JP2022021028A - Polycarbonate resin composition and molded article thereof - Google Patents

Abstract

To provide a polycarbonate (PC) resin composition excellent in heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry-heat resistance, flame retardancy and having high transparency.SOLUTION: A polycarbonate (PC) resin composition includes 0.01-0.18 pt.mass of an organometallic salt-based flame retardant (E) including fluoroalkyl groups based on 100 pts.mass of PC resin (D) which comprises: 5-15 mol% of the PC constitutional unit (A) having the structure derived from bisphenol having a fluorene structure; 20-60 mol% of the PC constitutional unit (B) having the structure derived from the bisphenol having the substituents such as an alkyl group on two benzene rings, respectively; and 25-75 mol% of the PC constitutional unit (C) having the structure derived from the bisphenol having no substituent on two benzene rings. The haze value in 2 mm thickness of a molded article formed from the PC resin composition based on JIS-K7136 is 5.0% or less.SELECTED DRAWING: None

Description

The present invention relates to a flame-retardant polycarbonate resin composition and a molded product containing a polycarbonate resin component containing a specific carbonate constituent unit and having excellent transparency. More specifically, the present invention contains heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and flame retardancy containing a polycarbonate resin having a specific structural unit and a specific flame retardant. The present invention relates to a polycarbonate resin composition and a molded product having excellent high transparency.

In recent years, from the viewpoint of reducing environmental load and designability, the demand for transparency of polycarbonate has increased even in fields such as OA equipment, electrical / electronic equipment, automobiles, and construction, which did not require transparency until now. ing. Among these application fields, high transparency and flame retardancy are required for transparent parts such as display covers for electric vehicles and aircraft passenger seat monitors, mainly in the fields of OA equipment and electric / electronic equipment. ..

However, the problem with the uncoated polycarbonate resin is that when exposed to a basic environment containing an amine, the polymer decomposes and the surface of the molded product is whitened, resulting in poor appearance. Further, the general paint test method described in JIS K5600-5-4-Part 5: Mechanical properties of the coating film-Section 4: Scratch hardness (pencil method), the pencil hardness of the polycarbonate resin is 2B. As a paint-less material, the problem is that the surface is easily scratched.

Therefore, it is known to use a copolymerized polycarbonate resin having a high surface hardness (for example, Patent Document 1). However, although the copolymerized polycarbonate resin has a high surface hardness and is excellent in ammonia resistance, it has a problem that it is inferior in impact resistance.

Further, a method of using polycarbonate or copolycarbonate having 2,2-bis (4-hydroxy-3-methylphenyl) propane as a constituent unit is described (for example, Patent Documents 2 to 6). Although the surface hardness of the polycarbonate resin is improved, there is a problem that the heat resistance is inferior to that of the polycarbonate resin.

Further, a method of using polycarbonate or copolycarbonate having 9,9-bis (4-hydroxyphenyl) fluorene as a constituent unit is described (Patent Document 7). The polycarbonate resin is excellent in surface hardness, impact resistance, heat resistance, and amine resistance, but a specific method for flame retardancy is not specified.

Therefore, there is not yet a polycarbonate resin composition having heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, weather resistance, and flame retardancy.

Japanese Patent No. 5173803 Japanese Unexamined Patent Publication No. 64-069625 Japanese Unexamined Patent Publication No. 08-183852 Japanese Unexamined Patent Publication No. 08-034846 Japanese Unexamined Patent Publication No. 2002-117580 Japanese Patent No. 3768903 International Publication No. 2017/073508

An object of the present invention is to provide a highly transparent polycarbonate resin composition having excellent heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, dry heat resistance, and flame retardancy. Another object of the present invention is to provide a polycarbonate resin molded product particularly suitable for flame-retardant transparent parts such as display covers for aircraft passenger seat monitors.

As a result of diligent research to achieve the above object, the present inventors have found that the above object can be achieved by using an organic metal salt-based flame retardant containing a specific amount of a fluoroalkyl group in a specific polycarbonate resin. The headline has reached the present invention. That is, it has been found that the transparency and flame retardancy of the obtained polycarbonate resin composition are compatible with each other by using an organic metal salt-based flame retardant containing a fluoroalkyl group in a specific amount range.

According to the present invention, the following (configuration 1) to (configuration 12) are provided.
(Structure 1)
As the main building blocks, (A) the following formula (1)

(In the formula (1), R ¹ to R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)
Structural unit (A) represented by
(B) The following formula (2)

(In the formula (2), R ³ to R ⁴ are independently alkyl groups or halogen atoms having 1 to 6 carbon atoms. X is a single-bonded, substituted or unsubstituted alkylene group, substituted or unsubstituted. Alkylidene group, sulfur atom or oxygen atom.)
The structural unit (B) represented by, and (C) the following formula (3)

(In formula (3), W represents a single bond, substituted or unsubstituted alkylene group, substituted or unsubstituted alkylidene group, sulfur atom or oxygen atom.)

It is composed of the constituent unit (C) represented by, the ratio of the constituent unit (A) in all the constituent units is 5 to 15 mol%, the proportion of the constituent unit (B) is 20 to 60 mol%, and the constituent unit (C). Polycarbonate resin composition containing 0.01 to 0.18 parts by mass of the organic metal salt-based flame retardant (E) containing a fluoroalkyl group with respect to 100 parts by mass of the polycarbonate resin (D) having a proportion of 25 to 75 mol%. JIS K, which is a product and is a molded product molded from a polycarbonate resin composition.
A polycarbonate resin composition having a haze value of 5.0% or less at a thickness of 2 mm according to 7136.

(Structure 2)
R ¹ to R ² in the formula (1) are independent hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, and R ³ to R ⁴ in the formula (2) are independent and have 1 to 6 carbon atoms, respectively. 6 is an alkyl group, X is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted an alkylidene group having 1 to 10 carbon atoms, and W in the formula (3). 1 is the polycarbonate resin composition according to Constituent 1, wherein is a single bond, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted alkylidene groups having 1 to 10 carbon atoms.

(Structure 3)
The polycarbonate resin composition according to the composition 1 or 2, wherein the viscosity average molecular weight is 15,000 to 40,000.

(Structure 4)
The polycarbonate resin composition according to any one of configurations 1 to 3, wherein the constituent unit (A) is a constituent unit derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

(Structure 5)
The polycarbonate resin composition according to any one of configurations 1 to 4, wherein the constituent unit (B) is a constituent unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane.

(Structure 6)
The polycarbonate resin composition according to any one of configurations 1 to 5, wherein the constituent unit (C) is a constituent unit derived from 2,2-bis (4-hydroxyphenyl) propane.

(Structure 7)
The polycarbonate resin composition according to any one of configurations 1 to 6, wherein the organic metal salt-based flame retardant (E) containing a fluoroalkyl group is a perfluoroalkylsulfonic acid alkali (earth) metal salt.

(Structure 8)
The polycarbonate resin composition according to any one of configurations 1 to 7, wherein the degree of yellow change (ΔYI) around 2000 hr in the weathering acceleration test is 12 or less.

(Structure 9)
The polycarbonate resin composition according to any one of configurations 1 to 8, wherein the degree of yellow change (ΔYI) at 120 ° C. and around 2000 hr in a dry heat test is 6 or less.

(Structure 10)
A molded product obtained by injection molding the polycarbonate resin composition according to any one of configurations 1 to 9.

(Structure 11)
A sheet or film obtained by extruding the polycarbonate resin composition according to any one of configurations 1 to 9.

(Structure 12)
An automobile interior part or an aircraft interior part using the molded product according to the configuration 10 or the sheet or film according to the configuration 11.

The polycarbonate resin composition of the present invention and a molded product thereof are excellent in heat resistance, impact resistance, scratch resistance (high hardness), amine resistance, flame retardancy and transparency, and thus are used for electric vehicles and aircraft passenger seats. It is suitably used for flame-retardant transparent parts such as display covers of monitors. Therefore, the industrial effect it produces is exceptional.

