JP6612144B2 - Method for producing recycled polycarbonate resin composition - Google Patents

Description

  The present invention relates to a method for producing a regenerated polycarbonate resin composition, and more specifically, a regenerated polycarbonate resin excellent in heat stability, wet heat stability and flame retardancy using a polycarbonate resin recovered from a polycarbonate resin molded article or the like. The present invention relates to a method for producing a composition.

  Polycarbonate resins are excellent in impact resistance, heat resistance, electrical insulation, dimensional stability, self-extinguishing properties, transparency, etc., so they are processed by various molding methods such as injection molding, compression molding, extrusion molding, and blow molding. Since then, it has been widely used in various applications including home appliance parts, electrical and electronic equipment parts, OA equipment parts, optical recording media, automobile parts, building materials, hollow containers, medical uses, and miscellaneous goods.

  In recent years, there has been a strong social demand for recycling of resins due to the growing awareness of environmental protection, and the molded products made of polycarbonate resin are collected, pulverized, and recycled pellets are used. (For example, refer to Patent Document 1).

JP 2001-26719 A

However, when recycled polycarbonate resin pellets are reused, mechanical properties and the like are lowered, and in many cases cannot be used for the original use of polycarbonate resin.
When the recovered polycarbonate resin is mixed with an unused polycarbonate resin to obtain a recycled polycarbonate resin composition, the rate of decrease in thermal stability and wet heat stability, in particular, tensile elongation at break after heat treatment, tends to increase.
An object (problem) of the present invention is to provide a method for producing a reclaimed polycarbonate resin composition having a low thermal breakage resistance, particularly a low rate of decrease in tensile elongation at break after heat treatment, and excellent flame retardancy. It is in.

As a result of intensive studies to achieve the above-mentioned problems, the inventor recovered the recovered polycarbonate resin with impurities adhering during use, or a step of recovering the recycled polycarbonate resin, for example, washing the recovered material with alkali or acid, or We assume that residual chemicals such as alkali metals derived from salt water used for pulverization and separation of specific gravity, and impurities, etc. are affecting the decrease in tensile elongation after heat treatment. Recycled polycarbonate obtained by selecting or adjusting according to (MVR), blending the blending ratio with the unused polycarbonate resin as a specific ratio, and blending the phosphorus flame retardant and fluoropolymer in a specific amount The resin composition has excellent thermal stability and wet heat stability, and is also excellent in flame retardancy. And, we have reached the present invention.
The present invention relates to the following.

[1] A method for producing a recycled polycarbonate resin composition containing a recovered polycarbonate resin (A) and an unused polycarbonate resin (B),
As the recovered polycarbonate resin (A), the polycarbonate resin component is 98% by mass or more and the viscosity average molecular weight (Mv) is 20,000 or more, and the MVR (measured at 300 ° C. × 1.2 kg) at the time of preheating for 30 minutes, For MVR (measured at 300 ° C x 1.2 kg) during preheating for 4 minutes, select the recovered polycarbonate resin (A) whose increase rate does not exceed 50%, and make the total of 100% by mass of (A) and (B). On the other hand, it is used at a ratio of 3 to 60% by mass,
Further, 2 to 20 parts by mass of the phosphorus-based flame retardant (C) and 0.5 parts by mass or less of the fluoropolymer (D) are added to 100 parts by mass of the total of (A) and (B). A method for producing a recycled polycarbonate resin composition.
[2] The method for producing a recycled polycarbonate resin composition according to [1], further including an ABS resin (E) or a thermoplastic polyester resin (F).
[3] The method for producing a recycled polycarbonate resin composition according to the above [1] or [2], wherein the content of the alkali metal in the recovered polycarbonate resin (A) is 10 mass ppm or less.
[4] The method for producing a recycled polycarbonate resin composition according to any one of the above [1] to [3], wherein the recovered polycarbonate resin (A) is a recovered polycarbonate resin mainly derived from a beverage container or a semiconductor transport container.

