JP2010261017A - Polycarbonate/polyethylene terephthalate composite resin composition, and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress staying thermal deterioration in a polycarbonate/polyethylene terephthalate composite resin composition. <P>SOLUTION: In the polycarbonate/polyethylene terephthalate composite resin composition, 0.01-0.5 pts.mass of a phosphor-based thermostabilizer and/or 0.01-1 pts.mass of a hindered phenol-based thermostabilizer are formulated to 100 pts.mass of a resin component comprising 95-30 mass% of a polycarbonate resin and 5-70 mass% of a polyethylene terephthalate resin, and the polyethylene terephthalate resin is a polyethylene terephthalate resin in which deactivation treatment of a polycondensation catalyst is performed. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polycarbonate / polyethylene terephthalate composite resin composition having improved thermal stability in a resin composition obtained by combining a polyethylene terephthalate resin with a polycarbonate resin for the purpose of imparting chemical resistance, and the polycarbonate / polyethylene terephthalate composite resin. The present invention relates to a molded product obtained by molding a composition.

  Polycarbonate resins, especially aromatic polycarbonate resins, are excellent in impact resistance, heat distortion resistance, rigidity, dimensional stability, etc., and are therefore used in a wide range of applications such as electrical equipment, communication equipment, precision machinery, and automotive parts. However, the polycarbonate resin has the disadvantage that it is inferior in chemical resistance, and in order to improve the chemical resistance of the polycarbonate resin, various composites with a polyethylene terephthalate resin have been studied (for example, see Patent Documents 1 and 2). ).

  However, when a polyethylene terephthalate resin is compounded with a polycarbonate resin, the chemical resistance is improved, but the resulting resin composition has poor thermal stability and is held at a high temperature in the cylinder during the molding process. And a transesterification reaction with polyethylene terephthalate resin, and generation of decomposition gas due to the reaction causes bubbles and poor appearance of molded products called silver. And the molecular weight of polycarbonate resin falls and the problem that polycarbonate resin original impact resistance, heat-resistant deformation property, etc. will be impaired arises.

Japanese Patent Laid-Open No. 2007-23118 JP 2009-1620 A

  The present invention solves the above-mentioned conventional problems and is formed by molding a polycarbonate / polyethylene terephthalate composite resin composition in which the residence heat deterioration in the polycarbonate / polyethylene terephthalate composite resin composition is suppressed, and the polycarbonate / polyethylene terephthalate composite resin composition. The object is to provide a molded product.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problem of residence heat deterioration in a polycarbonate / polyethylene terephthalate composite resin composition is used in the production process of polyethylene terephthalate resin and provided as a product. It can be attributed to the polycondensation catalyst contained in the polyethylene terephthalate resin, and therefore, as the polyethylene terephthalate resin, by using the polyethylene terephthalate resin in which this polycondensation catalyst is deactivated, it is possible to suppress residence heat deterioration, Moreover, it discovered that a residence heat deterioration could be suppressed more reliably by mix | blending a specific heat stabilizer after using such a polyethylene terephthalate resin.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] To 100 parts by mass of a resin component consisting of 95 to 30% by mass of a polycarbonate resin and 5 to 70% by mass of a polyethylene terephthalate resin, 0.01 to 0.5 parts by mass of a phosphorus-based heat stabilizer and / or a hindered phenol type A polycarbonate / polyethylene terephthalate composite resin composition comprising 0.01 to 1 part by mass of a heat stabilizer, wherein the polyethylene terephthalate resin is a polyethylene terephthalate resin that has been subjected to a deactivation treatment of a polycondensation catalyst. .

[2] In [1], the polyethylene terephthalate resin in which the polycondensation catalyst is deactivated has a terminal carboxyl group concentration of 5 to 40 μeq / g and an intrinsic viscosity [η] of 0.6 to 1.5 dl / g. The ratio of the oxyethylene oxyterephthaloyl unit to all the structural repeating units is 90 equivalent% or more, and the solid phase polymerization rate Ks calculated by the following formula (1) is 0.006 (dl / g · hr) or less. A polycarbonate / polyethylene terephthalate composite resin composition characterized by being.
Solid-phase polymerization rate Ks = ([η] s− [η] m) / T (1)
(Where [η] s is the intrinsic viscosity (dl / g) of the polyethylene terephthalate resin after holding the polyethylene terephthalate resin at 210 ° C. for 3 hours under a nitrogen stream, and [η] m is the polyethylene (The intrinsic viscosity (dl / g) of the polyethylene terephthalate resin after the terephthalate resin is held at 210 ° C. for 2 hours under a nitrogen stream. T is 1 (hour).)

[3] The polycarbonate / polyethylene terephthalate composite resin composition according to [1] or [2], wherein the phosphorous heat stabilizer is a phosphite compound.

[4] A polycarbonate / polyethylene terephthalate composite resin composition containing 95 to 30% by mass of a polycarbonate resin and 5 to 70% by mass of a polyethylene terephthalate resin as a resin component, which is soluble in chloroform after being held at 280 ° C. for 60 minutes. the number average molecular weight Mn _x of minute, polycarbonate / polyethylene terephthalate composite resin composition which is characterized in that at least 80% of the number average molecular weight Mn _o before chloroform soluble component holding 60 minutes at 280 ° C..

[5] A polycarbonate / polyethylene terephthalate composite resin composition containing 95 to 30% by mass of a polycarbonate resin and 5 to 70% by mass of a polyethylene terephthalate resin as a resin component, and the Charpy impact strength after being held at 280 ° C. for 60 minutes ip _x is a polycarbonate / polyethylene terephthalate composite resin composition which is characterized in that 80% or more of the preceding Charpy impact strength ip _o holding 60 minutes at 280 ° C..

[6] A polycarbonate / polyethylene terephthalate composite resin molded article obtained by molding the polycarbonate / polyethylene terephthalate composite resin composition according to any one of [1] to [5].

  According to the present invention, a polycarbonate / polyethylene terephthalate composite resin, which is a resin composition in which a polyethylene terephthalate resin for imparting chemical resistance is combined with a polycarbonate resin, and which has excellent thermal stability, in which residence heat deterioration is suppressed. A composition is provided.

  Such a polycarbonate / polyethylene terephthalate (PC / PET) composite resin composition of the present invention is used for various electrical and electronic equipment parts, OA equipment, machine parts, vehicle parts, building members, various containers, leisure goods and miscellaneous goods, etc. It is useful for applications, and can be expected to be applied especially to vehicle exterior / skin parts and vehicle interior parts.