Hereinafter, the details of the present invention will be described.

<Polycarbonate resin (D)>
The polycarbonate resin (D) used in the present invention (including a polycarbonate copolymer and a copolymerized polycarbonate blend) has (A) the following formula (1) as a main constituent unit.

(In the formula (1), R ¹ to R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)
Structural unit (A) represented by
(B) The following formula (2)

(In the formula (2), R ³ to R ⁴ are independently alkyl groups or halogen atoms having 1 to 6 carbon atoms. X is a single-bonded, substituted or unsubstituted alkylene group, substituted or unsubstituted. Alkylidene group, sulfur atom or oxygen atom.)
The structural unit (B) represented by, and (C) the following formula (3)

(In formula (3), W represents a single bond, substituted or unsubstituted alkylene group, substituted or unsubstituted alkylidene group, sulfur atom or oxygen atom.)
It is composed of the structural unit (C) represented by.

Here, the "main" is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, most preferably 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, out of 100 mol% of all carbonate constituent units excluding the terminal. It indicates that the ratio is preferably 100 mol%.

In the structural unit (A) represented by the formula (1), it is preferable that R ₁ and R ₂ are independently hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, respectively.

Examples of the divalent phenol that induces the structural unit (A) include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The most suitable divalent phenol is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene.

In the polycarbonate resin (D), the ratio of the constituent unit (A) to all the constituent units is 5 to 15 mol%. When the ratio of the structural unit (A) exceeds 15 mol%, the heat resistance is improved, but the impact resistance, the weather resistance, and the dry heat resistance are inferior, which is not preferable. If the ratio of the structural unit (A) is less than 5 mol%, the heat resistance is inferior, which is not preferable.

In the structural unit (B) represented by the formula (2), it is preferable that R ³ to R ⁴ are independently alkyl groups having 1 to 6 carbon atoms, and X is a single bond, substituted or unsubstituted. It is preferable that the alkylene group has 1 to 10 carbon atoms, and the substituted or unsubstituted alkylidene group has 1 to 10 carbon atoms.

Examples of the dihydric phenol that induces the structural unit (B) include 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as bisphenol C) and 2,2-bis (4-hydroxy-3). -Isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane and the like can be mentioned. The most suitable divalent phenol is bisphenol C.

In the polycarbonate resin (D), the ratio of the constituent unit (B) to all the constituent units is 20 to 60 mol%, preferably 30 to 50 mol%. If the ratio of the structural unit (B) exceeds 60 mol%, the impact resistance and heat resistance are inferior, which is not preferable. If the proportion of the structural unit (B) is less than 20 mol%, the amine resistance is inferior, which is not preferable.

In the structural unit (C) represented by the above formula (3), W is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms. Is preferable.

Examples of the divalent phenol that induces the structural unit (C) include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 4,4'-dihydroxy-1,1-biphenyl, 4, 4'-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylthioether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfooxide, 4,4'-dihydroxydiphenylsulfide, 1,1-bis (4-) Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4-bis (4,4-bis) Examples thereof include 4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, and 1,1-bis (4-hydroxyphenyl) decane. The most suitable divalent phenol is bisphenol A.

In the polycarbonate resin (D), the ratio of the constituent unit (C) to all the constituent units is 25 to 75 mol%, preferably 30 to 70 mol%, more preferably 35 to 65 mol%, and 40 to 60 mol%. More preferred. If the proportion of the structural unit (C) exceeds 75 mol%, scratch resistance and amine resistance are inferior, which is not preferable. If the ratio of the structural unit (C) is less than 25 mol%, the impact resistance is inferior, which is not preferable.

Further, as the divalent phenol for inducing a structural unit other than the structural units (A), (B) and (C), 2,6-dihydroxynaphthalene, hydroquinone, resorcinol, and an alkyl group having 1 to 3 carbon atoms are preferable. Resolsinol substituted with, 3- (4-hydroxyphenyl) -1,1,3-trimethylindan-5-ol, 1- (4-hydroxyphenyl) -1,3,3-trimethylindan-5-ol, 6,6'-Dihydroxy-3,3,3', 3'-Tetramethylspirindan, 1-methyl-1,3-bis (4-hydroxyphenyl) -3-isopropylcyclohexane, 1-methyl-2- ( Examples thereof include 4-hydroxyphenyl) -3- [1- (4-hydroxyphenyl) isopropyl] cyclohexane, 1,6-bis (4-hydroxyphenyl) -1,6-hexanedione and the like. Other details of such polycarbonate are described in, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, JP-A-2002-117580 and the like. Has been done.

The polycarbonate resin is obtained by reacting a divalent phenol with a carbonate precursor. Examples of the reaction method include an interfacial transesterification method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound. In the case of interfacial polycondensation, a terminal terminator of monohydric phenols is usually used. Further, it may be a branched polycarbonate obtained by polymerizing a trifunctional component, or may be a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a vinyl-based monomer.

In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used to promote the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using, for example, a carbonic acid diester as a carbonic acid precursor is carried out by a method of distilling the produced alcohol or phenol by stirring a predetermined ratio of aromatic dihydroxy components with the carbonic acid diester while heating them in an inert gas atmosphere. It is. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed by distilling off the produced alcohols or phenols under reduced pressure from the initial stage. It is also possible to use a catalyst usually used for transesterification reaction to promote the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

Monofunctional phenols commonly used as terminal inhibitors can be used. Especially in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as terminal inhibitors for molecular weight regulation and the resulting polycarbonate resins are based on monofunctional phenols at the ends. Since it is sealed by a group, it has better thermal stability than those that do not. Specific examples of the monofunctional phenols include, for example, phenol, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, and the like. Examples thereof include p-cumylphenol, isooctylphenol, and p-long-chain alkylphenol.

The polycarbonate resin (D) can be copolymerized with an aliphatic diol, if necessary. For example, isosorbide: 1,4: 3,6-dianhydro-D-sorbitol, tricyclodecanedimethanol (TCDDM), 4,8-bis (hydroxymethyl) tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2, 2,4,4-Tetramethylcyclobutane-1,3-diol, mixed isomer, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis (hydroxymethyl) cyclohexane, Cyclohex-1,4-yldimethanol, trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis (hydroxymethyl) cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis -1,4-bis (hydroxymethyl) cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi (cyclohexyl) -4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol , 4,4'-Dihydroxybicyclohexyl, and poly (ethylene glycol).

The polycarbonate resin (D) can be copolymerized with a fatty acid, if necessary. For example, 1,10-dodecandionic acid (DDDA), adipic acid, hexanedioic acid, isophthalic acid, 1,3-benzenedicarboxylic acid, terephthalic acid, 1,4-benzenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples thereof include 3-hydroxybenzoic acid (mHBA) and 4-hydroxybenzoic acid (pHBA).

The polycarbonate resin (D) contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosandioic acid, and cyclohexanedicarboxylic acid. An alicyclic dicarboxylic acid such as an acid is preferably used. These carboxylic acids may be copolymerized as long as they do not impair the purpose. The polycarbonate resin (D) can also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

The polycarbonate resin (D) may be obtained by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary, to obtain a branched polycarbonate. Trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonate include 4,6-dimethyl-2,4,6-tris (4-hydrochidiphenyl) heptene-2, 2,4,6-trimethyl-. 2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1 -Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, and 4- {4- [1,1-bis (1,1-bis) 4-Hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols are preferably exemplified. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane is preferable. The structural unit derived from such a polyfunctional aromatic compound is preferably 0.03 to 1.5 mol%, more preferably 0.1, based on 100 mol% in total including the structural unit from other divalent components. It is about 1.2 mol%, particularly preferably 0.2 to 1.0 mol%.

