JP2017186463A - Polycarbonate resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in flowability during molding processing without causing deterioration of the original properties of a polycarbonate resin.SOLUTION: A polycarbonate resin composition contains a flowability enhancer which is a polycondensate of a monomer mixture containing biphenol (A) of 0 to 55 mol%, bisphenol (B) of 5 to 60 mol% and dicarboxylic acid (C) of 40 to 60 mol%, where the contents of monomers (A), (B) and (C) (mol%) are values when the total content of (A), (B) and (C) is 100 mol%, and an inorganic filler.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 transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc., so electrical, electronic, OA equipment, optical parts, precision It is used in a wide range of fields such as machinery, automobiles, security / medical care, building materials, and miscellaneous goods. However, since the polycarbonate resin is usually amorphous, there is a problem that the molding process temperature is high and the melt fluidity is poor.

  In addition, a flame retardant polycarbonate resin composition containing a flame retardant has been proposed as a polycarbonate resin composition having improved flame retardancy without impairing the excellent properties of a molded article made of polycarbonate resin. . However, the flame retardant polycarbonate resin composition to which the above flame retardant is added also has the above-mentioned problems.

  In recent years, the molding of polycarbonate resin compositions has become larger, thinner, more complicated in shape and higher in performance, and with the growing interest in environmental issues, the superiority of molded products made of polycarbonate resin There is a need for a resin modifier that improves the melt flowability of the polycarbonate resin composition and improves the injection moldability without impairing the properties, and a polycarbonate resin composition using the same.

  As a method for obtaining such a polycarbonate-based resin composition, for example, Patent Document 1 discloses that flame retardancy is reduced by adding a pentaerythritol-based ester compound to a polycarbonate resin and reducing the polycarbonate resin by transesterification. A method for improving the fluidity while maintaining is described.

Patent No. 4866010 (issued February 1, 2012)

  However, in the method described in Patent Document 1, there is a concern that the impact strength of the obtained flame-retardant polycarbonate-based resin composition is lowered.

  The present invention has been made in view of the above problems, and its purpose is excellent in flowability during molding without impairing the original properties (mechanical strength, heat resistance, flame retardancy, etc.) of the polycarbonate resin. Another object is to provide a polycarbonate resin composition and a molded product thereof.

  As a result of intensive studies, the present inventors have obtained a fluidity improver comprising a polyester obtained by polycondensing a bisphenol component and an aliphatic dicarboxylic acid component, and optionally a biphenol component at a specific ratio, and has excellent flame retardancy. As a component that improves the fluidity of the polycarbonate resin, the polycarbonate resin composition can be obtained without impairing the original useful properties (mechanical strength, heat resistance, flame resistance, etc.) of the polycarbonate resin by melting and kneading into the polycarbonate resin. The present inventors have found that the fluidity at the time of molding a product can be improved, and have completed the present invention. That is, this invention is invention shown by following <1>-<8>.

  <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.)
A monomer mixture containing 40 to 60 mol% of a dicarboxylic acid (C) represented by the formula (However, the content (mol%) of the monomers (A), (B) and (C) shown above is the monomer (A), ( B), a fluidity improver comprising a polyester, which is a polycondensate of (C) when the total content is 100 mol%, a flame retardant, and a polycarbonate resin. Polycarbonate resin composition.

  <2> The polycarbonate resin composition according to <1>, wherein the fluidity improver has a number average molecular weight of 2000 to 30000.

<3> The part according to <1> or <2>, wherein the part corresponding to R ₁ of the part derived from the dicarboxylic acid (C) in the fluidity improver is a linear saturated aliphatic hydrocarbon chain. Polycarbonate resin composition.

<4> A divalent linear substituent in which the portion corresponding to R ₁ in the portion derived from the dicarboxylic acid (C) in the fluidity improver may include a branch having an even number of main chain atoms. The polycarbonate resin composition according to any one of <1> to <3>.

<5> A part of the end of the fluidity improver is sealed with a monofunctional low molecular compound,
The polycarbonate resin composition according to any one of <1> to <4>, wherein a terminal sealing ratio of the fluidity improver by the monofunctional low molecular compound is 50% or more.

  <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 improves the fluidity during molding of the resin composition without impairing the original properties (mechanical strength, heat resistance, flame retardancy, etc.) of the polycarbonate resin excellent in flame retardancy. There is an effect that it has been.

