JP5863350B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a polycarbonate resin composition, and more particularly, to a polycarbonate resin composition having an extremely high surface hardness and high flame retardancy as compared with the conventional one.

  Polycarbonate resin is tough and excellent in impact resistance and electrical characteristics, and the resulting molded product is also excellent in dimensional stability, so electrical and electronic equipment housings, automotive interior parts, or precision Widely used as a raw material resin for manufacturing molded parts. In particular, a flame retardant polycarbonate resin composition can be used for home appliances, electronic devices, liquid crystal display device members (housings), etc., and can obtain products with high commercial value by utilizing its beautiful appearance.

However, since the surface hardness of polycarbonate resin is lower than that of glass, it is inferior in scratch resistance, and when it is wiped with a cloth or handled roughly, the surface is easily scratched, and it is desired to have scratch resistance.
Conventionally, in order to improve the scratch resistance, various coatings have been applied to the surface of the polycarbonate resin molded product. However, in the processing such as coating, since processing costs and labor are required, It is desired to impart scratch resistance to the polycarbonate resin molded article itself by improving the composition of the polycarbonate resin composition.

Conventional techniques for increasing the altitude of the polycarbonate resin composition itself include those in which a silicone oil is blended with a polycarbonate resin (Patent Document 1), those in which a slidable filler such as a silicone compound is blended (Patent Document 2), and biphenyl. A compound containing an antiplasticizer such as a compound, a terphenyl compound, or polycaprolactone (Patent Document 3) has been proposed. However, although the surface hardness is improved to some extent, the impact resistance is not sufficient.
Patent Document 4 proposes a method of improving impact resistance by blending an acrylic elastomer and a polyester resin with an aromatic polycarbonate resin. However, this resin composition improves hardness and chemical resistance to some extent, but it does not satisfy both hardness and impact resistance.

JP 2004-210889 A JP 2007-51233 A JP 2007-326938 A Japanese Examined Patent Publication No. 62-37671

In recent years, in various fields such as electric and electronic equipment and in-vehicle equipment, the required specifications for surface hardness and flame retardancy have become increasingly sophisticated. The fact is that no high-level resin material with excellent flammability has been proposed.
An object of the present invention is to provide a polycarbonate resin composition having both high surface hardness and high flame retardancy.

The present inventors have found that a polycarbonate resin in which a flame retardant and an anti-drip agent are blended with a polycarbonate resin having specific melt viscosity characteristics has both extremely high surface hardness and high flame retardancy, and the present invention has been completed. I let you.
That is, the present invention provides the following polycarbonate resin composition, and a casing of an electric / electronic device or a cover, a single layer or a multilayer sheet, an LED lighting component, and a building member formed by molding the following polycarbonate resin composition.

[1] 300 ℃, the melt viscosity eta ₁₀ as measured at a shear rate of 10sec ^-1, 300 ℃, the ratio of the melt viscosity eta ₁₀₀₀ as measured at a shear rate ^{_{1000sec -1 (η 10 / η 1000}} ) is 3 to 8 For 100 parts by mass of a certain polycarbonate resin (A),
A polycarbonate resin composition comprising 2 to 30 parts by mass of a flame retardant (B), 0.01 to 1 part by mass of an anti-dripping agent (C), and having a pencil hardness of HB or more.
[2] Polycarbonate resin (A) having a structural unit of the following general formula (1) and a viscosity average molecular weight (Mv) of 20,000 to 35,000 and a structure of the following general formula (2) Containing a polycarbonate resin (A2) having a viscosity average molecular weight (Mv) of 16,000 to 28,000 having a unit at a mass ratio of (A1) / (A2) of 80/20 to 20/80. The polycarbonate resin composition as described in [1] above, which is characterized by the following.
(In the general formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X represents
R ³ and R ⁴ represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )
(X in the general formula (2) has the same meaning as the general formula (1).)

[3] the general formula (1) in which R ¹ is a methyl group, R ² is a hydrogen atom, the above-mentioned [1, characterized in that X in the general formula (1) and (2) is isopropylidene ] Or the polycarbonate resin composition as described in [2].
[4] The polycarbonate resin composition according to any one of the above [1] to [3], wherein the thickness of a test piece that achieves V-0 in the UL94 standard vertical combustion test is 1.0 mm or less.
[5] The polycarbonate resin composition according to any one of the above [1] to [4], wherein the flame retardant (B) is a phosphorus flame retardant or a bromine flame retardant.
[6] The polycarbonate resin composition according to any one of the above [1] to [5], wherein the anti-dripping agent (C) is a fluoropolymer.

[7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polycarbonate resin (A) is a polycarbonate resin produced by a melting method.
[8] The above [1], further comprising 0.01 to 1 part by mass of a phosphorus stabilizer and / or a hindered phenol stabilizer with respect to 100 parts by mass of the polycarbonate resin (A). -The polycarbonate resin composition in any one of [7].
[9] Any of [1] to [8] above, further comprising 0.05 to 1 part by mass of a fatty acid ester as a release agent with respect to 100 parts by mass of the polycarbonate resin (A). The polycarbonate resin composition described in 1.
[10] The polycarbonate resin composition as described in [9] above, wherein the release agent is at least one selected from pentaerythritol tetrastearate, stearic acid stearate, and stearic acid monoglyceride.
[11] The polycarbonate resin composition according to any one of [1] to [10], wherein 10% by mass or more in the polycarbonate resin (A) is a flaky powder.

[12] A casing or cover for an electric / electronic device formed by molding the polycarbonate resin composition according to any one of [1] to [11].
[13] A single layer or multilayer sheet formed by molding the polycarbonate resin composition according to any one of [1] to [11].
[14] An LED lighting component formed by molding the polycarbonate resin composition according to any one of [1] to [11].
[15] A building member formed by molding the polycarbonate resin composition according to any one of [1] to [11].

  According to the present invention, a polycarbonate resin composition having both high surface hardness and high flame retardancy, which has never been obtained, can be obtained.

<Summary of invention>
The polycarbonate resin composition of the present invention, 300 ° C., a melt viscosity eta ₁₀ as measured at a shear rate of 10sec ^-1, 300 ℃, the ratio (η ₁₀ / η ₁₀₀₀ and a melt viscosity eta ₁₀₀₀ as measured at a shear rate of 1,000 sec ^-1 ) Is a polycarbonate resin (A) of 3-8,
A polycarbonate resin composition containing 2 to 30 parts by mass of a flame retardant (B) and 0.05 to 1 part by mass of an anti-dripping agent (C) with respect to 100 parts by mass of the polycarbonate resin (A), and having a pencil hardness. It is more than HB.

