Resin composition

Abstract

To provide a resin composition containing a polyester-based resin or a polyamide-based resin which enables formation of a molding that sufficiently exhibits characteristics inherent to a resin while further containing a flame retardant.SOLUTION: A resin composition contains a copolyester-based resin A containing a structural unit derived from a terephthalic acid monomer and a structural unit derived from 1,4-cyclohexanedimethanol and / or a polyamide-based resin, and contains an organic phosphorus compound represented by formula (1). In the formula (1), R2 and R5 may be the same or different, and are a phenyl group, a naphthyl group and an anthryl group that may have a substituent, or a 1-4C branched or linear alkyl group that may have an aromatic substituent. R1, R3, R4 and R6 may be the same or different, and are a substituent selected from a hydrogen atom, a 1-4C branched or linear alkyl group, and a phenyl group, a naphthyl group and an anthryl group that may have a substituent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition. [Background technology]

[0002] Polyester resins and polyamide resins have traditionally been used in a wide variety of applications, including containers. Generally, various studies have been conducted on resin compositions containing these resins, with the aim of improving processability (e.g., fluidity) and the properties of molded articles (e.g., mechanical properties such as rigidity, appearance, etc.). Furthermore, additives have been added to the resin compositions to improve their functionality depending on the application. One such method is the addition of a flame retardant to impart flame retardancy. However, depending on the resin used, the addition of a flame retardant can inhibit the inherent properties of the resin, making it impossible to obtain a molded article with the desired mechanical properties, appearance, etc. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-83932 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a resin composition containing a polyester-based resin (in particular, a copolyester-based resin A containing structural units derived from terephthalic acid-based monomers and structural units derived from 1,4-cyclohexanedimethanol) or a polyamide-based resin, which resin composition can be used to form a molded article in which the inherent properties of the resin are fully exhibited, even while further containing a flame retardant. [Means for solving the problem]

[0005] The resin composition of the present invention contains, as resin components, a copolyester-based resin A and / or a polyamide-based resin containing a structural unit derived from a terephthalic acid-based monomer and a structural unit derived from 1,4-cyclohexanedimethanol, and also contains an organophosphorus compound represented by formula (1). [ka] In formula (1), R 2 , R 5 R may be the same or different and is a phenyl group, naphthyl group, anthryl group, or a branched or linear alkyl group having 1 to 4 carbon atoms, which may have a substituent, or which may have an aromatic substituent. 1 , R 3 , R 4 , R 6 may be the same or different and are a substituent selected from a hydrogen atom, a branched or linear alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group, or an anthryl group which may have a substituent. In one embodiment, the copolyester resin A is amorphous. In one embodiment, the copolyester resin A further contains a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. In one embodiment, the polyamide resin is polycapramide. In one embodiment, the content of the organophosphorus compound is 0.5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the resin component. In one embodiment, the resin composition further contains a flame retardant other than the organophosphorus compound. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a resin composition containing a copolyester-based resin A or a polyamide-based resin that contains a structural unit derived from a terephthalic acid-based monomer and a structural unit derived from 1,4-cyclohexanedimethanol, and that can form a molded article that fully exhibits the properties inherent to the resin (e.g., impact resistance, rigidity, appearance) while also containing a flame retardant. DETAILED DESCRIPTION OF THE INVENTION

[0007] A. Resin Composition The resin composition of the present invention contains, as a resin component, a copolyester-based resin A (hereinafter also simply referred to as copolyester-based resin A) and / or a polyamide-based resin containing a structural unit derived from a terephthalic acid-based monomer and a structural unit derived from 1,4-cyclohexanedimethanol, and also contains an organophosphorus compound represented by formula (1). [ka] In formula (1), R 2 , R 5 R may be the same or different and is a phenyl group, naphthyl group, anthryl group, or a branched or linear alkyl group having 1 to 4 carbon atoms, which may have a substituent, or which may have an aromatic substituent. 1 , R 3 , R 4 , R 6 may be the same or different and are a substituent selected from a hydrogen atom, a branched or linear alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group, or an anthryl group which may have a substituent.

