JP2017186464A - Polycarbonate resin composition, and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that shows excellent fluidity in molding and has low-temperature impact resistance, and a molding thereof.SOLUTION: A polycarbonate resin composition contains polyester of a specific structure with a number average molecular weight of 15,000-40,000 and polycarbonate resin in the weight ratio of 20:80-50:50.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded product thereof.

  Molded products made of polycarbonate resin are excellent in impact resistance, heat resistance, dimensional stability, self-digestibility (flame retardant), etc., so electrical / electronic / OA equipment, optical parts, precision machinery, automobiles It is used in a wide range of fields such as security / medicine, building materials, and miscellaneous goods. However, since polycarbonate resins usually have a high melt viscosity, they have drawbacks such as poor fluidity and inferior moldability, and insufficient impact resistance at low temperatures.

  As a method for improving the impact resistance at low temperatures described above, a method of adding an impact resistance improver to a polycarbonate resin is known. In this method, for example, an elastomer component such as a diene elastomer, an acrylic elastomer, a silicone elastomer, an olefin elastomer, or a modified product thereof is allowed to exist in a finely dispersed state in the polycarbonate resin, so that the polycarbonate resin A molded product with excellent impact resistance is obtained. It is known that the lower the glass transition temperature (Tg) of the elastomer component contained in these impact resistance improvers, the better the impact resistance improving effect.

  A method of adding such an impact resistance improver to a polycarbonate resin is disclosed in Patent Document 1, for example. Patent Document 1 discloses that the impact resistance at low temperatures can be improved to some extent by using a specific rubber craft copolymer as the impact resistance improver.

JP 2014-162878 A (published September 8, 2014)

  However, in the method described in Patent Document 1, since a non-thermoplastic impact resistance improver is added to the polycarbonate resin, there is a concern that the flowability of the polycarbonate resin during molding is reduced. As described above, according to the method disclosed in Patent Document 1, although the impact resistance at a low temperature can be improved to some extent, a further excellent low temperature impact resistance is required.

  The object of the present invention has been made in view of the above problems, and the object thereof is a polycarbonate resin composition excellent in moldability and low-temperature impact resistance without impairing the original properties of the polycarbonate resin, and the molding thereof. Is to provide goods.

  As a result of intensive studies, the present inventors have determined that a bisphenol component and an aliphatic dicarboxylic acid component, and optionally a specific high molecular weight polyester obtained by polycondensation of a biphenol component at a specific ratio, and a polycarbonate resin at a predetermined ratio. It was found that the resin composition contained can improve the moldability and low-temperature impact resistance of the polycarbonate-based resin, and the present invention has been completed. That is, this invention is invention shown by following <1>-<6>.

  <1> The following general formula (1)

(In the formula, X _{1 to} X ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)
Biphenol (A) represented by 0 to 55 mol%,
The following general formula (2)

(Wherein, X _{5 to} X ₈ may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Y represents a methylene group or an isopropylidene group. , cyclic alkylidene group, an aryl-substituted alkylidene group, arylene alkylidene group, -S -, - O-, carbonyl or -SO ₂ - shows a).
5 to 60 mol% of bisphenol (B) represented by
The following general formula (3)
HOOC-R ₁ -COOH (3)
(In the formula, R ₁ represents a divalent linear substituent which has 2 to 18 main chain atoms and may contain branches.)
25 to 60 mol% of a dicarboxylic acid (C) represented by:
The following general formula (4)
_{HOOC-R 2 -COOH ··· (4} )
(In the formula, R ₂ represents a divalent linear substituent having a number of main chain atoms larger than that of R ₁ , which may be branched with 4 to 20 main chain atoms.)
A monomer mixture containing 0 to 25 mol% of a dicarboxylic acid (D) represented by the formula (provided that the above mol% is the total of the monomers (A), (B), (C) and (D) being 100 mol%) A polyester having a number average molecular weight of 15,000 to 40,000, and a polycarbonate resin, a polycondensate of monomer (A) + (B) is 40 to 60 mol%) A polycarbonate resin composition containing a weight ratio of 20:80 to 50:50.

  <2> The polycarbonate resin composition according to <1>, wherein the polycarbonate resin has a viscosity average molecular weight of 17,000 or more.

<3> The portion corresponding to R ₁ and R ₂ of the portion derived from dicarboxylic acid (C) and dicarboxylic acid (D) in the polyester is a linear saturated aliphatic hydrocarbon chain, <1> or The polycarbonate resin composition as described in <2>.

<4><1> to <3>, wherein the number of main chain atoms of the portion corresponding to R ₁ and R ₂ of the portion derived from dicarboxylic acid (C) and dicarboxylic acid (D) in the polyester is an even number The polycarbonate resin composition as described in any one.

  <5> The terminal of the polyester is sealed with a monofunctional low molecular compound, and the terminal sealing rate of the polyester with the low molecular compound of the monofunctional group is 50% or more, <1> to <4> The polycarbonate resin composition according to any one of the above.

  <6> A molded product obtained by molding the polycarbonate resin composition according to any one of <1> to <5>.

  The polycarbonate resin composition of the present invention has an excellent moldability without impairing various properties inherent to the polycarbonate resin (for example, bending strength), and the molded product has an excellent low temperature impact resistance. Play.

  An embodiment of the present invention will be described below, but the present invention is not limited to this. The present invention is not limited to each configuration described below, and various modifications can be made within the scope shown in the claims, and technical means disclosed in different embodiments and examples respectively. Embodiments and examples obtained by appropriately combining them are also included in the technical scope of the present invention. Moreover, all the academic literatures and patent literatures described in this specification are used as references in this specification. Unless otherwise specified in this specification, “A to B” indicating a numerical range means “A or more and B or less”.

[Embodiment: Polycarbonate resin composition]
A polycarbonate resin composition according to an embodiment of the present invention has the following general formula (1):

(In the formula, X _{1 to} X ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)
Biphenol (A) represented by 0 to 55 mol%,
The following general formula (2)

(Wherein X _{5 to} X ₈ may be the same or different, and each represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Y represents a methylene group, an isopropylidene group, cyclic alkylidene group, an aryl-substituted alkylidene group, arylene alkylidene group, -S -, - O-, carbonyl or -SO ₂ - shows a).
5 to 60 mol% of bisphenol (B) represented by
The following general formula (3)
HOOC-R ₁ -COOH (3)
(In the formula, R ₁ represents a divalent linear substituent which has 2 to 18 main chain atoms and may contain branches.)
25 to 60 mol% of a dicarboxylic acid (C) represented by:
The following general formula (4)
_{HOOC-R 2 -COOH ··· (4} )
(In the formula, R ₂ represents a divalent linear substituent having a number of main chain atoms larger than that of R ₁ , which may be branched with 4 to 20 main chain atoms.)
A monomer mixture containing 0 to 25 mol% of a dicarboxylic acid (D) represented by the formula (provided that the above mol% is the total of the monomers (A), (B), (C) and (D) being 100 mol%) A polyester having a number average molecular weight of 15,000 to 40,000, and a polycarbonate resin, a polycondensate of monomer (A) + (B) is 40 to 60 mol%) It is contained in a weight ratio of 20:80 to 50:50.