Hereinafter, the contents of the present invention will be described in detail.
The constituent elements described below may be explained based on typical embodiments and specific examples of the present invention. However, the present invention is construed to be limited to such embodiments and specific examples. It is not something.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after the lower limit and the upper limit unless otherwise specified.

<Polycarbonate resin (A)>
Polycarbonate resin (A), 300 ° C., a melt viscosity eta ₁₀ as measured at a shear rate of 10sec ^-1, 300 ℃, the ratio of the melt viscosity eta ₁₀₀₀ as measured at a shear rate ^{_{1000sec -1 (η 10 / η 1000}} ) is 3-8.

Here, the measurement of the melt viscosity ratio (η ₁₀ / η ₁₀₀₀ ) is specifically performed as follows.
The melt viscosity by capillograph is measured using a capillary rheometer “Capillograph 1C” (manufactured by Toyo Seiki Seisakusho Co., Ltd.), with a die diameter of 1 mmφ × 10 mmL, a residence time of 5 minutes, a measurement temperature of 300 ° C., and a shear rate γ = 9.12 to 1824 sec. Measured in the range of ⁻¹ to obtain η ₁₀ and η ₁₀₀₀ . The polycarbonate resin (A) used for the measurement is one previously dried at 80 ° C. for 5 hours.

The melt viscosity η ₁₀ corresponds to the melt viscosity at the time of combustion in the combustibility test of the polycarbonate resin composition described later. The higher the melt viscosity eta _10, kindling is less likely to fall at the time of combustion is considered to be difficult to spread.
Melt viscosity eta ₁₀ of the polycarbonate resin (A) is preferably at 8,000Pa · s or more, more preferably 10,000 Pa · s or more. Further, the melt viscosity η ₁₀ is preferably 50,000 Pa · s or less. Melt viscosity eta ₁₀ is, there is too small tends to spark it is likely to fall at the time of combustion. Melt viscosity eta ₁₀ is, because the high viscosity at the time of kneading in the excessively large when the extruder, liable to poor dispersion of additives, or the motor load of the extruder tends to show troubles too large.

The melt viscosity η ₁₀₀₀ corresponds to, for example, the melt viscosity of the polycarbonate resin composition at the time of injection molding. The lower the melt viscosity η _{1000, the} better the fluidity during molding.
The melt viscosity η ₁₀₀₀ of the polycarbonate resin (A) is preferably 10,000 Pa · s or less, and more preferably 5,000 Pa · s or less. The melt viscosity η ₁₀₀₀ is preferably _1,000 Pa · s or more, more preferably 2,000 Pa · s or more. If the melt viscosity η ₁₀₀₀ is too small, the mechanical strength tends to be inferior. If the melt viscosity η ₁₀₀₀ is excessively large, the moldability tends to deteriorate due to insufficient fluidity.

As described above, the polycarbonate resin (A) has a property that the ratio (η ₁₀ / η ₁₀₀₀ ) between the melt viscosity η ₁₀ and the melt viscosity η ₁₀₀₀ is 3 to 8.
The ratio (η ₁₀ / η ₁₀₀₀ ) between the melt viscosity η ₁₀ and the melt viscosity η ₁₀₀₀ is the flame retardancy of the polycarbonate resin composition containing the polycarbonate resin (A), the flame retardant (B), and the anti-dripping agent (C). And has technical significance as an index that represents the balance of formability. That is, the melt viscosity η _{1000 at} a high shear rate can be a factor governing the moldability at the time of molding the polycarbonate resin composition. In addition, the melt viscosity η _{10 at} a low shear rate can be a factor governing the flame retardancy in the flammability test of the polycarbonate resin composition.
The ratio of melt viscosity (η ₁₀ / η ₁₀₀₀ ) is 3 or more, preferably 3.5 or more, and 8 or less, preferably 7 or less, more preferably 6.5 or less. If the ratio (η ₁₀ / η ₁₀₀₀ ) is too small, the flame retardancy, surface hardness and moldability tend to be inferior. When the ratio (η ₁₀ / η ₁₀₀₀ ) is excessively large, the ease of extrusion kneading and the mechanical strength tend to be inferior.

The ratio of the melt viscosity η ₁₀ to the melt viscosity η ₁₀₀₀ (η ₁₀ / η ₁₀₀₀ ) can be adjusted by various methods. In the production process of the polycarbonate resin described later, for example, stirring the reactor in the polycondensation reaction This can be done by adjusting the number of revolutions, the temperature, pressure and time of the reaction solution. As a specific example, in order to increase η ₁₀ / η ₁₀₀₀ , high temperature and high vacuum are used during the polycondensation reaction, and in order to decrease η ₁₀ / η ₁₀₀₀ , the temperature is low and low within a range not inhibiting the polycondensation reaction. This is possible by applying a vacuum.
Further, by mixing two or more kinds of polycarbonate resins having different (η ₁₀ / η ₁₀₀₀ ) depending on the difference in monomer type and degree of polymerization, the desired (η ₁₀ / η ₁₀₀₀ ) is obtained. A polycarbonate resin can also be used. By using this method, a polycarbonate resin composition having the desired physical properties can be obtained relatively easily.

The polycarbonate resin (A) preferably has a branching parameter G defined by [η] / [η] _lin of 0.1 to 0.9. The branching parameter G is more preferably 0.3 to 0.9, still more preferably 0.5 to 0.9. If the branching parameter G is too small, the melt tension tends to be too high and the fluidity tends to decrease, and if the branching parameter G is too large, it tends to behave as a Newtonian fluid in the molten state and the moldability tends to be insufficient. Yes, the balance between fluidity and flame retardancy may worsen.

  Here, [η] is the intrinsic viscosity (dl / g) at 20 ° C. in a methylene chloride solvent. [Η] is preferably in the range of 0.4 to 2 dl / g or less, more preferably 0.5 to 1 dl / g, and particularly preferably 0.5 to 0.8 dl / g. If the intrinsic viscosity [η] is excessively small, the mechanical strength tends to be inferior. If the intrinsic viscosity [η] is excessively large, the melt fluidity tends to deteriorate and the moldability tends to be inferior.