  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 1: Polycarbonate resin composition]
The polycarbonate resin composition according to Embodiment 1 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 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.)
A monomer mixture containing 40 to 60 mol% of a dicarboxylic acid (C) represented by the formula (However, the content (mol%) of the monomers (A), (B) and (C) shown above is the monomer (A), ( B), a fluidity improver composed of polyester which is a polycondensate of (C), which is a numerical value when the total content of (C) is 100 mol%), a flame retardant and a polycarbonate resin.

[Flowability improver]
The fluidity improver in the present invention includes a bisphenol (B) represented by the following general formula (2), an aliphatic dicarboxylic acid (C) represented by the following general formula (3), and optionally the following general formula It consists of polyester which is a polycondensate obtained by polycondensing the biphenol (A) represented by the formula (1) at a specific ratio.

  More specifically, the fluidity improver in the present invention has the following general formula (1) in the main chain structure.

(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%, and
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.)
40 to 60 mol% of a portion derived from the dicarboxylic acid (C) represented by the above (however, the content (mol%) of the portion derived from the biphenol shown above, the portion derived from bisphenol and the portion derived from dicarboxylic acid) ) Is a polyester (polycondensate) which is a numerical value when the total content of the part derived from biphenol, the part derived from bisphenol and the part derived from dicarboxylic acid is 100 mol%.

  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 a bisphenol component (B), and the part derived from the dicarboxylic acid (C) represented by the general formula (3) is referred to as a dicarboxylic acid component (C).

  The fluidity improver in the present invention is 5 to 60 mol% of bisphenol (B) represented by general formula (2) and 0 to 55 mol% of biphenol (A) represented by any general formula (1). Can be prepared by polycondensation of a monomer mixture containing 40 to 60 mol% of a dicarboxylic acid (C) represented by the general formula (3) (provided that the monomer in the monomer mixture shown above ( A), (B), and (C) content (mol%) are numerical values when the total content of monomers (A), (B), and (C) is 100 mol%).

  Since the fluidity improver is not a low molecular weight compound, it is possible to suppress the occurrence of bleed out when molding a polycarbonate resin composition containing the fluidity improver.

  In addition, since the fluidity improver having the molecular structure is highly compatible with the polycarbonate resin, the fluidity of the polycarbonate resin composition of the present invention obtained by adding the fluidity improver to the polycarbonate resin is improved. It can be improved efficiently, and fluidity can be imparted without impairing various properties inherent in polycarbonate resin (for example, mechanical strength, heat resistance, flame retardancy, etc.). is there.

  The content of the biphenol component (A) contained in the fluidity improver is obtained when the total content of the biphenol component (A), the bisphenol component (B) and the dicarboxylic acid component (C) is 100 mol%. 0 to 55 mol%, preferably 10 to 40 mol%, more preferably 20 to 30%. The content of the bisphenol component (B) is 5 to 60 mol% when the total content of the biphenol component (A), the bisphenol component (B) and the dicarboxylic acid component (C) is 100 mol%, Preferably it is 10-50 mol%, More preferably, it is 20-30 mol%. The content of the dicarboxylic acid component (C) is 40 to 60 mol% when the total content of the biphenol component (A), the bisphenol component (B) and the dicarboxylic acid component (C) is 100 mol%. , Preferably 45 to 55%. The content is the content of each monomer of biphenol (A), bisphenol (B), and dicarboxylic acid (C) in the monomer mixture used for polycondensation of the polyester as the fluidity improver (however, Equivalent to 100 mol% of the total of biphenol (A), bisphenol (B) and dicarboxylic acid (C). 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 fluidity improver comprises a bisphenol component (B) and an optional biphenol component (A). When the diol component is composed of the biphenol component (A) and the bisphenol component (B), the molar ratio ((A) / (B)) of the component (A) to the 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 (A) / (B) is 1/9 or more, when it contains a large amount of component (A), the crystallinity of the polyester itself is improved and the glass transition temperature is inhibited from being lowered, and stored. It is preferable in terms of preventing the occurrence of fusion between pellets of the fluidity improver at the time. When (A) / (B) contains a large amount of component (B) so that it is 9/1 or less, the compatibility with the polycarbonate resin is sufficient, and a fluidity improver is added to the polycarbonate resin. When the resulting resin composition is molded into a thick molded product having a thickness of 4 mm or more, it prevents the phase separation from occurring at the central portion of the thickness during the slow cooling, and decreases the various physical properties of the polycarbonate resin. It is preferable in terms of prevention.

