative Example 1-2) The mixture prepared in Comparative Example 1-1 was poured into the injection molding machine, allowed to remain in the cylinder of the injection molding machine for 3 minutes, and then injection molded. The same procedure as in Comparative Example 1-1 was repeated to produce one molded product of Comparative Example 1-2.

[0165] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Comparative Example 1-1 and Comparative Example 1-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=4.48.

[0166] (Bleeding resistance evaluation) The molded article of Comparative Example 1-1 was evaluated for bleeding resistance in the same manner as in Example 1-1. As a result, color transfer of the colorant to the contacted white piece was confirmed, and the evaluation was fair.

[0167] Table 4 shows the color difference ΔE of the molded articles of Examples 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.

[0168] [Table 4]

[0169] The colorant of the present invention in the examples showed very little change in color even when held at high temperatures inside an injection molding machine, and did not transfer color even when brought into contact with a white piece, demonstrating high bleeding resistance.

[0170] (Colorant Example 1) 100 g of the benzimidazole ring-containing fused ring compound, which is an orange dye obtained in Synthesis Example 1, 7.5 g of the perimidine ring-containing fused ring compound, which is a red dye obtained in Synthesis Example 3, and 100 g of titanium oxide (TIPAQUE (registered trademark) CR62, manufactured by Ishihara Sangyo Kaisha, Ltd.) as a white pigment were placed in a stainless steel tumbler and mixed with stirring for 1 hour to prepare Colorant Example 1.

[0171] (Colorant Example 2) 20 g of the benzimidazole ring-containing fused ring compound which is an orange dye obtained in Synthesis Example 1, 20 g of another benzimidazole ring-containing fused ring compound which is also an orange dye obtained in Synthesis Example 2, 10 g of the perimidine ring-containing fused ring compound which is a red dye obtained in Synthesis Example 3, and 200 g of titanium oxide (TIPAQUE (registered trademark) CR62, manufactured by Ishihara Sangyo Kaisha, Ltd.) as a white pigment were placed in a stainless steel tumbler and mixed with stirring for 1 hour to prepare Colorant Example 2.

[0172] (Masterbatch Example 1) 900 g of polyamide 66 resin (manufactured by DuPont, product name: Zytel (registered trademark) 101NC010) and 100 g of the colorant obtained in Colorant Example 1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour. The resulting mixture was melt-mixed at a cylinder temperature of 290°C using a single-screw extruder (manufactured by Enpla Sangyo Co., Ltd., product name: E30SV). While cooling in a water bath, the mixture was cut with a pelletizer to obtain colored pellets. This was then subjected to a drying process to obtain an orange masterbatch with a colorant concentration of 10% by mass.

[0173] (Masterbatch Example 2) 900 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., product name: Genestar (registered trademark) G1300A) and 100 g of the colorant obtained in Colorant Example 2 were placed in a stainless steel tumbler and mixed under stirring for 1 hour. The resulting mixture was melt-mixed at a cylinder temperature of 290°C using a single-screw extruder (manufactured by Enpla Sangyo Co., Ltd., product name: E30SV). While cooling in a water tank, the mixture was cut with a pelletizer to obtain colored pellets. This was followed by a drying process to obtain an orange masterbatch with a colorant concentration of 10% by mass.

[0174] (Masterbatch Example 3) 900 g of polyamide 66 resin (manufactured by DuPont, trade name: Zytel (registered trademark) 101NC010) and 100 g of the benzimidazole ring-containing fused ring compound obtained in Synthesis Example 1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour. The resulting mixture was melt-mixed at a cylinder temperature of 290°C using a single-screw extruder (manufactured by Enpla Sangyo Co., Ltd., trade name: E30SV). While cooling in a water bath, the mixture was cut with a pelletizer to obtain colored pellets. This was then subjected to a drying process to obtain an orange masterbatch with a colorant concentration of 10% by mass.