[Η] _lin is a linear polycarbonate resin having the same weight average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC) using a general-purpose calibration curve, in a methylene chloride solvent. Intrinsic viscosity at ° C. In the present embodiment, specifically, the same aromatic dihydroxy compound and carbonyl chloride as the aromatic dihydroxy compound used for the polycarbonate resin (A) are used as raw materials, and a straight chain is formed by an interfacial polymerization method without using a branching agent. The polycarbonate resin is polymerized so as to have a target weight average molecular weight. Then, the intrinsic viscosity of the obtained linear polycarbonate resin is measured, and [η] _lin can be obtained.

The branch parameter G is calculated by the following method. That is, the intrinsic viscosity [η] of the polycarbonate resin measured by the above-described method is divided by the intrinsic viscosity [η] _lin of the linear polycarbonate having the same weight average molecular weight to calculate the branching parameter G of the polycarbonate resin.

  Examples of the method for bringing the intrinsic viscosity [η] of the polycarbonate resin within the above range include the following examples. For example, when polymerizing by a transesterification method of a dihydroxy compound and a carbonic acid diester compound, which will be described later, the feed amount of the raw material carbonic acid diester compound and the aromatic dihydroxy compound is appropriately adjusted so that the target intrinsic viscosity [η] is obtained. The amount of catalyst added, reaction temperature, reaction pressure, and reaction time are adjusted. Moreover, it can adjust also by adding a terminal terminator etc. and performing polycondensation. On the other hand, in the case of the interfacial polymerization method to be described later, it is usually possible to achieve the target intrinsic viscosity by appropriately adding a terminal terminator, a branching agent and the like.

  The terminal hydroxyl group concentration of the polycarbonate resin (A) is not particularly limited, but when the transesterification method described later is adopted as the production method, the terminal hydroxyl group concentration of the obtained polycarbonate resin is usually 100 ppm by mass or more, preferably 200 masses. ppm or more, more preferably 300 mass ppm or more. However, it is usually 2,000 mass ppm or less, preferably 1,800 mass ppm or less, more preferably 1,200 mass ppm or less. When the terminal hydroxyl group concentration of the polycarbonate resin is excessively small, the initial hue of the molded product tends to deteriorate. When the terminal hydroxyl group concentration is excessively large, the residence heat stability tends to decrease. In order to make the terminal hydroxyl group concentration within the above range, a method of adjusting the monomer charge ratio and reaction temperature is generally employed.

Moreover, in this invention, it is preferable that 10 mass% or more in polycarbonate resin (A) is a flaky powder. The content ratio of the flaky powder is preferably 15% by mass or more, more preferably 20% by mass or more. By containing flaky powder in such a proportion, classification of flame retardants and other additive components blended as necessary at the time of polycarbonate resin composition production is prevented, generation of unmelted materials and additives It tends to be easy to obtain a molded product that suppresses aggregation of the resin and is excellent in flame retardancy, impact resistance, and transparency. The average particle size of the flaky powder is preferably 2 mm or less, and more preferably 1.5 mm or less.
The polycarbonate resin other than the flaky powder is preferably a pellet. The pellet length is preferably 1 to 5 mm, more preferably 2 to 4 mm. When the cross section is elliptical, the major axis is 2 to 3.5 mm, the minor axis is 1 to 2.5 mm, and the diameter is when the section is circular. The thing of 2-3 mm is preferable. The length and cross-sectional shape of the pellet can be adjusted by the number of rotations of the blade of the strand cutter, the winding speed, and the discharge amount of the extruder when the polycarbonate resin (A) is produced.

The polycarbonate resin preferable as the polycarbonate resin (A) used in the present invention is a polycarbonate resin (A1) having a structural unit of the following general formula (1) and a polycarbonate resin (A2) having a structural unit of the following general formula (2). Is a polycarbonate resin containing 80/20 to 20/80 by mass ratio.
(In the general formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X represents
R ³ and R ⁴ represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )
(X in the general formula (2) has the same meaning as the general formula (1).)

<Polycarbonate resin (A1)>
The polycarbonate resin (A1) is a polycarbonate resin having a structural unit represented by the following general formula (1).
(In the general formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom or a methyl group, and X represents
R ³ and R ⁴ represent a hydrogen atom or a methyl group, and Z represents a group that forms an alicyclic hydrocarbon which may combine with C to have a substituent having 6 to 12 carbon atoms. . )

As the polycarbonate (A1), in the above general formula (1), R ¹ is a methyl group, R ² is a hydrogen atom or a methyl group, and R ² is particularly preferably a hydrogen atom.

X is
Is preferably an isopropylidene group in which both R ³ and R ⁴ are methyl groups, and X is
In this case, Z is bonded to carbon C bonded to the two phenyl groups in the above formula (1) to form a bivalent alicyclic hydrocarbon group having 6 to 12 carbon atoms. Examples of the alicyclic carbon hydrogen group include a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, an adamantylidene group, a cyclododecylidene group, and the like. Examples of the substituted ones include those having these methyl substituents and ethyl substituents. Among these, a cyclohexylidene group, a methyl-substituted cyclohexylidene group (preferably 3,3,5-trimethyl-substituted), and a cyclododecylidene group are preferable.

Preferable specific examples of the polycarbonate resin (A1) used in the present invention include the following polycarbonate resins i) to iv).
i) Those having a 2,2-bis (3-methyl-4-hydroxyphenyl) propane structural unit, that is, R ¹ is a methyl group, R ² is a hydrogen atom, and X (or —CR ³ R ⁴ —) is isopropylidene. Having a structural unit as a group,
ii) 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane structural unit, that is, having a structural unit in which R ¹ is a methyl group, R ² is a methyl group, and X is an isopropylidene group,
iii) 2,2-bis (3-methyl-4-hydroxyphenyl) cyclohexane structural unit, that is, R ¹ is a methyl group, R ² is a hydrogen atom, and X (or -C (= Z)-) is a cyclohexylidene group Having a structural unit of
iv) 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane structural unit, that is, R ¹ is a methyl group, R ² is a hydrogen atom, and X (or —C (═Z) —) is cyclododecyl. Those having a structural unit which is a redene group.
Among these, the polycarbonate resin of i), ii) or iii), more preferably i) or iii), and particularly i) is more preferable.