[polyester]
The polyester in the present invention includes bisphenol (B) represented by the following general formula (2), carboxylic acid (C) represented by the following general formula (3), and optionally the following general formula (1). Is a polycondensate obtained by polycondensing a diphenol (A) represented by the following general formula (4) with a specific ratio.

  More specifically, the polyester in the present invention has the following general formula (1):

(In the formula, X _{1 to} X ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)
A portion derived from biphenol (A) represented by 0 to 55 mol%,
The following general formula (2)

(Wherein, X _{5 to} X ₈ may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Y represents a methylene group or an isopropylidene group. , cyclic alkylidene group, an aryl-substituted alkylidene group, arylene alkylidene group, -S -, - O-, carbonyl or -SO ₂ - shows a).
A portion derived from bisphenol (B) represented by 5 to 60 mol%,
The following general formula (3)
HOOC-R ₁ -COOH (3)
(In the formula, R ₁ represents a divalent linear substituent which has 2 to 18 main chain atoms and may contain branches.)
A portion derived from the dicarboxylic acid (C) represented by the formula:
The following general formula (4)
_{HOOC-R 2 -COOH ··· (4} )
(In the formula, R ₂ represents a divalent linear substituent having a number of main chain atoms larger than that of R ₁ , which may be branched with 4 to 20 main chain atoms.)
A monomer mixture containing 0 to 25 mol% of a moiety derived from the dicarboxylic acid (D) represented by the formula (wherein the number of moles is the sum of the monomers (A), (B), (C) and (D)) It is a numerical value when it is 100 mol%, and the monomer (A) + (B) is 40 to 60 mol%), and the number average molecular weight is 15,000 to 40,000.

  In the following description, in the polyester of the present invention, a portion derived from the biphenol (A) represented by the general formula (1) is referred to as a biphenol component (A), and the bisphenol represented by the general formula (2). The part derived from (B) is referred to as bisphenol component (B), the part derived from dicarboxylic acid (C) represented by general formula (3) is referred to as dicarboxylic acid component (C), and general formula (4) The part derived from dicarboxylic acid (D) represented by is called dicarboxylic acid component (D).

The polyester in the present invention comprises 5 to 60 mol% of bisphenol (B) represented by the general formula (2) and 0 to 55 mol% of the biphenol component (A) represented by any general formula (1). Monomer containing diol and dicarboxylic acid (C) 25 to 60 mol% represented by general formula (3) and dicarboxylic acid (D) 0 to 25 mol% represented by any general formula (4) It can be prepared by polycondensation of the mixture (however, these mole numbers are based on the sum of biphenol (A), bisphenol (B), dicarboxylic acid (C) and dicarboxylic acid (D) being 100 mol%) (It is a numerical value, and the total content of biphenol (A) and bisphenol (B) is 40 to 60 mol%.)
Since the said polyester is not a low molecular compound, when shape | molding the polycarbonate resin composition containing the said polyester, it can suppress that a bleed out generate | occur | produces.

  In addition, since the polyester having the molecular structure is highly compatible with the polycarbonate resin, it can efficiently improve the fluidity of the polycarbonate resin composition of the present invention obtained by adding the polyester to the polycarbonate resin. In addition, fluidity can be imparted without impairing various properties inherent to the polycarbonate resin (for example, bending strength).

  The content of the biphenol component (A) contained in the polyester is 100 mol% of the total content of the biphenol component (A), the bisphenol component (B), the dicarboxylic acid component (D) and the dicarboxylic acid component (D). In this case, it is 0 to 55 mol%, preferably 10 to 40 mol%, more preferably 20 to 30%. The content of the bisphenol component (B) is 5 when the total content of the biphenol component (A), the bisphenol component (B), the dicarboxylic acid component (D) and the dicarboxylic acid component (D) is 100 mol%. It is -60 mol%, Preferably it is 10-50 mol%, More preferably, it is 20-30 mol%. When the total content of the dicarboxylic acid component (C) is 100 mol% when the total content of the biphenol component (A), the bisphenol component (B), the dicarboxylic acid component (D) and the dicarboxylic acid component (D) is 100 mol%, It is 40-60 mol%, Preferably it is 45-55%. The content of the dicarboxylic acid component (D) is 100 mol% when the total content of the biphenol component (A), the bisphenol component (B), the dicarboxylic acid component (D), and the dicarboxylic acid component (D) is 100 mol%. It is 0-20 mol%, Preferably it is 0-10 mol%. The content is the content of each monomer of biphenol (A), bisphenol (B), dicarboxylic acid (C) and dicarboxylic acid (D) in the monomer mixture used for polycondensation of the polyester (however, , The total content of the biphenol component (A), the bisphenol component (B), the dicarboxylic acid component (D) and the dicarboxylic acid component (D) is 100 mol%. Each of the above components may be one kind or two or more kinds. The content rate of each said component is the sum total of the 2 or more types of component, when each component is 2 or more types.

  The diol component contained in the polyester comprises a bisphenol component (B) and an optional biphenol component (A). When the diol component is composed of a biphenol component (A) and a bisphenol component (B), the molar ratio ((A) / (B)) of the biphenol component (A) to the bisphenol component (B) is preferably 1/9 to 9/1, more preferably 1/7 to 7/1, still more preferably 1/5 to 5/1, and most preferably 1/3 to 3/1. When the biphenol component (A) is contained so much that the biphenol component (A) / bisphenol component (B) is 1/9 or more, the polyester itself becomes completely amorphous and the glass transition temperature is lowered. Is preferred in that it can inhibit the occurrence of fusion between the polyester pellets during storage. When the bisphenol component (B) is contained in a large amount so that the biphenol component (A) / bisphenol component (B) is 9/1 or less, the compatibility with the polycarbonate resin is insufficient, and the resistance of the polycarbonate resin is low. It is preferable in the aspect which can prevent that impact property is impaired.

  As the dicarboxylic acid component, only the dicarboxylic acid component (C) may be used, or even if the dicarboxylic acid component (C) and the dicarboxylic acid component (D) are copolymerized as the dicarboxylic acid component, fluidity and low-temperature impact resistance. Improve the improvement. In particular, when the biphenol component (A) is used in a large amount with respect to the bisphenol component (B), the polyester tends to become brittle, and processing such as pelletization becomes difficult. In that case, processing such as pelletization of the polyester is facilitated by copolymerizing the dicarboxylic acid component (D).