[0175] (Masterbatch Example 4) 900 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., product name: Genestar (registered trademark) G1300A) and 100 g of the benzimidazole ring-containing fused ring compound obtained in Synthesis Example 1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour. The resulting mixture was melt-mixed at a cylinder temperature of 290°C using a single-screw extruder (manufactured by Enpla Sangyo Co., Ltd., product name: E30SV). While cooling in a water bath, the mixture was cut with a pelletizer to obtain colored pellets. This was followed by a drying process to obtain an orange masterbatch with a colorant concentration of 10% by mass.

[0176] (Example 5-1) A colored resin composition was prepared by mixing 840 g of polyamide 66 resin (manufactured by Asahi Kasei Corporation, product name: Leona (registered trademark) FH772) and 10 g of the masterbatch of Masterbatch Example 1 in a stainless steel tumbler and stirring for 1 hour. This was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., product name: Si-50) set at a cylinder temperature of 290°C (nozzle tip temperature of 290°C) and a mold temperature of 85°C, and molded by a conventional method to produce one molded article of Example 5-1, which was rectangular in plan view, measuring 80 mm long x 50 mm wide, with 1 mm and 3 mm thick sections, and had an orange color.

[0177] (hue measurement) The hue of the molded article of Example 5-1 was measured in the same manner as in the "Evaluation of Heat Resistance of Molded Articles" for the molded article of Example 1-1. * =65.49 a * =38.49 b * =83.55, a dark orange hue.

[0178] (Example 5-2) The colored resin composition prepared in Example 5-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 5-1 was carried out, except that one molded article of Example 5-2 was produced.

[0179] (Evaluation of heat retention resistance of molded products) 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 therefrom and those values ​​of Example 5-1 obtained in the above "Hue Measurement" were calculated in the same manner as in "Evaluation of Heat Resistance of Molded Article" for the molded article of Example 1-1 to determine the color difference ΔE between the two. The result was ΔE = 2.05.

[0180] (Bleeding resistance evaluation) The molded article of Example 5-1 was evaluated for bleeding resistance in the same manner as in Example 1-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0181] (Example 6-1) A colored resin composition was prepared by mixing 840 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., product name: Genestar (registered trademark) G1300A) and 10 g of the masterbatch of Masterbatch Example 3 in a stainless steel tumbler and stirring for 1 hour. This was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., product name: Si-50) set at a cylinder temperature of 320°C (nozzle tip temperature 290°C) and a mold temperature of 135°C, and molded using a conventional method to produce one molded article of Example 6-1, which was rectangular in plan view, measuring 80 mm long x 50 mm wide, with 1 mm and 3 mm thick sections, and exhibiting an orange color.

[0182] (Example 6-2) The colored resin composition prepared in Example 6-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 6-1 was carried out, except that one molded article of Example 6-2 was produced.

[0183] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 6-1 and 6-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=4.36.

[0184] (Bleeding resistance evaluation) The bleeding resistance of the molded product of Example 7-1 was evaluated in the same manner as in Example 1-1, except that the temperature inside the tank was set to 130° C. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0185] Example 7-1 A colored resin composition was prepared by mixing 840 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., product name: Genestar (registered trademark) G1300A) and 10 g of the masterbatch of Masterbatch Example 2 in a stainless steel tumbler and stirring for 1 hour. This was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., product name: Si-50) set at a cylinder temperature of 320°C (nozzle tip temperature 290°C) and a mold temperature of 135°C, and molded using a conventional method to produce one molded article of Example 7-1, which was rectangular in plan view, measuring 80 mm long x 50 mm wide, with 1 mm and 3 mm thick sections, and exhibiting an orange color.

[0186] (hue measurement) The hue of the molded product of Example 7-1 was measured in the same manner as in the "Evaluation of Heat Resistance of Molded Product" for the molded product of Example 1-1. * =65.90 a * =42.70 b * =65.72, which is the same hue as RAL2003.

[0187] (Example 7-2) The colored resin composition prepared in Example 7-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 7-1 was carried out, except that one molded article of Example 7-2 was produced.

[0188] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 7-1 and 7-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=6.64.