  These polycarbonate resins (A1) are respectively 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- Bis (3-methyl-4-hydroxyphenyl) cyclohexane and 2,2-bis (3-methyl-4-hydroxyphenyl) cyclododecane can be used as dihydroxy compounds.

  The polycarbonate resin (A1) can also have a carbonate structural unit other than the structural unit of the general formula (1). For example, the structural unit of the general formula (2) (that is, a structural unit derived from bisphenol-A), Or you may have a structural unit derived from the other dihydroxy compound as mentioned later. The copolymerization amount of structural units other than the structural unit of the general formula (1) is usually 60 mol% or less, preferably 55 mol% or less, preferably 50 mol% or less, more preferably 40 mol% or less, and further 30 The mol% or less, particularly 20 mol% or less, 10 mol% or less, and most preferably 5 mol% or less.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A1) used in the present invention is preferably 20,000 to 35,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. When the viscosity average molecular weight is less than 20,000, impact resistance is lowered and cracking or chipping occurs when the product is produced. If it exceeds 35,000, the melt viscosity becomes too high and the fluidity is deteriorated, and in particular, injection molding of a thin product may be extremely difficult. The lower limit of the preferred molecular weight of the polycarbonate resin (A1) is 22,000, more preferably 23,000, still more preferably 24,000, and the upper limit is preferably 33,000, more preferably 32,500.
Here, the viscosity average molecular weight (Mv) is obtained by using methylene chloride as a solvent and using an Ubbelohde viscometer to determine the intrinsic viscosity ([η]) (unit dl / g) at a temperature of 20 ° C. Formula: means a value calculated from the formula η = 1.23 × 10 ⁻⁴ M ^0.83 .

  The polycarbonate resin (A1) may be used singly or in combination of two or more, and may be adjusted to the above viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

<Polycarbonate resin (A2)>
The polycarbonate resin (A2) used in the present invention is a polycarbonate resin having a structural unit represented by the following general formula (2).
(X in the general formula (2) has the same meaning as the general formula (1).)

A preferred specific example of the polycarbonate structural unit represented by the general formula (2) is 2,2-bis (4-hydroxyphenyl) propane, that is, a carbonate structural unit derived from bisphenol-A.
The polycarbonate resin (A2) may have a carbonate structural unit other than the structural unit of the general formula (2), and may have a carbonate structural unit derived from another dihydroxy compound. The copolymerization amount of structural units other than the structural unit of the general formula (2) is usually preferably less than 50 mol%, more preferably 40 mol% or less, further 30 mol% or less, particularly 20 mol% or less, 10 mol% or less, and most preferably 5 mol% or less.

Examples of other dihydroxy compounds include the following aromatic dihydroxy compounds.
Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-) (1-methylethyl) phenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3- (1-methylpropyl) phenyl) propane 2,2-bis (4-hydroxy-3-cyclohexylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) Phenylmethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3) -(1-methylethyl) phenyl) cyclohexane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) Cyclohexane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexane, 1,1- (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylethyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3- (1-methylpropyl) phenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-cyclohexylphenyl) -1- Phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclopent Tan, 1,1-bis (4-hydroxyphenyl) cyclooctane, 4,4 ′-(1,3-phenylenediisopropylidene) bisphenol, 4,4 ′-(1,4-phenylenediisopropylidene) bisphenol, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxyphenyl ether, 4,4 '-Dihydroxybiphenyl, 1,1-bis (4-hydroxyphenyl) -3,3-5-trimethylcyclohexane, 1,1-bis (4-hydroxy-6-methyl-3-tert-butylphenyl) butane, etc. Can be mentioned.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A2) used in the present invention is preferably 16,000 to 28,000. When the viscosity average molecular weight is within this range, a molded product having good moldability and high mechanical strength can be obtained. When the viscosity average molecular weight is less than 16,000, impact resistance is lowered and cracking or chipping occurs when the product is produced. If it exceeds 28,000, the melt viscosity becomes too high, the fluidity is deteriorated, and injection molding of a thin product may be particularly difficult. The lower limit of the preferred molecular weight of the polycarbonate resin (A2) is 17,000, more preferably 18,000, and the upper limit thereof is preferably 27,000.
The definition of the viscosity average molecular weight (Mv) is as described above.

  The polycarbonate resin (A2) may be used singly or in combination of two or more, and may be adjusted to the viscosity average molecular weight by mixing two or more types of polycarbonate resins having different viscosity average molecular weights. Moreover, you may mix and use the polycarbonate resin whose viscosity average molecular weight is outside said suitable range as needed.

<Ratio of polycarbonate resin (A1) and (A2)>
When using together said polycarbonate resin (A1) and polycarbonate resin (A2), the mixing ratio is polycarbonate resin (A1) / polycarbonate resin (A2) = 80 / 20-20 / 80 by mass ratio of both. It is preferable. By using it in such a mixing ratio, high surface hardness and high flame retardancy improvement can be achieved. When the mass ratio of the polycarbonate resin (A1) is less than 20, the surface hardness is lowered during the commercialization, and scratches are easily formed. If it exceeds 80, the physical properties (impact resistance, heat resistance, weather resistance, etc.) derived from the polycarbonate resin (A2) will be greatly different, and it tends to be difficult to use the same application.
A preferable mixing ratio is polycarbonate resin (A1) / polycarbonate resin (A2) = 80/20 to 30/70.

<Production method of polycarbonate resin (A)>
The method for producing the polycarbonate resin (A) used in the present invention is not particularly limited, and any method can be adopted. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, preferred ones of these methods will be described in detail, but particularly preferred is the melting method (melt transesterification method) described later because the effect of achieving flame retardancy is remarkable.

-Interfacial polymerization method First, the case where a polycarbonate resin (A) is manufactured by the interfacial polymerization method will be described.
In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, the pH is usually kept at 9 or more, and each dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted, followed by polymerization. A polycarbonate resin is obtained by performing interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for the purpose of preventing oxidation of the dihydroxy compound.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. In particular, it is preferably set to 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight regulator include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable.
Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where a polycarbonate resin (A) is manufactured by a melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the conditions in this range while removing by-products such as hydroxy compounds.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. In the case of a batch system, the order of mixing the reaction substrate, reaction medium, catalyst, additive, etc. is arbitrary as long as the desired polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. However, in view of the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 mass ppm or more normally with respect to polycarbonate resin, and is 100 mass ppm or less normally, Preferably it is 20 mass ppm or less.