  The molar ratio ({(A) + (B)}: {(C) + (D)}) of the biphenol component (A), the bisphenol component (B), the dicarboxylic acid component (C) and the dicarboxylic acid component (D) is 45: 55-55: 45. The molar ratio is preferably 48:52 to 52:48, and more preferably 49:51 to 51:49, in order to efficiently improve the molecular weight of the resulting polyester. However, in the polyester in the present invention, both the biphenol component (A) and the dicarboxylic acid component (D) may be either 0 mol.

X _{1 to} X ₄ in the general formula (1) may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. In order to improve the crystallinity of the polyester itself and to improve handling properties such as preventing fusion during storage of pellets, it is more preferable that all of X _{1 to} X ₄ are hydrogen atoms.

X _{5 to} X ₈ in the general formula (2) may be the same or different and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. In order to enhance the compatibility with the aromatic polycarbonate resin, it is more preferable that X _{5 to} X ₈ are all hydrogen atoms. Y represents a methylene group, an isopropylidene group, a cyclic alkylidene group, an aryl-substituted alkylidene group, an arylene alkylidene group, —S—, —O—, a carbonyl group, or —SO ₂ —.

  As the bisphenol component represented by the general formula (2), 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is particularly preferable in that the compatibility with the aromatic polycarbonate resin increases. is there. Examples of dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis ( 4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propa Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, etc .; 1,1-bis ( Bis (hydroxyaryl) cycloalkanes such as 4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane Dihydroxy aryl ethers such as 4,4′-dihydroxyphenyl ether and 4,4′-dihydroxy-3,3′-dimethylphenyl ether; 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3 , 3'-dimethyldiphenyl sulfide, etc. Dihydroxy diaryl sulfides; dihydroxy diaryl sulfoxides such as 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone, 4,4′- Examples include dihydroxydiaryl sulfones such as dihydroxy-3,3′-dimethyldiphenyl sulfone; dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl, and the like. These bisphenol components may be used singly or as a mixture of two or more of them without losing the effect of the present invention.

  The terminal structure of the polyester in the present invention is not particularly limited. In particular, in order to suppress transesterification with a polycarbonate resin, suppress yellowing of the polycarbonate resin composition, suppress hydrolysis, and ensure long-term stability. It is preferably sealed with a functional low molecular compound.

  Further, the sealing ratio with respect to all the ends of the molecular chain is preferably 50% or more, more preferably 70% or more, further preferably 80% or more, and most preferably 90% or more.

The terminal blocking rate of the polyester can be determined by the following formula (5) by measuring the number of terminal functional groups that are sealed and the number of terminal functional groups that are not sealed. As a specific calculation method of the terminal blocking rate, ¹ H-NMR is used to determine the number of each terminal group from the integral value of the characteristic signal corresponding to each terminal group. The method of calculating the terminal blocking rate using (5) is preferable in terms of accuracy and simplicity.

Terminal sealing rate (%) = {[number of sealed terminal functional groups] / ([number of sealed terminal functional groups] + [number of unsealed terminal functional groups])} × 100 (5)
Examples of the monofunctional low molecular compound used for sealing include monovalent phenol, monoamine having 1 to 20 carbon atoms, aliphatic monocarboxylic acid, carbodiimide, epoxy, or oxazoline. Specific examples of the monovalent phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, p-nonylphenol, pt-amylphenol, 4-hydroxybiphenyl, And any mixture thereof. Specific examples of aliphatic monocarboxylic acids include fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Group monocarboxylic acids, and arbitrary mixtures thereof. Among these, myristic acid, palmitic acid, and stearic acid are preferable from the viewpoint of high boiling point and easy polymerization. Specific examples of monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, and any of these A mixture etc. are mentioned. Examples of carbodiimides include dicyclohexyl carbodiimide, diisopropyl carbodiimide, dimethyl carbodiimide, diisobutyl carbodiimide, dioctyl carbodiimide, t-butyl isopropyl carbodiimide, diphenyl carbodiimide, di-t-butyl carbodiimide, di-β-naphthyl carbodiimide, bis-2,6-diisopropyl Phenylcarbodiimide, poly (2,4,6-triisopropylphenylene-1,3-diisocyanate), 1,5- (diisopropylbenzene) polycarbodiimide, 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide and their Arbitrary mixtures etc. are mentioned. Examples of epoxies include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, triethylolpropane polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, sorbitol polyglycidyl ether, bisphenol A- Diglycidyl ether, hydrogenated bisphenol A-glycidyl ether, 4,4'-diphenylmethane diglycidyl ether, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, methacrylic acid glycidyl ester, methacrylic acid glycidyl ester polymer Examples thereof include a sidyl ester polymer-containing compound and an arbitrary mixture thereof. Examples of oxazolines include styrene-2-isopropenyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 1,3-phenylenebis (2-oxazoline), and mixtures thereof.

In the dicarboxylic acid component (C), the following general formula (3)
HOOC-R ₁ -COOH (3)
R ₁ therein represents a divalent linear substituent which may be branched with 2 to 18 main chain atoms. Here, the number of main chain atoms is the number of atoms of the main chain skeleton. For example, when —R ₁ — is — (CH ₂ ) ₈ —, the number of main chain atoms is the number of carbon atoms, and “8 " Since the melt viscosity of the polyester itself is lowered, R ₁ is preferably a linear substituent not containing a branch, and more preferably a linear aliphatic hydrocarbon chain not containing a branch. R ₁ may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain. When the unsaturated bond is included, the above polyester may not be sufficiently flexible and may increase the melt viscosity of the polyester itself. R ₁ is preferably a straight-chain saturated aliphatic hydrocarbon chain having 2 to 18 carbon atoms and 4 carbon atoms in that both ease of polymerization of the polyester and improvement in glass transition point can be achieved. More preferably, it is a straight chain saturated aliphatic hydrocarbon chain having ˜16, more preferably a straight chain saturated aliphatic hydrocarbon chain having 8 to 14 carbon atoms, and a straight chain saturated fat having 8 carbon atoms. Most preferred are group hydrocarbon chains. Improvement of the glass transition point of the polyester leads to improvement of heat resistance of the resin composition. The number of main chain atoms of R ₁ is preferably an even number in that the melt viscosity of the polyester itself is lowered. From the above points, R ₁ is particularly preferably _one selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ —. A dicarboxylic acid component (C) may be used independently and may mix 2 or more types in the range which does not lose the effect of this invention.