  According to the method for producing a regenerated polycarbonate resin composition of the present invention, a polycarbonate resin composition having excellent thermal stability and wet heat stability, particularly a reduction in tensile elongation at break after heat-resistant treatment is remarkably suppressed, and excellent in flame retardancy. Can be manufactured.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

The method for producing a recycled polycarbonate resin composition of the present invention is a method for producing a recycled polycarbonate resin composition containing a recovered polycarbonate resin (A) and an unused polycarbonate resin (B),
As the recovered polycarbonate resin (A), the polycarbonate resin component is 98% by mass or more and the viscosity average molecular weight (Mv) is 20,000 or more, and the MVR (measured at 300 ° C. × 1.2 kg) at the time of preheating for 30 minutes, With respect to MVR (measured at 300 ° C. × 1.2 kg) at the time of preheating for 4 minutes, recovered polycarbonate resin having an increase rate not exceeding 50% is 3 to 60 with respect to 100% by mass in total of (A) and (B). Use at a mass percentage,
Further, 2 to 20 parts by mass of the phosphorus-based flame retardant (C) and 0.5 parts by mass or less of the fluoropolymer (D) are added to 100 parts by mass of the total of (A) and (B). Features.

[Polycarbonate resin]
The polycarbonate resin referred to in the present invention is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —. In the formula, X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced may be used.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, and any of them can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

A preferred specific example of the polycarbonate resin is 2,2-bis (4-hydroxyphenyl) propane, that is, a polycarbonate resin having a structural unit derived from bisphenol-A.
The polycarbonate resin having a structural unit derived from bisphenol-A may have a carbonate structural unit derived from another dihydroxy compound other than bisphenol-A. The copolymerization amount of structural units derived from other than bisphenol-A is usually preferably less than 50 mol%, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less, and 10 mol%. In the following, 5 mol% or less is most preferable.

Examples of other dihydroxy compounds include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxy) Phenyl) phenylmethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4'-dihydroxyphenyl ether, 4,4'-dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (3-methyl-4- Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, and the like.

  The method for producing the polycarbonate resin is not particularly limited, and any known method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Among these, the interfacial polymerization method and the melt transesterification method are preferable.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .). Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability You may comprise as.

  The polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. The polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

[Recovered polycarbonate resin (A)]
The recovered polycarbonate resin (A) used as a raw material in the method of the present invention (hereinafter also referred to as “recovered polycarbonate resin (A)”) is recovered from a molded product of the polycarbonate resin used in various applications. The The molded product is not limited, and is a molded product molded by various molding methods such as injection molding, compression molding, injection compression molding, extrusion molding, blow molding, melt extrusion, calendering, such as drinking water and various beverages. Containers and beverage containers such as water bottles for drinking water servers, semiconductor transport containers, various lamp lenses such as vehicle head lamps and tail lamps, various lighting covers, signal lamp covers, street lamp covers, windows as glass substitutes, sunroofs , Arcades, carports, lighted roofing materials, building materials for agricultural houses, veranda waistboards, translucent boards (sound insulation boards) along roads and tracks, optical recording media such as DVDs, CDs, CD-ROMs, Mobile phone, PC housing, battery pack case, various parts for liquid crystal, connector, door handle for automobile parts for electronic / OA applications Bumpers, fenders, roofs, roof rails, springs, console boxes, etc., transparent parts such as windshields, shields in front of helmets, goggles, sunglasses lenses, protective glasses, camera lenses, slinging cases for pachinko machines, beverage and food containers Etc. In addition, the molded product includes defective products, prototypes and the like generated in the product production process.

  As the recovered polycarbonate resin (A) to be reused in the present invention, among the above, various drinking containers such as drinking water and a drinking water server commonly referred to as a water server are generated because a large amount of recycled products and waste products are generated. A main component (for example, 50% by mass or more) of a recovered polycarbonate resin derived from a beverage container such as a water bottle or a semiconductor transport container is preferable.

In the present invention, as the recovered polycarbonate resin (A), a recovered material having a polycarbonate resin component content of 98% by mass or more, preferably more than 98% by mass is used.
Such a recovered polycarbonate resin (A) can be obtained by removing or separating foreign substances as necessary from a crushed product obtained by crushing a molded product of the polycarbonate resin as described above. The crushing can be produced by using a known crushing device such as a cutter mill, a roll crusher, a hammer crusher, a disc mill, a pin mill, a turbo mill, a jet mill and the like.
Components other than polycarbonate resin such as metal, metal deposit, and other resins in the crushed material are removed so as to be 2% by mass or less, preferably less than 2% by mass in the crushed material.

As a method for removing other components, various known methods such as a chemical treatment method (surfactant, alkali or acid washing), a washing method with water, and a specific gravity separation by adding to a salt solution whose specific gravity is adjusted with salt. For example, removal by a magnet, removal of colored foreign matters by foreign matter detection by an optical camera, etc., and combinations of these can also be applied.
Examples of the foreign matter removal by chemical treatment include treatment with an alkali, an acid, or a surfactant. Of these, alkali treatment with sodium hydroxide or the like is preferable.