Further, the branched structural unit is not only derived from the polyfunctional aromatic compound, but also derived without using the polyfunctional aromatic compound such as a side reaction generated during the polymerization reaction by the molten ester exchange method. You may. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

The polycarbonate resin (D) has a viscosity average molecular weight (Mv) of preferably 15,000 to 40,000, more preferably 16,000 to 30,000, and even more preferably 18,000 to 28, It is 000. A polycarbonate resin having a viscosity average molecular weight less than the above range may not have sufficient toughness and crack resistance for practical use. On the other hand, a polycarbonate resin having a viscosity average molecular weight exceeding the above range is inferior in versatility because it requires a high molding temperature or a special molding method, and further depends on the injection speed due to an increase in melt viscosity. The properties tend to be high, and the yield may decrease due to poor appearance or the like.

The viscosity average molecular weight of the polycarbonate resin (D) is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20 ° C. for the specific viscosity (η _SP ) calculated by the following formula. Ask,
Specific viscosity (η _SP ) = (tt ₀ ) / t ₀
[T ₀ is the number of seconds for methylene chloride to fall, and t is the number of seconds for the sample solution to fall]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP / c = [η] +0.45 × [η] ² c (however, [η] is the ultimate viscosity)
[Η] = 1.23 × 10 ^-4 Mv ^0.83
c = 0.7

<Organometallic salt flame retardant (E) containing a fluoroalkyl group>
Examples of the organic metal salt-based flame retardant (E) containing a fluoroalkyl group used in the present invention include perfluoroalkyl sulfonic acid alkali (earth) metal salt, perfluoroalkyl carboxylic acid alkali (earth) metal salt, and per. Fluoroalkylphenylsulfonic acid alkali (earth) metal salt, perfluoroalkylphenylcarboxylic acid alkali (earth) metal salt and the like can be mentioned, and the most preferable is perfluoroalkylsulfonic acid alkali (earth) metal salt. be.

Perfluoroalkylsulfonic acid alkaline (earth) metal salts include perfluoromethanesulfonate, perfluoroethanesulfonate, perfluoropropanesulfonate, perfluorobutanesulfonate, perfluoromethylbutanesulfonate. , Perfluorohexanesulfonate, perfluoroheptane sulfonate, perfluorooctanesulfonate and the like, and those having 1 to 8 carbon atoms are particularly preferable.

Specific examples of these include potassium perfluorobutane sulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium perfluorobutane sulfonate, sodium perfluorooctane sulfonate, lithium perfluorobutane sulfonate, per. Examples thereof include lithium fluoroheptane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, rubidium perfluorohexane sulfonate, and the like. Sodium fluorobutane sulfonate, potassium perfluorobutane sulfonate, cesium perfluorobutane sulfonate are particularly preferred.

Rubidium and cesium are preferred as alkaline (earth) metals in alkaline (earth) metal salts of perfluoroalkyl sulfonic acid when flame retardancy is higher, but they are also non-general. Since it is difficult to purify, it may result in a disadvantage in terms of cost. On the other hand, although it is advantageous in terms of cost, lithium and sodium may be disadvantageous in terms of flame retardancy. In consideration of these, the alkaline (earth) metal in the alkaline (earth) metal salt of perfluoroalkyl sulfonic acid can be used properly, but in all respects, potassium having an excellent balance of characteristics is most preferable. From these points, potassium perfluorobutanesulfonate is most preferable.

These flame retardants can be used alone or in combination of two or more.

The content of the organic metal salt-based flame retardant (E) containing a fluoroalkyl group contained in the resin composition of the present invention is 0.01 to 0.18 parts by mass with respect to 100 parts by mass of the polycarbonate resin (D). It is preferably 0.02 to 0.17 parts by mass, more preferably 0.03 to 0.16 parts by mass, and further preferably 0.05 to 0.15 parts by mass. If the content of the E component is too large, not only the transparency of the molded product, which is a feature of the present invention, is impaired, but also the resin is decomposed at the time of molding, and conversely, the flame retardancy is lowered. If the content is too small, the flame retardancy becomes insufficient and the flame retardancy which is the object of the present invention cannot be exhibited.

<Phosphorus stabilizer (F)>
Various phosphorus-based stabilizers (F) can be added to the polycarbonate resin composition of the present invention for the main purpose of improving the thermal stability during the molding process. Examples of such phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid, and esters thereof. Further such phosphorus-based stabilizers include tertiary phosphine.

As the phosphorus-based stabilizer (F), a phosphorus-based stabilizer having a melting point of 100 ° C. or higher is preferably used. When a phosphorus-based stabilizer having a melting point of 100 ° C. or higher is used, it has an advantage of being excellent in dry heat resistance. The melting point of the phosphorus-based stabilizer (F) is more preferably 130 ° C. or higher, further preferably 150 ° C. or higher, particularly preferably 180 ° C. or higher, and most preferably 220 ° C. or higher. The upper limit is not particularly limited, but it has sufficient characteristics at 300 ° C. or lower.

Specifically, examples of the phosphite compound include triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenyl. Phenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2, 6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-Methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis (nonylphenyl) penta Examples thereof include erythritol diphosphite and dicyclohexylpentaerythritol diphosphite.

Further, as another phosphite compound, a compound that reacts with divalent phenols and has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-). Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dioctyl phosphate. Examples thereof include diisopropyl phosphate, preferably triphenyl phosphate and trimethyl phosphate.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'biphenylenediphosphonite, Tetrakiss (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis ( 2,4-Di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di- n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- Examples thereof include 3-phenyl-phenylphosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which the above alkyl group is substituted by 2 or more, and is preferable.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like.

Examples of tertiary phosphine include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, and tri-p-tolyl. Examples thereof include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

The phosphorus-based stabilizer (F) can be used not only by one type but also by mixing two or more types.

Among the specific examples of the phosphorus-based stabilizer (F), tris (2,4-di-tert-butylphenyl) phosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol di. Phosphite is preferred.

The content of the phosphorus-based stabilizer (F) is preferably 0.01 to 0.5 parts by mass, and more preferably 0.02 to 0.4 parts by mass with respect to 100 parts by mass of the polycarbonate resin (D). It is more preferably 0.03 to 0.3 parts by mass, particularly preferably 0.04 to 0.2 parts by mass, and most preferably 0.05 to 0.1 parts by mass.

If the content of the phosphorus-based stabilizer (F) is too large, the physical characteristics (impact strength and hardness) of the material and the moisture and heat resistance may be deteriorated, and the mold may be easily contaminated during molding. Further, if the content of the phosphorus-based stabilizer (F) is too small, the transparency, hue and dry heat resistance may deteriorate.

<Hindered phenol-based stabilizer (G)>
The polycarbonate resin composition of the present invention is blended with a hindered phenolic stabilizer (G) for the main purpose of improving the thermal stability, heat aging resistance and dry heat resistance of the molded product during molding. Can be done.

Examples of such hindered phenol-based stabilizer (G) include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, and tetrakis [methylene-3- (3', 5'-di-tert-butyl-4). -Hydroxyphenyl) propionate], 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl -4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexyl) Phenol), 2,2'-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene -Bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4) -Hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4- Methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) Propionyloxy] -1,1,-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4 , 4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxy) Benzyl) sulfide, 4,4'-di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-te) rt-butylphenol), 2,2-thiodiethylenebis- [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, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide) ), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert) -Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl) -4-Hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6) -Dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and pentaerythritol tetrakis (3- (3,3) 5-Di-tert-butyl-4-hydroxyphenyl) propionate) and the like are exemplified.

Among the hindered phenolic stabilizers (G), pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and octadecyl-3- (3,5-di-tert-) Butyl-4-hydroxyphenyl) -propionate is preferred.