  Examples of vehicle exterior / skin parts to which the PC / PET composite resin composition of the present invention is applied include outer door handles, bumpers, fenders, door panels, trunk lids, front panels, rear panels, roof panels, bonnets, pillars, side moldings. , Garnish, wheel cap, hood bulge, fuel lid, various spoilers, motorbike cowl, etc.

  In addition, examples of vehicle interior parts include inner door handles, center panels, instrument panels, console boxes, luggage floor boards, display housings for car navigation, etc., and application of the PC / PET composite resin composition of the present invention. The field is not limited to these.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Polycarbonate resin]
Examples of the polycarbonate resin used in the PC / PET composite resin composition of the present invention include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aromatic-aliphatic polycarbonate resins, and aromatic polycarbonate resins are preferred.

  The aromatic polycarbonate resin is an optionally branched aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a phosgene or carbonic acid diester. The method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method). Further, it may be a polycarbonate resin produced by a melting method and produced by adjusting the amount of OH groups of terminal groups.

Typical examples of the aromatic dihydroxy compound that is one of the raw materials of the aromatic polycarbonate resin used in the present invention include, for example, bis (4-hydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl). Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone and the like.
Furthermore, polyvalent phenols having three or more hydroxy groups in the molecule such as 1,1,1-tris (4-hydroxylphenyl) ethane (THPE), 1,3,5-tris (4-hydroxyphenyl) benzene Etc. can be used together in small amounts as a branching agent.
Among these aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as “bisphenol A” and sometimes abbreviated as “BPA”) is preferable. These aromatic dihydroxy compounds can be used alone or in admixture of two or more.

  In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-3, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 -Polyhydroxy compounds such as tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. May be used as a part of the aromatic dihydroxy compound, and the amount used thereof may be And from 0.01 to 10 mol% against, and preferably 0.1 to 2 mol%.

  In the polymerization by the transesterification method, a carbonic acid diester is used as a monomer instead of phosgene. Representative examples of the carbonic acid diester include substituted diaryl carbonates typified by diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in admixture of two or more. Among these, diphenyl carbonate (hereinafter sometimes abbreviated as “DPC”) and substituted diphenyl carbonate are preferable.

  Moreover, said carbonic acid diester may substitute the quantity of the 50 mol% or less preferably 30 mol% or less with the dicarboxylic acid or dicarboxylic acid ester preferably. Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

  When an aromatic polycarbonate is produced by a transesterification method, a catalyst is usually used. Although there is no limitation on the catalyst species, generally basic compounds such as alkali metal compounds, alkaline earth metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds are used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more. In the transesterification method, the polymerization catalyst is generally deactivated with p-toluenesulfonic acid ester or the like.

  Preferred aromatic polycarbonate resins are polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane or derived from 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy compounds. And polycarbonate copolymers. Further, for the purpose of imparting flame retardancy and the like, a polymer or oligomer having a siloxane structure can be copolymerized. The aromatic polycarbonate resin may be a mixture of two or more polymers and / or copolymers of different raw materials, and may have a branched structure up to 0.5 mol%.

  The terminal hydroxyl group content of the polycarbonate resin has a great influence on the thermal stability, hydrolysis stability, color tone and the like of the molded product. In order to give practical physical properties, it is usually 30 to 2000 ppm, preferably 100 to 1500 ppm, more preferably 200 to 1000 ppm, and p-tert-butylphenol is used as a sealing end agent for adjusting the terminal hydroxyl group content. , Phenol, cumylphenol, p-long chain alkyl-substituted phenol, and the like can be used.

  As the amount of residual monomer in the polycarbonate resin, the aromatic dihydroxy compound is 150 ppm or less, preferably 100 ppm or less, and more preferably 50 ppm or less. When synthesized by the transesterification method, the residual amount of carbonic acid diester is 300 ppm or less, preferably 200 ppm or less, more preferably 150 ppm or less.

  The molecular weight of the polycarbonate resin is not particularly limited, but is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent, and preferably in the range of 10,000 to 50,000. More preferably, it is a thing of 11,000-40,000, Most preferably, it is a thing of the range of 12,000-30,000. By setting the viscosity average molecular weight to 10,000 or more, the mechanical properties are more effectively exhibited, and by setting the viscosity average molecular weight to 50,000 or less, the molding process becomes easier. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed, or a polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed to be within the above molecular weight range.

[Polyethylene terephthalate resin]
The polyethylene terephthalate resin used in the present invention is a ratio of oxyethylene oxyterephthaloyl units (hereinafter sometimes referred to as “ET units”) composed of terephthalic acid and ethylene glycol to all the structural repeating units (hereinafter referred to as “ET ratio”). Is preferably a polyethylene terephthalate resin that is 90 equivalent% or more, and the polyethylene terephthalate resin in the present invention may contain constituent repeating units other than ET units in a range of less than 10 equivalent%. . The polyethylene terephthalate resin in the present invention is produced using terephthalic acid or a lower alkyl ester thereof and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.

  Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

  Examples of diol components other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, cyclohexane Examples include alicyclic glycols such as dimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.

  The raw material containing terephthalic acid or an ester-forming derivative thereof and ethylene glycol as described above is subjected to esterification or transesterification in the presence of an esterification catalyst or transesterification catalyst, and bis (β-hydroxyethyl) terephthalate and Then, an oligomer thereof is formed, and then a melt polycondensation is performed under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer to obtain a polymer.

  The esterification catalyst is not particularly required because terephthalic acid serves as an autocatalyst for the esterification reaction. The esterification reaction can be carried out in the presence of an esterification catalyst and a polycondensation catalyst described later, and can be carried out in the presence of a small amount of an inorganic acid or the like. As the transesterification catalyst, alkali metal salts such as sodium and lithium, alkaline earth metal salts such as magnesium and calcium, and metal compounds such as zinc and manganese are preferably used. Above all, on the appearance of the obtained polyethylene terephthalate resin, Manganese compounds are particularly preferred.

  As the polycondensation catalyst, compounds soluble in a reaction system such as a germanium compound, an antimony compound, a titanium compound, a cobalt compound, and a tin compound are used alone or in combination. As the polycondensation catalyst, germanium dioxide is particularly preferable from the viewpoints of color tone and transparency. These polycondensation catalysts may be used in combination with a stabilizer in order to suppress the decomposition reaction during polymerization. Examples of the stabilizer include phosphate esters such as trimethyl phosphate, triethyl phosphate and triphenyl phosphate, and triphenyl phosphate. Phosphites such as phyto, trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate, monobutyl phosphate acidic phosphate, phosphorous compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid Or 2 or more types are preferable.