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 fluidity improver itself and to improve the handleability such as preventing fusion during pellet storage, 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 polycarbonate resin, it is more preferable that all of X _{5 to} X ₈ are 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 terms of increasing the compatibility with the polycarbonate resin. 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′- And the like. Dihydroxydiaryl sulfones such as dihydroxy-3,3′-dimethyldiphenylsulfone; dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl; These bisphenol components may be used alone, or two or more kinds may be mixed and used within a range not losing the effect of the present invention.

  The terminal structure of the fluidity improver in the present invention is not particularly limited, but particularly suppresses transesterification with a polycarbonate resin, and suppresses yellowing of the resin composition obtained by adding the fluidity improver to the polycarbonate resin. Therefore, in order to suppress hydrolysis and ensure long-term stability, it is preferably sealed with a monofunctional 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 end-capping rate of the fluidity improver can be determined by the following formula (4) by measuring the number of sealed end functional groups and the number of end functional groups 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 (4) 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 (4)
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. Among these, pt-butylphenol and p-cumylphenol are preferable from the viewpoint of high boiling point and easy polymerization. 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 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 fluidity improver itself is low, R ₁ is preferably a linear substituent not containing a branch, and more preferably a straight aliphatic hydrocarbon chain not containing a branch. Is preferred. R ₁ may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon chain. When the unsaturated bond is included, the fluidity improver may not be sufficiently flexible, and may increase the melt viscosity of the fluidity improver itself. R ₁ is preferably a straight-chain saturated aliphatic hydrocarbon chain having 2 to 18 carbon atoms from the viewpoint that both the ease of polymerization of the fluidity improver and the improvement of the glass transition point can be achieved. More preferably, it is a straight chain saturated aliphatic hydrocarbon chain having 4 to 16 carbon atoms, more preferably a straight chain saturated aliphatic hydrocarbon chain having 8 to 14 carbon atoms, and a straight chain having 8 carbon atoms. Most preferred is a saturated aliphatic hydrocarbon chain. The improvement of the glass transition point of the fluidity improver leads to the improvement of the heat resistance of the resin composition obtained by adding the fluidity improver to the polycarbonate resin. The number of main chain atoms of R ₁ is preferably an even number in that the melt viscosity of the fluidity improver itself decreases. From the above points, R ₁ is particularly preferably a substituent selected from — (CH ₂ ) ₈ —, — (CH ₂ ) ₁₀ —, and — (CH ₂ ) ₁₂ —.

  The fluidity improver 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 fluidity improver is less than 50 mol%, preferably less than 30 mol%, more preferably 10 mol, based on the total number of moles of the fluidity improver. %, And most preferably 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 fluidity improver, the compatibility of the fluidity improver with the polycarbonate resin is good, and the fluidity is good. The improver is preferable in terms of compatibility with the polycarbonate resin.

  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 fluidity improver 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 discoloration of the fluidity improver itself, and when the polymerization catalyst used for the polymerization of the fluidity improver is deactivated and the fluidity improver and the polycarbonate resin are mixed. This is considered to be because it is possible to prevent discoloration due to transesterification or hydrolysis reaction between polyester and polycarbonate resin contained in the fluidity improver. As a result, the decrease in the molecular weight of the polycarbonate resin can be more effectively suppressed, so that the resin composition containing the fluidity improver improves only the fluidity without impairing the original properties of the polycarbonate resin. Can do. The content of the phosphite-based antioxidant in the fluidity improver is preferably 0.005 to 5% by mass, and 0.01 to 2% by mass with respect to the weight of the fluidity improver. Is more preferable, 0.01 to 1% by mass is further preferable, and 0.02 to 0.05% by mass is most preferable. The content of the phosphite antioxidant is 0.005% by mass or more in terms of inhibiting the occurrence of coloring when the above fluidity improver is added to the polycarbonate resin by the phosphite antioxidant. preferable. Moreover, it is preferable in terms of the impact strength of the resin composition obtained by adding the said fluid improvement agent 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 fluidity improver in the present invention may contain a hindered phenol antioxidant in advance in that a polycarbonate resin composition having a good color tone can be obtained. The content of the hindered phenol antioxidant in the fluidity improver is preferably 0.005 to 5% by mass, and 0.01 to 2% by mass with respect to the weight of the fluidity improver. Is more preferable, 0.01 to 1% by mass is further preferable, and 0.02 to 0.05% by mass is most preferable. The hindered phenolic antioxidant content of 0.005% by mass or more inhibits the occurrence of coloration when the fluidity improver is added to the polycarbonate resin by the hindered phenolic antioxidant. In terms of surface. 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 fluidity improver 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-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t- 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-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate) 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-hydroxyphene Nyl) benzotriazole, 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), a hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pe Tamechiru 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 AO-330, ADK STAB AO-37 (all of which are manufactured by ADEKA CORPORATION), IRGANOX-245, IRGANOX-259, IRGANOX-56 , IRGANOX-1010, IRGANOX-1024, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all from BASF JAPAN Ltd.), Sumiliz 80 (above, manufactured by Sumitomo Chemical Co., Ltd.). Among these, Adeka Stub AO-60 and Adeka Stub AO-330 are particularly difficult to discolor, and the coloration of the resin can be efficiently suppressed by the combined use with a phosphite antioxidant. IRGANOX-1010 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 2112, ADK STAB PEP-36 and Irgafos 126, ADK STAB AO-60, ADK STAB AO-330 and IRGANOX-1010, It is preferable at the point which can suppress especially coloring.