The melting point of the hindered phenol-based stabilizer (G) is not particularly limited, but is preferably in the range of 30 to 300 ° C, more preferably in the range of 40 to 200 ° C, and further preferably in the range of 45 to 150 ° C. It is in the range, particularly preferably in the range of 50 to 100 ° C. When the melting point is within the above range, it is excellent in dry heat resistance, weather resistance, and the effect of suppressing mold adhesion during injection molding.

The above-mentioned hindered phenolic antioxidant can be used alone or in combination of two or more.

The content of the hindered phenol-based stabilizer (G) is 0.01 to 1 part by mass, preferably 0.02 to 0.8 part by mass, based on 100 parts by mass of the polycarbonate resin (D). It is more preferably 0.03 to 0.5 parts by mass, further preferably 0.04 to 0.3 parts by mass, and most preferably 0.05 to 0.2 parts by mass.

If the content of the hindered phenol-based stabilizer (G) is too large, the physical characteristics (impact strength and hardness) of the material may be deteriorated, and the mold may be easily contaminated during molding. Further, if the content of the hindered phenol-based stabilizer (G) is too small, the transparency, hue and dry heat resistance may be deteriorated.

Further, it is preferable to use the phosphorus-based stabilizer (F) and the hindered phenol-based stabilizer (G) in combination, and by using them in combination, physical characteristics (impact strength and hardness), dry heat resistance and gold. It is possible to obtain a polycarbonate resin composition having a well-balanced effect of suppressing mold adhesion.

<Ultraviolet absorber (H)>
The polycarbonate composition used in the present invention can contain an ultraviolet absorber (H). As the ultraviolet absorber (H), it is preferable to use an ultraviolet absorber having a melting point of 130 ° C. or higher. When an ultraviolet absorber having a melting point of 130 ° C. or higher is used, it has excellent dry heat resistance and weather resistance, reduces mold deposits during injection molding, and has good mold contamination and the hue and appearance of the obtained molded product. Is. The melting point of the ultraviolet absorber (H) is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 170 ° C. or higher, and particularly preferably 190 ° C. or higher. The upper limit is not particularly limited, but it has sufficient characteristics at 300 ° C. or lower.

Specific examples of the ultraviolet absorber (H) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4 in the benzophenone system. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis Examples thereof include (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-) Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3) -Tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3) , 5-Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octyl) Phenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6) -Benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidemethyl) ) -5-Methylphenyl] Benzotriazole, and a copolymer of 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer, or 2- A polymer having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as a copolymer of (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl-based monomer copolymerizable with the monomer. Etc. are exemplified.

In the hydroxyphenyltriazine system, for example, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazine-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) Examples thereof include -1,3,5-triazine-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-butyloxyphenol. Will be done. Further, the phenyl group of the above-exemplified compound such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. A compound that has become a phenyl group is exemplified.

In the cyclic iminoester system, for example, 2,2'-p-phenylene bis (3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene) bis (3,1-benzoxazine) -4-one), 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-4-one) and the like are exemplified.

As the ultraviolet absorber, specifically, in the case of cyanoacrylate, for example, 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-2-bis]. Examples thereof include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

Further, the ultraviolet absorber (H) has a structure of a monomer compound capable of radical polymerization, whereby the photostable monomer having such an ultraviolet absorbing monomer and / or a hindered amine structure and an alkyl ( A polymer-type ultraviolet absorber obtained by copolymerizing with a monomer such as a meta) acrylate may be used. As the ultraviolet-absorbing monomer, a compound containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth) acrylic acid ester is preferably exemplified. Ru.

These ultraviolet absorbers (H) may be used alone or in a mixture of two or more kinds.

Among the above, benzotriazole-based and hydroxyphenyltriazine-based are preferable in terms of ultraviolet absorption ability. Among them, specifically 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (4, 6-Diphenyl-1,3,5-triazine-2-yl) -5-hexyloxy-phenol is preferred.

The content of the ultraviolet absorber (H) is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, still more preferably, with respect to 100 parts by mass of the polycarbonate resin (D). Is 0.25 to 3 parts by mass, and particularly preferably 0.3 to 2 parts by mass. If the content of the ultraviolet absorber (H) is too large, the physical properties (impact strength and hardness) of the material may be deteriorated, the heat resistance during molding may be deteriorated, and the mold may be contaminated during molding. Further, if the content of the ultraviolet absorber (H) is too small, sufficient weather resistance may not be obtained.

<Other ingredients>
The polycarbonate resin composition of the present invention may contain a functional agent known per se, such as a mold release agent, a flow modifier and an antistatic agent, as long as the effects of the present invention are not impaired.

(I) Release agent The polycarbonate resin composition of the present invention may contain a release agent as long as the effects of the present invention are not impaired. As the release agent, for example, fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which is modified with a functional group-containing compound such as acid modification can also be used), fluorine compound (polyfluoroalkyl). Fluorooil represented by ether), paraffin wax, beeswax, etc. can be mentioned. Among these, fatty acid esters are preferable from the viewpoint of easy availability, releasability and transparency. The ratio of the release agent to be contained is preferably 0.005 to 0.5 parts by mass, more preferably 0.007 to 0.4 parts by mass, and further preferably 0 with respect to 100 parts by mass of the polycarbonate resin (D). It is 0.01 to 0.3 parts by mass. When the content is not less than the lower limit of the above range, the effect of improving the releasability is clearly exhibited, and when it is not more than the upper limit, adverse effects such as mold contamination during molding are reduced, which is preferable.

Among the above, the fatty acid ester used as a preferable mold release agent will be described in more detail. Such fatty acid esters are esters of fatty alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a divalent or higher polyhydric alcohol. The carbon number of the alcohol is preferably in the range of 3 to 32, and more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, triacanthanol and the like. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In fatty acid esters, polyhydric alcohols are more preferred.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid and icosanoic acid. And saturated aliphatic carboxylic acids such as docosanoic acid (bechenic acid), and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and sethalic acid. can. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferable. Since such aliphatic carboxylic acids are usually produced from natural fats and oils such as animal fats and oils (such as beef tallow and lard) and vegetable fats and oils (such as palm oil), these aliphatic carboxylic acids usually have carbon atoms. It is a mixture containing other carboxylic acid components different from each other. Therefore, it is also produced from such natural fats and oils in the production of aliphatic carboxylic acids, and is in the form of a mixture containing other carboxylic acid components. The acid value of the fatty acid ester is preferably 20 or less (substantially 0 can be taken). However, in the case of all esters (full esters), it is preferable to contain not a small amount of free fatty acids in order to improve releasability, and in this respect, the acid value of full esters is preferably in the range of 3 to 15. The iodine value of the fatty acid ester is preferably 10 or less (substantially 0 can be taken). These characteristics can be obtained by the method specified in JIS K 0070.

The fatty acid ester described above may be either a partial ester or a full ester, but a partial ester is preferable in terms of better releasability and durability, and a glycerin monoester is particularly preferable. The glycerin monoester is mainly composed of a monoester of glycerin and a fatty acid, and suitable fatty acids include saturated fatty acids such as stearate, partiminic acid, bechenic acid, araquinic acid, montanic acid, and lauric acid, and oleic acid and linoleic acid. , And unsaturated fatty acids such as sorbic acid, and those containing glycerin monoesters of stearic acid, behenic acid, and partiminic acid as main components are particularly preferable. The fatty acid is synthesized from a natural fatty acid and is a mixture as described above. Even in such a case, the ratio of the glycerin monoester in the fatty acid ester is preferably 60% by mass or more.

The partial ester is often inferior to the full ester in terms of thermal stability. In order to improve the thermal stability of the partial ester, the partial ester preferably has a sodium metal content of less than 20 ppm, more preferably less than 5 ppm, still more preferably less than 1 ppm. The fatty acid partial ester having a sodium metal content of less than 1 ppm can be produced by producing the fatty acid partial ester by a usual method and then purifying it by molecular distillation or the like.