  The use ratio of the above catalyst is usually in the range of 1 to 2000 ppm, preferably 3 to 500 ppm as the weight of the metal in the catalyst in the total polymerization raw material, and the use ratio of the stabilizer is the stabilizer in the total polymerization raw material. The weight of the phosphorus atom is usually 10 to 1000 ppm, preferably 20 to 200 ppm. The catalyst and the stabilizer can be supplied at any stage of the esterification reaction or transesterification reaction in addition to the preparation of the raw slurry. Further, it can be supplied at the beginning of the polycondensation reaction step.

The reaction temperature during the esterification reaction or transesterification reaction is usually 240 to 280 ° C., and the reaction pressure is usually 0.2 to 3 kg / cm ² G (20 to 300 kPa) as a relative pressure to the atmosphere. The reaction temperature during polycondensation is usually 250 to 300 ° C., and the reaction pressure is usually 500 to 0.1 mmHg (67 to 0.013 kPa) as an absolute pressure. Such esterification or transesterification reaction and polycondensation reaction may be performed in one step or in multiple steps. The polyethylene terephthalate resin thus obtained has an intrinsic viscosity of usually 0.45 to 0.70 dl / g, and is chipped by a conventional method. The average particle diameter of this chip is usually in the range of 2.0 to 5.5 mm, preferably 2.2 to 4.0 mm.

  Next, the polymer obtained by melt polycondensation as described above is usually subjected to solid phase polymerization. A polymer chip subjected to solid phase polymerization may be subjected to solid phase polymerization after preliminarily crystallizing by heating to a temperature lower than the temperature at which solid phase polymerization is performed in advance. Such precrystallization includes (a) a method in which a dry polymer chip is heated at a temperature of usually 120 to 200 ° C., preferably 130 to 180 ° C. for 1 minute to 4 hours, and (b) a dry polymer chip. A method of heating the water in an atmosphere of water vapor or water vapor-containing inert gas at a temperature of usually 120 to 200 ° C. for 1 minute or longer, (c) a polymer chip that absorbs moisture in a water, water vapor or water vapor-containing inert gas atmosphere and adjusts the humidity Can be performed by a method of heating at a temperature of usually 120 to 200 ° C. for 1 minute or more. The humidity control of the polymer chip is carried out so that the moisture content is usually in the range of 100 to 10,000 ppm, preferably 1000 to 5000 ppm. By subjecting the conditioned polymer chip to crystallization or solid phase polymerization, it is possible to further reduce the amount of acetaldehyde contained in PET and impurities contained in a trace amount.

The solid phase polymerization step consists of at least one stage, and usually has a polymerization temperature of 190 to 230 ° C., preferably 195 to 225 ° C., usually 1 kg / cm ² G to 10 mmHg (absolute pressure 200 to 1.3 kPa), preferably 0. The reaction is carried out under a flow of inert gas such as nitrogen, argon, carbon dioxide or the like under conditions of a polymerization pressure of 5 kg / cm ² G to 100 mmHg (150 to 13 kPa as an absolute pressure). The solid phase polymerization time may be shorter as the temperature is higher, but is usually 1 to 50 hours, preferably 5 to 30 hours, and more preferably 10 to 25 hours. The intrinsic viscosity of the polymer obtained by solid phase polymerization is usually in the range of 0.70 to 0.90 dl / g.

  The intrinsic viscosity [η] of the polyethylene terephthalate resin used in the present invention 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. -1.0 dl / g is preferred. By setting the intrinsic viscosity [η] to 0.5 dl / g or more, particularly 0.7 dl / g or more, the mechanical properties, residence heat stability, chemical resistance, and heat and humidity resistance in the resin composition of the present invention are improved. It tends to improve, which is preferable. On the other hand, the intrinsic viscosity is preferably less than 2 dl / g, particularly less than 1.0 dl / g, which tends to improve the fluidity of the resin composition.

  In the present invention, the intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1).

  The density | concentration of the terminal carboxyl group of the polyethylene terephthalate resin used for this invention is 1-60microeq / g normally, and it is preferable that it is 3-50microeq / g especially 5-40microeq / g. When the terminal carboxyl group concentration is 60 μeq / g or less, the mechanical properties of the resin composition tend to be improved. Conversely, when the terminal carboxyl group concentration is 1 μeq / g or more, the heat resistance of the resin composition is increased. It is preferable because the thermal stability and hue tend to be improved.

  The terminal carboxyl group concentration of the polyethylene terephthalate resin can be determined by dissolving 0.5 g of polyethylene terephthalate resin in 25 ml of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. it can.

  The polyethylene terephthalate resin used in the present invention is obtained by subjecting the above-described polyethylene terephthalate resin to a polycondensation catalyst deactivation treatment. There is no restriction | limiting in particular as a deactivation processing method of the polycondensation catalyst of a polyethylene terephthalate resin, A conventionally well-known deactivation process can be given according to the polycondensation catalyst used. Examples of the deactivation processing method include the following methods.

Deactivation treatment method of polycondensation catalyst 1: Hot water (steam) treatment of germanium catalyst A method of deactivating the germanium catalyst in the polyethylene terephthalate resin by treating the polyethylene terephthalate resin with hot water (steam).
Specifically, the container is filled with polyethylene terephthalate resin, and steam of 70 to 150 ° C., for example, about 100 ° C. is steamed in an amount of 1 to 100% by weight per hour for 5 to 6000 minutes with respect to the polyethylene terephthalate resin. Dry after treatment.
The polyethylene terephthalate resin is immersed in distilled water 0.3 to 10 times the weight of the polyethylene terephthalate resin in the container, and then the container containing the polyethylene terephthalate resin and distilled water is heated from the outside, and the internal temperature is set to 70 to 110. The temperature is controlled at 3 ° C. and the mixture is kept for 3 to 3000 minutes for hot water treatment, then dehydrated and dried.
The said drying is normally performed for 3 to 8 hours at 120-180 degreeC in inert gas, such as nitrogen.