  In the present invention, a recovered polycarbonate resin (A) having a viscosity average molecular weight (Mv) of 20,000 or more is used. The viscosity average molecular weight (Mv) of the recovered polycarbonate resin (A) is more preferably 20,500 or more, further preferably 21,000 or more, preferably 35,000 or less, more preferably 30,000 or less. When the viscosity average molecular weight is 20,000 or more, a recycled polycarbonate resin composition having stable strength and toughness is easily obtained.

In the present invention, the viscosity average molecular weight [Mv] of the polycarbonate resin is determined by using methylene chloride as a solvent and determining the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, It means a value calculated from Schnell's viscosity formula: η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

In the present invention, as the recovered polycarbonate resin (A), when the melt volume rate MVR measured at 300 ° C. and a 1.2 kg load is compared with the MVR at the time of preheating for 4 minutes and the MVR at the time of preheating for 30 minutes, It is characterized by using a recovered polycarbonate resin whose MVR at the time of preheating for 4 minutes does not exceed 50% of the MVR at the time of preheating for 4 minutes. By blending recovered polycarbonate resin (A) with an increase rate of 50% or less into unused polycarbonate resin (B), it is excellent in thermal stability and moist heat stability, especially suppressing the decrease in elongation at break after heat treatment. It becomes possible to do.
The rate of increase in MVR is preferably 45% or less, more preferably 40% or less, still more preferably 35% or less, and particularly preferably 30% or less. The lower limit of the rate of increase is preferably 5%, more preferably 3%, and even more preferably 0%.

  In the present invention, the MVR of the polycarbonate resin is measured at a measurement temperature of 300 ° C. and a measurement load of 1.2 kg in accordance with ISO 1133.

  When the rate of increase in MVR of the recovered polycarbonate resin exceeds 50%, it can be reduced to 50% or less by, for example, a method of cleaning the recovered polycarbonate resin by enhancing water cleaning or acid cleaning. In order to reduce the MVR increase rate of the recovered polycarbonate resin to 50% or less, it is preferable to reduce the content of alkali metal in the recovered polycarbonate resin to 10 mass ppm or less, more preferably 8 mass ppm or less, Preferably it is 5 mass ppm or less. Here, preferred examples of the alkali metal include sodium, potassium, lithium, cesium and the like.

[Unused polycarbonate resin (B)]
The recovered polycarbonate resin (A) is mixed with an unused polycarbonate resin (B).
Here, the unused polycarbonate resin is also referred to as a so-called virgin material, and represents a state in which the above-described polycarbonate resin is produced, or one that is preformed into a powder, a granular material, a pellet, or the like.
The polycarbonate resin used as an unused polycarbonate resin (B) (hereinafter sometimes referred to as “unused polycarbonate resin (B)”) is not limited in its type, and the polycarbonate resin as described above is used. it can.

The viscosity average molecular weight (Mv) of the unused polycarbonate resin (B) is preferably 10,000 to 50,000, more preferably 12,000 or more, still more preferably 14,000 or more, and particularly preferably 18,000. More preferably, it is 40,000 or less, more preferably 36,000 or less, and particularly preferably 33,000 or less. If the viscosity average molecular weight exceeds the above upper limit, compatibility with the recovered polycarbonate resin (A) becomes difficult, and the toughness of the recycled polycarbonate resin composition or unmelted may be caused. When it is, it will become easy to recognize the fall of chemical resistance or a mechanical characteristic.
Two or more kinds of unused polycarbonate resins (B) having different viscosity average molecular weights may be mixed to adjust the viscosity average molecular weight. Moreover, you may mix and use the aromatic polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

  The compounding amount of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B) is 3 to 60% by mass with respect to the total of 100% by mass of the recovered polycarbonate resin (A) and (A) and (B). use. When the amount of the recovered polycarbonate resin (A) exceeds 60% by mass, it is difficult to ensure stable quality such as strength and hue of the recycled polycarbonate resin composition. A preferable blending amount of the recovered polycarbonate resin (A) is 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly 20% by mass or more, and particularly preferably 25% by mass or more. Preferably, it is 58 mass% or less.

[Phosphorus flame retardant (C)]
In the production method of the recycled polycarbonate resin composition of the present invention, the phosphorus-based flame retardant (C) is 3 to 30 parts by mass with respect to a total of 100 parts by mass of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). It mixes in the ratio. Thus, by mix | blending a phosphorus flame retardant, a high flame retardance can be improved, maintaining the heat stability and wet heat stability of the reproduction | regeneration polycarbonate resin composition obtained suitably.