<Flame retardant (B)>
Examples of the flame retardant (B) used in the present invention include phosphorus flame retardants, bromine flame retardants, organic sulfonic acid metal salt flame retardants, and silicon-containing compound flame retardants. Among these, Phosphorus flame retardants and bromine flame retardants are preferred.

<Phosphorus flame retardant>
As the phosphorus-based flame retardant, a phosphate ester-based compound is preferable. The phosphate ester compound is a compound containing phosphorus in the molecule, and may be a low molecule, an oligomer, or a polymer. For example, the following general formula (3) or (4 The phosphorus-based flame retardant represented by the general formula (3) is particularly preferable from the viewpoint of thermal stability.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, X represents an arylene group, p, q, r and s are each 0 or 1, and k is an integer of 1 to 5.)

(Wherein R ₅ , R ₆ and R ₇ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and h, i and j) Represents 0 or 1 respectively.)

  The phosphorus compound represented by the general formula (3) is a condensed phosphate ester having k of 1 to 5. For a mixture of condensed phosphate esters having different k, k is an average value of the mixture. X represents an arylene group and is a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A, and the like.

  As a specific example of the phosphorus compound represented by the general formula (3), when resorcinol is used as a dihydroxy compound, phenyl resorcinol polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, Xylyl resorcin polyphosphate, phenyl-pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcin polyphosphate Etc.

  The phosphorus compound represented by the general formula (4) can be produced from phosphorus oxychloride or the like by a known method. Specific examples of the phosphorus compound represented by the general formula (4) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, and phenylphosphonic acid. Examples include diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

The phosphorus flame retardant may be a phosphazene compound.
The phosphazene compound is at least one selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound, and a crosslinked phenoxyphosphazene compound.

<Brominated flame retardant>
Brominated flame retardants include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polystyrene resin, brominated bisphenol A, glycidyl brominated bisphenol A, pentabromobenzyl polyacrylate, bromine Examples include brominated imides (brominated phthalimides, etc.), among which brominated polycarbonates are preferred from the viewpoint of dispersibility in the polycarbonate resin (A). Of these, a brominated polycarbonate obtained by reacting (condensation polymerization) tetrabromobisphenol A (sometimes abbreviated as “TBA”) with phosgene or a carbonic acid diester using an appropriate molecular weight regulator is particularly preferable. . Further, it may be a copolymer type in which a part of tetrabromobisphenol A is replaced with another dihydric phenol, and the dihydric phenol described in the above aromatic polycarbonate resin is used as the other dihydric phenol. Furthermore, bisphenol A (sometimes abbreviated as “BPA”) is preferable from the viewpoint of yield during synthesis, ease of solidification, and high versatility (price).
Such a brominated polycarbonate is likely to bleed out from the molded product at the time of molding at a polymerization degree of 1, and on the other hand, it becomes difficult to obtain satisfactory fluidity when the degree of polymerization is increased. More preferably, it is ~ 15.

  Such brominated polycarbonate is commercially available and can be easily obtained. For example, an oligomer (average degree of polymerization of 5) obtained by reacting TBA and phosgene using 2,4,6-tribromophenol (sometimes abbreviated as “TBPH”) as a molecular weight regulator is Mitsubishi Engineering. From the Plastics Co., Ltd., as a trade name “Iupilon FR-53”, and TBPH as a molecular weight regulator, a copolymerized oligomer (average degree of polymerization 3) obtained by reacting TBA, BPA and phosgene is It is commercially available from Mitsubishi Engineering Plastics Co., Ltd. under the trade name “Iupilon FR-34”.

  The content of the flame retardant (B) is 2 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), the upper limit is 30 parts by mass or less, preferably 3 parts by mass or more, and more preferably 5 parts by mass. It is above, Preferably it is 20 mass parts or less. When the blending amount of the flame retardant is less than 2 parts by mass, the expression of the flame retardant effect tends to be insufficient, and when it exceeds 30 parts by mass, a remarkable decrease in heat resistance and mechanical properties are likely to occur.

<Anti-dripping agent (C)>
The polycarbonate resin composition of the present invention contains an anti-dripping agent (C). The content is 0.01-1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). Thus, by containing a dripping inhibitor, the melting characteristic of the resin composition can be improved, and specifically, the dripping preventing property at the time of combustion can be improved.
When the content of the anti-dripping agent (C) is less than 0.01 parts by mass, the flame retardancy improving effect by the anti-drip agent is insufficient, and when it exceeds 1 part by mass, the appearance of the molded article is poor or mechanical. The strength tends to decrease. The lower limit of the content is preferably 0.03 parts by mass or more, and the upper limit of the content is preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less.

  The anti-dripping agent (C) is preferably a fluoropolymer, and one kind of fluoropolymer may be used, or two or more kinds may be used in any combination and in any ratio.

  An example of the fluoropolymer is a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. Can be mentioned. Further, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Teflon (registered trademark) 31-JR”, “Fluon D- manufactured by Daikin Chemical Industries, Ltd.” 1 "etc. are mentioned. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

<Stabilizer>
The polycarbonate resin composition of the present invention preferably contains a stabilizer in order to prevent a decrease in molecular weight or deterioration in transparency during molding or the like.
As the stabilizer, a phosphorus stabilizer and a hindered phenol stabilizer are preferable.
Examples of the phosphorus stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, mono Butyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4,6- G-t rt-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, Triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphosphinic acid tetrakis (2,4-di-tert-butylphenyl), Examples thereof include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Examples of the hindered phenol stabilizer include pentaerythritol tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-) Hydroxyphenyl) propionate) and the like.
Among these, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate is preferred. These two hindered phenolic antioxidants are commercially available from BASF under the names “Irganox 1010” and “Irganox 1076”.

  The content of the phosphorus stabilizer and / or the hindered phenol stabilizer is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). Moreover, 1 mass part or less is preferable, More preferably, it is 0.5 mass part or less, More preferably, it is 0.2 mass part or less, Most preferably, it is 0.1 mass part or less. When the stabilizer content is less than or equal to the lower limit of the above range, the effect of improving molecular weight reduction or transparency deterioration may not be obtained, and when the stabilizer content exceeds the upper limit of the above range, the reverse It tends to be unstable to heat and moisture.