  The number average molecular weight of the fluidity improver in the present invention is a mixed solvent having a volume ratio of p-chlorophenol and toluene of 3: 8 using polystyrene as a standard substance, and the concentration of the resin in the present invention is 0.25 weight. It is a value measured at 80 ° C. by GPC using a solution prepared by dissolving to be%. The number average molecular weight of the fluidity improver in the present invention is preferably 2000 to 30000, more preferably 3000 to 20000, and further preferably 4000 to 15000. When the number average molecular weight of the fluidity improver is 2000 or more, the fluidity improver bleeds out when molding a resin composition obtained by adding the fluidity improver to the polycarbonate resin. It is preferable in terms of prevention. Moreover, when the number average molecular weight of the fluidity improver is 30000 or less, the melt viscosity of the fluidity improver itself is prevented from becoming too high, and a resin composition obtained by adding a fluidity improver to a polycarbonate resin. It is preferable in terms of effectively improving the fluidity during the molding process.

  The fluidity improver 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. When solid-phase polymerization is performed, the obtained polyester resin is mechanically pulverized into particles having a particle size of 3 mm or less, preferably 1 mm or less, and an inert gas such as nitrogen gas at 100 to 350 ° C. in a solid state. It is preferable to perform the treatment for 1 to 30 hours under an atmosphere or under reduced pressure. It is preferable that the particle diameter of the polyester resin particles is 3 mm or less from the viewpoint of performing sufficient treatment and preventing the occurrence 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 resin particles do not cause fusion.

  The acid anhydride of the lower fatty acid used for the production of the fluidity improver in the present invention includes an acid anhydride of a lower fatty acid having 2 to 5 carbon atoms such as acetic anhydride, propionic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, Examples include trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, and pivalic anhydride. Of these, acetic anhydride, propionic anhydride, and trichloroacetic anhydride are particularly preferably used. The amount of the lower fatty acid anhydride used is 1.01 to 1.5 times equivalent, preferably 1.02 to 1.2 times the total of the monomers used and the functional groups such as hydroxyl groups of the end-capping agent. It is a double equivalent. 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.

  A polymerization catalyst may be used for the production of the fluidity improver in the present invention. 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 fluidity improver itself can be prevented and discoloration of the polycarbonate resin composition can be prevented.

The addition amount of the polymerization catalyst is usually 0 to 100 × 10 ⁻² mass%, preferably 0.5 × 10 ⁻³ to 50 × 10 ⁻² mass%, based on the total weight of the polyester resin. .

  There is no restriction | limiting in particular regarding the shape of the fluid improvement agent in this invention, For example, a pellet form, flake form, powder form etc. are mentioned. The particle diameter should just be as small as it can be thrown into the extruder melt-kneaded with polycarbonate resin, and it is preferable that it is 6 mm or less.