Specifically, after removing gas and low boiling point substances with a spray nozzle type degassing device, glycerin is used under the conditions of a distillation temperature of 120 to 150 ° C. and a vacuum degree of 0.01 to 0.03 kPa using a downflow membrane type distillation device. Distillation of high-purity fatty acid partial ester under the conditions of distillation temperature 160-230 ° C. and vacuum degree 0.01-0.2 Torr after removing polyhydric alcohols such as Sodium metal can be removed as a distillation residue. By repeatedly performing molecular distillation on the obtained distillate, it is possible to further increase the purity and obtain a fatty acid partial ester having a lower sodium metal content. It is also important to thoroughly clean the inside of the molecular distillation apparatus by an appropriate method in advance and to prevent the mixing of sodium metal components from the external environment by improving the airtightness. Such fatty acid esters can be obtained from specialists (for example, Riken Vitamin Co., Ltd.).

(Ii) Flow modifier The polycarbonate resin composition of the present invention may contain a fluid modifier as long as the effects of the present invention are not impaired. Examples of such flow modifiers include styrene-based oligomers, polycarbonate oligomers (including highly branched, hyperbranched and cyclic oligomer types), and polyalkylene terephthalate oligomers (including highly branched, hyperbranched and cyclic oligomer types). Branched and hyperbranched aliphatic polyester oligomers, terpene resins, polycaprolactone and the like are preferably exemplified. The flow modifier is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and further preferably 2 to 15 parts by mass per 100 parts by mass of the polycarbonate resin (D). Polycaprolactone is particularly preferable, and the composition ratio is 2 to 7 parts by mass, particularly preferably 2 to 7 parts by mass per 100 parts by mass of the polycarbonate resin (D). The molecular weight of polycaprolactone is 1,000 to 70,000 in terms of number average molecular weight, preferably 1,500 to 40,000, more preferably 2,000 to 30,000, and 2,500 to 15,000. More preferred.

(Iii) Antistatic Agent The polycarbonate resin composition of the present invention may contain an antistatic agent mainly for the purpose of improving antistatic properties. As the antistatic agent, a sulfonic acid phosphonium salt, a phosphite ester, a caprolactone-based polymer and the like can be used, and the sulfonic acid phosphonium salt is preferably used. Specific examples of such sulfonic acid phosphonium salts include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate, and dibutyl. Examples thereof include tributylmethylphosphonium benzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, trioctylmethylphosphonium diisopropylnaphthylsulfonate and the like. Of these, tetrabutylphosphonium dodecylbenzene sulfonate is preferable because of its compatibility with polycarbonate and easy availability. The amount of the antistatic agent is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, and further preferably 0.3 to 0.3 parts by mass with respect to 100 parts by mass of the polycarbonate resin (D). It is blended in an amount of 2.0 parts by mass, particularly preferably 0.5 to 1.8 parts by mass. When it is 0.1 part by mass or more, the effect of antistatic is obtained, and when it is 5.0 parts by mass or less, the transparency and mechanical strength are excellent, and silver or peeling does not occur on the surface of the molded product, and it is difficult to cause an appearance defect.

The polycarbonate resin composition of the present invention can also contain various additives such as a bluing agent, a fluorescent dye, a dye and a pigment, and other flame retardants and flame retardant aids (drip inhibitor). These can be appropriately selected and contained as long as the effects of the present invention are not impaired.

The bluing agent preferably contains 0.05 to 3.0 ppm (mass ratio) in the polycarbonate resin (D). Typical examples of the bluing agent include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polysynthslen Blue RLS.

Examples of fluorescent dyes (including fluorescent whitening agents) include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthracinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, and xantone-based fluorescent dyes. , Thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, diaminostilben-based fluorescent dyes, and the like. The blending amount of the fluorescent dye (including the fluorescent whitening agent) is preferably 0.0001 to 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin (D).

The polycarbonate resin composition of the present invention is excellent in flame retardancy, but in order to further reinforce such performance, a usual drip inhibitor can be used in combination. In order not to impair the transparency of the polycarbonate resin composition of the present invention, the blending amount of the drip inhibitor is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin (D), and 0.003 to 0. 1 part by mass is more preferable, 0.005 to 0.08 part by mass is further preferable, and 0.01 to 0.05 part by mass is particularly preferable. Examples of such a drip inhibitor include a fluoropolymer having a fibril-forming ability. In particular, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable. The term "not impairing transparency" as used herein means that, for example, the amount of PTFE used in a plate having a thickness of 2 mm does not exceed 5.0%. The molecular weight of PTFE having a fibril-forming ability has an extremely high molecular weight, and exhibits a tendency to bond PTFE to each other to form a fibrous form due to an external action such as shearing force. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight obtained from the quasi-specific gravity. As the PTFE, not only a solid form but also an aqueous dispersion form can be used. Further, the PTFE having such a fibril-forming ability improves the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with another resin in order to obtain better flame retardancy and transparency. .. Commercially available mixed-form PTFE includes "Metabren A3000" (trade name), "Metabren A3700" (trade name), "Metabren A3750" (trade name), Shinepoly SN3307 (trade name), and Mitsubishi Rayon Co., Ltd. And "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals Co., Ltd. can be mentioned.

<Manufacturing method of polycarbonate resin composition>
The method for blending various additives with the polycarbonate resin composition of the present invention is not particularly limited, and known methods can be used. The most commonly used method is to premix the polycarbonate resin and additives, then put them in an extruder for melt kneading, cool the extruded threads, and cut them with a pelletizer to produce pellet-shaped molding materials. There is a way to do it.

As the extruder in the above method, either a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is preferable from the viewpoint of productivity and kneadability. As a typical example of such a twin-screw extruder, ZSK (manufactured by Werner & Pfreederer, trade name) can be mentioned. Specific examples of the same type include TEX (manufactured by Japan Steel Works, Ltd., product name), TEM (manufactured by Toshiba Machine Co., Ltd., product name), KTX (manufactured by Kobe Steel, Ltd., product name), etc. Can be mentioned. As the extruder, one having a vent capable of degassing the moisture in the raw material and the volatile gas generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed from the vent to efficiently discharge the generated water and volatile gas to the outside of the extruder. It is also possible to install a screen for removing foreign matter and the like mixed in the extruded raw material in the zone in front of the die portion of the extruder to remove the foreign matter from the resin composition. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (disc filter, etc.) and the like.

Further, although the additive can be independently supplied to the extruder, it is preferable to premix it with the resin raw material as described above. Examples of such premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. A more preferred method is, for example, to prepare a master agent by mixing a part of the raw material resin and the additive with a high-speed stirrer such as a Henschel mixer, and then leaving the remaining master agent as a total amount of the resin raw material and a Nauter mixer. It is a method of mixing with a non-high speed stirrer.

The resin composition extruded from the extruder is directly cut and pelletized, or after forming the strands, the strands are cut with a pelletizer and pelletized. When it is necessary to reduce the influence of external dust and the like, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs are used to narrow the shape distribution of pellets, further reduce miscuts, and generate fine powder during transportation or transportation. It is preferable to further reduce the amount of bubbles (vacuum bubbles) generated inside the strands and pellets. To reduce miscuts, measures such as controlling the temperature of threads during cutting with a pelletizer, blowing ion air during cutting, optimizing the rake angle of the pelletizer, and properly formulating a release agent, as well as cutting were performed. Examples thereof include a method of filtering a mixture of pellets and water to separate the pellets from water and miscut. An example of the measuring method is disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-200421. With these formulations, it is possible to increase the cycle of molding and reduce the rate of defects such as silver.