  The phosphorus-based flame retardant (C) is a compound containing phosphorus in the molecule and may be a low molecule, an oligomer, or a polymer. From the viewpoint of thermal stability, for example, the following The phosphate compound represented by the general formula (1) and the phosphazene compounds represented by the following general formulas (2) and (3) are particularly preferable.

Phosphate ester compound The phosphate ester compound represented by the general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphate esters having different k, k Is the average of their mixture. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

Specific examples of the phosphate ester compound represented by the general formula (1) include
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A-bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

  The acid value of the phosphoric acid ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less, particularly preferably Is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero.

  As the phosphate ester compound used in the present invention, in addition to the above-mentioned compounds, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3 -Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphoric acid Naturally, polyester resins, polycarbonate resins or epoxy resins containing an ester moiety are also included.

Phosphazene Compound Examples of the phosphazene compound represented by the general formulas (2) and (3) include phenoxyphosphazene and (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyl). Oxyphosphazenes, o, m-tolyloxyphosphazenes, o, p-tolyloxyphosphazenes, m, p-tolyloxyphosphazenes, o, m, p-tolyloxyphosphazenes), (poly) xylyloxyphosphazenes and the like / or or linear _{C 1-6} alkyl _{C 6-20} aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- tolyloxy phosphite Azen, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene), (poly) phenoxyxyloxyphosphazene And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene.
Of these, cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 Aryloxyphosphazenes (eg, cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.).

In the cyclic phosphazene compound represented by the general formula (2), R ⁵ and R ⁶ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ⁵ and R ⁶ are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in general formula (2), although t represents the integer of 3-25, the compound whose t is an integer of 3-8 is preferable especially, and the mixture of the compound from which t differs may be sufficient. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

In the general formula (3), R ⁷ and R ⁸ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, and the like, and a chain phenoxyphosphazene in which R ⁷ and R ⁸ are phenyl groups is particularly preferable.
Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above method to reverse polymerization at a temperature of 220 to 250 ° C., and obtaining a linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

Also, R ⁹ is represented by -N = P (OR ⁷ ) ₃ groups, -N = P (OR ⁸ ) ₃ groups, -N = P (O) OR ⁷ groups, and -N = P (O) OR ⁸ groups. At least one selected is shown, and R ¹⁰ is -P (OR ⁷ ) ₄ group, -P (OR ⁸ ) ₄ group, -P (O) (OR ⁷ ) ₂ group, -P (O) (OR ⁸ ) At least one selected from _two groups.

  Moreover, in general formula (3), u shows the integer of 3-10,000, Preferably it is 3-1,000, More preferably, it is 3-100, More preferably, it is 3-25.

Further, the phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
As such a crosslinked phosphazene compound, a crosslinked structure represented by the following general formula (4), for example, a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, bisphenol S residue), 2,2- ( 4,4′-diphenylene) isopropylidene group-crosslinked structure, 4,4′-oxydiphenylene group-crosslinked structure, 4,4′-thiodiphenylene group-crosslinked structure, etc. And compounds having a crosslinked structure of 4,4′-diphenylene group.

[In Formula (4), X ² is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and v is 0 or 1. ]

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ⁵ and R ⁶ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (4). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (3) with a crosslinking group represented by the general formula (4) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (2) and the cyclic phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  As described above, the amount of the phosphorus-based flame retardant (C) is 3 to 30 parts by mass with respect to 100 parts by mass in total of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). It is preferably 5 parts by mass or more, more preferably 4 parts by mass or more, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.

[Fluoropolymer (D)]
In the production method of the present invention, the fluoropolymer (D) is further blended as an anti-dripping agent.
Examples of the fluoropolymer (D) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J”, “Teflon (registered trademark) 6C” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Daikin Industries, Ltd. “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500H”, and the like are available. Further, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon D manufactured by Daikin Industries, Ltd.” -210C "and the like.

Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like.
In addition, 1 type may contain fluoropolymer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The blending amount of the fluoropolymer (D) is 0.5 parts by mass or less, preferably 0.001 parts by mass with respect to 100 parts by mass in total of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). Or more, more preferably 0.01 parts by mass or more, still more preferably 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, and more preferably 0.45 parts by mass or less, More preferably, it is 0.4 mass part or less. When the compounding quantity of fluoropolymer (D) exceeds the said upper limit, the external appearance defect of the molded article which shape | molded the reproduction | regeneration polycarbonate resin composition and the fall of mechanical strength are easy to arise.