  The resin composition in the present invention contains 70 to 99.9% by mass of a polycarbonate resin and 0.1 to 30% by mass of a fluidity improver in the present invention in the resin component. The content of the fluidity improver in the resin component (100% by mass) is more preferably 0.5% by mass or more, further preferably 1% by mass or more, and particularly preferably 3% by mass or more. The content of the fluidity improver in the resin component (100% by mass) is more preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. When the content of the fluidity improver in the resin component (100% by mass) is 0.1% by mass or more, the fluidity at the time of molding is improved. When the content of the fluidity improver in the resin component (100% by mass) is 30% by mass or less, the heat resistance and mechanical properties of the polycarbonate resin are not significantly impaired. Since the flowability improver in the present invention has a glass transition temperature lower than that of the polycarbonate resin, it lowers the glass transition point of the resin composition obtained by being dissolved in the polycarbonate resin. Therefore, it is preferable in terms of heat resistance of the obtained polycarbonate resin composition to suppress the content of the fluidity improver to 30% by weight or less.

[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, polycarbonate resin produced by a method of interfacial polycondensation of divalent phenol and carbonyl halide, a method of melt polymerization of divalent phenol and carbonic acid diester (transesterification method), 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 is a copolymer having a polycarbonate structural unit and a polyorganosiloxane structural unit in addition to a homopolymer produced using only the above divalent phenol, or a homopolymer thereof. And a resin composition comprising a copolymer. 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. Furthermore, a resin composition obtained by melt-kneading a polycarbonate resin having various structural units can also be used.

[Flame retardants]
The resin composition of the present invention contains a flame retardant. The resin composition of this invention is excellent in a flame retardance by including a flame retardant.

  The amount of the flame retardant used is more preferably 0.1 to 80 parts by weight, and further preferably 10 to 60 parts by weight with respect to 100 parts by weight of the resin component comprising the polycarbonate resin and the fluidity improver. The amount is preferably 12 to 40 parts by weight. The amount of the flame retardant used is preferably 0.1 parts by weight or more in terms of improving the flame retardancy of the resulting resin composition and molded product. Moreover, it is preferable that the amount of the flame retardant used is 80 parts by weight or less in terms of improving the heat resistance and impact resistance of the molded product.

  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.

  In addition, brominated flame retardants such as tetrabromobisphenol A and decabromodiphenyl oxide, halogen-based flame retardants such as chlorinated paraffins such as chlorinated paraffin and chlorinated polyethylene; non-halogen phosphate ester-based flame retardants (monophosphate) / Condensation), halogen-containing phosphate ester flame retardants (monophosphate / condensation), inorganic phosphate flame retardants, red phosphorus flame retardants, etc .; antimony trioxide, aluminum hydroxide, hydroxide Examples include inorganic flame retardants such as magnesium; organic salt flame retardants, silicone flame retardants, and the like. These may be used alone or in combination of two or more.

  Preferred flame retardants include halogens in which halogenated bisphenol A, halogenated polycarbonate oligomers, halogenated bisphenol A polycarbonate flame retardants, halogenated compounds such as brominated epoxy compounds, and flame retardant aids such as antimony oxide are combined. Organic flame retardants; Organic salt flame retardants; Phosphorus flame retardants such as aromatic phosphate ester flame retardants and halogenated aromatic phosphate ester flame retardants; Organos such as branched phenyl silicone compounds and phenyl silicone resins Examples include silicone flame retardants such as polysiloxane. These may be used alone or in combination of two or more.

  Examples of the polycarbonate-type flame retardant of halogenated bisphenol A include a polycarbonate-type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate-type flame retardant of tetrabromobisphenol A and bisphenol A, and the like.

  Organic salt flame retardants include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trichlorobenzenesulfone. Potassium phosphate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, bis ( 2,4,6-tribromophenyl) potassium phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, perfluoro Potassium butanesulfonate, sodium lauryl sulfate Beam or potassium, and the like hexadecyl sodium or potassium sulfate.

  Examples of the halogenated aromatic phosphate ester type flame retardant include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like. .

  Aromatic phosphate ester flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, the aromatic ring source is resorcin and phenol Aromatic polyphosphates that do not contain phenolic hydroxyl groups (OH groups), aromatic ring sources that contain resorcinol and phenol and that contain phenolic OH groups, aromatic ring sources that contain hydroquinone and phenol Aromatic polyphosphates that do not contain phenolic OH groups, aromatic polyphosphates whose aromatic ring source is hydroquinone and phenol and that contain phenolic OH groups (the “aromatic polyphosphate” shown below refers to phenolic OH groups Aromatic polyphosphates with and without aromatic polyphosphates), aromatic polyphosphates with aromatic ring sources of bisphenol A and phenol, aromatics with aromatic ring sources of tetrabromobisphenol A and phenol Aromatic polyphosphates, aromatic polyphosphates whose aromatic ring source is resorcinol and 2,6-xylenol, aromatic polyphosphates whose aromatic ring source is hydroquinone and 2,6-xylenol, aromatic ring source is bisphenol A Beauty 2,6-xylenol in which an aromatic polyphosphate, aromatic ring sources and aromatic polyphosphates, and the like are tetrabromobisphenol A and 2,6-xylenol.