Deactivation treatment method 2 of polycondensation catalyst: Addition of phosphorus compound to titanium catalyst A phosphorus compound is added to a polyethylene terephthalate resin to deactivate the titanium catalyst in the polyethylene terephthalate resin. In this case, the amount of phosphorus atoms added is preferably in the range of 7 to 145 ppm based on the weight of the polyethylene terephthalate resin. When the addition amount of phosphorus element is less than 7 ppm, the deactivation of the catalyst is insufficient, and the intended effect of the present invention may not be obtained. When the addition amount of phosphorus atoms exceeds 145 ppm, the phosphorus compound itself becomes coarse aggregated particles, causing problems such as poor appearance and reduced impact resistance.

  In addition, as a phosphorus compound to add, conventionally well-known phosphate ester compounds, phosphite ester compounds, phosphonate compounds, etc. are mentioned. Among these, phosphonate compounds represented by the following general formula (2) are preferable.

R ¹ OC (O) XP (O) (OR ² ) ₂ (2)
Wherein R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, X is —CH ₂ — or —CH (Y) — (Y represents a phenyl group), and R ¹ and R ² are Each may be the same or different.)

  Among the phosphonate compounds represented by the above formula (2), alkyl phosphonate compounds are preferably exemplified, and among these, triethylphosphonoacetic acid is particularly preferable. These may be used alone or in combination of two or more.

  The deactivation treatment method of the polycondensation catalyst of the polyethylene terephthalate resin is an example of a deactivation treatment that can be adopted in the present invention, and the deactivation treatment according to the present invention is not limited to the above method.

  Hereinafter, the polyethylene terephthalate resin subjected to the deactivation treatment of the polycondensation catalyst is referred to as “deactivated PET”, and the untreated polyethylene terephthalate resin is referred to as “untreated PET”.

The deactivated PET used in the present invention is such that the polycondensation catalyst in the polyethylene terephthalate resin is deactivated as described above, so that the solid phase polymerization rate Ks calculated by the following formula (1) is 0.006 ( dl / g · hr) or less, particularly 0.005 (dl / g · hr) or less, and particularly about 0.001 to 0.004 (dl / g · hr) is preferable.
Solid-phase polymerization rate Ks = ([η] s− [η] m) / T (1)
Here, [η] s is the intrinsic viscosity (dl / g) of the polyethylene terephthalate resin after the polyethylene terephthalate resin is held at 210 ° C. for 3 hours under a nitrogen stream, and [η] m is the polyethylene terephthalate. It is the intrinsic viscosity (dl / g) of the polyethylene terephthalate resin after holding the resin at 210 ° C. for 2 hours under a nitrogen stream. T is 1 (hour). That is, in the present invention, the intrinsic viscosity after holding at 210 ° C. for 3 hours under a nitrogen stream is [η] s, and the intrinsic viscosity after holding for 2 hours under the same conditions is [η] m. The solid phase polymerization rate Ks calculated by the above-described equation (1) was used as the solid phase polymerization rate Ks.

  When the solid phase polymerization rate Ks of the deactivated PET exceeds 0.006 (dl / g · hr), the deactivation treatment of the polycondensation catalyst is insufficient, and the effect of suppressing the residence heat deterioration according to the present invention is sufficiently obtained. Can't get. However, it is difficult to make the solid phase polymerization rate Ks excessively small, and it is usually 0.001 (dl / g · hr) or more.

[Resin component]
The resin component which concerns on this invention consists of 95-30 mass% of 1 type or 2 types or more of the above-mentioned polycarbonate resin, and 5-70 mass% of 1 type or 2 types or more of the above-mentioned deactivated PET.

  If the proportion of polycarbonate resin in the resin component is greater than the above upper limit and the proportion of deactivated PET is less than the above lower limit, the effect of improving chemical resistance by using PET cannot be sufficiently obtained, and conversely If the proportion of the polycarbonate resin is less than the above lower limit and the proportion of the deactivated PET is greater than the above upper limit, the original properties of the polycarbonate resin are impaired, and the impact resistance, the heat deflection temperature under load and the like are not preferable.

  A preferable ratio is polycarbonate resin 90-40 mass%, deactivated PET 10-60 mass%, More preferably, polycarbonate resin 85-60 mass% and deactivated PET 15-40 mass%.

[Thermal stabilizer]
The resin composition of the present invention is required to contain a phosphorus-based heat stabilizer and / or a hindered phenol-based heat stabilizer with respect to the resin component described above, and by including these specific heat stabilizers, polyethylene By using deactivated PET as the terephthalate resin, the effect of suppressing residence heat deterioration can be further remarkably enhanced, and a resin composition having excellent resistance to residence heat deterioration can be realized. That is, the thermal degradation can be suppressed by the phosphorus thermal stabilizer by the decomposition of the peroxide and the hindered phenol thermal stabilizer by capturing the peroxide radical.

  Examples of phosphorus heat stabilizers include phosphorus heat stabilizers such as phosphites and phosphates.

  Examples of phosphites include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl Phenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert) Butylphenyl) triesters of phosphorous acid such as octyl phosphite, diesters, monoesters, and the like.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, tetrakis (2,4-di-). tert-butylphenyl) -4,4-diphenylphosphonite and the like.

  Among the above phosphorus-based heat stabilizers, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4) -Methylphenyl) pentaerythritol phosphite, phosphite compounds such as tris (2,4-di-tert-butylphenyl) phosphite are preferred, and among them bis (2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol phosphite and tris (2,4-di-t-butylphenyl) phosphite are particularly preferred.

  As the hindered phenol heat stabilizer, 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-hydroxyphenylpropionamide), 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-tolyl) 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 and the like.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic heat stabilizers are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  A phosphorus heat stabilizer may be used individually by 1 type, and may use 2 or more types together. Moreover, about a hindered phenol-type heat stabilizer, 1 type may be used independently and 2 or more types may be used together. Moreover, you may use together a phosphorus thermal stabilizer and a hindered phenol thermal stabilizer.

  The phosphorus-based heat stabilizer is used in an amount of 0.01 to 0.5 parts by weight, preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the resin component composed of polycarbonate resin and deactivated PET. The hindered phenol heat stabilizer is used in an amount of 0.01 to 1 part by mass, preferably 0.05 to 0.2 part by mass, based on 100 parts by mass of the resin component composed of polycarbonate resin and deactivated PET. If the blending amount of these heat stabilizers is too small, it is not possible to sufficiently obtain the effect of suppressing the thermal deterioration due to the blending of the heat stabilizer, and if it is too much, the effect reaches a peak and is not economical. In addition, when using together a phosphorus heat stabilizer and a hindered phenol heat stabilizer, after making each heat stabilizer into the said mixing | blending range, a total compounding ratio is from polycarbonate resin and deactivated PET. It is preferable to use it so that it may become 0.07-0.4 mass part with respect to 100 mass parts of resin components.