In the dicarboxylic acid component (D), the following general formula (4)
_{HOOC-R 2 -COOH ··· (4} )
R ₂ therein may be branched with a main chain atom number of 4 to 20, and represents a divalent linear substituent having a larger number of main chain atoms than R ₁ . R ₂ is preferably a linear substituent containing no branch, more preferably a straight aliphatic hydrocarbon chain containing no branch, because the melt viscosity of the polyester itself is low. R ₂ may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain. When the unsaturated bond is included, the above polyester may not be sufficiently flexible and may increase the melt viscosity of the polyester itself. R ₂ is preferably a linear saturated aliphatic hydrocarbon chain having 4 to 20 carbon atoms, more preferably a linear saturated aliphatic hydrocarbon chain having 8 to 18 carbon atoms, and a carbon number of 10 More preferably, it is a -18 linear saturated aliphatic hydrocarbon chain. The number of main chain atoms of R ₁ is preferably an even number in that the melt viscosity of the polyester itself is lowered. The greater the difference in the number of main chain atoms between R ₁ and R _2, the lower the crystallinity of the polyester and the greater the processability of the polyester into a pellet. In particular, from the viewpoint of obtaining a polyester having low crystallinity and excellent workability, it is preferable that the number of main chain atoms m and n corresponding to R ₁ and R ₂ satisfy the following general formula (6).
nm−4 (6)
From the viewpoints of chemical stability and availability, R ₂ is preferably one selected from — (CH ₂ ) ₁₀ —, — (CH ₂ ) ₁₂ —, and — (CH ₂ ) ₁₈ —.

  The polyester in the present invention may be copolymerized with other monomers to such an extent that the effect is not lost. Other monomers include, for example, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatic aminocarboxylic acids or caprolactams, caprolactones, aliphatic dicarboxylic acids, fatty acids Aromatic diols, aliphatic diamines, alicyclic dicarboxylic acids, and alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols.

  The content of the other monomer constituting the polyester is less than 50 mol%, preferably less than 30 mol%, more preferably less than 10 mol%, most preferably relative to the total number of moles of the polyester. It is less than 5 mol%. When the content of the other monomer is less than 50 mol% with respect to the total number of moles of the polyester, the polyester has good compatibility with the polycarbonate resin and is compatible with the polyester polycarbonate resin. In terms of surface.

  Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy -7-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, and them And alkyl, alkoxy or halogen-substituted products.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl, 4,4 ″ -dicarboxyterphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenoxy) butane, bis (4-carboxyphenyl) ethane, bis (3-carboxy Phenyl) ether, bis (3-carboxyphenyl) ethane, and alkyl, alkoxy or halogen-substituted products thereof.

  Specific examples of the aromatic diol include pyrocatechol, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′- Examples include dihydroxybiphenyl, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenol ether, bis (4-hydroxyphenyl) ethane, 2,2′-dihydroxybinaphthyl, and alkyl, alkoxy or halogen substituents thereof. It is done.

  Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4′-hydroxybiphenyl, 4-amino-4′-hydroxybiphenyl ether, 4-amino-4′-hydroxybiphenylmethane, 4-amino-4′-hydroxybiphenyl sulfide, 2,2′-diaminobinaphthyl, and their Examples thereof include alkyl, alkoxy, and halogen-substituted products.

  Specific examples of the aromatic diamine and aromatic aminocarboxylic acid include 1,4-phenylenediamine, 1,3-phenylenediamine, N-methyl-1,4-phenylenediamine, N, N′-dimethyl-1,4. -Phenylenediamine, 4,4'-diaminophenyl sulfide (thiodianiline), 4,4'-diaminobiphenyl sulfone, 2,5-diaminotoluene, 4,4'-ethylenedianiline, 4,4'-diaminobiphenoxyethane 4,4′-diaminobiphenylmethane (methylenedianiline), 4,4′-diaminobiphenyl ether (oxydianiline), 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, 7-amino-2-naphthoic acid, and alkyl, alkoxy or halogen substituted products thereof It is.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid Etc.

  Specific examples of the aliphatic diamine include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine and the like can be mentioned.

  Specific examples of the alicyclic dicarboxylic acid, aliphatic diol and alicyclic diol include hexahydroterephthalic acid, trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, and trans-1,4-cyclohexane. Dimethanol, cis-1,4-cyclohexanedimethanol, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexanedimethanol, ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neo Linear chain such as pentyl glycol Or branched chain aliphatic diols, and the like their reactive derivatives.

  Specific examples of the aromatic mercaptocarboxylic acid, aromatic dithiol and aromatic mercaptophenol include 4-mercaptobenzoic acid, 2-mercapto-6-naphthoic acid, 2-mercapto-7-naphthoic acid, benzene-1,4- Dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, 2,7-naphthalene-dithiol, 4-mercaptophenol, 3-mercaptophenol, 6-mercapto-2-hydroxynaphthalene, 7-mercapto-2 -Hydroxynaphthalene, and reactive derivatives thereof.

  The polyester in the present invention may contain a phosphite antioxidant in advance in that a resin composition having a good color tone can be obtained. The reason for this is to prevent the discoloration of the polyester itself, and to deactivate the polymerization catalyst used for the polymerization of the polyester, which may occur when the polyester and the polycarbonate resin are mixed. This is considered to be because discoloration due to transesterification with the resin or hydrolysis reaction can be prevented. As a result, a decrease in molecular weight of the polyester or polycarbonate resin can be more effectively suppressed, so that the polycarbonate resin composition containing the polyester in the present invention has fluidity without impairing the original properties of the polycarbonate resin. Can be improved. The content of the phosphite antioxidant in the polyester is preferably 0.005 to 5 mass%, more preferably 0.01 to 2 mass%, based on the weight of the polyester, It is more preferably ˜1% by mass, and most preferably 0.02˜0.05% by mass. It is preferable that the content of the phosphite antioxidant is 0.005% by mass or more in terms of inhibiting the occurrence of coloring when the polyester is blended with the polycarbonate resin by the phosphite antioxidant. Moreover, it is preferable in terms of the impact strength of the resin composition obtained by adding the said polyester to polycarbonate resin that content of a phosphite type antioxidant is 5 mass% or less.

  Various compounds are known as phosphite antioxidants, such as “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (pages 235 to 242) published by CMC Publishing, etc. Although not limited to various compounds described in (1). Examples of phosphite antioxidants include tris (2,4-di-t-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester Phosphoric acid, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol-di-phosphite and the like. In the product name, ADK STAB PEP-36, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8F, ADK STAB PEP-8W, ADK STAB PEP-11C, ADK STAB PEP-24G, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB P, ADK STAB QL, ADK STAB 522A, ADK STAB 329K, ADK STAB 1178, ADK STAB 1500, ADK STAB 135, ADK STAB 3010, ADK STAB TPP (all of which are manufactured by ADEKA CORPORATION), Irgafos 38, Irgafos 126, IrgaFos As mentioned above, all can illustrate BASF JAPAN Ltd. etc.). Among these, Adeka Stub PEP-36 and Adeka Stub HP-10 are particularly effective in suppressing the transesterification reaction and hydrolysis reaction, and the antioxidant itself has a high melting point and hardly volatilizes from the resin. Adeka Stub 2112, Adeka Stub PEP-24G, Irgafos 126 and the like are more preferable.

