Bisphenol inhibitor, resin composition, and molded article

Abstract

The bisphenol inhibitor contains an acidic phosphorus compound and is for addition to a polycarbonate resin. The acidic phosphorus compound is preferably an acidic phosphoric acid ester or an acidic phosphate, more preferably an acidic phosphoric acid ester represented by formula (1) or (3). In formula (1), R1 represents a C8-40 alkyl, a C8-40 alkenyl, a C6-40 aryl, or a group represented by formula (2), and n represents an integer of 1 or 2. In formula (2), R2 represents a hydrogen atom or a C1-18 alkyl, m represents an integer such that the number average molecular weight of the group represented by formula (2) is 100-10,000, and * represents a bond. In formula (3), R3 to R6 each independently represent a hydrogen atom or a C1-9 alkyl, and R7 represents a C1-4 alkanediyl.

Description

Bisphenol inhibitor, resin composition, and molded article

[0001] The present invention relates to a bisphenol inhibitor for use in polycarbonate resins, a resin composition containing the bisphenol inhibitor, and a molded article.

[0002] Polycarbonate resins have excellent impact resistance, heat resistance, dimensional stability, and the like. Furthermore, polymer alloys composed of polycarbonate resins and polyester resins have improved chemical resistance while maintaining the excellent properties of polycarbonate resins. These polycarbonate resins are widely used in various fields, including electrical, electronic, optical, building materials, medical, food, and vehicle applications. However, polycarbonate resins contain bisphenols as residual monomers. Bisphenols, such as bisphenol A, have been identified as having endocrine-disrupting effects on humans and the environment, and there has been a growing movement to regulate the bisphenols contained in molded products. For this reason, there is a market demand for minimizing the concentration of bisphenols remaining in polycarbonate resins and their molded products. Examples of techniques for reducing the content of bisphenols remaining in polymers include those described in Patent Documents 1 to 3. Patent Document 1 describes a production method in which, when melt-kneading a polycarbonate resin using an extruder having a pressure-reducing vent port, carbon dioxide is supplied under pressure to a kneading section of the extruder, and then pressure is released and / or reduced, thereby removing bisphenols from the polymer.

[0003] Patent Document 2 describes a method for producing a resin having bisphenol A as a basic skeleton, which includes an extraction and separation step of extracting and separating residual bisphenol A contained in the resin into a solvent. Patent Document 3 describes a production method for reducing the amount of residual dihydric phenol compounds and the like in a polycarbonate resin, which includes a step of adding a scavenger having a specific structure to the polycarbonate resin and reacting the scavenger with residual components in the resin, such as dihydric phenol compounds.

[0004] JP 2000-302879 A JP 2018-131552 A US 2003 / 0100704 A1

[0005] However, the technology described in Patent Document 1 requires the installation of special equipment for pressurizing and supplying carbon dioxide to the extruder, which increases equipment costs and complicates the production process. The technology described in Patent Document 2 requires many steps, such as extraction, separation, washing, and drying, and the solvent-based extraction and drying steps each require long times. These factors make it disadvantageous in terms of productivity and cost, making it unsuitable for commercial implementation. The technology described in Patent Document 3 requires a heating step in which a scavenger is mixed with the resin before use after production and heated to a predetermined temperature or higher. This additional heating step may reduce productivity and may lead to deterioration in physical properties, such as discoloration of the resin. Furthermore, even when bisphenols are removed from polycarbonate resins using the above-mentioned methods, the bisphenol content in molded products still does not meet the required level. Therefore, an object of the present invention is to provide a technology that can reduce the bisphenol content in molded products.

[0006]

[0006] Even if bisphenols can be removed from polycarbonate resins by the above-mentioned methods, the amount of bisphenols increases during molding, and the need to minimize the concentration of bisphenols remaining in molded articles made from polycarbonate resins cannot be met. As a result of studies, the present inventors have found that adding an agent containing an acidic phosphorus compound having a specific structure to a polycarbonate resin can suppress the increase in the bisphenol content in the resin, leading to the completion of the present invention.

[0007] According to the present invention, there is provided a bisphenol inhibitor containing an acidic phosphorus compound for addition to polycarbonate-based resins.

[0008] In the bisphenol inhibitor of the present invention, the acidic phosphorus compound is preferably an acidic phosphate ester or an acidic phosphate salt.

[0009] In the bisphenol inhibitor of the present invention, the acidic phosphorus compound is preferably an acidic phosphoric acid ester represented by the following general formula (1) or (3). In general formula (1), R １ represents an alkyl group having 8 to 40 carbon atoms, an alkenyl group having 8 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, two R １ may be the same or different. In general formula (2), R ２ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000, and * represents a bond. In general formula (3), R ３ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms; R ７ represents an alkanediyl group having 1 to 4 carbon atoms.

[0010] In the bisphenol inhibitor of the present invention, the acidic phosphorus compound is preferably an acidic phosphoric acid ester represented by the general formula (1).

[0011] In the bisphenol inhibitor of the present invention, R in the general formula (1) １ is preferably a group represented by the general formula (2).

[0012] In the bisphenol inhibitor of the present invention, R in the general formula (2) ２ is preferably an alkyl group having 1 to 4 carbon atoms.

[0013] In the bisphenol inhibitor of the present invention, m in the general formula (2) is preferably an integer such that the number average molecular weight of the group represented by the general formula (2) is 400 to 5,000.

[0014] In the bisphenol inhibitor of the present invention, R in the general formula (1) １ is preferably an alkyl group having 28 to 36 carbon atoms.

[0015] Furthermore, according to the present invention, it is possible to provide a resin composition containing a polycarbonate resin and the above-mentioned bisphenol inhibitor.

[0016] In the resin composition of the present invention, the polycarbonate resin is preferably a recycled resin.

[0017] Furthermore, according to the present invention, a molded article obtained from the above resin composition can be provided.

[0018] Furthermore, according to the present invention, there can be provided a method for producing a molded article, which comprises a step of molding the above-mentioned resin composition.

[0019] Furthermore, the present invention can provide a method for reducing the content of bisphenols in a polycarbonate resin by adding an acidic phosphorus compound to the polycarbonate resin.

[0020] The present invention also provides use of an acidic phosphorus compound for producing a bisphenol inhibitor to be added to a polycarbonate resin.