  A non-drip agent may be added to the polycarbonate resin composition of the present invention for the purpose of preventing melt dripping during combustion. Examples of the non-drip agent include fluoroolefin resins mainly composed of a fluoroolefin resin. The fluoroolefin resin is a polymer, copolymer, or composite containing a fluoroethylene structure. Examples of the fluoroolefin resin include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a copolymer of tetrafluoroethylene and an ethylene monomer not containing fluorine, and tetrafluoroethylene. Examples thereof include a composite of a polymer and a vinyl resin such as an acrylic resin. Of these, polytetrafluoroethylene (PTFE) is preferred. The mass average molecular weight of polytetrafluoroethylene is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000. As polytetrafluoroethylene, all known compounds can be used.

  Of polytetrafluoroethylene, a compound having a fibril-forming ability is preferable because it can provide higher melt dripping prevention properties. Examples of polytetrafluoroethylene having fibril-forming ability include compounds classified as type 3 in the ASTM standard. Examples of polytetrafluoroethylene classified as type 3 include Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries). CD1, CD076 (manufactured by Asahi IC Fluoropolymers Co., Ltd.) and the like.

  Examples of the polytetrafluoroethylene other than the compound classified as type 3 include Argoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.), and the like. These polytetrafluoroethylenes may be used alone or in combination of two or more.

  The amount of the non-drip agent used is preferably 0.05 to 5 parts by weight and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the resin component comprising the polycarbonate resin and the fluidity improver. The amount of the non-drip agent added is preferably 0.05 parts by weight or more from the viewpoint of preventing melt dripping during combustion. The amount of the non-drip agent added is preferably 5 parts by weight or less from the viewpoint of not adversely affecting the impact resistance and appearance of the molded product while sufficiently maintaining the effect of preventing melting and dropping during combustion. The amount of the non-drip agent added depends on the degree of flame retardancy required for the molded product, for example, UL94 V-0, V-1, V-2, etc. May be determined as appropriate.

  The method for producing the resin composition of the present invention is not particularly limited. The resin composition of the present invention includes, for example, a flow improver, a polycarbonate resin, a device such as a Henschel mixer, a Banbury mixer, a simple screw extruder, a twin screw extruder, a two roll, a kneader, and a Brabender. It is produced by a known method in which a flame retardant and, if necessary, an additive such as a light diffusing agent are blended and melt-kneaded. 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 contained in the fluidity improver and the yellowing of the resin composition due to thermal degradation of the polycarbonate resin.

[Embodiment 2: Molded product]
The molded product according to Embodiment 2 of the present invention is formed by molding the polycarbonate resin composition according to Embodiment 1 of the present invention.

  By subjecting the resin composition of the present invention to various extrusion moldings, the molded product of the present invention can be molded into, for example, various deformed extrusion molded products, extruded sheets, films and the like. 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 product by molding the 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 of the polycarbonate resin using the above-described fluidity improver. In other words, the present invention may include a method for improving the fluidity of the polycarbonate resin, including the step of mixing the above-described fluidity improver and the polycarbonate resin. In another aspect, it can be expressed as the use of the above-described fluidity improver for improving the fluidity of the polycarbonate resin.

  Next, the 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 only to such Examples. Each reagent listed below was used without purifying a reagent manufactured by Wako Pure Chemical Industries, Ltd. unless otherwise specified in the name of the company.

<Evaluation method>
[Measurement method of number average molecular weight]
The fluidity improver in the present invention is dissolved in a mixed solvent having a volume ratio of p-chlorophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene of 3: 8 so that the concentration is 0.25% by weight. A sample solution was 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 1 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.), in accordance with JIS K 7191 (test conditions: load 1.8 MPa, heating rate 120 ° C./hour), deflection temperature under load of resin composition (° C.) Was measured.