  The polyester in the present invention may contain a hindered phenol antioxidant in advance in that a polycarbonate resin composition having a good color tone is obtained. The content of the hindered phenolic antioxidant in the polyester is preferably 0.005 to 5% by mass, more preferably 0.01 to 2% by mass, based on the weight of the polyester. The content is more preferably 01 to 1% by mass, and most preferably 0.02 to 0.05% by mass. It is preferable that the content of the hindered phenolic antioxidant is 0.005% by mass or more in terms of inhibiting the occurrence of coloring when the polyester is blended with the polycarbonate resin by the hindered phenolic antioxidant. . It is preferable that the content of the hindered phenol antioxidant is 5% by mass or less in terms of impact strength of a resin composition obtained by adding the above polyester to a polycarbonate resin.

  Examples of the hindered phenol-based antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di, or tri) (Α-methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl Hydroquinone, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5- Di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5- Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2- Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzene Nzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5 Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [ 3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivatives, 2- (3,5 -Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl) 4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

  In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above) Ouchi Shinsei Chemical Co., Ltd.), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-616, ADK STAB AO-635, ADK STAB AO-658, ADK STAB AO-80, ADK STAB AO-15, ADK STAB AO-18, ADK STAB 328, ADK STAB AO330, ADK STAB AO-37 (all of which are manufactured by ADK), IRGANOX-245, IRGANOX-259, IRGANOX-565 IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of which are manufactured by BASF JAPAN Ltd.), Sumilizer GA80 (Above, manufactured by Sumitomo Chemical Co., Ltd.). Among these, ADK STAB AO-60, IRGANOX-1010, and the like, since the antioxidant itself is particularly difficult to discolor, and the coloration of the resin can be efficiently suppressed by the combined use with the phosphite antioxidant. Is more preferable.

  Furthermore, a monoacrylate phenol-based stabilizer having both an acrylate group and a phenol group can be used as the phenol-based antioxidant. Examples of monoacrylate phenol-based stabilizers include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilyzer GS).

  As a combination of a phosphite antioxidant and a hindered phenol antioxidant, a combination of ADK STAB PEP-36, ADK STAB 2112 and Irgafos 126, and ADK STAB AO-60 and IRGANOX-1010 particularly suppresses coloring of the resin. It is preferable in that it can be performed.

  The number average molecular weight of the polyester in the present invention means that the concentration of the polyester in the present invention is 0.25% by mass in a mixed solvent having a volume ratio of p-chlorophenol and toluene of 3: 8 using polystyrene as a standard substance. It is the value measured at 80 degreeC by GPC using the solution prepared by melt | dissolving in this way. The number average molecular weight of the polyester in the present invention is preferably 15000 to 40000, more preferably 17000 to 35000, and further preferably 20000 to 30000. When the number average molecular weight of the polyester is 15000 or more, it is preferable in terms of improving the low temperature impact strength of the polycarbonate resin composition. In addition, when the number average molecular weight of the polyester is 40000 or less, it is possible to prevent the melt viscosity of the polyester itself from becoming too high, and to effectively improve the fluidity during the molding process of the polycarbonate resin composition. Is preferable.

  The polyester in the present invention may be produced by any known method. As an example of the production method, the hydroxyl group of the monomer is individually or collectively made into a lower fatty acid ester using a lower fatty acid such as acetic anhydride, and then removed from the carboxylic acid in another reaction vessel or the same reaction vessel. The method of making a lower fatty acid polycondensation reaction is mentioned. The polycondensation reaction is carried out in the presence of an inert gas such as nitrogen gas in the presence of an inert gas, usually at a temperature of 220 to 330 ° C., preferably 240 to 310 ° C. in the absence of a solvent. It is performed for 0.5 to 5 hours. When the reaction temperature is lower than 220 ° C., the reaction proceeds slowly, and when it is higher than 330 ° C., side reactions such as decomposition tend to occur. When making it react under reduced pressure, it is preferable to raise a pressure reduction degree in steps. When the pressure is rapidly reduced to a high degree of vacuum, the dicarboxylic acid monomer and the low molecular weight compound used for end-capping may volatilize, and a resin having a desired composition or molecular weight may not be obtained. The ultimate vacuum is preferably 40 Torr or less, more preferably 30 Torr or less, further preferably 20 Torr or less, and particularly preferably 10 Torr or less. When the ultimate vacuum is higher than 40 Torr, deoxidation does not proceed sufficiently, the polymerization time becomes long, and the resin may be colored. The polycondensation reaction may employ a multi-stage reaction temperature. If necessary, the reaction product may be withdrawn in a molten state and recovered as soon as the temperature rises or when the maximum temperature is reached. The obtained polyester resin may be used as it is, or solid phase polymerization may be further performed for the purpose of removing unreacted raw materials or improving physical properties. In the case of performing solid-phase polymerization, the obtained polyester is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and an inert gas atmosphere such as nitrogen gas at 100 to 350 ° C. in a solid state. It is preferable to process for 1 to 30 hours under or under reduced pressure. It is preferable that the particle size of the polyester particles is 3 mm or less from the viewpoint of sufficient treatment and prevention of problems in physical properties. It is preferable to select the treatment temperature and the rate of temperature increase during solid phase polymerization so that the polyester particles do not cause fusion.

  Examples of the acid anhydride of the lower fatty acid used in the production of the polyester in the present invention include acid anhydrides of lower fatty acids having 2 to 5 carbon atoms, such as acetic anhydride, propionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride. Monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, and the like. Of these, acetic anhydride, propionic anhydride, and trichloroacetic anhydride are particularly preferably used. The amount of the anhydride of the lower fatty acid used is 1.01 to 1.5 times equivalent, preferably 1.02 to 1.2 times equivalent to the total of the monomers used and the functional groups such as hydroxyl groups of the terminal blocking agent. It is. When the amount of the lower fatty acid anhydride used is less than 1.01 equivalents, the lower fatty acid anhydride is volatilized, so that the functional group such as a hydroxyl group does not completely react with the lower fatty acid anhydride. In some cases, a low molecular weight resin may be obtained.

  In the production of the polyester in the present invention, a polymerization catalyst may be used. As the polymerization catalyst, conventionally known catalysts can be used as polyester polymerization catalysts, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. Examples thereof include metal salt catalysts, organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole. Among these, sodium acetate, potassium acetate, and magnesium acetate are more preferable because discoloration of the polyester itself can be prevented and discoloration of the resin composition can be prevented.