[0021] According to the present invention, it is possible to provide a bisphenol inhibitor having excellent bisphenol inhibitor performance, a resin composition containing the bisphenol inhibitor, and a molded article obtained from the resin composition.

[0022] Embodiments of the present invention are described in detail below. <Bisphenol Inhibitor, Method for Suppressing Bisphenol Content, and Use of Acidic Phosphorus Compound> The bisphenol inhibitor of the present invention contains an acidic phosphorus compound and is an agent to be added to a polycarbonate resin. The bisphenol inhibitor of the present invention has an acidic phosphorus compound as an active ingredient. Examples of the polycarbonate resin include those exemplified as polycarbonate resins contained in the resin composition described below. In the present invention, "bisphenols" refers to a divalent hydroxy aromatic compound. Examples of the divalent hydroxy aromatic compound include those exemplified as polymerization raw materials for polycarbonate resins described below. In this specification, "bisphenol inhibitor" refers to an agent used to suppress the content of bisphenols in a polycarbonate resin, and includes "suppressing the content of bisphenols in a molded product containing a polycarbonate resin." Furthermore, in this specification, "suppressing the content of bisphenols" includes suppressing an increase in the content of bisphenols, typically suppressing an increase in the content of bisphenols when a resin composition containing a polycarbonate resin is molded.

[0023] The acidic phosphorus compound is a compound having a phosphorus atom and exhibiting acidity, and examples thereof include inorganic phosphoric acid, acidic phosphate esters, and acidic phosphate salts. Examples of the inorganic phosphoric acid include phosphoric acid, phosphorous acid, pyrophosphoric acid, and polyphosphoric acid. The inorganic phosphoric acid is preferably an inorganic phosphoric acid having two or more phosphorus atoms in the molecule, more preferably an inorganic phosphoric acid having two to three phosphorus atoms in the molecule, and even more preferably pyrophosphoric acid. Examples of the acidic phosphate ester include phosphate esters, pyrophosphate esters, and polyphosphate esters that have one or more hydroxy groups directly bonded to the phosphorus atom. Examples of the acidic phosphate ester include compounds represented by the following general formula (1) or (3):

[0024] In general formula (1), R １represents an alkyl group having 8 to 40 carbon atoms, an alkenyl group having 8 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, two R １ may be the same or different. In general formula (2), R ２ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000, and * represents a bond. In general formula (3), R ３ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms; R ７ represents an alkanediyl group having 1 to 4 carbon atoms.

[0025] R in general formula (1) １ Examples of the alkyl group having 8 to 40 carbon atoms that can be taken include an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a 2-propylheptyl group, an undecyl group, an isoundecyl group, a dodecyl group, an isododecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a henicosyl group, a docosyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a henicosyl group, a docosyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a nonadecyl group, a hex ... Examples of the alkyl group include linear or branched alkyl groups such as a cyclohexyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, an octacosyl group, a triacontyl group, a dotriacontyl group, a hexatriacontyl group, a tetracontyl group, a 2-decylhexadecyl group, a 2-dodecylhexadecyl group, a 2-decyloctadecyl group, a 2-tetradecyloctadecyl group, a 2-hexadecyloctadecyl group, a 2-tetradecyleicosyl group, and a 2-hexadecyleicosyl group.

[0026] R in general formula (1) １Examples of alkenyl groups having 8 to 40 carbon atoms that may be included include linear, branched, or cyclic alkenyl groups such as octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, hexacosenyl, octacosenyl, triacontenyl, dotriacontenyl, hexatriacontenyl, tetracontenyl, 2-dodecylhexadecenyl, 2-dodecyloctadecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4,8,12-tetradecatrienylallyl. The position of the double bond may be the α-position, internal, or ω-position.

[0027] R in general formula (1) １ Examples of the aryl group having 6 to 40 carbon atoms that may be taken by the formula (I) include a phenyl group, a biphenylyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a tert-butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a tert-octylphenyl group, an isooctylphenyl group, a nonylphenyl group, a dinonylphenyl group, a decylphenyl group, an undecylphenyl group, a dodecylphenyl group, a tetradecylphenyl group, a hexadecylphenyl group, an octadecylphenyl group, a 2,4-di-tert-butylphenyl group, a 2,4-di-tert-oct ... Examples of such groups include amylphenyl group, 2-tert-butyl-4-methylphenyl group, 2,4-di-tert-butyl-5-methylphenyl group, 2,6-di-tert-butyl-4-methylphenyl group, 2-cyclohexylphenyl group, p-(4-hydroxytamyl)phenyl group, benzyl group, phenethyl group, γ-phenylpropyl group, styryl group, cinnamyl group, benzhydryl group, trityl group, cyclohexylphenyl group, styrenated phenyl group, p-cumylphenyl group, benzylphenyl group, α-naphthyl group, β-naphthyl group, di(1,1-dimethylethyl)-4-methylphenyl group, tri(1,1-dimethylethyl)phenyl group, and di(1,1-dimethylethyl)phenyl group.

[0028] R in general formula (2) ２ Examples of the alkyl group having 1 to 18 carbon atoms that may be taken by include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, tert-hexyl, heptyl, isoheptyl, tert-heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, 2-propylheptyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, and octadecyl.

[0029] R in general formula (2) ２ As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, a methyl group or an ethyl group is even more preferred, and a methyl group is particularly preferred. This improves the heat resistance and bisphenol inhibitor performance of the bisphenol inhibitor of the present invention.

[0030] In general formula (2), m is an integer that results in the number average molecular weight of the group represented by general formula (2) being 100 or more, preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 400 or more, more preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 800 or more, even more preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 1,000 or more, and particularly preferably an integer that results in the number average molecular weight of the group represented by general formula (2) being 1,500 or more. This allows the bisphenols inhibitor of the present invention to have an even better balance between heat resistance and bisphenols inhibition performance. On the other hand, m in the above general formula (2) is an integer such that the number average molecular weight of the group represented by general formula (2) is 10,000 or less, preferably an integer such that the number average molecular weight of the group represented by general formula (2) is 5,000 or less, more preferably an integer such that the number average molecular weight of the group represented by general formula (2) is 4,500 or less, even more preferably an integer such that the number average molecular weight of the group represented by general formula (2) is 3,500 or less, and particularly preferably an integer such that the number average molecular weight of the group represented by general formula (2) is 2,500 or less. This further improves the heat resistance and bisphenols inhibition performance of the bisphenols inhibitor of the present invention.