[0008] In the present invention, by combining the copolyester resin A or polyamide resin with the specific organophosphorus compound, a resin composition can be obtained that possesses the flame retardancy inherent to the organophosphorus compound and can form molded articles that fully utilize the properties inherent to the resin components. More specifically, while the addition of a flame retardant to a resin composition has traditionally resulted in problems such as reduced mechanical strength and poor appearance, the use of the specific organophosphorus compound in the present invention allows the flame retardancy inherent to the organophosphorus compound to be imparted while maintaining the mechanical properties (particularly impact resistance and rigidity) inherent to the polyester resin or polyamide resin within a desired range. Furthermore, the resin composition of the present invention allows molded articles to be obtained with excellent appearance. More specifically, while combining a polyester resin or polyamide resin with a conventional flame retardant can sometimes result in poor appearance due to the flame retardant (opacity (particularly when copolyester resin A is used), color unevenness such as spots or patches (particularly when polyamide resin is used)), the present invention allows molded articles to be obtained with excellent appearance despite containing an organophosphorus compound that can function as a flame retardant.

[0009] The present invention is also advantageous in that the fluidity of the resin composition is not impaired even when the specific organophosphorus compound is added, and depending on the composition of the resin composition, the addition of the specific organophosphorus compound can improve the fluidity.

[0010] The melt flow rate of the resin composition (for example, a resin composition containing a polyamide resin) at 275°C and 5 kgf is preferably 100 g / 10 min to 1000 g / 10 min, more preferably 300 g / 10 min to 900 g / 10 min, and even more preferably 400 g / 10 min to 900 g / 10 min. If the melt flow rate is within this range, a resin composition having particularly excellent moldability can be obtained.

[0011] The melt flow rate of the resin composition (for example, a resin composition containing copolyester resin A) at 270°C and 2.16 kgf is preferably 5 g / 10 min to 100 g / 10 min, more preferably 8 g / 10 min to 50 g / 10 min. If the melt flow rate is within this range, a resin composition with particularly excellent moldability can be obtained.

[0012] A-1. Resin components The content of the resin component in the resin composition is preferably 55 parts by weight or more, more preferably 60 parts by weight or more, and even more preferably 80 parts by weight or more, relative to 100 parts by weight of the resin composition. The upper limit of the content of the resin component is, for example, 99 parts by weight, relative to 100 parts by weight of the resin composition.

[0013] A-1-1. Copolyester resin A The content of the copolyester resin A is preferably 30 parts by weight or more, more preferably 55 parts by weight or more, even more preferably 80 parts by weight or more, and even more preferably 90 parts by weight or more, relative to 100 parts by weight of the resin composition. The upper limit of the content of the polyester resin is, for example, 99 parts by weight, relative to 100 parts by weight of the resin composition.

[0014] Copolyester resin A is a resin obtained from a monomer composition containing a terephthalic acid monomer as a dicarboxylic acid component and 1,4-cyclohexanedimethanol as a diol component. By using such a specific copolyester resin A, it is possible to form a molded product with excellent mechanical properties (especially impact resistance and rigidity). Furthermore, a resin composition with excellent fluidity can be obtained. The copolyester resin is preferably amorphous. Herein, whether the resin is crystalline or amorphous can be determined by DSC measurement. Specifically, this can be determined by the following method. A resin sample is heated and melted from -100°C to 300°C at a heating rate of 10°C / min according to JIS K 7121 using a differential scanning calorimeter (DSC), and then held at 300°C for 10 minutes. The sample is then cooled to -100°C at a cooling rate of 10°C / min. Next, the sample is heated and melted from -100°C to 300°C at a heating rate of 10°C / min. In this second heating step, samples that do not show a melting peak are considered amorphous, and samples that show a melting peak are considered crystalline.

[0015] The terephthalic acid monomer may be terephthalic acid or a derivative of terephthalic acid, that is, the copolyester resin may contain structural units derived from terephthalic acid and / or structural units derived from a derivative of terephthalic acid.

[0016] Examples of the derivatives of terephthalic acid include halides, esters, half esters, salts, half salts, anhydrides, mixed anhydrides, and mixtures thereof of terephthalic acid. Examples of the derivatives of terephthalic acid include dialkyl esters and diaryl esters of terephthalic acid, specific examples of which include dimethyl terephthalate (DMT) and diethyl terephthalate.