[Other ingredients]
In the resin composition according to the present invention, in addition to the above-mentioned polycarbonate resin, deactivated PET, and heat stabilizer, other various additions contained in a normal polycarbonate resin composition, as long as the effects of the present invention are not impaired. An agent may be contained.

  As various additives that can be contained, antioxidants, mold release agents, dyes and pigments, reinforcing agents, flame retardants, impact resistance improvers, ultraviolet absorbers, antistatic agents, antifogging agents, lubricants and antiblocking agents, Examples thereof include a fluidity improver, a plasticizer, a dispersant, and a fungicide. Two or more of these may be used in combination. Hereinafter, an example of an additive suitable for the resin composition of the present invention will be specifically described.

  The release agent includes at least one compound selected from the group consisting of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, and polysiloxane silicone oil. Can be mentioned.

  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 the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic saturated monohydric alcohol or polyhydric alcohol having 30 or less carbon atoms is more preferable. Here, aliphatic includes alicyclic compounds. 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 compound may contain aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a some compound.

  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 having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, as the aliphatic hydrocarbon, alicyclic hydrocarbon is also included. Moreover, these hydrocarbon compounds may be partially oxidized. Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. Two or more of these may be used in combination.

  Content of a mold release agent is 0.001-2 mass parts normally with respect to a total of 100 mass parts of polycarbonate resin and deactivated PET, Preferably it is 0.01-1 mass part. When the content of the release agent is less than 0.001 part by mass, the effect of releasability may not be sufficient. When the content exceeds 2 parts by mass, the hydrolysis resistance is deteriorated and the mold is contaminated during injection molding. There are problems such as.

  Specific examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds in addition to inorganic ultraviolet absorbers such as cerium oxide and zinc oxide. Of these, organic ultraviolet absorbers are preferred. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. Two or more of these may be used in combination.

  Of the above, preferably 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl)- 6- (2N-benzotriazol-2-yl) phenol].

  Content of a ultraviolet absorber is 0.01-3 mass parts normally with respect to a total of 100 mass parts of polycarbonate resin and deactivated PET, Preferably it is 0.1-1 mass part. When the content of the ultraviolet absorber is less than 0.01 parts by mass, the effect of improving the weather resistance may be insufficient, and when it exceeds 3 parts by mass, a problem such as mold deposit may occur.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; zinc white, petal, chromium oxide, titanium oxide, iron black, titanium yellow, and zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as yellow lead and molybdate orange; Examples include Russian pigments. Organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone And condensed polycyclic dyes such as quinophthalone; anthraquinone, heterocyclic, and methyl dyes and the like. Two or more of these may be used in combination. Among these, carbon black, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass in total of the polycarbonate resin and deactivated PET. When the content of the dye / pigment exceeds 5 parts by mass, the impact resistance may not be sufficient.

  Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate, potassium perfluorobutanesulfonate, and polyorganosiloxane flame retardants are preferable, but phosphate ester flame retardants are particularly preferable. .

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Examples thereof include bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4′-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. Two or more of these may be used in combination. In these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  Content of a flame retardant is 1-30 mass parts normally with respect to a total of 100 mass parts of polycarbonate resin and deactivated PET, Preferably it is 3-25 mass parts, More preferably, it is 5-20 mass parts. When the content of the flame retardant is less than 1 part by mass, the flame retardancy may not be sufficient, and when it exceeds 30 parts by mass, the heat resistance may decrease.

  Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and polytetrafluoroethylene having fibril forming ability is particularly preferable. This shows the tendency to disperse | distribute easily in a polymer and to couple | bond together polymers and to make a fibrous material. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include “Teflon (registered trademark) 6J” or “Teflon (registered trademark) 30J” from Mitsui DuPont Fluorochemical Co., Ltd. and “Polyflon (trade name) from Daikin Industries, Ltd. Is commercially available.

  Content of a dripping inhibitor is 0.02-4 mass parts normally with respect to a total of 100 mass parts of polycarbonate resin and deactivated PET, Preferably it is 0.03-3 mass parts. When the compounding amount of the dripping inhibitor exceeds 5 parts by mass, the appearance of the molded product may be deteriorated.

  The resin composition according to the present invention may contain other resin components and rubber components other than the polycarbonate resin and deactivated PET. In this case, as other resin or rubber component, for example, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene resin such as polystyrene resin, polyolefin resin such as polyethylene resin and polypropylene resin, polyamide resin , Polyimide resin, polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenol resin, epoxy resin, etc., but the content of these other resins or rubber components is In order to sufficiently secure the effect of the combined use of the polycarbonate resin and the deactivated PET, it is preferably 30 parts by mass or less with respect to 100 parts by mass in total of the polycarbonate resin and the deactivated PET.

  The resin composition according to the present invention includes glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads; carbon fibers, short carbon fibers, carbon nanotubes, graphite, and the like. Carbon-based fillers; whiskers such as potassium titanate and aluminum borate; silicate compounds such as talc, mica, wollastonite, kaolinite, zonotlite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate It is also possible to include inorganic fillers such as.

[Method for producing PC / PET composite resin composition]
The PC / PET composite resin composition of the present invention uses a polycarbonate resin, deactivated PET, a phosphorus heat stabilizer and / or a hindered phenol heat stabilizer, and other additives added as necessary. Any conventionally known method can be appropriately selected and produced.

  Specifically, polycarbonate resins, deactivated PET, phosphorus-based heat stabilizers and / or hindered phenol-based heat stabilizers, and additives blended as necessary are mixed with various mixers such as tumblers and Henschel mixers. After mixing in advance, the resin composition can be produced by melt-kneading with a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like. Moreover, it is also possible to produce a resin composition without mixing each component in advance, or by mixing only some components in advance and supplying them to an extruder using a feeder and melt-kneading them.

[Preferable physical properties of PC / PET composite resin composition]
Of PC / PET composite resin composition of the present invention, preferred is a number average molecular weight Mn _x chloroform solubles was held 60 minutes at 280 ° C. is before the 60 minute hold at 280 ° C. chloroform-soluble retention of minute number average molecular weight Mn _{o, i.e.,} the number average molecular weight of retention after heat retention calculated by Mn x / Mn _o × 100 is 80% or more. If the retention of this number average molecular weight is less than 80%, it cannot be said that the effect of suppressing the residence heat degradation intended in the present invention is sufficient, and there is a problem of residence heat degradation. Preferably, the number average molecular weight retention is 85% or more, more preferably 90% or more.