[0031] The number average molecular weight (Mn) of the group represented by general formula (2) can be measured by the following method. <Method for measuring the number average molecular weight of the group represented by general formula (2)> In a chromatogram obtained by gel permeation chromatography (GPC) measurement of the compound represented by general formula (1), the number average molecular weight (Mn) of the acidic phosphate monoester is determined using a calibration curve prepared using polystyrene or polymethyl methacrylate (PMMA) standard substances for the peak derived from the acidic phosphate monoester. １ ) is calculated. １ The number average molecular weight (Mn) of the group represented by general formula (2) is calculated from the following formula (i): Mn = Mn １ −80 (i)

[0032] The GPC measurement conditions may be, for example, as follows: Column: SHODEX LF-804 Mobile phase: chloroform Detector: differential refractive index detector Flow rate: 0.5 mL / min Column temperature: 40°C

[0033] R in general formula (1) １ As the bisphenol group, an alkyl group having 8 to 40 carbon atoms or a group represented by general formula (2) is preferred, and a group represented by general formula (2) is more preferred, in terms of achieving an excellent balance between the heat resistance and bisphenol inhibition performance of the bisphenol group inhibitor of the present invention.

[0034] R in general formula (1) １ When R is an alkyl group, from the viewpoint of the heat resistance of the bisphenol inhibitor of the present invention, it is preferably an alkyl group having 12 or more carbon atoms, more preferably an alkyl group having 16 or more carbon atoms, and even more preferably an alkyl group having 18 or more carbon atoms. １ When the alkyl group is an alkyl group, from the viewpoint of the ability to inhibit bisphenols, the alkyl group preferably has 40 or less carbon atoms, and more preferably has 36 or less carbon atoms.

[0035] The compound represented by general formula (1) may be an acidic phosphoric acid monoester in which n in general formula (1) is 1, or an acidic phosphoric acid diester in which n in general formula (1) is 2. However, from the viewpoint of the heat resistance and bisphenol inhibitory performance of the bisphenol inhibitor of the present invention, it is preferable to include an acidic phosphoric acid monoester and an acidic phosphoric acid diester. In this case, the content ratio of the acidic phosphoric acid monoester to the acidic phosphoric acid diester, in mass ratio (acidic phosphoric acid monoester:acidic phosphoric acid diester), is preferably 100:1 to 100:10,000, more preferably 100:3 to 100:500, and even more preferably 100:5 to 100:100. This further improves the heat resistance and bisphenol inhibitory performance of the bisphenol inhibitor of the present invention.

[0036] The mass ratio of the acidic phosphate monoester to the acidic phosphate diester can be measured by analysis using a nuclear magnetic resonance (NMR) spectrometer.

[0037] When n in the general formula (1) is 2, two R １ may be the same or different, but are preferably the same. This further improves the heat resistance and bisphenol inhibitor performance of the bisphenol inhibitor of the present invention. The compound represented by general formula (1) can be produced by a conventionally known method. For example, １ It can be obtained by reacting the corresponding alcohol with diphosphorus pentoxide.

[0038] R in general formula (3) ３ , R ４ , R ５ and R ６ Examples of the alkyl group having 1 to 9 carbon atoms represented by the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, isoheptyl, tert-heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, and isononyl. Among these, the tert-butyl group is preferred from the viewpoint of bisphenol inhibition performance.

[0039] R in general formula (3) ７ Examples of the alkanediyl group having 1 to 4 carbon atoms represented by the formula (3) include a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, a 1,4-butylene group, an ethylidene group, a 1,1-propylidene group, a 2,2-propylidene group, a 1,1-butylidene group, and a 2,2-butylidene group. Of these, a methylene group is preferred from the viewpoint of bisphenol inhibition performance. A conventionally known method can be used to produce the compound represented by formula (3). For example, the compound can be obtained by reacting phosphorus trichloride (or phosphorus oxychloride) with 2,2'-alkylidenebisphenol, followed by hydrolysis.

[0040] As the acidic phosphate ester, from the viewpoint of bisphenol suppression performance, a compound represented by general formula (1) or a compound represented by general formula (3) is preferred, and a compound represented by general formula (1) is more preferred.

[0041] Examples of the acidic phosphate salts include dihydrogen phosphate salts, hydrogen phosphate salts, and acidic pyrophosphate salts. Examples of the dihydrogen phosphate salts include alkali metal dihydrogen phosphate salts, dihydrogen phosphate salts of divalent or higher metals, and ammonium dihydrogen phosphate salts. Examples of the alkali metal dihydrogen phosphate salts include lithium dihydrogen phosphate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate salts. Examples of the dihydrogen phosphate salts of divalent or higher metals include calcium dihydrogen phosphate, barium dihydrogen phosphate, and zinc dihydrogen phosphate salts. Examples of the hydrogen phosphate salts include divalent metal hydrogen phosphate salts (e.g., alkaline earth metals), alkali metal hydrogen phosphate salts, ammonium hydrogen phosphate, and hydrogen phosphate salts having an alkali metal cation and an ammonium cation. Examples of the acidic pyrophosphate salts include magnesium hydrogen phosphate, strontium hydrogen phosphate, barium hydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, and sodium ammonium hydrogen phosphate. Examples of the acidic pyrophosphate salts include acidic pyrophosphate salts having an alkali metal cation and / or an ammonium cation. Examples include disodium dihydrogen pyrophosphate (sodium acid pyrophosphate), ammonium acid pyrophosphate, and potassium acid pyrophosphate. Acid pyrophosphates are preferably salts bound to two monovalent cations. Among these, acid pyrophosphates are particularly preferred, and disodium dihydrogen pyrophosphate is more preferred, in terms of bisphenol inhibition performance.

[0042] As the acidic phosphorus compound, acidic phosphate esters and acidic phosphate salts are preferred, and acidic phosphate esters are more preferred, from the viewpoint of bisphenol-inhibiting performance.