[0017] The copolyester resin A may further contain structural units derived from other monomers. In one embodiment, the copolyester resin A further contains structural units derived from dicarboxylic acids other than terephthalic acid-based monomers (other dicarboxylic acids). Examples of the other dicarboxylic acids include cyclohexanedicarboxylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and stilbene dicarboxylic acid. Examples of cyclohexanedicarboxylic acids include 1,3- and / or 1,4-cyclohexanedicarboxylic acid. When the copolyester resin A contains structural units derived from other dicarboxylic acids, the content of the structural units derived from terephthalic acid-based monomers is preferably 40 mol % or more, more preferably 40 mol % to 90 mol %, and even more preferably 50 mol % to 85 mol %, based on the total amount of dicarboxylic acids (the total amount of structural units derived from terephthalic acid-based monomers and structural units derived from other dicarboxylic acids).

[0018] The copolyester resin A may further contain a structural unit derived from a diol other than 1,4-cyclohexanedimethanol (another diol). Examples of the other diol include aliphatic or alicyclic glycols (preferably having 2 to 20 carbon atoms). Examples of the other diol include ethylene glycol, diethylene glycol, triethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, and 2,2,4,4-tetramethylcyclobutanediol.

[0019] In one embodiment, the copolyester resin A further contains structural units derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Using a copolyester resin containing such structural units allows for the production of a resin composition capable of forming molded articles with superior mechanical properties. When the copolyester resin A contains structural units derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD), the content of structural units derived from 1,4-cyclohexanedimethanol (CHDM) is preferably 10 mol % to 90 mol %, more preferably 20 mol % to 85 mol %, and even more preferably 30 mol % to 80 mol %, based on the total of the structural units derived from TMCD and the structural units derived from CHDM. Furthermore, the content of structural units derived from TMCD is preferably 10 mol % to 90 mol %, more preferably 15 mol % to 80 mol %, and even more preferably 20 mol % to 70 mol %, based on the total of the structural units derived from TMCD and the structural units derived from CHDM.

[0020] The copolyester resin A can be produced by any suitable method. Alternatively, a commercially available product may be used as the copolyester resin. Examples of commercially available copolyester resins include TRITAN (registered trademark, hereinafter the same) manufactured by Eastman Chemical Company.

[0021] The glass transition temperature (Tg) of the copolyester resin A is preferably 90° C. to 200° C., more preferably 100° C. to 180° C., even more preferably 100° C. to 160° C., and particularly preferably 100° C. to 140° C. If the temperature is within this range, a resin composition capable of forming a molded product having excellent heat resistance can be obtained.

[0022] The deflection temperature under load (according to ISO 75; load of 0.45 MPa) of the copolyester resin A is preferably 60°C to 150°C, more preferably 90°C to 150°C, and even more preferably 95°C to 120°C. Note that TRITAN TX1001 has a deflection temperature under load of 99°C, and TX2001 has a deflection temperature under load of 1.80 MPa. The deflection temperature under load of the copolyester resin A is preferably 60°C to 150°C, more preferably 90°C to 120°C, and even more preferably 80°C to 100°C. Note that TRITAN TX1001 has a deflection temperature of 85°C, and TX2001 has a deflection temperature of 92°C. Within these ranges, a resin composition capable of forming a molded product having excellent heat resistance can be obtained.

[0023] In one embodiment, the resin composition containing the copolyester resin A further contains a crystalline polyester resin as a resin component. Examples of the crystalline polyester resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polytrimethylene naphthalate. Of these, polyethylene terephthalate or polybutylene terephthalate is preferred, and polybutylene terephthalate is more preferred. By including a crystalline polyester resin (preferably polyethylene terephthalate or polybutylene terephthalate, more preferably polybutylene terephthalate), a resin composition capable of forming a molded product having excellent heat resistance can be obtained.

[0024] A-1-2. Polyamide resin The content of the polyamide resin is preferably 30 parts by weight or more, more preferably 55 parts by weight or more, and even more preferably 80 parts by weight or more, relative to 100 parts by weight of the resin composition. The upper limit of the content of the polyamide resin is, for example, 99 parts by weight, relative to 100 parts by weight of the resin composition.