The amount of miscut in the molding material (pellet) is preferably 10 ppm or less, more preferably 5 ppm or less. Here, the miscut means a powder or granular material finer than a pellet of a desired size that passes through a JIS standard sieve having an opening of 1.0 mm. The shape of the pellet can be a general shape such as a cylinder, a prism, and a sphere, but more preferably a cylinder (including an elliptical pillar), and the diameter of the cylinder is preferably 1.5 to 4 mm, more preferably. Is 2 to 3.5 mm. In the elliptical column, the ratio of the minor axis to the major axis is preferably 60% or more, more preferably 65% or more. On the other hand, the length of the cylinder is preferably 2 to 4 mm, more preferably 2.5 to 3.5 mm.

<Characteristics of polycarbonate resin composition>
The polycarbonate resin composition of the present invention can suppress polymer decomposition in a basic environment containing an amine. As a result of various studies, it was found that in the depolymerization reaction of polycarbonate by an amine compound, the amine compound acts on the carbonate bond of the polycarbonate and the depolymerization proceeds while producing a carbamic acid ester oligomer as an intermediate. Therefore, in order to suppress the reaction of the amine compound to the carbonate bond, the substituent of the aromatic ring is attached to the carbonate bond by being composed of the structural unit (B) represented by the above formula (2) as the main structural unit. We found that it plays a role of steric hindrance.

Further, the polycarbonate resin composition of the present invention has (A) a structural unit (A) represented by the above formula (1), (B) a structural unit (B) represented by the above formula (2), and (C). ) By configuring the structural unit (C) represented by the above formula (3) in a specific ratio, the balance of scratch resistance (high hardness), impact resistance, and flame retardancy is excellent while maintaining amine resistance. I found that.

Further, the polycarbonate resin composition of the present invention is a specific polycarbonate resin (D).
By combining an organometallic flame retardant containing a fluoroalkyl group with a specific amount of the flame retardant, the above-mentioned amine resistance, scratch resistance (high hardness), impact resistance, and heat resistance are maintained. Further, it was found that the transparency is excellent and the flame retardancy is exhibited.

The polycarbonate resin composition of the present invention preferably has a glass transition temperature of 130 to 160 ° C, more preferably 135 to 155 ° C, and even more preferably 140 to 150 ° C. When the glass transition temperature is at least the lower limit of the above range, the heat resistance is sufficient, and when it is at least the upper limit of the above range, it is not necessary to raise the molding processing temperature to a high temperature, and molding becomes easy.

The polycarbonate resin composition of the present invention preferably has an impact energy of 25 J or more, more preferably 28 J or more, as measured by a high-speed surface impact test according to JIS K7211-2. Further, it is preferable that the fracture form is ductile fracture. When the impact energy is equal to or higher than the above value, brittle fracture does not occur and the impact resistance is excellent, which is preferable. The impact energy is 50 J or less and has sufficient characteristics.

The polycarbonate resin composition of the present invention conforms to JIS K7202-2 and has a Rockwell hardness of 90 or more, more preferably 95 or more, as measured on an M scale. When the Rockwell hardness is equal to or higher than the above value, it is preferable because it has excellent scratch resistance. The Rockwell hardness of 120 or less has sufficient characteristics.

The polycarbonate resin composition of the present invention was measured according to the general paint test method described in JIS K5600-5-4-Part 5: Mechanical properties of the coating film-Section 4: Scratch hardness (pencil method). The pencil hardness is preferably F to 4H, more preferably H to 2H. When the pencil hardness is within the above range, it is preferable that the surface of the molded body is less likely to be scratched.

The polycarbonate resin composition of the present invention is excellent in dry heat resistance. Regarding the dry heat resistance, ΔYI measured by the following method is preferably 6 or less, more preferably 5.8 or less, and further preferably 5.6 or less.

As a method for measuring the dry heat resistance, a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm was used for the polycarbonate resin composition pellets, and an injection molding machine J-75E3 manufactured by Japan Steel Works was used. Under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm) and 2 mm (length) from the gate side at a holding time of 20 seconds and a cooling time of 20 seconds. A three-stage plate having a diameter of 45 mm and a length of 1 mm (length 25 mm) was formed, and the obtained plate was treated with a hot air dryer at 120 ° C. for 2,000 hr, and then a dry heat test 2, The YI (yellowness) of the plate thickness 2 mm portion was measured before and after the 000 hr treatment, and the yellow change degree (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Co., Ltd. was used for measurement with a C light source, a viewing angle of 2 °, and a transmission method.

The polycarbonate resin composition of the present invention has excellent weather resistance. As for the weather resistance, ΔYI measured by the following method is preferably 12 or less, more preferably 11.5 or less, still more preferably 11 or less, and particularly preferably 10.5 or less.

As a method for measuring weather resistance, a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm was used for the polycarbonate resin composition pellets, and an injection molding machine J-75E3 manufactured by Japan Steel Works was used. Under the conditions of cylinder temperature 290 ° C and mold temperature 80 ° C, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm) and 2 mm (length) from the gate side at a holding time of 20 seconds and a cooling time of 20 seconds. A three-stage plate with a diameter of 45 mm and a length of 1 mm (length 25 mm) was formed, and the obtained plate was subjected to an irradiation illuminance of 180 W / m ² (300) using a Super Xenon Weather Meter Tester SX75 manufactured by Suga Test Instruments Co., Ltd. -400 nm), with rain (18 minutes / 120 minutes), irradiation: black panel temperature 63 ° C, humidity 50%, rainfall: tank temperature 38 ° C, humidity 95%, after 2,000 hr treatment, weather resistance Acceleration test Before and after the 2,000 hr treatment, YI (yellowness) of a plate thickness of 2 mm was measured, and the degree of yellow change (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Co., Ltd. was used for measurement with a C light source, a viewing angle of 2 °, and a transmission method.

The polycarbonate resin composition of the present invention is excellent in transparency. That is, the haze value of the molded product molded from the polycarbonate resin composition at a thickness of 2 mm according to JIS K 7136 is 5.0% or less, preferably 3.0% or less, and more preferably 2.0%. It is less than or equal to, more preferably 1.0% or less.

The polycarbonate resin composition of the present invention is excellent in flame retardancy. The flame retardancy is preferably V-2 or higher, more preferably V-1 or higher, and even more preferably V-0, as evaluated by the following method.

As a method for measuring flame retardancy, the polycarbonate resin composition pellets are dried at 120 ° C. for 5 hours in a hot air circulation type dryer, and the cylinder temperature is 310 ° C. by an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. After molding a test piece for flame retardancy evaluation at a mold temperature of 90 ° C., a vertical combustion test of UL standard 94 was performed with a thickness of 1.6 mm to evaluate the grade.

In the polycarbonate resin composition of the present invention, the molded product was cut from the soft urethane foam used for the seat cushion material into a shape having a length and width of 50 mm and a thickness of 5 mm, both of which were sealed in a closed glass container and set at 85 ° C. It is preferable that the appearance of the test piece does not change after being left in the hot air dryer for 1,000 hours.

<Amine compounds used to form polyurethane foam>
Polyurethane resins are generally produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a flame retardant, a cross-linking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts in the production of polyurethane resins. These catalysts are widely used industrially by being used alone or in combination. Among these catalysts, tertiary amine compounds are widely used in the production of polyurethane foams using water, low boiling point organic compounds, or both as foaming agents because of their excellent productivity and moldability. There is. Examples of such a tertiary amine compound include conventionally known triethylenediamine, N, N, N', N'-tetramethylhexanediamine, N, N, N', N'-tetramethylpropanediamine, and N. , N, N', N'-tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N', N'-trimethylamino Examples thereof include ethyl piperazine, N, N-dimethylbenzylamine, N-methylmorpholin, N-ethylmorpholin, N, N-dimethylethanolamine and the like.

<Molded product>
The polycarbonate resin composition of the present invention can obtain a desired molded product by a method such as injection molding, injection compression molding, injection blow molding, two-color molding, extrusion molding or blow molding.