[Measurement method of flame retardancy]
A plurality of test pieces having a thickness of 1/8 inch were produced by injection molding, and the flame retardancy of the five test pieces obtained was measured according to a combustion test UL94.

<Materials used>
[resin]
(A-1) Polycarbonate: Panlite L1225Y (manufactured by Teijin Limited)
[Antioxidant]
(B-1) Phosphite antioxidant: PEP36 (manufactured by Adeka Corporation)
(B-2) Hindered phenol antioxidant: AO60 (manufactured by Adeka Corporation)
[Additive]
(C-1) Flame retardant (aromatic condensed phosphate ester): PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.)
(C-2) Non-drip agent (PTFE): DF-31 (manufactured by Shandong Dongyue Chemical Co., Ltd.).

[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, and sebacic acid were mixed at a molar ratio of 20:30:50. Then, 1.05 equivalent of acetic anhydride was added to the phenolic hydroxyl group (OH 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 pressure reduction, the inside of the sealed reactor was returned to normal pressure with nitrogen gas, and 0.2% by mass of each of the antioxidants (B-1) and (B-2) with respect to the mass of the produced polyester. Each was added and stirred for 5 minutes to obtain a fluidity improver. Thereafter, the fluidity improver was taken out from the reactor. The number average molecular weight of the obtained polyester was 10,200. Let the obtained polyester be (D-1).

[Example 1, Comparative Example 1]
In order to evaluate the performance of the fluidity improver, a resin, an antioxidant, an additive, and the fluidity improver obtained in Production Example 1 are blended in the proportions (parts by weight) shown in Table 1, and a twin screw extruder. And melt-kneaded at 260 ° C. to obtain a resin composition. And the performance of the fluidity improver was evaluated by measuring the physical properties of the resin composition. Table 2 shows various physical properties of the resin composition.

  As described in Table 1, the resin composition produced in Example 1 and the resin composition produced in Comparative Example 1 have the same composition except that they contain the fluidity improver. The resin composition produced by the same method. Here, based on the description in Table 2, the resin composition produced in Example 1 and the resin composition produced in Comparative Example 1 are compared in terms of physical properties. As a result, both were substantially equivalent in bending strength, flexural modulus, and flame retardancy, and the resin composition produced in Example 1 was more preferable in terms of resin flowability (spiral flow). I found it excellent.

  That is, according to the present invention, the resin composition containing a fluidity improver and a flame retardant has a bending strength, a flexural modulus, and a resin composition containing a conventional flame retardant containing no fluidity improver. It was found that the flame retardancy was not lowered and the fluidity (spiral flow) of the resin was improved.

  The polycarbonate resin composition of the present invention contains the above-described fluidity improver, so that the polycarbonate resin is excellent in flame retardancy without impairing the original properties (mechanical strength, heat resistance, flame retardancy, etc.) of the polycarbonate resin. The fluidity during resin molding is improved. Therefore, the polycarbonate resin composition of the present invention can realize molding of molded products that are large, thin, and complicated in shape, for electrical / electronic / OA equipment, for optical parts, for precision machinery, for automobiles. Suitable for a wide range of applications such as security / medical use, 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)

(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.)
A monomer mixture containing 40 to 60 mol% of a dicarboxylic acid (C) represented by the formula (However, the content (mol%) of the monomers (A), (B) and (C) shown above is the monomer (A), ( B), a fluidity improver comprising a polyester, which is a polycondensate of (C) when the total content is 100 mol%, a flame retardant, and a polycarbonate resin. Polycarbonate resin composition.   The polycarbonate resin composition of Claim 1 whose number average molecular weights of the said fluid improvement agent are 2000-30000. 3. The polycarbonate resin composition according to claim 1, wherein the portion corresponding to R ₁ of the portion derived from the dicarboxylic acid (C) in the fluidity improver is a linear saturated aliphatic hydrocarbon chain. The portion corresponding to R ₁ of the portion derived from the dicarboxylic acid (C) in the fluidity improver is a divalent linear substituent which may contain a branch having an even number of main chain atoms. The polycarbonate resin composition according to any one of claims 1 to 3. A part of the end of the fluidity improver is sealed with a monofunctional low molecular compound,
The polycarbonate resin composition according to any one of claims 1 to 4, wherein a terminal sealing ratio by the monofunctional low molecular weight compound of the fluidity improver is 50% or more.   The molded article formed by shape | molding the polycarbonate resin composition of any one of Claims 1-5.