The smaller the amount of the polymerization catalyst added, the more the molecular weight reduction and yellowing of the polycarbonate resin can be suppressed. Therefore, the addition amount of the polymerization catalyst is usually 0 to 100 × 10 ⁻² mass%, preferably 0 to 50 × 10 ⁻² mass%, based on the total weight of the polyester.

  The polycarbonate resin composition in the present invention contains the polyester and the polycarbonate resin in a weight ratio of 20:80 to 50:50 in the resin component. In order to further improve the fluidity of the polycarbonate resin composition while maintaining high heat resistance, the weight ratio of polyester to polycarbonate resin is preferably 25:75 to 45:55, and 30:70 to 40: More preferably, the weight ratio is 60. Suppressing the polyester content in the polycarbonate resin composition to a weight ratio of 20:80 or more between the polyester and the polycarbonate resin is preferable in terms of preventing a decrease in low-temperature impact strength at −30 ° C. Moreover, it is preferable in terms of the heat resistance of the obtained polycarbonate resin composition to suppress the polyester content in the polycarbonate resin composition to a weight ratio of 50:50 or less between the polyester and the polycarbonate resin. The improvement of the low temperature impact strength by blending a predetermined amount of the high molecular weight polyester having a specific structure is considered to be caused by lowering the glass transition point and elastic modulus of the polycarbonate and imparting flexibility at low temperatures.

[Polycarbonate resin]
The polycarbonate resin in the present invention is not particularly limited, and polycarbonate resins having various structural units can be used. For example, a polycarbonate resin produced by a method of interfacial polycondensation of divalent phenol and carbonyl halide, a method of melt polymerization (transesterification) of divalent phenol and carbonic acid diester, or the like can be used.

  Examples of the divalent phenol that is a raw material of the polycarbonate resin include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2- Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ) Ketone, hydroquinone, resorcin, catechol, etc. It is. Among these divalent phenols, bis (hydroxyphenyl) alkanes are preferable, and divalent phenols mainly composed of 2,2-bis (4-hydroxyphenyl) propane are particularly preferable. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like. Specifically, phosgene; diaryl carbonate such as dihaloformate of divalent phenol, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate; dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, dia Examples thereof include aliphatic carbonate compounds such as mil carbonate and dioctyl carbonate.

  The polycarbonate resin may be a resin having a branched structure in addition to a resin having a linear chain molecular structure. As a branching agent for introducing such a branched structure, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3, 5-triisopropylbenzene, phloroglucin, trimellitic acid, isatin bis (o-cresol), etc. Further, as molecular weight regulators, phenol, pt-butylphenol, pt-octylphenol, p-cumylphenol, etc. Can be used.

  Furthermore, the polycarbonate resin used in the present invention includes a homopolymer produced using only the above divalent phenol, a copolymer having a polycarbonate structural unit and a polyorganosiloxane structural unit, or these homopolymers. A resin composition comprising a copolymer may be used. Moreover, the polyester-polycarbonate resin obtained by performing polymerization reaction of bivalent phenol etc. in presence of ester precursors, such as bifunctional carboxylic acid, such as terephthalic acid, and its ester formation derivative | guide_body may be sufficient.

  From the viewpoint of obtaining a resin composition having high impact strength, the molecular weight of the polycarbonate resin is preferably 17,000 or more in terms of a viscosity average molecular weight converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. More preferably, it is 2000 or more, and more preferably 22000 or more. The upper limit of the molecular weight is not particularly limited, but is preferably 40000 or less, more preferably 35000 or less, and even more preferably 30000 or less in order to increase the fluidity during molding.

  The polycarbonate resin composition in the present invention may further contain a phosphite antioxidant regardless of whether or not a phosphite antioxidant is previously contained in the polyester. The content of the phosphite antioxidant is preferably 0.005 to 5 mass%, more preferably 0.01 to 2 mass%, based on the total mass of the polycarbonate resin and the polyester, More preferably, it is 0.01-1 mass%, and it is most preferable that it is 0.02-0.05 mass%.

  Regardless of whether or not the hindered phenolic antioxidant is previously contained in the polyester, a hindered phenolic antioxidant may be additionally contained. The content of the hindered phenolic antioxidant is preferably 0.005 to 5% by mass and more preferably 0.01 to 2% by mass with respect to the total mass of the polycarbonate resin and the polyester. Preferably, the content is 0.01 to 1% by mass, and most preferably 0.02 to 0.05% by mass.

  In the polycarbonate resin composition of the present invention, any component other than the aromatic polycarbonate resin, polyester, and antioxidant (phosphite-based antioxidant, hindered phenol-based antioxidant) may be used depending on the purpose. Ingredients such as reinforcing agents, light diffusing agents, thickeners, mold release agents, coupling agents, flame retardants, flame retardants, pigments, colorants, other auxiliaries and the like, or fillers are included in the present invention. As long as the effect of is not lost, it can be added. The amount of these additives used is preferably in the range of 0 to 100 parts by weight in total with respect to 100 parts by weight of the resin composition obtained by adding polyester to the polycarbonate resin.

  The amount of the flame retardant used is more preferably 7 to 80 parts by weight, and more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the polycarbonate resin composition obtained by adding polyester to the polycarbonate resin. The amount is preferably 12 to 40 parts by weight. Various compounds are known as flame retardants, for example, various compounds described in “Technology and Application of Polymer Flame Retardation” (pages 149 to 221) published by CMC Publishing Co., Ltd. It is not limited. Among these flame retardants, phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants can be preferably used.

  Specific examples of the phosphorus-based flame retardant include phosphoric acid ester, halogen-containing phosphoric acid ester, condensed phosphoric acid ester, polyphosphate, and red phosphorus. These phosphorus flame retardants may be used alone or in combination of two or more.

  Specific examples of the halogen flame retardant include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, deca Examples thereof include bromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, and brominated crosslinked aromatic polymers. Of these, brominated polystyrene and brominated polyphenylene ether are particularly preferred. These halogen flame retardants may be used alone or in combination of two or more. The halogen element content of these halogen flame retardants is preferably 15 to 87%.

  An inorganic filler may be further added to the polycarbonate resin composition of the present invention in order to improve mechanical strength, dimensional stability, etc., or for the purpose of increasing the amount.

  Examples of the inorganic filler include zinc sulfate, potassium hydrogen sulfate, aluminum sulfate, antimony sulfate, sulfate ester, potassium sulfate, cobalt sulfate, sodium hydrogen sulfate, iron sulfate, copper sulfate, sodium sulfate, nickel sulfate, barium sulfate, Metal sulfate compounds such as magnesium sulfate and ammonium sulfate; Titanium compounds such as titanium oxide; Carbonate compounds such as potassium carbonate; Metal hydroxide compounds such as aluminum hydroxide and magnesium hydroxide; Silica compounds such as synthetic silica and natural silica; Calcium aluminate, dihydrate gypsum, zinc borate, barium metaborate, borax; nitrate compounds such as sodium nitrate, molybdenum compounds, zirconium compounds, antimony compounds and their modified products; composite fine particles of silicon dioxide and aluminum oxide Etc. It is.