[0043] More specifically, examples of the bisphenol inhibitor of the present invention include compounds represented by the following formulas (4) to (9), although the present invention is not limited to these compounds. In formulas (4) to (6), n represents an integer of 1 or 2. In formula (4), m represents an integer that makes the number average molecular weight of the structural portion in the square brackets 100 to 10,000.

[0044] In the bisphenol inhibitor of the present invention, the acidic phosphoric acid compound is preferably one or more selected from the group of compounds represented by the above formulas (4) to (9). Among these, the acidic phosphoric acid compound is more preferably one or more selected from the group of compounds represented by the above formula (4), the above formula (5), and the above formula (9), more preferably the compound represented by the above formula (4), and even more preferably the compound represented by the above formula (4) in which m is an integer such that the number average molecular weight of the structural portion in square brackets is 400 to 5,000. This further improves the heat resistance and bisphenol inhibitor performance of the bisphenol inhibitor of the present invention.

[0045] The bisphenol inhibitor of the present invention may be a single compound or a mixture of two or more compounds. The bisphenol inhibitor of the present invention preferably contains an acidic phosphoric acid compound in an amount of 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and may even contain 100% by mass.

[0046] According to the present disclosure, the bisphenol inhibitor of the present invention exhibits the effect of excellent bisphenol inhibitor performance. The reason for this effect is unclear, but is presumed to be as follows: During the production of a polycarbonate resin composition, trace amounts of highly polar impurities, such as metal ions, originating from the manufacturing and processing equipment are introduced into the polycarbonate resin during the production and processing steps. It is believed that these highly polar impurities cause molecular chain scission of the polycarbonate resin, resulting in the generation of bisphenols in a free form from the polycarbonate resin. When the bisphenol inhibitor of the present invention is added during molding and processing of a polycarbonate resin, the acidic phosphorus compound forms a complex, such as a chelate complex, with the highly polar impurities during molding, thereby suppressing molecular chain scission of the resin and suppressing the generation of bisphenols. From the above, the bisphenol inhibitor exhibits the effect of excellent bisphenol inhibitor performance. Furthermore, since the bisphenol inhibitor is believed to inhibit molecular chain scission of polycarbonate resins, it is believed to have the effect of improving the physical properties of the resin as a secondary effect to the above-mentioned effect.

[0047] <Resin Composition> The resin composition of the present invention contains the above-mentioned bisphenol inhibitor and a polycarbonate resin.

[0048] The content of the bisphenol inhibitor in the resin composition of the present invention, as the content of the acidic phosphoric acid compound, is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.08 parts by mass or more, and particularly preferably 0.15 parts by mass or more, relative to 100 parts by mass of the resin composition. This allows the resin composition of the present invention to more effectively exhibit the effect of excellent bisphenol inhibitor performance. On the other hand, the content of the bisphenol inhibitor, as the content of the acidic phosphoric acid compound, relative to 100 parts by mass of the resin composition, is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1.5 parts by mass or less, and particularly preferably 0.8 parts by mass or less. This suppresses the occurrence of bleeding on the surface of the molded article, allowing a molded article with a good appearance to be obtained.

[0049] The content of the bisphenol inhibitor, expressed as the acidic phosphoric acid compound, is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.08 parts by mass or more, and particularly preferably 0.15 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin. This allows the resin composition of the present invention to more effectively exhibit the effect of excellent bisphenol inhibitor performance. On the other hand, the content of the bisphenol inhibitor, expressed as the acidic phosphoric acid compound, is preferably 10 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1.5 parts by mass or less, and particularly preferably 0.8 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin. This suppresses bleeding on the surface of the molded article, allowing a molded article with a good appearance to be obtained.

[0050] In the present invention, the term "polycarbonate-based resin" refers to a polycarbonate resin or a polymer alloy containing a polycarbonate resin. The polycarbonate resin is a resin having a carbonate bond. In the present invention, the polycarbonate resin refers to a resin obtained by a polymerization reaction using a divalent hydroxy aromatic compound and a carbonate precursor as raw materials. "Used from a divalent hydroxy aromatic compound" means that the divalent hydroxy aromatic compound must be the main component of the divalent hydroxy compound used as the polycarbonate resin raw material. The term "main component" refers to the divalent hydroxy aromatic compound being 50% by mass or more of the divalent hydroxy compound, and may be 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[0051] The divalent hydroxy aromatic compound is an aromatic compound having two hydroxy groups directly bonded to an aromatic ring, and examples thereof include a compound in which two hydroxy groups are directly bonded to one aromatic ring, and a compound having a structure in which aromatic rings each having one hydroxy group directly bonded thereto are linked by a linking group. Examples of the linking group include a single bond, -O-, -S-, -CO-, and -SO ２ -, -C(=CR ２)-, a divalent alkanediyl group having 1 to 20 carbon atoms, or a group having 8 to 20 carbon atoms that is a combination of an alkanediyl group and an arylene group. R represents a hydrogen atom or a halogen atom. In this specification, examples of halogen atoms include fluorine, chlorine, iodine, and bromine. The linking group preferably has 1 to 20 carbon atoms. The number of atoms constituting the shortest path connecting the rings in the linking group may be 8 or less, 3 or less, or 1 or less. The number of atoms constituting the shortest path connecting the rings in the linking group is, for example, 0 for a single bond and 1 for -O-. The number of rings contained in the divalent hydroxy aromatic compound is preferably 4 or less, more preferably 2 or less, and particularly preferably 2. Here, the number of rings refers to the number of rings constituting one fused ring.

[0052] In the divalent alkanediyl group having 1 to 20 carbon atoms and the group having 8 to 20 carbon atoms in which an alkanediyl group and an arylene group are combined (hereinafter collectively referred to as a "divalent alkanediyl-containing group having 1 to 20 carbon atoms"), the hydrogen atom or methylene group in these groups may be substituted with a substituent. Examples of the substituent substituting the hydrogen atom include a halogen atom and a carboxy group. Examples of the substituent substituting the methylene group include -O-, -S-, and -CO-. When a methylene group is substituted, it is preferable that the methylene group in the side chain of the linking group is substituted.