The production method of the polycarbonate resin composition of the present invention is not particularly limited, and for example, a sheet-shaped or film-shaped molded product can be obtained by a method such as a melt extrusion method or a solution casting method (casting method). .. As a specific method of the melt extrusion method, for example, a polycarbonate resin composition is quantitatively supplied to an extruder, melted by heating, and the molten resin is extruded from the tip of a T-die into a sheet on a mirror surface roll to form a plurality of rolls. When it is solidified, it is cut to an appropriate size or wound up. As a specific method of the solution casting method, for example, a solution (concentration of 5% to 40%) in which a polycarbonate resin composition is dissolved in methylene chloride is poured from a T-die onto a mirror-polished stainless steel plate in a stepwise manner. A method is used in which the sheet is peeled off while passing through a temperature-controlled oven, the solvent is removed, and then the solution is cooled and wound up.

The polycarbonate resin composition may also be a laminate. Any method may be used for producing the laminated body, and it is particularly preferable to use a thermocompression bonding method or a coextrusion method. Any method is adopted as the thermocompression bonding method, but for example, a method of thermocompression bonding a sheet with a laminating machine or a press machine, a method of thermocompression bonding immediately after extrusion, and particularly a method of continuously thermocompression bonding to a sheet immediately after extrusion is preferable. The method is industrially advantageous.

Further, the polycarbonate resin composition of the present invention is excellent in scratch resistance, impact resistance, amine resistance, flame retardancy and transparency, and is therefore suitably used as an interior component of an electric vehicle or an aircraft. Interior parts for electric vehicles and aircraft include lamp lenses for interior lighting, meter covers for displays, meter dials, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, etc. Examples include various display devices such as head-up displays, protective parts, and translucent parts. Further, since the interior component of the present invention has the above-mentioned characteristics, it does not require a coating treatment and has an advantage that the molded product obtained from the polycarbonate resin composition can be used as it is.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the measurement method of each characteristic is as follows.

(1) Viscosity average molecular weight The viscosity average molecular weight of the polycarbonate resin composition is measured and calculated by the following method.

First, the polycarbonate resin composition pellets obtained by extrusion were mixed and dissolved with 30 times the mass of methylene chloride, and the soluble component was collected by Celite filtration. After removing the solvent from the obtained solution, the obtained solid was sufficiently dried, and 0.7 g of the solid was dissolved in 100 ml of methylene chloride to obtain the specific viscosity (η _sp ) of the solution at 20 ° C. It was measured. Then, Mv calculated by the following formula was used as the viscosity average molecular weight.
η _sp / c = [η] +0.45 × [η] ² c
[Η] = 1.23 × 10 ^-4 Mv ^0.83
η _sp : Specific viscosity η: Extreme viscosity c: Constant (= 0.7)
Mv: Viscosity average molecular weight

(2) Composition ratio 40 mg of polycarbonate resin was dissolved in 0.6 ml deuterated chloroform solution, ¹ H-NMR was measured by a nuclear magnetic resonance apparatus manufactured by JEOL Ltd. at 400 MHz, and the spectral peak area ratio characteristic of each structural unit was used. , The composition ratio of the polycarbonate resin was calculated.

(3) Glass transition temperature Using the thermal analysis system DSC-2910 manufactured by TA Instruments, the temperature rise rate: 20 ° C / mi under a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) according to JIS K7121.
It was measured under n conditions.

(4) High-speed surface impact test Using Shimadzu Hydroshot HTM-1, the test speed was 7 m / sec, the impact core radius was 6.4 mm, and the thickness of the 3-stage plate obtained when measuring the pencil hardness was 2 mm. The impact energy was measured and the fracture morphology was visually observed.

(5) Push-in hardness (Rockwell hardness)
The test was carried out on the M scale in accordance with JIS K7202-2. As the test piece, a flat plate having a length and width of 100 mm and a thickness of 8 mm was used.

(6) Pencil hardness Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, using an injection molding machine J-75E3 manufactured by Japan Steel Works, a cylinder temperature of 290 ° C and a mold temperature. Under the condition of 80 ° C., the holding time is 20 seconds and the cooling time is 20 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side. A three-stage plate was formed. The pencil hardness of the three-stage plate at a thickness of 2 mm was measured according to JIS K5600.

(7) Evaluation of amine resistance Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm, a mold with a cylinder temperature of 290 ° C and a mold using an injection molding machine J-75E3 manufactured by Japan Steel Works, Ltd. Under the condition of a temperature of 80 ° C., the holding time is 20 seconds and the cooling time is 20 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side. ) Was formed into a three-stage plate. The soft urethane foam used for the cushioning material for automobile seats is cut into a shape with a length and width of 50 mm and a thickness of 5 mm using a cutter, sealed in a glass airtight container together with a three-stage plate, and inside a hot air dryer set at 85 ° C. The appearance of the test piece after being left for 1000 hours was visually observed.
○: No change ×: Surface whitening

(8) Dry heat resistance Using the pellets obtained in each example, a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm was used, and an injection molding machine J-75E3 manufactured by Japan Steel Works was used. With a cylinder temperature of 290 ° C and a mold temperature of 80 ° C, the holding time is 20 seconds and the cooling time is 20 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm) and 2 mm (length) from the gate side. A three-stage plate having a size of 45 mm) and 1 mm (length 25 mm) was formed. The obtained plate was treated with a hot air dryer at 120 ° C. for 2,000 hr. Before and after the dry heat test of 2,000 hr, YI (yellowness) of a plate thickness of 2 mm was measured, and the degree of yellow change (ΔYI) was evaluated. Measurement was performed using a SE2000 type manufactured by Nippon Denshoku Co., Ltd. as an evaluation device with a C light source, a viewing angle of 2 °, and a transmission method.

(9) Weather resistance For the pellets obtained in each example, a mold having a cavity surface having an arithmetic average roughness (Ra) of 0.03 μm was used, and an injection molding machine J-75E3 manufactured by Japan Steel Works was used. With a cylinder temperature of 290 ° C and a mold temperature of 80 ° C, the holding time is 20 seconds and the cooling time is 20 seconds, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm (length 20 mm) and 2 mm (length) from the gate side. A three-stage plate having a size of 45 mm) and 1 mm (length 25 mm) was formed. For the obtained plate, using the Super Xenon Weather Meter Tester SX75 manufactured by Suga Test Instruments Co., Ltd., irradiance 180 W / m ² (300-400 nm), rain (18 minutes / 120 minutes), irradiation: black panel temperature 2,000 hr treatment was performed under the conditions of 63 ° C. and humidity of 50% and rainfall: tank temperature of 38 ° C. and humidity of 95%. The YI (yellowness) of the plate thickness 2 mm portion was measured before and after the weather resistance acceleration test of 2,000 hr, and the yellow change degree (ΔYI) was evaluated. As an evaluation device, SE2000 type manufactured by Nippon Denshoku Kogyo Co., Ltd. was used, and the measurement was performed by a C light source, a viewing angle of 2 °, and a transmission method.

(10) Flame Retardant The pellets obtained from each composition of the examples were dried at 120 ° C. for 5 hours in a hot air circulation type dryer, and the cylinder temperature was 310 by an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at ° C. and a mold temperature of 90 ° C. A vertical combustion test of UL standard 94 was performed with a thickness of 1.6 mm, and the grade was evaluated. If the determination cannot meet any of the criteria of V-0, V-1, and V-2, it is indicated as "notV".

(11) Transparency (haze value)
Using the three-stage plate prepared in (6) above, the haze at a thickness of 2.0 mm was measured using Haze Meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. according to JIS K 7136.