[0025] Any appropriate resin can be used as the polyamide-based resin, for example, an aliphatic polyamide, an aromatic polyamide (semi-aromatic polyamide, fully aromatic polyamide), or the like.Specific examples of polyamide resins include polycapramide (nylon 6), poly-ω-aminoheptanoic acid (nylon 7), poly-ω-aminononanoic acid (nylon 9), polyundecaneamide (nylon 11), polylauryllactam (nylon 12), polyethylenediamineadipamide (nylon 26), polytetramethyleneadipamide (nylon 46), polyhexamethyleneadipamide (nylon 66), polyhexamethylenesebacamide (nylon 610), polyhexamethylenedodecaamide (nylon 612), poly Lioctamethylene adipamide (nylon 86), polydecamethylene adipamide (nylon 106), caprolactam / lauryllactam copolymer (nylon 6 / 12), caprolactam / ω-aminononanoic acid copolymer (nylon 6 / 9), caprolactam / hexamethylenediammonium adipate copolymer (nylon 6 / 66), lauryllactam / hexamethylenediammonium adipate copolymer (nylon 12 / 66), ethylenediammonium adipate / hexamethylenediammonium adipate copolymer (nylon Aliphatic polyamides such as nylon 26 / 66), caprolactam / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon 6 / 66 / 610), ethylenediammonium adipate / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon 26 / 66 / 610), polyhexamethylenecyclohexylamide, polynonamethylenecyclohexylamide; polyhexamethyleneisophthalamide (nylon 6I), polyhexamethylene Examples of suitable polyamides include semi-aromatic polyamides having an aliphatic skeleton, such as hexamethylene isophthalamide / hexamethylene terephthalamide copolymer (nylon 6I / 6T), 11-aminoundecanamide / hexamethylene terephthalamide copolymer, polynonamethylene terephthalamide (nylon 9T), and polydecamethylene terephthalamide (nylon 10T); and modified polyamides obtained by modifying these polyamides with aromatic amines, such as methylenebenzylamine and metaxylenediamine. Among these, polycapramide (nylon 6) is preferred.

[0026] The glass transition temperature (Tg) of the polyamide resin is preferably 90° C. to 200° C., more preferably 100° C. to 180° C., even more preferably 100° C. to 160° C., and particularly preferably 100° C. to 140° C. If the temperature is within this range, a resin composition capable of forming a molded product having excellent heat resistance can be obtained.

[0027] A-1-3. Other resins The resin composition may further contain other resins as resin components. Thermoplastic resins are preferably used as the other resins. Examples of the other resins include polyolefin resins such as polyethylene resins and polypropylene resins, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, epoxy resins, and polycarbonate resins.

[0028] The content of the other resins is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, even more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less, per 100 parts by weight of the resin component.

[0029] A-2. Organophosphorus compounds As described above, the organophosphorus compound used in the present invention is an organophosphorus compound represented by formula (1). [ka] In formula (1), R 2 , R 5 R may be the same or different and is a phenyl group, naphthyl group, anthryl group, or a branched or linear alkyl group having 1 to 4 carbon atoms, which may have a substituent, or which may have an aromatic substituent. 1 , R 3 , R 4 , R6 may be the same or different and are substituents selected from a hydrogen atom, a branched or linear alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group, or an anthryl group. Organophosphorus compounds represented by formula (1) are described, for example, in JP-A-2019-135286 and JP-A-2020-83932. The disclosures of these publications are incorporated herein by reference.

[0030] Preferably, R 2 , R 5 are the same or different and are phenyl, naphthyl, anthryl, benzyl, or phenethyl groups, and more preferably, R 2 , R 5 are the same or different phenyl groups or benzyl groups. 1 , R 3 , R 4 , R 6 are the same or different and are a hydrogen atom, methyl, ethyl, various propyl groups, various butyl groups, phenyl groups, various toluyl groups, naphthyl groups, and anthryl groups, and more preferably, R 1 , R 3 , R 4 , R 6 are the same or different and are a hydrogen atom, a methyl group, an ethyl group, or a phenyl group.