[0053] Examples of the alkanediyl group having 1 to 20 carbon atoms include the above-mentioned alkanediyl groups having 1 to 4 carbon atoms, as well as 1-phenylethane-1,1-diyl, hexafluoropropane-2,2-diyl, diphenylmethane-1,1-diyl, cyclohexane-1,1-diyl, 3,3,5-trimethylcyclohexane-1,1-diyl, etc. Examples of groups having 8 to 20 carbon atoms in combination of an alkanediyl group and a phenylene group include groups in which the above-mentioned alkanediyl group having 1 to 4 carbon atoms and an arylene group such as a phenylene group or a methylphenylene group are combined to form the main chain of the linking group, such as a 1,3-phenylenediisopropylidene group and a 1,4-phenylenediisopropylidene group.

[0054] Among divalent hydroxy aromatic compounds, examples of compounds in which two hydroxy groups are directly bonded to one aromatic ring include dihydroxybenzenes such as resorcinol and hydroquinone.Furthermore, examples of compounds having a structure in which aromatic rings each having one directly bonded hydroxy group are linked together by a linking group include bishydroxyaryls, bis(hydroxyaryl)alkanes, dihydroxyaryl ketones, dihydroxyaryl ethers, and dihydroxyaryl sulfur compounds.

[0055] Bishydroxyaryls are compounds in which the linking group is a single bond, such as 4,4'-dihydroxydiphenyl. Bis(hydroxyaryl)alkanes are compounds in which the linking group is an alkanediyl-containing group having 1 to 20 carbon atoms, such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenoxy)ethane, and 2,2-bis(4-hydroxyphenyl)propane, in which the linking group is an alkanediyl group having 1 to 20 carbon atoms; and 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, in which the linking group is a group having 8 to 20 carbon atoms in which an alkanediyl group having 1 to 20 carbon atoms and an arylene group are linked to form the main chain of the linking group. Furthermore, the alkanediyl moiety in the linking group of the bis(hydroxyaryl)alkanes may be substituted with one or more substituents (such as an organic group, a halogen atom, a hydroxyl group, a carbonyl group, a sulfur atom, a sulfone group, an amino group, an amide group, a nitro group, or a silyl group), and a plurality of such substituents may be bonded to each other to form a ring structure (such as a lactone ring or a lactam ring) that may contain a heteroatom. An example of a bis(hydroxyaryl)alkane having such a linking group is phenolphthalein. Dihydroxyaryl ketones are compounds in which the linking group is a ketone group (—CO—), such as bis(4-hydroxyphenyl)ketone and bis(4-hydroxy-3-methylphenyl)ketone. Dihydroxyaryl ethers are compounds in which the linking group is an ether group (—O—), such as 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethylphenyl ether, and 4,4′-dihydroxy-2,5-dihydroxydiphenyl ether. Dihydroxyaryl sulfur compounds are compounds in which the linking group is a sulfide (—S—) or sulfoxide (—SO ２-), and examples thereof include bis(4-hydroxyphenyl)sulfide (4,4'-thiodiphenol), 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 2,2'-bis(4-hydroxyphenyl)sulfone, 4,4'-dihydroxydiphenyl sulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. A benzene ring is particularly preferred as the aromatic ring. These may be used alone or in combination of two or more, and may also be used in combination with a polyvalent hydroxy aromatic compound having three or more hydroxy groups. Among these, in the present invention, compounds having a structure in which aromatic rings each having one hydroxy group directly bonded thereto are linked by a linking group are preferred, and bis(hydroxyaryl)alkanes are preferred, with bis(hydroxyaryl)alkanes in which the linking group is an alkanediyl group being even more preferred.

[0056] Specific examples of suitable carbonate precursors include phosgene, carbonic acid diesters, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof. The polycarbonate resins can be used singly or in combination of two or more.

[0057] As the polycarbonate-based resin, a so-called polymer alloy, which is a mixture of a polycarbonate resin and another resin, can be used. Examples of resins that can be combined with a polycarbonate resin to form a polymer alloy include polyester resins, ABS resins, AS resins, ASA resins, AES resins, and rubber-based polymer compounds. One or more of these resins can be used in combination with polycarbonate. Among these, polyester resins, ABS resins, AS resins, ASA resins, and AES resins are preferred, polyester resins and ABS resins are more preferred, and polyester resins are even more preferred, as they exhibit a good balance between the physical properties of the polycarbonate-based resin and the bisphenol inhibitor performance of the bisphenol inhibitor of the present invention.

[0058] Examples of the polyester resin include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, and polycyclohexanedimethylene terephthalate; polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone). Among these, polyalkylene terephthalates are preferred, polyethylene terephthalate and polybutylene terephthalate are more preferred, and polybutylene terephthalate is even more preferred, in view of achieving a good balance between the physical properties of the polycarbonate resin and the bisphenols suppression performance of the bisphenols suppressor of the present invention.

[0059] In the present invention, when the polycarbonate resin is a polymer alloy, the content of the polycarbonate resin in the polymer alloy is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more. This allows the inherent physical properties of the polycarbonate resin to be fully exhibited. These polycarbonate resins and resins constituting the polymer alloy can be used regardless of molecular weight, degree of polymerization, polymerization method, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomers, type of polymerization catalyst, etc. In the present invention, when the polycarbonate resin is a polymer alloy of a polycarbonate resin and a polyester resin, in order to achieve a good balance between the physical properties of the polycarbonate resin and the bisphenols suppression performance of the bisphenols suppressor of the present invention, the content ratio of the polycarbonate resin to the polyester resin is preferably 5 parts by mass or more, more preferably 5.3 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin. In addition, the content of the polyester resin is preferably 2,000 parts by mass or less, more preferably 1,900 parts by mass or less, more preferably 1,000 parts by mass or less, even more preferably 500 parts by mass or less, and even more preferably 250 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin.

[0060] The content of the polycarbonate resin is preferably 90 parts by mass or more, more preferably 93 parts by mass or more, even more preferably 95 parts by mass or more, and particularly preferably 97 parts by mass or more, relative to 100 parts by mass of the resin composition of the present invention. On the other hand, the content of the polycarbonate resin is preferably 99.99 parts by mass or less, more preferably 99.98 parts by mass or less, even more preferably 99.95 parts by mass or less, and particularly preferably 99.9 parts by mass or less, relative to 100 parts by mass of the resin composition of the present invention. This allows the resin composition of the present invention to more effectively exhibit the effect of excellent bisphenol suppression performance.