Also, of the PC / PET composite resin composition of the present invention, preferred are 280 Charpy impact strength Ip _x after holding for 60 minutes at ° C. is before the 60 minute hold at 280 ° C. Charpy impact strength Ip _o 80%, _i.e., retention of Charpy impact strength after heat retention calculated by Ip x / Ip _o × 100 is 80% or more. If the Charpy impact strength retention rate is less than 80%, it cannot be said that the effect of suppressing the residence heat deterioration intended in the present invention is sufficient, and there is a problem of residence heat degradation. Preferably, the Charpy impact strength retention is 85% or more, more preferably 90% or more.

Incidentally, the Charpy impact strength Ip _o of PC / PET composite resin composition of the present invention is 8.0kJ / ^{m 2} or more, and particularly preferably 10.0 kJ / ^{m 2} or more.

  In the present invention, the number average molecular weight and Charpy impact strength of the PC / PET composite resin composition are values measured by the methods described in the Examples section below.

  In addition, the PC / PET composite has a holding condition in the evaluation of the number average molecular weight and Charpy impact strength holding ratio of the PC / PET composite resin composition described above as “280 ° C., 60 minutes (1 hour)”. In the injection molding of a resin composition, the longest time is assumed in the set temperature of a cylinder that is normally used and the normally assumed residence time, and there is a problem of residence heat deterioration of the resin composition at 280 ° C. for 1 hour. If it is not present, it is based on the assumption that the accumulated heat deterioration hardly occurs in normal use.

[Method for producing PC / PET composite resin molded product]
The method for producing a molded product from the PC / PET composite resin composition of the present invention is not particularly limited, and a molding method generally employed for thermoplastic resins, that is, a general injection molding method, an ultra-high-speed injection method. Molding method, injection compression molding method, multicolor injection molding method, gas assist injection molding method, molding method using heat insulation mold, molding method using rapid heating / cooling mold, foam molding (including supercritical fluid), Insert molding, IMC (in-mold coating) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method and the like can be employed. Also, in various injection molding methods, a molding method using a hot runner method can be selected.

  Further, the PC / PET composite resin composition of the present invention can be subjected to multicolor composite molding with another thermoplastic resin composition to form a composite molded product.

  In addition, in this invention, while using deactivated PET as a polyethylene terephthalate resin and using a specific heat stabilizer, the residence heat deterioration of the resin composition by having combined the polyethylene terephthalate resin with the polycarbonate resin is suppressed. Therefore, the problem of staying heat deterioration in the molding process is prevented, but if this staying temperature is excessively high and the staying time is excessively long, the problem of staying heat deterioration may occur. Therefore, the residence temperature of the resin composition in the molding step of the PC / PET composite resin composition of the present invention is preferably 280 ° C. or less and the residence time is 60 minutes or less.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.

  In addition, the compounding component of the resin composition used in the Example and the comparative example is as follows.

  Polycarbonate resin 1: Product from Mitsubishi Engineering Plastics Co., Ltd. Aromatic polycarbonate resin “Product name: Iupilon (registered trademark) S-3000”, viscosity average molecular weight 21,500, terminal hydroxyl group content 150 ppm

  Polycarbonate resin 2: Products manufactured by Mitsubishi Engineering Plastics Co., Ltd. Aromatic polycarbonate resin "Product name: Iupilon (registered trademark) S-3000" (viscosity average molecular weight 21,500, terminal hydroxyl group content 150 ppm) and Mitsubishi Engineering Plastics Products Co., Ltd. Aromatic polycarbonate resin “trade name: Iupilon (registered trademark) H-4000” (viscosity average molecular weight 16,000, terminal hydroxyl group content 100 ppm), a mixture, S-3000 / H-4000 = 55 / 45 (weight ratio), viscosity average molecular weight 18,500

  Untreated PET1: Mitsubishi Chemical Corporation PET “GG500S”, using a germanium dioxide catalyst as a polycondensation catalyst, intrinsic viscosity [η]: 0.76 dl / g, terminal carboxyl group concentration AV: 28 μeq / g, ET ratio: 97.8 equivalent%, solid phase polymerization rate Ks: 0.0085 dl / g · hr (all physical property values are according to the measurement method described later)

  Untreated PET2: Mitsubishi Chemical Co., Ltd. PET "Novapex (registered trademark) RF543DE", using a titanium-based catalyst as a polycondensation catalyst, intrinsic viscosity [η]: 0.74 dl / g, terminal carboxyl group concentration AV : 8.4 μeq / g, ET ratio: 97.6 equivalent%, solid phase polymerization rate Ks: 0.0078 dl / g · hr (all physical property values are according to the measurement method described later)

Deactivated PET1: The above-mentioned untreated PET1 was subjected to the following polycondensation catalyst deactivation treatment, intrinsic viscosity [η]: 0.75 dl / g, terminal carboxyl group concentration AV: 30 μeq / g, ET ratio : 97.8 equivalent%, solid-phase polymerization rate Ks: 0.0031 dl / g · hr (physical property values are all based on the measurement method described later.)
<Deactivation method>
50 kg of untreated PET was boiled in 50 kg of distilled water at 100 ° C. for 1 hour, dehydrated, and dried in a nitrogen atmosphere at 120 ° C. for 6 hours.

Deactivated PET2: Untreated PET2 subjected to the deactivation treatment of the following polycondensation catalyst, intrinsic viscosity [η]: 0.73 dl / g, terminal carboxyl group concentration AV: 12 μeq / g, ET ratio : 97.6 equivalent%, solid phase polymerization rate Ks: 0.0042 dl / g · hr (all physical property values are according to the measurement method described later)
<Deactivation method>
0.01 parts by mass of the following phosphorus-based heat stabilizer 2 (ADK STAB AX-71) and 0.03 parts by mass of the following phosphorus-based heat stabilizer 1 (Irgaphos 168) are added to 100 parts by mass of untreated PET2. Then, after uniformly mixing with a tumbler mixer, using a twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, number of barrels 12), cylinder temperature 270 ° C., screw rotation speed 200 rpm, discharge amount 15 kg The pellet of inactivated PET2 was produced by feeding to the extruder from the barrel at / hr and melt-kneading.