  Other inorganic fillers include, for example, potassium titanate whiskers, mineral fibers (rock wool, etc.), glass fibers, carbon fibers, metal fibers (stainless fibers, etc.), aluminum borate whiskers, silicon nitride whiskers, boron fibers. , Tetrapotted zinc oxide whisker, talc, clay, kaolin clay, natural mica, synthetic mica, pearl mica, aluminum foil, alumina, glass flakes, glass beads, glass balloon, carbon black, graphite, calcium carbonate, calcium sulfate, silica Examples include calcium acid, titanium oxide, zinc oxide, silica, asbestos, and quartz powder.

  These inorganic fillers may be untreated or may be subjected to chemical or physical surface treatment in advance. Examples of the surface treatment agent used for the surface treatment include compounds such as silane coupling agent, higher fatty acid, fatty acid metal salt, unsaturated organic acid, organic titanate, resin acid, and polyethylene glycol. It is done.

  The manufacturing method of the polycarbonate resin composition in this invention is not specifically limited. The polycarbonate resin composition is prepared by using, for example, a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two roll, a kneader, a Brabender, etc. It is produced by a known method of blending and melt-kneading. The melt kneading temperature is preferably as low as possible for the purpose of suppressing the transesterification reaction between the polyester and the polycarbonate resin and the yellowing of the resin composition due to the thermal deterioration of the polycarbonate resin.

  By subjecting the polycarbonate resin composition of the present invention to various extrusion moldings, the molded product of the present invention can be molded into, for example, various irregular extrusion molded products, sheets, films, etc. by extrusion molding. The various extrusion molding methods include cold runner and hot runner molding methods, as well as injection compression molding, injection press molding, gas assist injection molding, foam molding (including the case of supercritical fluid injection), inserts. Examples thereof include injection molding methods such as molding, in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, an inflation method, a calendar method, a casting method, or the like can be used for forming a sheet or a film. Furthermore, it can be formed as a heat-shrinkable tube by applying a specific stretching operation. Moreover, it is also possible to make a hollow molded article by molding the polycarbonate resin composition of the present invention by rotational molding, blow molding or the like.

  The molded product of the present invention can be used in a wide range of applications such as various cases, hard coat products, glazing materials, light diffusion plates, optical disk substrates, light guide plates, medical materials, and miscellaneous goods. Specifically, the molded article of the present invention includes, for example, exterior materials for OA equipment and home appliances, various containers, miscellaneous goods, such as personal computers, notebook computers, game machines, display devices (CRT, liquid crystal, plasma, projector, and Organic EL, etc.), mice, and exterior materials such as printers, copiers, scanners and fax machines (including these multifunction devices), keyboard keys, switch molded products, personal digital assistants (so-called PDAs), mobile phones, and mobile books (Dictionaries, etc.), mobile TV, drive for recording media (CD, MD, DVD, Blu-ray disc, hard disk, etc.), reader for recording media (IC card, smart media, memory stick, etc.), optical camera, digital camera, parabolic Antenna, electric tool, VTR, iron, hair dryer, rice cooker, electric Range, audio equipment, lighting equipment, refrigerators, air conditioners, air cleaners, can be used as a negative ion generator, and type resin products formed like writer. Also, trays, cups, dishes, shampoo bottles, OA housings, cosmetic bottles, beverage bottles, oil containers, injection molded products (golf tees, cotton swab cores, candy sticks, brushes, toothbrushes, helmets, syringes, dishes, Cups, combs, razor handles, tape cassettes and cases, disposable spoons and forks, stationery such as ballpoint pens, etc.).

  In addition, the molded product of the present invention includes a binding tape (a binding band), a prepaid card, a balloon, a pantyhose, a hair cap, a sponge, a cellophane tape, an umbrella, a feather, a plastic glove, a hair cap, a rope, a tube, a foam tray, a foam It can be used for various fields such as cushioning materials, cushioning materials, packing materials, and cigarette filters.

  Furthermore, the molded article of the present invention is also used for vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, car audio visual parts, and auto mobile computer parts. be able to.

  The present invention may also include a method for improving the fluidity and low-temperature impact strength of the polycarbonate resin using the polyester having the specific structure described above. In other words, the present invention may include a method for improving the fluidity and low-temperature impact strength of the polycarbonate resin, including a step of mixing the above-described polyester and the polycarbonate resin.

  Next, the polyester and polycarbonate resin composition of the present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to such examples. The reagents listed below were used without purification from Wako Pure Chemical Industries, Ltd. unless otherwise specified.

<Evaluation method>
[Measurement method of number average molecular weight]
The sample solution was prepared by dissolving the polyester in the present invention in a mixed solvent having a volume ratio of p-chlorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene of 3: 8 so as to have a concentration of 0.25% by weight. Prepared. The standard material was polystyrene, and a similar sample solution was prepared. And it measured on condition of column temperature 80 degreeC and flow rate 1.00mL / min using high temperature GPC (The product made by Viscotek: 350HT-GPCSystem). A differential refractometer (RI) was used as a detector.

[Measurement method of fluidity]
The spiral flow (mm) of the resin composition was evaluated using an injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.). The polycarbonate resin composition had a molding temperature of 280 ° C., a mold temperature of 100 ° C., an injection pressure of 200 MPa, and the thickness of the molded product was 2 mm and the width was 10 mm.

[Measurement method of bending elastic modulus and bending strength]
In order to evaluate mechanical properties, using AUTOGRAPH AG-I (manufactured by Shimadzu Corporation), in accordance with JIS K7171 (measurement temperature 23 ° C., dimensions of bending test piece: length 80 mm × width 10 mm × thickness) 4 mm), the flexural modulus (MPa) and the flexural strength (MPa) of the resin composition were measured.

[Measurement method of deflection temperature under load]
In order to evaluate heat resistance, HOT. Using tester S-3 (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the deflection temperature under load of the polycarbonate resin composition (° C.) in accordance with JIS K 7191 (test conditions: load 1.8 MPa, temperature rising rate 120 ° C./hour). ) Was measured.

[Measurement method of impact strength]
ASTM D-256, 1/4 inch, notched, measured at 23 ° C., 0 ° C., −30 ° C.