[0061] Recycled resins can also be used as the polycarbonate-based resin. Recycled resins refer to resins obtained by recovering used resin products and regenerating them from the resin products. This can reduce carbon dioxide emissions and conserve resources, thereby reducing the environmental impact. The resin composition of the present invention may contain other optional components in addition to the bisphenol inhibitor. The timing of mixing the bisphenol inhibitor and other optional components with the polycarbonate-based resin is not particularly limited. For example, two or more components selected from the components other than the polycarbonate-based resin may be premixed and then blended with the polycarbonate-based resin, or each component other than the polycarbonate-based resin may be blended sequentially with the polycarbonate-based resin. When multiple components are premixed, each component may be pulverized and then mixed, or mixed and then pulverized. When the polycarbonate-based resin is a polymer alloy, each component other than the polycarbonate-based resin may be added to a compound resin that has already been alloyed, or may be added during the alloying process.

[0062] The bisphenol inhibitor may be mixed with the polycarbonate resin in an amount ranging from 10 to 90 parts by mass per 100 parts by mass of the masterbatch. Alternatively, the bisphenol inhibitor may be mixed with a portion of the polycarbonate resin to prepare a masterbatch, and the masterbatch may then be mixed with the remaining polycarbonate resin. The masterbatch may also contain the optional components described above. The content of the bisphenol inhibitor in the masterbatch may be 1 part by mass or more, and may be from 10 to 90 parts by mass per 100 parts by mass of the masterbatch.

[0063] Other optional components that can be blended into the resin composition of the present invention will be described below. It is preferable to add a phenolic antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, a hindered amine-based light stabilizer, or the like to the resin composition of the present invention as needed to stabilize the resin composition.

[0064] Examples of the phenolic antioxidant include 2,6-di-tert-butyl p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4, 4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4 -hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate methyl]methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] diphenyl) propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}ethyl]-2,4,8,Examples include 10-tetraoxaspiro[5,5]undecane and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. These phenolic antioxidants may be used alone or in combination of two or more. From the viewpoint of antioxidant effect, the content of the phenolic antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0065] Examples of the phosphorus-based antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, didecyl monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol tetritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(tridecyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4, 4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexakis(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite Examples of suitable phosphorus-based antioxidants include 2,2'-methylenebis(4,6-tert-butylphenyl)octadecylphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. These phosphorus-based antioxidants may be used alone or in combination of two or more. From the viewpoint of antioxidant effect, the content of the phosphorus-based antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0066] Examples of the thioether-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetrakis(β-alkylmercaptopropionates). These thioether-based antioxidants may be used alone or in combination of two or more. From the viewpoint of antioxidant effect, the content of the thioether-based antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the polycarbonate-based resin.

[0067] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'- 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; phenyl salicylate benzoates such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. These ultraviolet absorbers may be used alone or in combination of two or more.From the viewpoint of ultraviolet absorbing effect, the content of the ultraviolet absorber is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0068] Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2 ,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxybenzyl)- polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidinol) / diethyl succinate, polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine, polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine, polycondensation product of 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino]hexane / 2,4-dichloro-6-tert-octylamino-s-triazine, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,Examples of suitable hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)amino)-s-triazin-6-yl)aminoundecane, bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)decanedioate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl)carbonate, and TINUVIN NOR 371 manufactured by BASF. These hindered amine light stabilizers may be used alone or in combination of two or more. From the viewpoint of light stabilization effect, the content of the hindered amine light stabilizer is preferably 0.001 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the polycarbonate resin.

[0069] The resin composition of the present invention may further contain additives commonly used in synthetic resins, such as crosslinkers, antistatic agents, antifogging agents, antiplateout agents, surface treatment agents, plasticizers, lubricants, reinforcing agents, nucleating agents, flame retardants, flame retardant assistants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, silicone oils, silane coupling agents, fillers, hydrotalcites, metal soaps, pigments, dyes, etc., as long as the effects of the present invention are not impaired. The form of the resin composition of the present invention is not particularly limited, but from the viewpoint of the handleability of the resin composition, pellets, powders, granules, or flakes are preferred, and pellets are more preferred. The resin composition of the present invention can be used alone or in combination with compositions other than the present invention, additive components, or mixtures thereof for molding, etc. The resin composition of the present invention can also be used as a masterbatch.

[0070] <Molded Article, Method for Producing Molded Article> The molded article of the present invention can be obtained by molding the resin composition of the present invention using a known method. The method for producing a molded article of the present invention includes a step of molding the resin composition of the present invention (molding step). The molding method in the molding step is not particularly limited, and examples include extrusion molding, calendar molding, injection molding, roll molding, compression molding, and blow molding. These molding methods can produce molded articles of various shapes, such as resin plates, sheets, films, pellets, and irregularly shaped articles. The molding temperature is preferably 400°C or lower, more preferably 380°C or lower, and even more preferably 360°C or lower. The molding temperature is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 230°C or higher. This molding temperature can more effectively exhibit the effects of the present invention.

[0071] The resin composition of the present invention and molded articles thereof can be used in a wide range of industrial fields, including electricity, electronics, and communications, agriculture, forestry, and fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision instruments, wood, building materials, civil engineering, furniture, printing, and musical instruments. More specifically, they can be used in office automation equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, and stationery, home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsu tables, audio-visual equipment such as TVs, VTRs, video cameras, radio-cassette players, tape recorders, minidiscs, CD players, speakers, and liquid crystal displays, and electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulating materials, LED encapsulating materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks.

[0072] The resin composition of the present invention and its molded article can also be used for optical materials such as optical disks, CD disks, DVD disks, and lenses, or as a glass substitute. Furthermore, the resin composition of the present invention and its molded article can be used for seats (padding, surface, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, hand straps, hand straps, wire covering materials, electrical insulating materials, paints, coating materials, covering materials, flooring materials, partition walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, deck materials, wall materials, It is used for a variety of purposes, including materials for automobiles, vehicles, ships and aircraft, such as pillars, floor boards, fence materials, frames and moldings, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, heat insulating boards, window materials, etc., as well as materials for buildings, houses and construction and civil engineering materials; clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and other daily necessities and sporting goods.