[ABS resin (E)]
In the production method of the present invention, it is also preferable to add an ABS resin (E). ABS resin refers to a resin composed of a thermoplastic graft copolymer obtained by graft copolymerizing a diene rubber component with a vinyl cyanide compound and an aromatic vinyl compound.

  As the diene rubber component of the ABS resin, for example, a rubber component such as polybutadiene, polyisoprene, styrene-butadiene copolymer is used, and the ratio of the diene rubber component in the ABS resin is 100% by mass of the ABS resin. The range is preferably 5 to 80% by mass, more preferably 7 to 50% by mass, still more preferably 8 to 25% by mass, and particularly preferably 9 to 18% by mass. is there.

Examples of the aromatic vinyl compound in the ABS resin include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene, methoxy styrene, mono Examples thereof include bromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.
Examples of the vinyl cyanide compound in the ABS resin include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
The amount of the vinyl cyanide compound and the aromatic vinyl compound is preferably 5 to 50% by mass, more preferably 15 to 35% by mass, and the aromatic vinyl compound to 100% by mass of the total amount. Preferably it is 95-50 mass%, More preferably, it is 65-85 mass%.

  The ABS resin (E) may be further copolymerized with other vinyl monomers copolymerizable therewith. In this case, examples of other copolymerizable vinyl monomers include maleimide, N-methylmaleimide, Maleimide monomers such as N-cyclohexylmaleimide and N-phenylmaleimide; acrylamide monomers such as acrylamide and N-methylacrylamide; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Saturated acid, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate and the like can be mentioned.

As specific examples of the ABS resin (E), acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer and the like are preferable. Illustrated.
The ABS resin is usually produced by a method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and any one of the methods may be used.

  A preferable blending amount of the ABS resin (E) is 5 to 40 parts by mass with respect to a total of 100 masses of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). When there are too many ABS resin (E), the mechanical strength of the resin composition obtained, heat resistance, a flame retardance, etc. will become inferior easily. The blending amount of the ABS resin (E) is more preferably 3 parts by mass or more, more preferably 8% by mass or more, further preferably 10 parts by mass or more, more preferably 35 parts by mass or less, and further preferably 30 parts by mass. Hereinafter, it is particularly preferably 25 parts by mass or less.

[Thermoplastic polyester resin (F)]
In the production method of the present invention, it is also preferable to blend the thermoplastic polyester resin (F). As preferred specific examples of the thermoplastic polyester resin (F), polyethylene terephthalate resin (PET), polypropylene terephthalate resin (PPT), polybutylene terephthalate resin (PBT), polyhexylene terephthalate resin, polyethylene naphthalate resin (PEN), Examples thereof include polybutylene naphthalate resin (PBN), poly (1,4-cyclohexanedimethylene terephthalate) resin (PCT), polycyclohexyl cyclohexylate (PCC), and the like. Among these, polyethylene terephthalate resin (PET) and polybutylene terephthalate resin (PBT) are preferable from the viewpoint of fluidity and impact resistance.

The polybutylene terephthalate resin is a polymer obtained by polycondensation of 1,4-butanediol and terephthalic acid or a lower alcohol ester thereof, and is a copolymer containing more than 95 mol% of polybutylene terephthalate units. Also good.
As a comonomer in the case of a copolymer, as dibasic acid components other than terephthalic acid or its lower alcohol ester, aliphatic, aromatic such as adipic acid, sebacic acid, trimellitic acid, succinic acid, isophthalic acid, and naphthalenedicarboxylic acid Aromatic polybasic acids, or ester-forming derivatives thereof, aromatic hydroxycarboxylic acids such as hydroxybenzoic acid and hydroxyquinophthalic acid, or ester-forming derivatives thereof.
Further, as glycol components other than 1,4-butanediol, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethanol, etc., lower alkylene glycol such as 1,3-octanediol, etc. Bisphenol A, aromatic alcohols such as 4,4′-dihydroxybiphenyl, ethylene oxide 2-mole adducts of bisphenol A, alkylene oxide adducts such as bisphenol A propylene oxide 3-mole adducts, glycerin, pentaerythritol, etc. Examples include polyhydroxy compounds or ester-forming derivatives thereof.