[0031] Specific examples of the organic phosphorus compound represented by formula (1) include 3,9-bis(phenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((3-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-methylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((3,5-dimethylphenyl)methyl)-3,9-dioxo-2,4,8, 10-Tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-trimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphospha Spiro[5.5]undecane, 3,9-bis((2,4-di-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,6-di-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-tri-sec-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Decane, 3,9-bis((2,6-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2,4,6-tri-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((4-biphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((1-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-naphthyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((1-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((2-anthryl)methyl)-3,9-dioxo-2 ,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis((9-anthryl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2-methyl-2-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(diphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(triphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3-phenylmethyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-phenylmethyl-9-diphenylmethyl-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Pyro[5.5]undecane, 3-((2,6-dimethylphenyl)methyl)-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-((2,4-di-tert-butylphenyl)methyl)-9-(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-(1-phenylethyl)-3,9-di Examples include oxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3-diphenylmethyl-9-((2,6-dimethylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 3-diphenylmethyl-9-((2,4-di-tert-butylphenyl)methyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0032] In one embodiment, the organophosphorus compound represented by formula (1) is 3,9-bis(phenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; 3,9-bis(1-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; 3,9-bis(2-phenylethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane; or 3,9-bis(diphenylmethyl)-3,9-dioxo-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. Particularly preferred is 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide, from the viewpoint of making the effects of the present invention more pronounced.

[0033] The organic purity of the organophosphorus compound represented by formula (1) is 98% or more, preferably 98.5% or more, and particularly preferably 99.0% or more. The organic purity can be measured, for example, using a Waters Separations Module 2690 HPLC system, a Waters Dual λ Absorbance Detector 2487 (UV-264 nm) detector, and a Tosoh TSKgel ODS-120T 2.0 mm × 150 mm (5 μm) column, using a mixture of distilled water and acetonitrile as the eluent, at a column temperature of 40° C., using a gradient program of 0 → 12 min: 50% acetonitrile, 12 → 17 min: 50 → 80% acetonitrile, 17 → 27 min: 80% acetonitrile, 27 → 34 min: 80 → 100% acetonitrile, and 34 → 60 min: 100% acetonitrile. The measurement is performed by dissolving 50±0.5 mg of pentaerythritol diphosphonate in 25 ml of acetonitrile, filtering through a PTFE filter with a pore size of 0.2 μm, and measuring the purity, which is calculated as an area percentage.

[0034] The content of the organophosphorus compound represented by formula (1) is preferably 3 to 20 parts by weight, more preferably 4 to 15 parts by weight, and even more preferably 5 to 10 parts by weight, relative to 100 parts by weight of the resin component. Within this range, a resin composition can be obtained that can form a molded article having excellent flame retardancy and mechanical properties. In one embodiment, the amount of the organophosphorus compound added can be set to an appropriate amount based on the desired balance between the degree of flame retardancy, the appearance (transparency of the molded article), and the like.

[0035] A-3. Other ingredients The resin composition may further contain any appropriate additives as needed. Examples of additives include stabilizers such as flow modifiers, anti-stain agents, heat stabilizers, and weathering agents, colorants such as pigments and dyes, lubricants, crosslinking agents, crosslinking aids, antiblocking agents, antistatic agents, anti-fogging agents, and solvents. The resin composition may also contain fillers such as talc, magnesium sulfate fiber, glass fiber, carbon fiber, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate salts, silicates, carbonates, and carbon black.

[0036] In one embodiment, the resin composition further includes a flame retardant other than the organophosphorus compound represented by formula (1). According to the present invention, the addition of the organophosphorus compound represented by formula (1) can improve mechanical strength, appearance, and fluidity without impairing the benefits of the other flame retardant (particularly flame retardancy and heat resistance). Examples of the other flame retardant include phosphorus-based flame retardants other than the organophosphorus compound represented by formula (1), nitrogen-based flame retardants, antimony-based flame retardants, and metal hydroxides. Examples of phosphorus-based flame retardants other than the organophosphorus compound represented by formula (1) include phosphate ester-based flame retardants, melamine polyphosphate-based flame retardants, phosphazene-based flame retardants, phosphinic acid-based flame retardants, and red phosphorus-based flame retardants. Among these, phosphinic acid-based flame retardants are preferred.

[0037] When another flame retardant is contained, the content ratio of the other flame retardant is preferably 2000 parts by weight or less, more preferably 1000 parts by weight or less, per 100 parts by weight of the organophosphorus compound represented by formula (1).