[0073] The present disclosure includes the following aspects: [1] A bisphenol inhibitor for addition to a polycarbonate resin, the inhibitor containing an acidic phosphorus compound.

[0074] [2] The bisphenol inhibitor according to [1], wherein the acidic phosphorus compound is an acidic phosphate ester or an acidic phosphate salt.

[0075] [3] The bisphenol inhibitor according to [1] or [2], wherein the acidic phosphorus compound is an acidic phosphoric acid ester represented by the following general formula (1) or general formula (3): In general formula (1), R １ represents an alkyl group having 8 to 40 carbon atoms, an alkenyl group having 8 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, two R １ may be the same or different. In general formula (2), R ２represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000, and * represents a bond. In general formula (3), R ３ ~R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms; R ７ represents an alkanediyl group having 1 to 4 carbon atoms.

[0076] [4] The bisphenol inhibitor according to any one of [1] to [3], wherein the acidic phosphorus compound is an acidic phosphate ester represented by the general formula (1).

[0077] [5] R in the general formula (1) １ is a group represented by the general formula (2).

[0078] [6] R in the general formula (2) ２ is an alkyl group having 1 to 4 carbon atoms.

[0079] [7] The bisphenol inhibitor according to any one of [3] to [6], wherein m in the general formula (2) is an integer such that the number average molecular weight of the group represented by the general formula (2) is 400 to 5,000.

[0080] [8] R in the general formula (1) １ is an alkyl group having 18 to 36 carbon atoms. [9] The inhibitor for bisphenols according to [1], wherein the acidic phosphorus compound is at least one selected from the compounds represented by the following formulas (4) to (9): In formulas (4) to (6), n represents an integer of 1 or 2. In formula (4), m represents an integer such that the number average molecular weight of the structural portion in the square brackets is 100 to 10,000.

[10] The bisphenols inhibitor according to [9], wherein the acidic phosphorus compound is one or more compounds selected from the group consisting of compounds represented by formula (4), compounds represented by formula (5), and compounds represented by formula (9).

[0081]

[11] A resin composition containing a polycarbonate resin and the bisphenol inhibitor according to any one of [1] to

[10] .

[0082]

[12] The resin composition according to

[11] , wherein the polycarbonate resin is a recycled resin.

[0083]

[13] A molded article obtained from the resin composition according to

[11] or

[12] .

[0084]

[14] A method for producing a molded article, comprising a step of molding the resin composition according to

[11] .

[0085]

[15] A method for suppressing the content of bisphenols in a polycarbonate-based resin, comprising adding an acidic phosphorus compound to the polycarbonate-based resin.

[16] Use of an acidic phosphorus compound for producing a bisphenols inhibitor to be added to a polycarbonate-based resin.

[0086] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0087] Details of the components in Tables 1 to 7 are shown below. PC resin: polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, product name: Iupilon S-2000F, bisphenol A content: less than 5 ppm, resin obtained by polymerization reaction using bisphenol A and a carbonate precursor as raw materials) PBT resin: polybutylene terephthalate resin (manufactured by Toray, product name: TORAYCON 1200M, bisphenol A content: less than 5 ppm) PET resin: polyethylene terephthalate resin (manufactured by Teijin, product name: TRN-RTJ, bisphenol A content: less than 5 ppm) Bisphenol inhibitor (A)-1: mixture of monostearyl acid phosphate and distearyl acid phosphate (mass ratio of monostearyl acid phosphate:distearyl acid phosphate = 100:150-250) Bisphenol inhibitor (A)-2: acidic phosphate ester produced in Production Example 1 below Bisphenol inhibitor (A)-3: Disodium dihydrogen pyrophosphate Bisphenol inhibitor (A)-4: 2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin-6-oxide Bisphenol inhibitor (A)-5: Pyrophosphate Comparative compound (B)-1: Tris(2,4-di-tert-butylphenyl)phosphite Comparative compound (B)-2: Tetrasodium pyrophosphate

[0088] <Production Example 1: Production of Bisphenol Inhibitor (A)-2> 489 g of methoxypolyethylene glycol (number average molecular weight: 2,000) and 440 g of orthoxylene were added to a flask equipped with a stirrer and a condenser, and the mixture was purged with nitrogen under reduced pressure. The mixture was then heated to 90°C in an oil bath while stirring. Thereafter, 11 g of diphosphorus pentoxide was added, and the mixture was heated to 110°C and reacted for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was cooled to room temperature to obtain bisphenol inhibitor (A)-2: an acidic phosphate ester of methoxypolyethylene glycol (number average molecular weight: 2,000). The content ratio (mass ratio) of the acidic phosphate monoester to the acidic phosphate diester in resin additive (A)-2 was 59:41. The content ratio (mass ratio) of the acidic phosphate monoester to the acidic phosphate diester was ３１The measurement was carried out using P-NMR under the following conditions. ３１ The mass ratio was calculated from the integral ratio of the peak (1.7 ppm to 2.5 ppm) derived from the acidic phosphate monoester and the peak (0.4 ppm to 1.2 ppm) derived from the acidic phosphate diester in the P-NMP spectrum, and the substance amount of each phosphate.

[0089] [ ３１ P-NMR measurement conditions] Apparatus: Ascend 400 (manufactured by Bruker Corporation) Solvent: deuterated chloroform Number of accumulations: 256

[0090] <Method for preparing molded articles (PC / PBT)> The components listed in Tables 1 to 6 were dry-blended and then heated and melt-kneaded at 260°C using a twin-screw extruder (machine name: TEX30α, manufactured by The Japan Steel Works, Ltd.) to obtain a pellet-shaped resin composition. The obtained resin composition was molded using an injection molding machine (machine name: EC60NII, manufactured by Toshiba Machine) at a cylinder temperature of 260°C and a mold temperature of 60°C to obtain a plate-shaped molded article (60mm x 60mm x 2mm) and a rod-shaped molded article (80mm x 20mm x 4mm). The composition values ​​shown in Tables 1 to 6 represent mass ratios.

[0091] <Method for producing molded articles (PC / PET)> The components listed in Table 7 were dry blended and then heated and melted at 280 ° C. using a twin-screw extruder (machine name: TEX30α, manufactured by The Japan Steel Works) to obtain a pellet-shaped resin composition. The obtained resin composition was molded using an injection molding machine (machine name: EC60NII, manufactured by Toshiba Machine) under conditions of a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. to obtain a plate-shaped molded article (60 mm × 60 mm × 2 mm) and a rod-shaped molded article (80 mm × 20 mm × 4 mm). The composition values ​​shown in Table 7 represent mass ratios.