  The polybutylene terephthalate resin may be used alone or in combination of two or more. As the polybutylene terephthalate resin, a homopolymer of polybutylene terephthalate is preferable.

The intrinsic viscosity ([η]) of the polybutylene terephthalate resin may be appropriately selected and determined. Usually, it is preferably 0.5 to 2 dl / g, among which the moldability and mechanical properties of the resin composition From the viewpoint, it is preferably 0.6 to 1.5 dl / g. If an intrinsic viscosity of 0.5 dl / g or more is used, the mechanical strength of the molded product tends to be sufficiently high, and if it is 2 dl / g or less, the fluidity of the resin composition is improved and the moldability is improved. Tend to.
In the present specification, the intrinsic viscosity of the thermoplastic polyester resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

The polyethylene terephthalate resin is a polymer obtained by polycondensation of ethylene glycol and terephthalic acid or a lower alcohol ester thereof, and may be a copolymer containing more than 95 mol% of polyethylene terephthalate units.
As a comonomer in the case of a copolymer, as dibasic acid components other than terephthalic acid or its lower alcohol ester, aliphatic, aromatic such as adipic acid, sebacic acid, trimellitic acid, succinic acid, isophthalic acid, and naphthalenedicarboxylic acid Aromatic polybasic acids, or ester-forming derivatives thereof, aromatic hydroxycarboxylic acids such as hydroxybenzoic acid and hydroxyquinophthalic acid, or ester-forming derivatives thereof.
Examples of glycol components other than ethylene glycol include diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethanol, lower alkylene glycol such as 1,3-octanediol, bisphenol A, 4,4 Aromatic alcohols such as' -dihydroxybiphenyl, ethylene oxide 2 mol adducts of bisphenol A, alkylene oxide adduct alcohols such as propylene oxide 3 mol adducts of bisphenol A, polyhydroxy compounds such as glycerin and pentaerythritol or ester formation thereof Sex derivatives and the like.

  Polyethylene terephthalate resin may be used alone or in combination of two or more. The polyethylene terephthalate resin is preferably a polyethylene terephthalate homopolymer.

  The intrinsic viscosity of the polyethylene terephthalate resin may be appropriately selected and determined, but is usually 0.5 to 2 dl / g, particularly 0.6 to 1.5 dl / g, particularly 0.7 to 1.0 dl / g. Preferably there is. It is preferable that the intrinsic viscosity is 0.5 dl / g or more, particularly 0.7 dl / g or more because mechanical properties, residence heat stability, and heat-and-moisture resistance tend to be improved. Conversely, an intrinsic viscosity of less than 2 dl / g, particularly less than 1.0 dl / g, is preferred because the fluidity of the resin composition tends to improve.

  The blending amount of the thermoplastic polyester resin (F) is preferably 5 to 60 parts by mass with respect to a total of 100 masses of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). If the blending amount of the polyester resin (B) exceeds 60 parts by mass, heat resistance and impact resistance may be lowered. The blending amount is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less.

[Elastomer]
In the production method of the present invention, it is also preferable to blend an elastomer. By blending the elastomer, the impact resistance of the resulting resin composition can be improved.
The elastomer used in the present invention is preferably a graft copolymer obtained by graft copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

The rubbery polymer generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, (partial) hydrogenated polybutadiene rubber, butadiene-styrene copolymer, (partial) hydrogenated polybutadiene-styrene copolymer, butadiene-styrene block copolymer, (partial) water. One or more vinyl monomers that can be copolymerized with butadiene and butadiene, such as a polybutadiene-styrene block copolymer, a butadiene-acrylonitrile copolymer, and an acrylic rubber copolymer based on butadiene-isobutyl acrylate Butadiene rubbers such as copolymers with polyisobutylene, polyisobutylene, polyisobutylene-styrene copolymers, isobutylene rubbers such as polyisobutylene-styrene block copolymers, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl) Acrylate), butyla Polyalkyl acrylate rubber such as relate / 2-ethylhexyl acrylate copolymer, silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene -Ethylene-alpha olefin rubbers such as propylene rubber, ethylene-butene rubber, ethylene-octene rubber, ethylene-acrylic rubber, fluorine rubber, and the like. These may be used alone or in admixture of two or more.
Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, butadiene-styrene copolymer, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN (Interpenetrating Polymer composed of polyorganosiloxane rubber and polyalkyl acrylate rubber). Network) type composite rubber is preferred.