[0038] A-4. Method for producing resin composition The resin composition of the present invention can be produced by any appropriate method. Examples of the production method include a method of melt-kneading a resin composition containing a resin component, the organophosphorus compound, and other components used as needed (melt blending method). Examples of the melt-kneading method include methods using a single-screw extruder, a multi-screw extruder, a tandem extruder, a Banbury mixer, or the like. By producing a resin composition by melt-kneading, a resin composition capable of forming a molded article having excellent rigidity can be obtained.

[0039] The processing temperature in the melt-kneading is preferably a temperature at which the resin contained in the resin composition can melt, for example, 150°C to 330°C.

[0040] B. Molded object A molded article can be provided by using the resin composition.The method for molding the molded article can include, for example, injection molding, injection compression molding, profile extrusion molding, foam molding, ram extrusion molding, solidification extrusion, pipe molding, tube molding, heterogeneous molded body covering molding, injection blow molding, direct blow molding, T-die sheet or film molding, stretch molding, inflation molding, calendar molding, press molding, rotational molding, vacuum molding, pressure molding, melt spinning, etc.

[0041] The molded article has excellent flame retardancy and mechanical properties (particularly rigidity). Furthermore, by using the resin composition of the present invention, it is possible to obtain a molded article having excellent appearance, for example, with little occurrence of dotted patterns, spotted patterns, etc., derived from the flame retardant. [Example]

[0042] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Evaluation methods in the examples are as follows. Parts and percentages are based on weight unless otherwise specified.

[0043] (1) Specific gravity The specific gravity of the resin sample was measured in accordance with ISO1183.

[0044] (2) Melt mass flow rate (MFR) The flowability of the resin compositions obtained in the examples and comparative examples was evaluated by measuring the melt mass flow rate (MFR) of a resin sample piece in accordance with ISO 1133. The test conditions for the MFR test of the resin composition were a temperature of 275°C and a load of 5 kgf, or a temperature of 270°C and a load of 2.16 kg.

[0045] (3) Tensile strength, elongation at break, and yield elongation The resin sample pieces were measured in accordance with ISO527 (measurement temperature: 23°C, tensile speed: 50 mm / min).

[0046] (4) Bending strength and elastic modulus The resin sample pieces were measured in accordance with ISO178 (measurement temperature: 23°C).

[0047] (5) Charpy impact strength The resin sample pieces were measured in accordance with ISO179 (measurement temperature: 23°C). (Measurement conditions) Pendulum energy: 4J Impact speed: 2.9 m / s (±5%) With notch

[0048] (6) Deflection temperature under load Measurements were carried out on resin sample pieces in accordance with ISO 75. The load was set to 0.45 MPa and / or 1.80 MPa.

[0049] (7) Flame retardancy The resin sample pieces were subjected to a V test in accordance with UL 94. If the result did not meet any of the criteria of V-0, V-1, or V-2, it was marked as "not."

[0050] [Example 1-1] 95 parts by weight of an amorphous copolyester resin (manufactured by Eastman Chemical Company, trade name "TRITAN TX1001") and 5 parts by weight of an organophosphorus compound (I) (manufactured by Teijin Limited, trade name "FCX-210", 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide) were melt-kneaded at a melt temperature of 280°C using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM18SS, screw diameter 18 mm). The molten material was extruded from the twin-screw extruder in the form of a strand, cooled and solidified, and then cut into pellets to obtain a resin composition. The obtained resin composition was injection molded using an injection molding machine (PLASTAR SI80-IV, manufactured by Toyo Machinery & Metal Co., Ltd.) under conditions of a cylinder temperature of 270°C and a mold temperature of 60°C to prepare resin sample pieces. As the resin sample pieces, ISO standard type A1 dumbbell-shaped test pieces were prepared for the tests (3) to (6) above, and strip test pieces (thickness: 1.6 mm, 3.2 mm) were prepared for the test (7) above. The resin composition was subjected to the above evaluations, and the results are shown in Table 1.