[0189] (Bleeding resistance evaluation) The molded article of Example 7-1 was evaluated for bleeding resistance in the same manner as in Example 6-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0190] Example 8-1 A colored resin composition was prepared by mixing 499.5 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar (registered trademark) G1300A) and 0.5 g of the perimidine ring-containing fused ring compound obtained in Synthesis Example 3 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 320°C and a mold temperature of 135°C. This resulted in the production of one molded article with a 1 mm thick section. The appearance and surface gloss of this molded article were good, and it exhibited a uniform red color without color unevenness.

[0191] (Example 8-2) The colored resin composition prepared in Example 8-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 8-1 was carried out, except that one molded article of Example 8-2 was produced.

[0192] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 8-1 and 8-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=1.40.

[0193] (Bleeding resistance evaluation) The molded article of Example 8-1 was evaluated for bleeding resistance in the same manner as in Example 6-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0194] (Example 9-1) A colored resin composition was prepared by mixing 499.5 g of polyamide 9T resin (manufactured by Kuraray Co., Ltd., trade name: Genestar (registered trademark) G1300A) and 0.5 g of the isoindolinone ring-containing fused ring compound obtained in Synthesis Example 4 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 320°C and a mold temperature of 135°C. This resulted in the production of one molded article with a 1 mm thick section. The appearance and surface gloss of this molded article were good, and it exhibited a uniform red color without color unevenness.

[0195] (Example 9-2) The colored resin composition prepared in Example 9-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 9-1 was carried out, except that one molded article of Example 9-2 was produced.

[0196] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 9-1 and 9-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=0.83.

[0197] (Bleeding resistance evaluation) The molded article of Example 9-1 was evaluated for bleeding resistance in the same manner as in Example 6-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0198] (Example 10-1) A colored resin composition was prepared by mixing 399.6 g of polyphenylene sulfide resin (manufactured by Polyplastics Co., Ltd., trade name: DURAFIDE® 1130A6), 0.32 g of the benzimidazole ring-containing fused ring compound (orange dye) obtained in Synthesis Example 1, and 0.08 g of another benzimidazole ring-containing fused ring compound (orange dye) obtained in Synthesis Example 2 in a stainless steel tumbler and stirring for 1 hour. The mixture was then placed in an injection molding machine (manufactured by Toyo Machinery & Metal Co., Ltd., trade name: Si-50-6s) and injection molded using a conventional method at a cylinder temperature of 310°C and a mold temperature of 140°C. This resulted in the production of a molded product with a 1 mm thick section. The molded product had good appearance and surface gloss, and exhibited a uniform orange color without color unevenness.

[0199] (hue measurement) The hue of the molded product of Example 10-1 was measured in the same manner as in the "Evaluation of Heat Resistance of Molded Product" for the molded product of Example 1-1. * =66.24 a * =39.64 b * =62.68, a dark orange hue.

[0200] (Example 10-2) The colored resin composition prepared in Example 10-1 was poured into the injection molding machine, and then allowed to remain in the cylinder of the injection molding machine for 3 minutes, followed by injection molding. The same procedure as in Example 10-1 was carried out, except that one molded article of Example 10-2 was produced.

[0201] (Evaluation of heat retention resistance of molded products) The hues of the molded articles of Examples 10-1 and 10-2 were measured in the same manner as in Examples 1-1 and 1-2, and the color difference ΔE was calculated from the results, which was ΔE=4.54.

[0202] (Bleeding resistance evaluation) The molded article of Example 10-1 was evaluated for bleeding resistance in the same manner as in Example 6-1. As a result, there was no color transfer to the contacted white piece, and the evaluation was good.

[0203] (Comparative Example 2-1) 499.5 g of polyamide 9T resin (Kuraray Co., Ltd., trade name: Genestar® G1300A) and 0.5 g of CI Pigment Orange 43 (Clariant, trade name: PV Fast Orange GRL) as a colorant were placed in a stainless steel tumbler and mixed with stirring for 1 hour. The resulting mixture was placed in an injection molding machine (Toyo Machinery & Metal Co., Ltd., trade name: Si-50) and injection molded using a conventional method at a cylinder temperature of 320°C and a mold temperature of 135°C. This resulted in the production of a molded product with a 1 mm thick section. The molded product had good appearance and surface gloss, and exhibited a uniform orange color with no color unevenness.