Specific examples of the monomer component that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more.
Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth) acrylic acid ester compounds are preferable, and (meth) acrylic acid ester compounds are more preferable from the viewpoint of mechanical properties and surface appearance. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same shall apply hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kane Ace (registered trademark, same applies hereinafter) M-511 "," Kane Ace M-711 "," Kane Ace M-731 "manufactured by Kaneka Corporation Kane Ace M-600 " "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01", and the like.

  The blending amount of the elastomer in the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further with respect to 100 parts by mass in total of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). The amount is preferably 1.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, and particularly preferably 5 parts by mass or less. When the amount of elastomer is less than the lower limit of the above range, the impact resistance improvement effect by the elastomer may be insufficient, and when the amount of elastomer exceeds the upper limit of the above range, flame retardancy In addition, there is a possibility that a decrease in heat resistance and a defective appearance of a molded product obtained by molding the resin composition may occur.

[Other ingredients]
In the method for producing a recycled polycarbonate resin composition of the present invention, other components other than those described above may be blended as necessary, as long as desired physical properties are not significantly impaired. Examples of other components include resins other than the above polycarbonate resins and various resin additives other than those described above. In addition, as for another component, 1 type may be mix | blended and 2 or more types may be mix | blended by arbitrary combinations and ratios.

Other resins Examples of other resins include polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), and acrylonitrile-ethylene. Styrene resin such as propylene rubber-styrene copolymer (AES resin); Polyolefin resin such as polyethylene resin and polypropylene resin; Polyamide resin; Polyimide resin; Polyetherimide resin; Polyphenylene ether resin; Polyphenylene sulfide resin; Is mentioned.

In addition, 1 type of other resin may be mix | blended and 2 or more types may be mix | blended by arbitrary combinations and ratios.
When blending other resins, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less, in a total of 100 parts by mass of the polycarbonate resin and other resins. More preferably it is.

Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, fillers, glass fibers, UV absorbers, dyes and pigments (including carbon black), titanium oxide, antistatic agents, and anti-static agents. Examples include clouding agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersants, and antibacterial agents. In addition, 1 type of resin additives may be mix | blended and 2 or more types may be mix | blended by arbitrary combinations and ratios.
Hereinafter, the example of an additive suitable for the manufacturing method of the reproduction | regeneration polycarbonate resin composition of this invention is demonstrated concretely.

Thermal Stabilizer Examples of the thermal stabilizer include phosphorous compounds such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, polyphosphoric acid, and other phosphorus oxo acids; acidic sodium pyrophosphate, acidic potassium pyrophosphate, acidic pyrophosphate Acid pyrophosphate metal salts such as calcium phosphate; Group 1 or Group 2B metal phosphates such as potassium phosphate, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphite compounds, organic phosphonite compounds, etc. However, organic phosphite compounds are particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
In addition, 1 type of heat stabilizers may be mix | blended and 2 or more types may be mix | blended by arbitrary combinations and ratios.

  The blending amount of the heat stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 100 parts by mass in total of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). Is 0.03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the blending amount of the heat stabilizer is less than the lower limit of the above range, the heat stabilizing effect may be insufficient, and if the blending amount of the heat stabilizer exceeds the upper limit of the above range, the effect will reach its peak. And may become less economical.

Antioxidant Examples of the antioxidant include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-( Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-triyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di tert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Examples of such commercially available phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-60”, “Adekastab AO-50” manufactured by ADEKA, and the like. It is done.
In addition, 1 type of antioxidant may be mix | blended and 2 or more types may be mix | blended by arbitrary combinations and ratios.

  The blending amount of the antioxidant is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part or less. When the blending amount of the antioxidant is less than the lower limit of the above range, the effect as the antioxidant may be insufficient, and when the blending amount of the antioxidant exceeds the upper limit of the above range, There is a possibility that the effect reaches its peak and is not economical.

[Release agent]
Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon compound include liquid paraffin, paraffin wax, micro wax, polyethylene wax, Fischer-Tropsch wax, α-olefin oligomer having 3 to 12 carbon atoms, and the like. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized. Moreover, the number average molecular weight of the aliphatic hydrocarbon compound is preferably a number average molecular weight of 200 to 15,000, more preferably 5,000 or less.

  Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, paraffin wax and polyethylene wax are more preferable, and polyethylene wax is particularly preferable.