[0051] [Example 1-2] A resin composition and a resin sample were obtained in the same manner as in Example 1-1, except that the amount of amorphous copolyester resin was 97 parts by weight and the amount of organic phosphorus compound (I) was 3 parts by weight. The resin composition was subjected to the above evaluations. The results are shown in Table 1.

[0052] [Examples 1-3] A resin composition and a resin sample were obtained in the same manner as in Example 1-1, except that the amount of amorphous copolyester resin was 99 parts by weight and the amount of organophosphorus compound (I) was 1 part by weight. The resin composition was subjected to the above evaluations. The results are shown in Table 1.

[0053] [Examples 1-4] A resin composition and a resin sample were obtained in the same manner as in Example 1-1, except that 90 parts by weight of an amorphous copolyester resin (manufactured by Eastman Chemical Company, trade name "TRITAN TX2001") was used instead of 95 parts by weight of an amorphous copolyester resin (manufactured by Eastman Chemical Company, trade name "TRITAN TX1001"), and the amount of organic phosphorus compound (I) was 10 parts by weight. The resin composition was subjected to the above evaluations. The results are shown in Table 1.

[0054] [Comparative Example 1] A resin composition and a resin sample were obtained in the same manner as in Example 1-1, except that the organic phosphorus compound (I) was not added. The resin composition was subjected to the above evaluations. The results are shown in Table 1.

[0055] [Table 1]

[0056] As is clear from Table 1, the resin composition of the present invention, by containing a specific organophosphorus compound, can form a molded article that has both good mechanical properties and flame retardancy. Furthermore, the resin compositions of Examples 1-1 to 1-4 were excellent in processability, and the resulting molded articles had excellent appearance and sufficient transparency.

[0057] [Example 2-1] 95 parts by weight of polyamide resin, 5 parts by weight of organophosphorus compound (I) (Teijin Limited, trade name "FCX-210", 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide), and 15 parts by weight of flame retardant (II) (Clariant OP1230, diethylphosphinic acid aluminum complex salt (average particle size 20-40 μm)) were melt-kneaded at a melt temperature of 240°C using a twin-screw extruder (Toshiba Machine Co., Ltd. TEM26SS, screw diameter 26 mm). The molten material was extruded from the twin-screw extruder in the form of a strand, cooled and solidified, and then cut into pellets to obtain a resin composition. The obtained resin composition was injection molded using an injection molding machine (PLASTAR SI80-IV, manufactured by Toyo Machinery & Metal Co., Ltd.) under conditions of a cylinder temperature of 240°C and a mold temperature of 75°C to prepare resin sample pieces. As the resin sample pieces, ISO standard type A1 dumbbell-shaped test pieces were prepared for the tests (3) to (6) above, and strip test pieces (thickness: 0.8 mm, 1.6 mm, 3.2 mm) were prepared for the test (7) above. The resin composition was subjected to the above evaluations, and the results are shown in Table 2. Furthermore, when the appearance of the resin sample piece was visually inspected, it was found to have an excellent appearance with a uniform hue.

[0058] [Comparative Example 2-1] A resin composition and a resin sample were obtained in the same manner as in Example 2-1, except that the organophosphorus compound (I) and the flame retardant (II) were not added. The resin composition was subjected to the above evaluations. The results are shown in Table 2.

[0059] [Comparative Example 2-2] A resin composition and a resin sample were obtained in the same manner as in Example 2-1, except that the organic phosphorus compound (I) was not added, the amount of polyamide resin (manufactured by Refinverse Co., Ltd., trade name "RA6F1") added was 80 parts by weight, and the amount of flame retardant (II) added was 20 parts by weight. The resin composition was subjected to the above evaluations. The results are shown in Table 2. Furthermore, when the appearance of the obtained resin sample was visually inspected, spotted unevenness (whitening) was observed.

[0060] [Table 2]

[0061] As is clear from Table 2, the resin composition of the present invention, by including a specific organophosphorus compound, can form a molded article that combines mechanical properties and flame retardancy. Furthermore, by including a specific organophosphorus compound, a resin composition with excellent flowability can be obtained while maintaining excellent flame retardancy. Furthermore, as is clear from a comparison between Example 2-1 and Comparative Example 2-2, the addition of a specific organophosphorus compound eliminates the poor appearance caused by the use of another phosphorus-based flame retardant.