<Ultraviolet absorber>
The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber. In particular, when used in combination with the above-mentioned phosphorus stabilizer and / or phenol stabilizer, the weather resistance tends to be more improved.
Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, and the like. Of these, benzotriazole-based UV absorbers, triazine-based UV absorbers, or malonic ester-based UV absorbers are more preferable.
In particular, when the polycarbonate resin (A1) and the polycarbonate resin (A2) are used in combination, it is recognized that the effect of improving the weather resistance against the polycarbonate resin (A1) is better than that of the polycarbonate resin (A2) and the change in color tone is smaller. It was.

  Specific examples of the benzotriazole ultraviolet absorber include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α -Dimethylbenzyl) phenyl] -benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'- Hydroxy-3 ′, 5′-di-tert-amyl) -benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotria Sol, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2 '-Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) Phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred.

  Specific examples of the triazine-based ultraviolet absorber include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4- Diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3 , 5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydro Ci-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl -6- (2-hydroxy-4-butoxyethoxyphenyl) -1,3,5-triazine and the like.

  Specific examples of the malonic acid ester ultraviolet absorber include 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters, and such malonic acid ester ultraviolet absorbers. Specific examples include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF, and the like.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is 0.6 mass part or less, More preferably, it is 0.4 mass part or less. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination.

<Release agent>
The polycarbonate resin composition of the present invention preferably contains a release agent.
Examples of the release agent include aliphatic carboxylic acids, fatty acid esters composed of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like. A fatty acid ester composed of an aliphatic carboxylic acid and an alcohol is more preferable.

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

  As alcohol which comprises fatty acid ester, a saturated or unsaturated monohydric alcohol, a saturated or unsaturated polyhydric alcohol, etc. can be mentioned. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, aliphatic includes alicyclic compounds. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.

Specific examples of fatty acid esters composed of aliphatic carboxylic acids and alcohols include beeswax (mixture based on myristyl palmitate), stearic acid stearate, behenic acid behenate, behenic acid stearate, palmitic acid monoglyceride, stearic acid Examples include monoglyceride, stearic acid diglyceride, stearic acid triglyceride, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate. Among these, it is more preferable to use at least one mold release agent selected from pentaerythritol tetrastearate, stearic acid stearate, and stearic acid monoglyceride.
The content of the release agent is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), and the upper limit thereof is preferably 1 part by mass. Part or less, more preferably 0.6 part by weight or less, and still more preferably 0.4 part by weight or less. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

<Other additives>
The polycarbonate resin composition of the present invention may contain other various additives as necessary. Examples of additives include colorants, antistatic agents, thermoplastic resins, thermoplastic elastomers, glass fibers, glass flakes, glass beads, carbon fibers, wollastonite, calcium silicate, aluminum borate whiskers, and the like.

<Pencil hardness>
Further, the polycarbonate resin composition of the present invention has a very high pencil hardness of HB or higher.
Here, the pencil hardness is measured according to JIS K5600-5-4. In the present invention, measurement is performed on a 100 × 100 × 2 mm test piece.
If the pencil hardness is lower than HB, the surface hardness is insufficient when the product is manufactured, and it becomes easy to be damaged and scratched during use, causing a problem. The pencil hardness is preferably F or higher, particularly H or higher, particularly 2H or higher.

<UL94 flame retardancy test>
Furthermore, the polycarbonate resin composition of the present invention preferably has a high flame retardancy that the thickness of a test piece that achieves V-0 in the UL94 standard vertical combustion test is 1 mm or less.

  As described above, the polycarbonate resin composition of the present invention includes the polycarbonate resin (A1) having a viscosity average molecular weight (Mv) of 20,000 to 35,000 and the polycarbonate resin (A2) having an Mv of 16,000 to 28,000. In combination with the resin composition not having such a structure, the hardness becomes better, the pencil hardness shows a high value of HB or more, and also tends to show high flame retardancy. It is in.

As described above, when the polycarbonate resin (A1) and the polycarbonate resin (A2) are used in combination as the polycarbonate resin (A), the reason why the polycarbonate resin composition of the present invention tends to exhibit the above-described characteristics is as follows. Although it is not clear, for example, a polycarbonate resin (“C”) obtained by using 2,2-bis (3-methyl-4-hydroxyphenyl) propane, which is an aromatic dihydroxy compound, as a raw material monomer for the polycarbonate resin (A1). -PC ")) is used as an example, for example, it is estimated as follows.
That is, C-PC is a polycarbonate resin (A2) obtained by using 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) as a raw material monomer (referred to as “A-PC”). The compatibility is very good and the haze is not lowered, and the addition of a small amount of about 20% by mass makes the effect of improving the hardness of the composition remarkable. The improvement in hardness is presumed that C-PC or the like tends to be unevenly distributed in the surface portion of the molded body as compared with A-PC, and the surface hardness is increased. Moreover, when the ratio (η ₁₀ / η ₁₀₀₀ ) to the melt viscosity η ₁₀₀₀ is 3 to 8, it is easy to achieve both high flame retardancy and fluidity.

<Manufacture of polycarbonate resin composition>
When producing the polycarbonate resin composition of the present invention, the mixing method of the polycarbonate resin (A), the flame retardant (B), the anti-dripping agent (C), and the above-described additives blended as necessary is particularly limited. First, a known method for producing a polycarbonate resin composition can be widely adopted.
Specific examples include polycarbonate resin (A) flame retardant (B) and anti-drip agent (C), and various components such as tumblers and Henschel mixers. Examples thereof include a method of premixing using a machine and then melt-kneading with a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also.
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The polycarbonate resin composition of the present invention can also be produced.