Deactivated PBT: Products produced by Mitsubishi Engineering Plastics Co., Ltd. PBT resin "Novaduran (registered trademark) 5020" is subjected to the following deactivation treatment of polycondensation catalyst
<Deactivation method>
0.1 parts by mass of the following phosphorus stabilizer 2 (Adeka Stub AX-71) and 0.03 parts by mass of the following phosphorus thermal stabilizer 1 (Irgaphos 168) are added to 100 parts by weight of the PBT resin, After mixing uniformly with a tumbler mixer, using a twin screw extruder (manufactured by Nippon Steel, TEX30XCT, L / D = 42, number of barrels 12), cylinder temperature 240 ° C., screw rotation speed 200 rpm, discharge rate 15 kg / hr The pellets of inactivated PBT were prepared by feeding from the barrel to the extruder and melting and kneading.

Phosphorus heat stabilizer 1: “Irgaphos 168” (Tris (2,4-di-t-butylphenyl) phosphite) manufactured by Ciba Specialty Chemicals Co., Ltd.
Phosphorus-based thermal stabilizer 2: “ADEKA STAB AX-71 (trade name)” manufactured by ADEKA (mono or di-stearyl acid phosphate)
Hindered phenol heat stabilizer: Ciba Specialty Chemicals “Irganox 1076” (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)

  Carbon black: “# 1000” furnace carbon black manufactured by Mitsubishi Chemical Corporation

  In addition, evaluation methods for various physical properties and characteristics are as follows.

<Terminal carboxyl group concentration of PET>
Weigh 0.5 g of resin chips accurately, dissolve in 25 ml of benzyl alcohol at 195 ° C., cool in ice water for several tens of seconds, add 2 ml of ethyl alcohol, and use an automatic titrator (“AUT-301” manufactured by Toa Denpa). And neutralized titration with 0.01N NaOH benzyl alcohol solution. From the measurement titration amount A (ml), the blank titration amount B (ml), the titer F of NaOH benzyl alcohol, and the weighed value W (g) of the sample, the amount of terminal carboxyl group AV (μeq / g) according to the following formula: Asked.
AV = (A−B) × 0.01 × F × 1000 / W

<Intrinsic viscosity of PET>
A solution having a concentration (c) of 1.0 g / dl was prepared using 0.50 g of freeze-pulverized PET sample using a mixed solution of phenol / tetrachloroethane (weight ratio 1/1) as a solvent. Here, the sample was dissolved at 120 ° C. for 30 minutes. The relative viscosity (η _rel ) of this solution with respect to the solvent alone (c = 0) was measured at 30 ° C. using an Ubbelohde viscometer, and this relative viscosity (η _rel ) -1 was _defined as the specific viscosity (η _sp ). The ratio (η _sp / c) to the concentration (c) was determined. Similarly, the concentration (c) is 0.5 g / dl, 0.2 g / dl, and 0.1 g / dl, and the respective ratios (η _sp / c) are obtained. From these values, the concentration (c) is set to 0. The ratio (η _sp / c) when extrapolated to was calculated as intrinsic viscosity [η] (dl / g).

<Composition analysis of PET>
¹ H-NMR was measured with a nuclear magnetic resonance apparatus (“JNM-EX270 type” manufactured by JEOL Ltd.) using a 3 wt% solution obtained by dissolving a resin sample in deuterated trifluoroacetic acid at room temperature, Assign the peak, determine the proportion of terephthalic acid and dicarboxylic acid components other than terephthalic acid, and ethylene glycol and other diol components from the integral ratio, and the content of oxyethyleneoxyterephthaloyl units (ET ratio) ) Was calculated.

<Solid-state polymerization rate of PET>
10 g of PET chip cut so that the average grain weight per grain becomes 24 mg is put in a container made of stainless steel mesh with a diameter of 30 mmφ and a height of 30 mm, and an inert oven (“IPHH-201 type” manufactured by ESPEC) It was dried at 160 ° C. for 4 hours under a nitrogen stream of 40 liters / minute. Thereafter, the temperature was raised from 160 ° C. to 210 ° C. over 1 hour while maintaining the nitrogen flow, and from the intrinsic viscosity [η] s after 3 hours after holding at 210 ° C., from the intrinsic viscosity [η] m after 2 hours. It was calculated by the following equation (1).
Solid phase polymerization rate Ks = ([η] s− [η] m) / 1 (1)

[Examples 1-17, Comparative Examples 1-10]
After uniformly mixing the components shown in Tables 1 and 2 with a tumbler mixer in the ratios shown in Tables 1 and 2, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30XCT, L / D = 42, barrel number 12) The pellets of the resin composition were prepared by feeding to an extruder from a barrel at a cylinder temperature of 280 ° C., a screw rotation speed of 200 rpm, and a discharge rate of 30 kg / hr, and melt-kneading.

  After the pellets obtained by the above method were dried at 120 ° C. for 6 hours or more, using an injection molding machine (“M150AII-SJ type” manufactured by Meiki Seisakusho), the cylinder temperature was 280 ° C., the mold temperature was 80 ° C., Normal molding in which the resin does not stay in the cylinder under the molding cycle condition of 55 seconds, that is, the molten resin composition was injected into the cylinder, and the injection quantity was sufficient immediately after the filling amount was sufficient for injection molding ( In the case of no holding time), a test piece obtained under each condition was produced when molding was performed after holding in the cylinder for 60 minutes, and when molding was performed after holding in the cylinder for 30 minutes. (A test piece without holding time, a test piece after holding for 60 minutes, and a test piece after holding for 30 minutes). The shape of the test piece conformed to ISO 3167 multipurpose test piece type A.

<Number average molecular weight retention of resin composition>
The number average molecular weight Mn _x number-average molecular weight Mn _o and 60 minute hold after the test piece specimens without retention time obtained by the above-mentioned molding was measured, from these values, the holding of a number average molecular weight The rate (Mn _x / Mn _o × 100) was calculated.

The number average molecular weight was measured by the following method.
(Number average molecular weight of resin composition)
About 50 mg was cut out from the molded piece of the resin composition, immersed in chloroform so as to be 0.1 wt%, and allowed to stand at room temperature for 24 hours. This solution was filtered through a 0.45 μm polytetrafluoroethylene membrane filter to obtain a chloroform-soluble component for gel chromatography measurement. 0.1 ml of chloroform-soluble matter of the obtained resin composition was injected into Tosoh HLC-8220GPC (R), and GPC measurement was performed at a flow rate of 1.0 ml / min using chloroform as a mobile phase. PL 10 μm Mixed B (7.5 mm ID × 30 cm × 2) was used for the column, the column temperature was 40 ° C., and the built-in RI was used as a detector. A monodisperse polystyrene was used for the calibration sample, and the number average molecular weight was measured by a polystyrene conversion method. The measurement was performed twice per sample, and the average value of the two times was defined as the number average molecular weight Mn.