[0062] [Example 3-1] 80 parts by weight of polyamide resin, 5 parts by weight of organophosphorus compound (I) (Teijin Limited, trade name "FCX-210", 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide), and 15 parts by weight of flame retardant (III) (Clariant, trade name "OP1312", a composite of aluminum diethylphosphinate complex salt and a nitrogen-based flame retardant aid) were melt-kneaded at a melt temperature of 240°C using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM18SS, screw diameter 18 mm). The molten material was extruded from the twin-screw extruder in the form of a strand, cooled and solidified, and then cut into pellets to obtain a resin composition. The obtained resin composition was injection molded using an injection molding machine (PLASTAR SI80-IV, manufactured by Toyo Machinery & Metal Co., Ltd.) under conditions of a cylinder temperature of 240°C and a mold temperature of 75°C to prepare a resin sample piece. The appearance of the obtained resin sample piece was visually inspected and found to be excellent with a uniform hue.

[0063] [Example 3-2] 80 parts by weight of polyamide resin, 5 parts by weight of organophosphorus compound (I) (Teijin Limited, trade name "FCX-210", 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide), and 15 parts by weight of flame retardant (IV) (Clariant, trade name "OP930", diethylphosphinic acid aluminum complex salt (fine particle type of OP1230, average particle size 3-5 μm)) were melt-kneaded at a melt temperature of 240°C using a twin-screw extruder (Toshiba Machine Co., Ltd., TEM18SS, screw diameter 18 mm). The melt was extruded from the twin-screw extruder in the form of a strand, cooled and solidified, and then cut into pellets to obtain a resin composition. The obtained resin composition was injection molded using an injection molding machine (PLASTAR SI80-IV, manufactured by Toyo Machinery & Metal Co., Ltd.) under conditions of a cylinder temperature of 240°C and a mold temperature of 75°C to prepare a resin sample piece. The appearance of the obtained resin sample piece was visually inspected and found to be excellent with a uniform hue.

[0064] [Comparative Example 3-1] A resin sample piece was obtained in the same manner as in Example 3-1, except that the organic phosphorus compound (I) was not added and the amount of the flame retardant (III) was 20 parts by weight. When the appearance of the obtained resin sample piece was visually inspected, stains caused by the mold were observed.

[0065] [Comparative Example 3-2] A resin sample piece was obtained in the same manner as in Example 3-2, except that the organic phosphorus compound (I) was not added and the amount of the flame retardant (IV) was 20 parts by weight. When the appearance of the obtained resin sample piece was visually inspected, the entire molded article was whitened. [Industrial Applicability]

[0066] The resin composition of the present invention can be suitably used mainly as a material for hoses and tubes, belts, electric wires, cables, pipes, footwear, automobile parts, seats, adhesives, sealing materials, tableware, vibration-proof and sound-proof parts, and various molded articles.

Claims

1. The resin component includes an amorphous copolyester resin A including a structural unit derived from a terephthalic acid monomer, a structural unit derived from 1,4-cyclohexanedimethanol, and a structural unit derived from 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and Contains an organophosphorus compound represented by formula (1), the copolyester resin A has a deflection temperature under load (in accordance with ISO 75; load of 0.45 MPa) of 60°C to 150°C; resin composition; 【Chemical 1】 In formula (1), R ２ , R ５ R may be the same or different and are an optionally substituted phenyl group, naphthyl group, anthryl group, or a branched or linear alkyl group having 1 to 4 carbon atoms and optionally having an aromatic substituent. １ , R ３ , R ４ , R ６ may be the same or different and are a substituent selected from a hydrogen atom, a branched or linear alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, a naphthyl group, or an anthryl group which may have a substituent.

2. 2. The resin composition according to claim 1, wherein the content of the organic phosphorus compound is 0.5 to 20 parts by weight per 100 parts by weight of the resin component.

3. The resin composition according to claim 1, wherein the organic phosphorus compound is 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-dibenzyl-3,9-dioxide.

4. A resin composition described in any one of claims 1 to 3, which is transparent.

5. A resin composition described in any one of claims 1 to 4, wherein the load deflection temperature of the copolyester resin A (in accordance with ISO 75; load of 0.45 MPa) is 90°C to 120°C.

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