In addition, 1 type or 2 or more types of mold release agents may be mix | blended by arbitrary combinations and ratios.
The compounding amount of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, with respect to a total of 100 parts by mass of the recovered polycarbonate resin (A) and the unused polycarbonate resin (B). Moreover, it is 2 mass parts or less normally, Preferably it is 1 mass part or less. If the compounding amount of the release agent is less than the lower limit of the above range, the effect of releasability may not be sufficient, and if the compounding amount of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[Production Method of Recycled Polycarbonate Resin Composition]
The recycled polycarbonate resin composition of the present invention is produced by adjusting or selecting a recovered polycarbonate resin (A) that satisfies the above-mentioned regulations and kneading it with an unused polycarbonate resin (B) and other components.
There are no restrictions on the blending method, mixing, and kneading method in this case, and a wide variety of known polycarbonate resin composition production methods can be used. The recovered polycarbonate resin (A), unused polycarbonate resin (B), and phosphorus-based flame retardant (C), the fluoropolymer (D), and other components to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, Brabender, single Examples thereof include a melt kneading method using a mixer such as a shaft kneading extruder, a twin screw kneading extruder, or a kneader.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molding]
The pellets obtained by pelletizing the obtained recycled polycarbonate resin composition are molded by various molding methods into a molded product. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, a plate shape, a plate shape, a rod shape, a sheet shape, a film shape, a cylindrical shape, an annular shape, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.

  The method for molding the molded body is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And a pressure molding method.

  A molded article obtained by molding the recycled polycarbonate resin composition can be suitably used for various applications such as electric and electronic parts, home appliance parts, automobile parts, various building materials, containers, and miscellaneous goods.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

As the recovered polycarbonate resin, those shown in Table 1 below were used.
The MVR increase rate can be calculated by the following formula.

Each raw material component other than the above is as shown in Table 2 below.

(Examples 1-9, Comparative Examples 1-3)
Each component described in Tables 1 and 2 above was blended in the proportions shown in Tables 3 and 4 below (all expressed in parts by mass) and uniformly mixed with a tumbler mixer, and then a twin screw extruder ( Nippon Steel Works TEX30HSST) is fed to the extruder from the barrel upstream of the extruder at a cylinder temperature of 280 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 20 kg / hr, and melt-kneaded to obtain a polycarbonate resin composition. Pellets were obtained.

[Evaluation of tensile breaking elongation]
The polycarbonate resin composition pellets obtained above are dried at 120 ° C. for 5 hours or longer, and then used with an injection molding machine (“Roboshot α2000i-150T type” manufactured by FANUC). The cylinder temperature is 280 ° C. and the mold temperature is 80. An ISO tensile test piece was produced under the conditions of ℃ and a molding cycle of 45 seconds.
About the produced tensile test piece, the heat processing for 150 hours was implemented in 70 degreeC temperature environment. The tensile elongation at break (unit:%) before and after the heat treatment was measured at 23 ° C. according to ISO 527-1.
The tensile elongation retention after heat treatment (unit:%) was calculated based on the following formula.
Tensile elongation retention after heat treatment (%) =
[(Tensile elongation after heat treatment) / (Tensile elongation before heat treatment)] × 100 (%)
The above evaluation results are shown in Tables 3 and 4.

  According to the method for producing a recycled polycarbonate resin composition of the present invention, a recovered polycarbonate resin can be used to produce a polycarbonate resin composition having excellent thermal stability, wet heat stability and flame retardancy, and industrial use. Some are very high.

Claims (2)

A method for producing a recycled polycarbonate resin composition comprising a recovered polycarbonate resin (A) and an unused polycarbonate resin (B),
The recovered polycarbonate resin (A) is a recovered polycarbonate resin derived from a beverage container or a semiconductor transport container, wherein the polycarbonate resin component is 98% by mass or more and the viscosity average molecular weight (Mv) is 20,500 or more , The content is 2 mass ppm or more and 10 mass ppm or less , and the MVR during 30 minutes preheating (measured at 300 ° C. × 1.2 kg) is compared with the MVR during 4 minutes preheating (measured at 300 ° C. × 1.2 kg). The recovered polycarbonate resin (A) having an increase rate of 3% to 45% is used in a ratio of 3 to 60% by mass with respect to 100% by mass of the total of (A) and (B).
Further, 2 to 20 parts by mass of the phosphorus-based flame retardant (C) and 0.5 parts by mass or less of the fluoropolymer (D) are added to 100 parts by mass of the total of (A) and (B). A method for producing a recycled polycarbonate resin composition.   Furthermore, the manufacturing method of the reproduction | regeneration polycarbonate resin composition of Claim 1 which mix | blends ABS resin (E) or a thermoplastic polyester resin (F).