<Polycarbonate resin molding>
A polycarbonate resin molded article is produced using the above-described polycarbonate resin composition of the present invention. The molding method of the polycarbonate resin molding is not particularly limited, and a molded product can be produced by molding pellets obtained by pelletizing the resin composition of the present invention by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.
Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  As described above, the polycarbonate resin composition of the present invention can provide a resin molded product having both high surface hardness and high flame retardancy, and examples of molded products include electrical and electronic equipment, OA equipment, and information terminals. Equipment, lighting equipment parts, home appliances, interior and exterior of home appliances, interior parts for vehicles, building members, various containers, parts for leisure goods, miscellaneous goods, etc., LED reflectors, covers, LED mounting boards or heat dissipation members It is preferably used for LED lighting parts, sheets and the like. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, interior and exterior of home appliance parts, and parts for LED lighting. However, it is suitable for applications such as housings or covers for electrical and electronic equipment, LED lighting components, single-layer or multilayer sheets, interior and exterior of home appliances, and building materials.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

Each component used in the examples and comparative examples is as follows.
[Polycarbonate resin (A1)]
The following polycarbonate resin (C-PC-1) was used as the polycarbonate resin (A1).

(1) Production of polycarbonate resin (C-PC-1) by melting method:
2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter referred to as “BPC”) 26.14 mol (6.75 kg) and diphenyl carbonate 26.66 mol (5.71 kg) The reactor was placed in a SUS reactor (with an internal volume of 40 liters) equipped with a stirrer and a distillation condenser, and after the inside of the reactor was replaced with nitrogen gas, the temperature was raised to 220 ° C. over 30 minutes in a nitrogen gas atmosphere.
Next, the reaction solution in the reactor is stirred, and cesium carbonate (Cs ₂ CO ₃ ) is used as a transesterification reaction catalyst in the molten reaction solution so that the amount becomes 1.5 × 10 ⁻⁶ mol per 1 mol of BPC. In addition, the reaction solution was stirred and brewed at 220 ° C. for 30 minutes in a nitrogen gas atmosphere. Next, under the same temperature, the pressure in the reactor was reduced to 100 Torr over 40 minutes, and the reaction was further performed for 100 minutes to distill phenol.

Next, the temperature in the reactor was raised to 280 ° C. over 60 minutes and the pressure was reduced to 3 Torr to distill phenol corresponding to almost the entire distillation theoretical amount. Next, the pressure in the reactor was kept below 1 Torr under the same temperature, and the reaction was further continued for 80 minutes to complete the polycondensation reaction. At this time, the stirring rotation speed of the stirrer was 38 rotations / minute, the reaction liquid temperature immediately before the completion of the reaction was 300 ° C., and the stirring power was 1.40 kW.
Next, the reaction solution in a molten state is fed into a twin screw extruder, and 4-fold molar amount of butyl p-toluenesulfonate is supplied from the first supply port of the twin screw extruder with respect to cesium carbonate, After kneading with the reaction solution, the reaction solution was extruded in a strand shape through a die of a twin screw extruder and cut with a cutter to obtain carbonate resin pellets.
The physical properties of the obtained polycarbonate resin (C-PC-1) were as follows.
Pencil hardness: 2H
Viscosity average molecular weight (Mv): 32,000
η ₁₀ / η ₁₀₀₀ 7.9

[Polycarbonate resin (A2)]
The following polycarbonate resins (A-PC-1) to (A-PC-3) were used as the polycarbonate resin (A2).
(1) A-PC-1:
Polycarbonate resin using bisphenol-A as a starting material by a melting method, manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name “NOVAREX M7027BF” (pellet form)
Pencil hardness 2B
Viscosity average molecular weight (Mv) 27,000
η ₁₀ / η ₁₀₀₀ 5.3
(2) A-PC-2:
Polycarbonate resin by the interfacial method using bisphenol-A as a starting material, manufactured by Mitsubishi Engineering Plastics, Inc., trade name “Iupilon S-3000”
Flake powder pencil hardness 2B
Viscosity average molecular weight (Mv) 21,000
η ₁₀ / η ₁₀₀₀ 2.3
(3) A-PC-3:
Polycarbonate resin by the interfacial method using bisphenol-A as a starting material, trade name “Iupilon H-4000” manufactured by Mitsubishi Engineering Plastics
Flake powder pencil hardness 2B
Viscosity average molecular weight (Mv) 18,000
η ₁₀ / η ₁₀₀₀ 2.1

[Flame retardants]
Phosphorus flame retardants and condensed phosphates: resorcinol bis (dixylenyl phosphate)
Product name “PX200” manufactured by Daihachi Chemical Industry Co., Ltd.
・ Phosphazene compound: Phosphazene compound mainly composed of cyclic products, Fushimi Pharmaceutical Co., Ltd., trade name “FP-100”
Brominated flame retardant and brominated polycarbonate:
Product name "Iupilon (registered trademark) FR-53" manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Organic sulfonic acid metal salt:
・ Perfluorobutanesulfonic acid potassium salt:
Product name "F-114" manufactured by DIC

[Anti-drip agent]
-Polytetrafluoroethylene having fibril-forming ability:
Product name "Polyflon FA500B", manufactured by Daikin Industries

[Other additives]
[Stabilizer]
・ Phosphorus heat stabilizer:
Tris (2,4-di-tert-butylphenyl) phosphite manufactured by ADEKA, trade name “ADK STAB 2112”
・ Hindered phenol stabilizers:
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Product name "Irganox 1010" manufactured by BASF

[Release agent]
・ Pentaerythritol tetrastearate:
Product name “Roxyol VPG861” manufactured by Cognis
・ Stearic acid stearate:
Product name “Unistar M9766” manufactured by NOF Corporation

(Examples 1-6) (Comparative Examples 1-5)
Each of the resins and additives described above are blended and mixed in the composition (parts by mass) shown in the following table, and kneaded at a barrel temperature of 280 ° C. with a twin-screw extruder (TEX30XCT manufactured by Nippon Steel Works) to obtain a polycarbonate resin composition. After manufacturing and obtaining a pellet and drying at 80 degreeC for 5 hours, according to the following procedures, various test pieces were created and the following evaluation was performed.

The evaluation and measurement methods performed in the examples and comparative examples are as follows.
(A) Melt viscosity The melt viscosity of the polycarbonate resin is a capillary rheometer ("Capillograph 1C" manufactured by Toyo Seiki Co., Ltd.) with a die diameter of 1 mmφ x 30 mmL, a residence time of 5 minutes, a measurement temperature of 300 ° C, and a shear rate. It measured in the range of (gamma) = 9.12-1824sec- ¹ . The polycarbonate resin used was previously dried at 80 ° C. for 5 hours. Eta ₁₀ and eta ₁₀₀₀ polycarbonate resin reads the melt viscosity at the melt viscosity and shear rate of 1,000 sec ^-1 at a shear rate of 10 sec ^-1, respectively, was measured.