[0204] (Comparative Example 2-2) One molded product of Comparative Example 2-2 was produced in the same manner as in Comparative Example 1-1, except that the mixture prepared in Comparative Example 2-1 was poured into the injection molding machine, allowed to remain in the cylinder of the injection molding machine for 3 minutes, and then injection molded.

[0205] (Evaluation of heat retention resistance of molded products) 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 calculated from the results, which was ΔE=7.50.

[0206] (Bleeding resistance evaluation) The molded article of Comparative Example 1-1 was evaluated for bleeding resistance in the same manner as in Example 6-1. As a result, color transfer of the colorant to the contacted white piece was confirmed, and the evaluation was fair.

[0207] Table 5 shows the color difference ΔE of the molded articles of Examples 6-1, 7-1, 8-1, 9-1, and 10-1 and Comparative Example 2-1 and the results of the bleeding test at a tank temperature of 130°C.

[0208] [Table 5]

[0209] The colorant of the present invention in the examples showed very little change in color even when held at high temperatures inside an injection molding machine, and did not transfer color even when brought into contact with a white piece, demonstrating high bleeding resistance.

[0210] Example 11 A connector housing for an automobile wire harness was produced by insert molding using the colored resin composition prepared in Example 1-1 and fixing a metal part for electrical connection to a mold. This connector housing had a bright orange color. [Industrial Applicability]

[0211] The colorant of the present invention, as well as a masterbatch and a colored resin composition containing the colorant, are used to produce colored molded articles, and these molded articles are used as connector housings and wire coating materials for high-voltage wire harnesses used in automobiles, laser-welded parts produced by laser welding multiple members together, such as intake manifolds and engine covers for internal combustion engines, medical tubes used for intravenous infusion of infusion fluids and nutrients, food packaging materials such as spout pouches containing liquid food and beverage compositions, and caps and labels for PET bottles.

Claims

1. The following chemical formula (1a) 【Chemistry 1】 (In chemical formula (1a), R １ and R ２ are each independently a hydrogen atom or at least one nitrogen-containing heterocyclic group selected from a morpholino group, a piperidinyl group, a pyrrolidinyl group, and a piperazinyl group, and both are not simultaneously hydrogen atoms; R ３ is at least one selected from a linear or branched alkoxy group having 1 to 4 carbon atoms, a carboxy group, a hydroxy group, a sulfo group, and a sulfonamido group, and p is a number from 0 to 2, and / or The following chemical formula (1b) 【Chemistry 2】 (In chemical formula (1b), R ４ and R ５ are each independently a hydrogen atom or at least one nitrogen-containing heterocyclic group selected from a morpholino group, a piperidinyl group, a pyrrolidinyl group, and a piperazinyl group, and both 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 carboxy group, a hydroxy group, a sulfo group, and a sulfonamide group, and q is a number of 0 to 4.

2. The masterbatch described in Claim 1, characterized in that the nitrogen-containing heterocyclic group has at least one 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 hydroxy group, and a carboxy group.

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

4. A colored resin composition comprising the masterbatch according to any one of claims 1 to 3 and a second thermoplastic resin.

5. A colored resin composition as described in claim 4, characterized in that the first thermoplastic resin and the second thermoplastic resin are of the same type.

6. 5. The colored resin composition according to claim 4, wherein the first and second thermoplastic resins comprise at least one selected from the group consisting of polyamide resins, polyolefin resins, polyester resins, polycarbonate resins, and polyphenylene sulfide resins.

7. A molded article, characterized by being molded from the colored resin composition according to any one of claims 4 to 6.

8. 8. The molded product according to claim 7, which is a connector housing for an automobile wiring harness.

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