<Materials used>
Polycarbonate resin: Toughlon A2200 (manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight 22,000)
[Production Example 1]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirring rod, 4,4′-dihydroxybiphenyl, bisphenol A, sebacic acid, and tetradecanedioic acid in a molar ratio of 45: 5: Charged at a ratio of 35:15, 1.05 equivalents of acetic anhydride and AO330 (manufactured by Adeka Co., Ltd.) as an antioxidant were added to the phenolic hydroxyl group in the monomer. The monomer was reacted at 145 ° C. under atmospheric pressure and nitrogen gas atmosphere to obtain a uniform solution, and then the temperature was raised to 255 ° C. at 2 ° C./min while distilling off the generated acetic acid. Stir. While maintaining the temperature, the pressure was reduced to 5 Torr over about 60 minutes, and then the reduced pressure state was maintained. Three hours after the start of pressure reduction, the inside of the sealed reactor was returned to normal pressure with nitrogen gas, and the polyester was taken out of the reactor. The number average molecular weight of the obtained polyester was 22,000. Let the obtained polyester be (A-1).

[Production Example 2]
Polymerization was conducted in the same manner as in Production Example 1 except that the polymerization time from the start of decompression in Production Example 1 was changed from 3 hours to 1.5 hours to obtain a polyester having a number average molecular weight of 14,000. Let the obtained polyester be (A-2).

[Production Example 3]
In a closed reactor equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirring rod, 4,4′-dihydroxybiphenyl, bisphenol A, and sebacic acid were mixed at a molar ratio of 20:30:50. In addition, 4,4′-dihydroxybiphenyl was added as a terminal blocking agent at a ratio of 0.02 mol% with respect to 100 mol% of the monomer. Further, 1.05 equivalents of acetic anhydride and AO330 (manufactured by Adeka Co., Ltd.) as an antioxidant were added to the phenolic hydroxyl group in the monomer. The monomer was reacted at 145 ° C. under atmospheric pressure and nitrogen gas atmosphere to obtain a uniform solution, and then the temperature was raised to 240 ° C. at 2 ° C./min while distilling off the acetic acid produced, and the mixture was heated at 240 ° C. for 2 hours. Stir. While maintaining the temperature, the pressure was reduced to 5 Torr over about 60 minutes, and then the reduced pressure state was maintained. Three hours after the start of depressurization, the inside of the sealed reactor was returned to normal pressure with nitrogen gas, and the fluidity improver was taken out of the reactor. The number average molecular weight of the obtained polyester was 22,000, and it was confirmed by NMR that the terminal had no carboxylic acid component and was sealed with almost 100% acetoxybiphenyl. Let the obtained polyester be (A-3).

[Examples 1-3, Comparative Examples 1-3]
Table 1 shows polyesters, polycarbonate resins, phosphite stabilizers 2112 (manufactured by Adeka Corporation, B-1) and hindered phenol stabilizers AO60 (manufactured by Adeka Corporation, B-2) obtained in the above production examples. Preliminary mixing was performed at the ratio shown in the following to obtain a resin composition. Then, each resin composition was melt-kneaded at 280 ° C. using a twin-screw extruder to produce pellets. Using the obtained pellets, test pieces were prepared at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine FN-1000 manufactured by Nissei Plastic Industry Co., Ltd., and evaluated by the above method. The results are shown in Table 1.

  As described in Table 1, the pellets produced in Examples 1 to 3 all had an impact strength exceeding 300 (J / m) even at a low temperature (−30 ° C.). From these results, it was found that the resin compositions in Examples 1 to 3 were excellent in low temperature impact strength (−30 ° C.).

  On the other hand, the pellets manufactured in Comparative Examples 1 to 3 all had a low temperature (−30 ° C.) impact strength of less than 200 (J / m). From these results, it was found that the resin compositions in Comparative Examples 1 to 3 had low low-temperature impact strength (−30 ° C.).

  As described above, as is clear from the evaluation results, the resin compositions obtained in Examples 1 to 3 have good fluidity (spiral flow) because they contain polyester having a specific structure, and the molded product has heat resistance, The balance of bending strength was excellent, and in particular, the low temperature impact strength (−30 ° C.) was excellent. On the other hand, since the resin compositions obtained in Comparative Examples 1 to 3 did not contain the polyester in the present invention, sufficient fluidity was not obtained and the low temperature impact strength (−30 ° C.) was low.

  The polycarbonate resin composition of the present invention is a polycarbonate resin that is excellent in low-temperature impact resistance without impairing the original properties (for example, bending strength) of the polycarbonate resin by containing the above-described polyester. Therefore, the poly or boronate resin composition of the present invention can realize molding of a molded product having excellent low-temperature impact resistance, such as electrical / electronic / OA equipment, optical parts, confidential machinery, automobiles, security / medical, It is suitably used in a wide range of fields such as building materials and miscellaneous goods.

Claims (6)

The following general formula (1)

(In the formula, X _{1 to} X ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)
Biphenol (A) represented by 0 to 55 mol%,
The following general formula (2)

(In the formula, X _{5 to} X ₈ may be the same or different, and each represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Y represents a methylene group, an isopropylidene group, cyclic alkylidene group, an aryl-substituted alkylidene group, arylene alkylidene group, -S -, - O-, carbonyl or -SO ₂ - shows a).
5 to 60 mol% of bisphenol (B) represented by
The following general formula (3)
HOOC-R ₁ -COOH (3)
(In the formula, R ₁ represents a divalent linear substituent which has 2 to 18 main chain atoms and may contain branches.)
25 to 60 mol% of a dicarboxylic acid (C) represented by:
The following general formula (4)
_{HOOC-R 2 -COOH ··· (4} )
(In the formula, R ₂ represents a divalent linear substituent having a number of main chain atoms larger than that of R ₁ , which may be branched with 4 to 20 main chain atoms.)
A monomer mixture containing 0 to 25 mol% of a dicarboxylic acid (D) represented by the formula (provided that the above mol% is the total of the monomers (A), (B), (C) and (D) being 100 mol%) A polyester having a number average molecular weight of 15,000 to 40,000, and a polycarbonate resin, a polycondensate of monomer (A) + (B) is 40 to 60 mol%) A polycarbonate resin composition comprising a weight ratio of 20:80 to 50:50.   The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin has a viscosity average molecular weight of 17,000 or more. The part corresponding to R ₁ and R ₂ of the part derived from dicarboxylic acid (C) and dicarboxylic acid (D) in the polyester is a straight-chain saturated aliphatic hydrocarbon chain. Polycarbonate resin composition. The number of main chain atoms of a portion corresponding to R ₁ and R ₂ of the portion derived from dicarboxylic acid (C) and the dicarboxylic acids of the polyester (D) is an even number, to any one of claims 1 to 3 The polycarbonate resin composition as described. The end of the polyester is sealed with a monofunctional low molecular compound,
The polycarbonate resin composition according to any one of claims 1 to 4, wherein a terminal blocking rate of the polyester by the monofunctional low molecular compound is 50% or more.   The molded article formed by shape | molding the polycarbonate resin composition of any one of Claims 1-5.