<Charpy impact strength of resin composition>
It was measured Charpy impact strength Ip _o notched compliant test piece without retention time obtained by the above-mentioned molding method ISO179 standard.

<Charpy impact strength retention ratio of resin composition>
The Charpy impact strength Ip _x of the test piece after 60 minutes retention obtained by the molding method described above was measured, retention of Charpy impact strength and a Charpy impact strength Ip _o specimens without retention times (Ip _x / Ip _o × 100) was calculated.

<MFR reduction rate of resin composition>
The test piece without holding time and the test piece held for 30 minutes formed by the above method were each cut with a pruning shear, and each was subjected to MFR (melt flow rate) measurement. The measurement conditions were 280 ° C. and a load of 2.16 kg, and conformed to ASTM D1238.
The MFR of the test piece after 30 minutes holding is set to [R _x ], the MFR of the test piece without holding time is set to [R _o ], and these values are used to calculate the MFR reduction rate based on the following formula. Calculated.
MFR decrease rate = ([R _o ] − [R _x ]) / [R _o ] × 100

<Elastic modulus of resin composition>
Based on ISO527, the elastic modulus of the resin composition was measured for the test piece without holding time.

<Appearance of molded product>
After holding for 60 minutes in the cylinder, the appearance of the molded product was visually observed for the ISO test piece obtained by the above-described molding method, and evaluated according to the following criteria.
(Double-circle): Silver, a foaming mark, etc. are not seen, but a glossy surface appearance is exhibited.
○: A glossy surface appearance is exhibited, but slight irregularities are observed near the gate.
X: Silver is generated on the most part of the surface, and the appearance without surface gloss is exhibited.

  The evaluation results are shown in Tables 1 and 2.

Tables 1 and 2 show the following.
Examples 1 to 7 of the present invention are less susceptible to changes in viscosity due to retention during injection molding, have excellent thermal and molding stability, and balance of mechanical properties such as Charpy impact strength and elastic modulus. It turns out to be excellent.
From Examples 3 to 5, it can be seen that various types of polycarbonate resin and deactivated PET can be applied.
From Example 3 and Examples 6 and 7, it can be seen that the blending ratio of polycarbonate resin and deactivated PET is effective within the scope of the present invention.

Comparative Example 1 uses untreated PET, does not contain a thermal stabilizer, and results in poor number average molecular weight retention, Charpy impact strength retention, MFR reduction, and surface appearance of the molded product.
Comparative Examples 2, 7, and 8 use deactivated PET, but do not include a thermal stabilizer, resulting in poor number average molecular weight retention and Charpy impact strength retention.
Comparative Examples 3 and 4 contain heat stabilizers but use untreated PET, resulting in poor number average molecular weight retention rate, Charpy impact strength retention rate, MFR reduction rate, and surface appearance of the molded product. .
Comparative Examples 5, 9, and 10 are those in which a phosphorus-based heat stabilizer 2 for deactivation of PET is blended by post-addition, number average molecular weight retention, Charpy impact strength retention, MFR reduction rate, molding Any surface appearance of the product is inferior.
In Comparative Example 6, deactivated PBT was used instead of deactivated PET, and the number average molecular weight retention rate, Charpy impact strength retention rate, MFR reduction rate, and surface appearance of the molded product were all inferior.

Claims (6)

  To 100 parts by mass of a resin component consisting of 95 to 30% by mass of a polycarbonate resin and 5 to 70% by mass of a polyethylene terephthalate resin, 0.01 to 0.5 parts by mass of a phosphorus-based heat stabilizer and / or a hindered phenol-based heat stabilizer. A polycarbonate / polyethylene terephthalate composite resin composition comprising 0.01 to 1 part by mass, wherein the polyethylene terephthalate resin is a polyethylene terephthalate resin in which a polycondensation catalyst is deactivated. 2. The polyethylene terephthalate resin subjected to the deactivation treatment of the polycondensation catalyst according to claim 1, wherein the terminal carboxyl group concentration is 5 to 40 μeq / g, the intrinsic viscosity [η] is 0.6 to 1.5 dl / g, The ratio of the oxyethyleneoxyterephthaloyl unit to the repeating unit is 90 equivalent% or more, and the solid phase polymerization rate Ks calculated by the following formula (1) is 0.006 (dl / g · hr) or less. A polycarbonate / polyethylene terephthalate composite resin composition.
Solid-phase polymerization rate Ks = ([η] s− [η] m) / T (1)
(Where [η] s is the intrinsic viscosity (dl / g) of the polyethylene terephthalate resin after holding the polyethylene terephthalate resin at 210 ° C. for 3 hours under a nitrogen stream, and [η] m is the polyethylene (The intrinsic viscosity (dl / g) of the polyethylene terephthalate resin after the terephthalate resin is held at 210 ° C. for 2 hours under a nitrogen stream. T is 1 (hour).)   3. The polycarbonate / polyethylene terephthalate composite resin composition according to claim 1, wherein the phosphorous heat stabilizer is a phosphite compound. A polycarbonate / polyethylene terephthalate composite resin composition containing, as a resin component, 95 to 30% by mass of a polycarbonate resin and 5 to 70% by mass of a polyethylene terephthalate resin, and the number of chloroform-soluble components after being held at 280 ° C. for 60 minutes average molecular weight Mn _x is a polycarbonate / polyethylene terephthalate composite resin composition which is characterized in that at least 80% of the number average molecular weight Mn _o before chloroform soluble component holding 60 minutes at 280 ° C.. A polycarbonate / polyethylene terephthalate composite resin composition containing, as a resin component, 95 to 30% by mass of a polycarbonate resin and 5 to 70% by mass of a polyethylene terephthalate resin, and having a Charpy impact strength Ip _x after being held at 280 ° C. for 60 minutes , polycarbonate / polyethylene terephthalate composite resin composition which is characterized in that 80% or more of the preceding Charpy impact strength Ip _o holding 60 minutes at 280 ° C..   A polycarbonate / polyethylene terephthalate composite resin molded article obtained by molding the polycarbonate / polyethylene terephthalate composite resin composition according to any one of claims 1 to 5.