[0092] <Bisphenol A Quantification Method> The bisphenol A content in the molded product obtained above was quantified using the following method. Approximately 0.5 g of the plate-shaped molded product obtained above was cut out and precisely weighed. 10 mL of chloroform was added thereto, and the mixture was allowed to stand for 24 hours until the cut-out molded product was completely dissolved in chloroform. The resulting chloroform solution was filtered through a disk filter with a pore size of 0.25 μm to prepare a sample solution for measurement. The sample solution was measured using a high-performance liquid chromatograph under the HPLC measurement conditions below, and the bisphenol A contained in the sample solution was quantified using a calibration curve method. The bisphenol A content (ppm) in the molded product was calculated based on the obtained quantitative value and the weight of the weighed molded product. The results are shown in Tables 1 to 7.

[0093] <HPLC measurement conditions> Apparatus: LC-20, manufactured by Shimadzu Corporation Column: PLgel PL1110-6520, manufactured by Agilent Technologies Detector: SPD-M20A, manufactured by Shimadzu Corporation Mobile phase: chloroform Flow rate: 0.6 mL / min Column temperature: 40°C Detector wavelength: 254 nm

[0094] <Method for evaluating mechanical properties> The heat distortion temperature (HDT) of the rod-shaped molded article obtained above was measured using an HDT tester manufactured by Toyo Seiki Seisakusho, Ltd. under a load of 1.8 MPa in accordance with ISO 75. The impact strength was also measured using a Charpy impact tester manufactured by Toyo Seiki Seisakusho, Ltd. under a condition of 23°C in accordance with ISO 179. Note that, depending on the molded article, a notch was made in the molded article before the measurement.

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Table 1 shows the evaluation results of molded articles (Examples 1-1 to 1-13) in which bisphenol inhibitors (A)-1 to (A)-5 of the present invention were added to an alloy of PC resin and PBT resin (mass ratio of PC resin:PBT resin = 35:65), and molded articles (Comparative Examples 1-1 to 1-3) in which no bisphenol inhibitor of the present invention was added. Comparison of Examples 1-1 to 1-13 with Comparative Example 1-1 revealed that the addition of the bisphenol inhibitor of the present invention significantly reduced the bisphenol A content in the molded article, thereby demonstrating the full effectiveness of the bisphenol inhibitor. Additionally, the molded articles with reduced bisphenol A content described in Examples 1-1 to 1-13 exhibited improved mechanical properties, such as HDT and impact strength, compared to the molded article with a high bisphenol A content described in Comparative Example 1-1. This is presumably a secondary effect of suppressing the generation of bisphenol A via molecular chain scission of the PC resin. Furthermore, when comparative compound (B)-1, which is not an acidic phosphorus compound, was added (Comparative Examples 1-2 to 1-3), the effect of inhibiting bisphenols was small.

[0103] Tables 2 to 6 show the evaluation results of molded articles using alloys of PC resin and PBT resin with different contents than those shown in Table 1. Table 7 shows the evaluation results of molded articles using alloys of PC resin and PET resin. In all resin compositions, molded articles containing the bisphenol inhibitor of the present invention had a significantly reduced bisphenol A content compared to molded articles not containing the bisphenol inhibitor of the present invention. Furthermore, molded articles containing comparative compounds (B)-1 and (B)-2, which are not acidic phosphorus compounds, showed a small bisphenol inhibitor effect. Furthermore, molded articles containing reduced bisphenol A contents as shown in the examples of Tables 2 to 7 had higher mechanical properties, such as HDT and impact strength, compared to molded articles containing higher bisphenol A contents as shown in the comparative examples of each table.

[0104] The above results demonstrate that the bisphenol inhibitor of the present invention has excellent bisphenol inhibitor performance.

Claims

1. A bisphenol inhibitor containing an acidic phosphorus compound for addition to polycarbonate resins.

2. The bisphenol inhibitor according to claim 1, wherein the acidic phosphorus compound is an acidic phosphate ester or an acidic phosphate salt.

3. The bisphenol inhibitor according to claim 1, wherein the acidic phosphorus compound is an acidic phosphoric acid ester represented by the following general formula (1) or (3): In general formula (1), R １ represents an alkyl group having 8 to 40 carbon atoms, an alkenyl group having 8 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a group represented by the following general formula (2), and n represents an integer of 1 or 2. When n is 2, two R １ may be the same or different. In general formula (2), R ２ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, m represents an integer such that the number average molecular weight of the group represented by general formula (2) is 100 to 10,000, and * represents a bond. In general formula (3), R ３ , R ４ , R ５ and R ６ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms; R ７ represents an alkanediyl group having 1 to 4 carbon atoms.

4. The bisphenol inhibitor according to claim 3, wherein the acidic phosphorus compound is an acidic phosphate ester represented by the general formula (1).

5. R in the general formula (1) １ The bisphenol inhibitor according to claim 4, wherein: is a group represented by the general formula (2).

6. R in the general formula (2) ２ The bisphenol inhibitor according to claim 5, wherein is an alkyl group having 1 to 4 carbon atoms.

7. The bisphenol inhibitor according to claim 5, wherein m in the general formula (2) is an integer that gives a number average molecular weight of 400 to 5,000 for the group represented by the general formula (2).

8. R in the general formula (1) １ The bisphenol inhibitor according to claim 3, wherein is an alkyl group having 18 to 36 carbon atoms.

9. A resin composition comprising a polycarbonate resin and the bisphenol inhibitor according to any one of claims 1 to 8.

10. The resin composition according to claim 9, wherein the polycarbonate resin is a recycled resin.

11. A molded article obtained from the resin composition according to claim 9.

12. A method for producing a molded product, comprising the step of molding the resin composition according to claim 9.

13. A method for reducing the content of bisphenols in polycarbonate resins by adding an acidic phosphorus compound to the polycarbonate resins.

14. Use of an acidic phosphorus compound to produce a bisphenol inhibitor to be added to a polycarbonate-based resin.

Images