(B) Pencil hardness The pencil hardness of the polycarbonate resin composition is such that the above pellets are injected using an injection molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.), cylinder set temperature 260 to 280 ° C, mold temperature 80 ° C, screw A plate having a thickness of 2 mm, a length of 100 mm, and a width of 100 mm was injection molded under the condition of a rotation speed of 100 rpm. About the obtained plate, based on JISK5600-5-4, the pencil hardness was measured with a 1000-g load using the pencil hardness tester (made by Toyo Seiki Co., Ltd.).

(C) UL94 Flame Retardancy Test Using a polycarbonate resin composition pellet obtained by the above-described method, a cylinder temperature of 260 to 280 ° C., gold using an injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) Under the conditions of a mold temperature of 80 ° C. and a molding cycle of 30 seconds, a plurality of UL test specimens (length 125 mm × width 13 mm × thickness 0.6 to 2.0 mm) having different thicknesses are injection molded in accordance with the UL94 standard. The UL standard 94 vertical combustion test was performed, and the evaluation was performed based on the thickness of the test piece that was able to achieve “V-0”.

In the UL class, “V-0 NG” means V-0 failure.
The determination of V-0, V-1, and V-2 is the flaming combustion duration after the first and second flame contact ends, the flammable combustion duration and the flameless combustion duration after the second flame termination. It is determined by the total time, the total flammable combustion duration of the five test pieces, and the presence or absence of combustion drops (drip).
At the time of the first flame contact, V-0 is judged within 10 seconds, and V-1 and V-2 are judged by whether or not flaming combustion is finished within 30 seconds. Further, the sum of the second flammable combustion duration and the flameless combustion duration is determined based on whether V-0 disappears within 30 seconds and V-1 and V-2 disappear within 60 seconds.
Furthermore, the total of the flammable combustion durations of the five test pieces is determined based on whether V-0 is within 50 seconds and V-1 and V-2 are within 250 seconds. Moreover, combustion dripping is permitted only for V-2. All specimens must not burn out.
The above evaluation results are shown in the following table.

  From the results shown in Table 1 and Table 2, it can be seen that the polycarbonate resin composition satisfying all the specific requirements of the present invention is excellent in high surface hardness and high flame retardancy.

  Since the polycarbonate resin composition of the present invention is excellent in surface hardness and flame retardancy, it can be used as a molded product in various applications, and can be used for electrical and electronic equipment, OA equipment, information terminal equipment, lighting equipment parts, sheets, home appliances, and vehicles. It can be suitably used in a wide range of parts such as interior parts, building components, various containers, leisure goods, miscellaneous goods, etc., and its industrial utility is very high.

Claims (16)

A viscosity average molecular weight (Mv) having a structural unit of the following general formula (1) and a viscosity average molecular weight (Mv) having a structural unit of the following general formula (2): containing 16,000～28,000 of polycarbonate resin (A2), 300 ℃, the melt viscosity eta ₁₀ as measured at a shear rate of 10sec ^-1, 300 ℃, the melt viscosity eta ₁₀₀₀ as measured at a shear rate of 1,000 sec ^-1 Of 100 parts by mass of the polycarbonate resin (A) in which the ratio (η ₁₀ / η ₁₀₀₀ ) is 3 to 8,
A polycarbonate resin composition containing 2 to 30 parts by mass of a flame retardant (B) and 0.01 to 1 part by mass of an anti-dripping agent (C),
A polycarbonate resin composition, wherein the molded article obtained by molding the polycarbonate resin composition has a pencil hardness of HB or more.
(In general formula (1), R ¹ represents a methyl group, R ² represents a hydrogen atom, and X represents an isopropylidene group.)
(X in the general formula (2) is an isopropylidene group.)   Content of polycarbonate resin (A1) in a total of 100 mass parts of polycarbonate resin (A1) and polycarbonate resin (A2) is 15 mass parts or more, The polycarbonate resin composition of Claim 1 characterized by the above-mentioned.   The polycarbonate resin according to claim 1 or 2, wherein the polycarbonate resin (A1) and the polycarbonate resin (A2) are contained at a mass ratio of (A1) / (A2) of 80/20 to 20/80. Resin composition. Polycarbonate resin composition according to claim 1, wherein the melt viscosity eta ₁₀ is 8,000~50,000Pa · s. The polycarbonate resin composition according to claim 1, wherein the melt viscosity η ₁₀₀₀ is 1,000 to 10,000 Pa · s.   The polycarbonate resin composition according to any one of claims 1 to 5, wherein a test piece thickness for achieving V-0 in the UL94 standard vertical combustion test is 1.0 mm or less.   The polycarbonate resin composition according to any one of claims 1 to 6, wherein the flame retardant (B) is a phosphorus flame retardant or a bromine flame retardant.   The polycarbonate resin composition according to any one of claims 1 to 7, wherein the anti-dripping agent (C) is a fluoropolymer. Moreover, phosphorus-based stabilizer and / or a hindered phenol stabilizer, relative to the polycarbonate resin (A) 100 parts by mass of any of claims 1-8, characterized in that it contains 0.01 to 1 parts by weight A polycarbonate resin composition according to any one of the above. Furthermore, a fatty acid ester as the release agent, relative to the polycarbonate resin (A) 100 parts by mass of a polycarbonate resin composition according to any one of claims 1 to 9, characterized in that it contains 0.05 to 1 parts by weight object. 11. The polycarbonate resin composition according to claim 10 , wherein the release agent is at least one selected from pentaerythritol tetrastearate, stearic acid stearate, and stearic acid monoglyceride. Polycarbonate resin composition according to any one of claims 1 to 11, at least 10 wt% of a polycarbonate resin (A) is characterized in that it is a flaky powder. Housing or cover of the electrical and electronic equipment and formed by molding the polycarbonate resin composition according to any one of claims 1 to 12. Monolayer or multilayer sheet formed by molding the polycarbonate resin composition according to any one of claims 1 to 12. Shaped LED lighting component comprising a polycarbonate resin composition according to any one of claims 1 to 12. Construction member obtained by molding the polycarbonate resin composition according to any one of claims 1 to 12.