<Manufacturing of polycarbonate resin>
[Manufacturing Example 1]
A reactor equipped with a thermometer, agitator and a reflux cooler was charged with 4,555 parts of a 48% sodium hydroxide aqueous solution and 22,730 parts of ion-exchanged water, which was charged with 9,9-bis (4-hydroxyphenyl). 596 parts of Fluorene (manufactured by Honshu Kagaku), 2,023 parts of bisphenol C (manufactured by Honshu Kagaku), 1,439 parts of bisphenol A (manufactured by Nippon Steel Chemical Co., Ltd.), and 7.94 parts of hydrosulfite (manufactured by Wako Junyaku). After dissolution, 13,415 parts of methylene chloride was added, and 2,000 parts of bisphenol was blown at 15 to 25 ° C. over about 70 minutes with stirring. After the injection of phosgene was completed, 650 parts of a 48% aqueous sodium hydroxide solution and 87.6 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.94 parts of triethylamine was added, and the mixture was further stirred at 28 to 35 ° C. for 1 hour. And the reaction was finished.

After completion of the reaction, the product is diluted with methylene chloride and washed with water, then hydrochloric acid is added to make it acidic and washed with water, and then water washing is repeated until the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water. A methylene solution was obtained. Next, this solution was passed through a filter with a mesh opening of 0.3 μm, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing portion, and the polycarbonate resin was flaked while distilling off methylene chloride, and then the solution was continued. The liquid-containing flakes were pulverized and dried to obtain a powder (D-1). The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 2]
9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) 298 parts, bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.) 1,820 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,799 parts, p-tert- Polycarbonate resin powder (D-2) was obtained by the same method as in Production Example 1 except that 71.0 parts of butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 3]
9,9-Bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) 894 parts, bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.) 1,213 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,979 parts, p-tert- Polycarbonate resin powder (D-3) was obtained by the same method as in Production Example 1 except that 106.5 parts of butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 4]
9,9-Bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) is not used, bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.) 2,023 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,799 parts, p- Polycarbonate resin powder (D-4) was obtained by the same method as in Production Example 1 except that 87.6 parts of tert-butylphenol was used. The results of evaluating the powder are shown in Table 1.

[Manufacturing Example 5]
Without using bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.), 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by Honshu Chemical Industry Co., Ltd.) 2,386 parts, bisphenol A (manufactured by Nippon Steel Chemical Industry Co., Ltd.) 1,439 parts, p- Polycarbonate resin powder (D-5) was obtained in the same manner as in Production Example 1 except that 92.3 parts of tert-butylphenol was added, and 95 parts of p-tert-butylphenol and 5.6 parts of triethylamine were added. The results of evaluating the powder are shown in Table 1.

[Examples 1 to 7 and Comparative Examples 1 to 4]
<Manufacturing of Polycarbonate Resin Composition>
Each component shown in Tables 1 and 2 was weighed and mixed at the ratios shown in Tables 1 and 2, mixed by a blender, and then melt-kneaded using a bent twin-screw extruder to prepare a polycarbonate resin composition. Pellets were obtained. The additive to be added to the PC was completely mixed by a blender. The vent type twin-screw extruder was manufactured by Japan Steel Works, Ltd .: TEX30α (complete meshing, same-direction rotation, double-threaded screw). The kneading zone is one type in front of the vent opening. The extrusion conditions are a discharge rate of 30 kg / hr, a screw rotation speed of 250 rpm, a vent vacuum degree of 1 kPa, and an extrusion temperature of 220 to 250 ° C. from the first supply port to the front of the kneading zone and 250 to 260 ° C. in the kneading zone. After that, the temperature up to the die was set to 260 to 270 ° C. The above resin composition was produced in an atmosphere in which clean air passed through a HEPA filter circulates, and sufficient care was taken not to allow foreign matter to enter during the work.

<Organometallic salt flame retardant (E) containing a fluoroalkyl group>
E-1: Potassium perfluorobutane sulfonic acid (Megafuck F-114P manufactured by Dainippon Ink Co., Ltd.)
E-2: Perfluorobutane sulfonic acid sodium salt (Megafuck F-114S manufactured by Dainippon Ink Co., Ltd.)

<Organometallic salt flame retardant containing no fluoroalkyl group>
E-3: Sodium paratoluenesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.)

<Phosphorus stabilizer (F)>
F; Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (melting point: 235 ° C., ADEKA PEP-36)

<Phenolic stabilizer (G)>
G; Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (melting point: 52 ° C., BASF's Ilganox 1076)

<Ultraviolet absorber (H)>
H; 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol] (melting point: 200 ° C., LA-manufactured by ADEKA) 31)

Since the polycarbonate resin composition of the present invention does not require a coating treatment and has excellent flame retardancy and transparency, it is a lamp lens for interior lighting of electric vehicles and aircraft, a meter cover for display, a meter dial, and various switches. It can be suitably used as a flame-retardant transparent material for various display devices such as covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, head-up displays, protective parts, translucent parts, etc. ..

Claims (12)

As the main building blocks, (A) the following formula (1)

(In the formula (1), R ¹ to R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 9 carbon atoms which may contain an aromatic group, or a halogen atom.)
Structural unit (A) represented by
(B) The following formula (2)

(In the formula (2), R ³ to R ⁴ are independently alkyl groups or halogen atoms having 1 to 6 carbon atoms. X is a single-bonded, substituted or unsubstituted alkylene group, substituted or unsubstituted. Alkylidene group, sulfur atom or oxygen atom.)
The structural unit (B) represented by, and (C) the following formula (3)

(In formula (3), W represents a single bond, substituted or unsubstituted alkylene group, substituted or unsubstituted alkylidene group, sulfur atom or oxygen atom.)
It is composed of the constituent unit (C) represented by, the ratio of the constituent unit (A) in all the constituent units is 5 to 15 mol%, the proportion of the constituent unit (B) is 20 to 60 mol%, and the constituent unit (C). Polycarbonate resin composition containing 0.01 to 0.18 parts by mass of the organic metal salt-based flame retardant (E) containing a fluoroalkyl group with respect to 100 parts by mass of the polycarbonate resin (D) having a proportion of 25 to 75 mol%. JIS K, which is a product and is a molded product molded from a polycarbonate resin composition.
A polycarbonate resin composition having a haze value of 5.0% or less at a thickness of 2 mm according to 7136. R ¹ to R ² in the formula (1) are independent hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, and R ³ to R ⁴ in the formula (2) are independent and have 1 to 6 carbon atoms, respectively. 6 is an alkyl group, X is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted an alkylidene group having 1 to 10 carbon atoms, and W in the formula (3). The polycarbonate resin composition according to claim 1, wherein is a single-bonded, substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, and substituted or unsubstituted an alkylidene group having 1 to 10 carbon atoms. The polycarbonate resin composition according to claim 1 or 2, wherein the viscosity average molecular weight is 15,000 to 40,000. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the structural unit (A) is a structural unit derived from 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the constituent unit (B) is a constituent unit derived from 2,2-bis (4-hydroxy-3-methylphenyl) propane. The polycarbonate resin composition according to any one of claims 1 to 5, wherein the structural unit (C) is a structural unit derived from 2,2-bis (4-hydroxyphenyl) propane. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the organic metal salt-based flame retardant (E) containing a fluoroalkyl group is a perfluoroalkylsulfonic acid alkali (earth) metal salt. The polycarbonate resin composition according to any one of claims 1 to 7, wherein the degree of yellow change (ΔYI) around 2000 hr in the weathering acceleration test is 12 or less. The polycarbonate resin composition according to any one of claims 1 to 8, wherein the degree of yellow change (ΔYI) at a dry heat test of 120 ° C. and around 2000 hr is 6 or less. A molded product obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 9. A sheet or film obtained by extruding the polycarbonate resin composition according to any one of claims 1 to 9. An automobile interior part or an aircraft interior part using the molded product according to claim 10 or the sheet or film according to claim 11.