JPH0680869A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in abrasion and impact resistance, surface appearance, moldability and flame retardancy by blending a polycarbonate with specific polytetrafluoroethylene and specified polyvinylidene fluoride in a specific proportion. CONSTITUTION:The objective composition is obtained by respectively blending (A) a polycarbonate with (B) polytetrafluoroethylene without forming fibrils in receiving mechanical shear and (C) polyvinylidene fluoride having <=10 melt flow rate (at 230 deg.C temperature under 5kg load) so as to provide 60-90 pts.wt. component (A) and 1-40 pts.wt. total amount of the components (B) and (C) based on 100 pts.wt. total amount of the components (A), (B) and (C) at (1/2) to (1/0.1) weight ratio of the components (B)/(C). Furthermore, a metallic salt of an aromatic sulfonimide of the formula [Ar is (substituted)aromatic group; M is metallic cation] and the polytetrafluoroethylene capable of forming the fibrils in receiving the mechanical shear are preferably added in combination to this composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition which is excellent in abrasion resistance and surface appearance, and is excellent in impact resistance, moldability and flame retardancy.

[0002]

2. Description of the Related Art Polycarbonate is excellent in impact resistance, heat resistance and the like, and is widely used in various fields such as vehicle field, weak electric current, medical care, food, etc. Limited use. In order to improve the abrasion resistance of this polycarbonate, it has been conventionally practiced to add polytetrafluoroethylene (Japanese Patent Laid-Open No. 34051/50). However, in this method, the impact resistance, which is a property peculiar to polycarbonate, is reduced, and the surface appearance of the molded product (the surface roughness of the molded product) is significantly reduced, so that only products with low commercial value can be obtained. is there.

By blending a rubber-reinforced resin such as MBS resin in order to improve the impact resistance of such a polycarbonate, the impact resistance is improved, but the surface appearance of the molded product is not improved and the abrasion resistance is improved. Is inferior to Further, a material excellent in flame retardancy in addition to these performances has been demanded, but at present, a material satisfying these performances has not yet been obtained.

[0004]

DISCLOSURE OF THE INVENTION The object of the present invention is to obtain a polycarbonate resin composition which is excellent in abrasion resistance and surface appearance, and is excellent in impact resistance, moldability and flame retardancy.

[0005]

As a result of intensive studies on the above problems, the present inventors have found that specific polytetrafluoroethylene and specific polyvinylidene fluoride at a specific ratio with respect to polycarbonate, and further The present inventors have found that the above-mentioned problems can be solved by adding a metal salt of aromatic sulfone imide and / or a specific polytetrafluoroethylene, and arrived at the present invention.

That is, according to the present invention, polycarbonate (A), polytetrafluoroethylene (B) which does not form fibrils when subjected to mechanical shearing, and polyvinylidene fluoride (melt flow rate (230 ° C., 5 Kg) 10 or less ( C), 60 to 99 parts by weight of (A) and 1 to 40 parts by weight of (B) + (C) per 100 parts by weight of (A), (B) and (C) in total, and
Polycarbonate resin composition characterized in that (B) / (C) is in a weight ratio of 1/2 to 1 / 0.1, and further, an aromatic sulfonimide represented by the following general formula for the composition. And a polytetrafluoroethylene (E) that forms fibrils when subjected to mechanical shearing.

[0007]

[Chemical 2]

(In the formula, Ar is an aromatic group or a substituted aromatic group, and M is a metal cation.)

The present invention will be described in detail below. The polycarbonate (A) used in the present invention is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate. And a typical example is a polycarbonate produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

As the above-mentioned dihydroxydiaryl compound, in addition to bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxy diaryl ethers such as 3,3′-dimethyldiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Examples thereof include dihydroxydiaryl sulfoxides such as 3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, and dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone. To be

These may be used alone or in admixture of two or more, but in addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be mixed and used.

Further, the above-mentioned dihydroxyaryl compound and a phenol compound having a valence of 3 or more as shown below may be mixed and used.

Examples of trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,6-dimethyl-2,4,6-tri. -(4-Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4,4-
(4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

The viscosity average molecular weight of polycarbonate is usually
It is 10,000 to 100,000, preferably 15,000 to 35,000.
In producing such a polycarbonate, a molecular weight modifier, a catalyst and the like can be used if necessary.

The polytetrafluoroethylene (B) used in the present invention must be a type of polytetrafluoroethylene that does not form fibrils when subjected to mechanical shearing and does not cause sticking of particles to each other. There is. When polytetrafluoroethylene of the type that forms fibrils when subjected to mechanical shearing is used as the component (B), the surface appearance is inferior, which is not preferable.

The mechanical shearing may be simply rubbing by hand. If particles stick to each other at that time, they are not suitable as the component (B) used in the present invention.

The polytetrafluoroethylene (B) is used in the form of powder consisting of particles or minute aggregates. The average particle diameter or the diameter of primary particles forming aggregates and the diameter of aggregates are 0.01 to 500 µ, preferably 0.05 to 100 µ.

The polyvinylidene fluoride used in the present invention has a melt flow rate (230 ° C., 5 Kg) of 10
It should be (g / 10 minutes) or less. When the melt flow rate is 10 or more, the surface appearance and impact resistance are poor, which is not preferable.

The present invention provides the above polycarbonate (A),
Consists of polytetrafluoroethylene (B) and polyvinylidene fluoride (C), (A), (B) and (C)
Of (A) 60 to 99 parts by weight and (B) + (C) 1 to 40 parts by weight, and
It is necessary that (B) / (C) be 1/2 to 1 / 0.1 in weight ratio.

When the proportion of the polycarbonate (A) is less than 60 parts by weight, impact resistance and moldability are poor, and when it exceeds 99 parts by weight, abrasion resistance is poor, which is not preferable. Preferably 6
0 to 95 parts by weight.

If the weight ratio of (B) / (C) is less than 1/2, abrasion resistance and moldability are poor, and if it exceeds 1 / 0.1, impact resistance and surface appearance are inferior.

The metal salt (D) of aromatic sulfonimide used in the present invention is a compound represented by the following general formula.

[0023]

[Chemical 3]

(In the formula, Ar is an aromatic group or a substituted aromatic group, and M is a metal cation.)

The above-mentioned suitable metals include Group I and Group II metals and copper, aluminum, antimony and the like, but alkali metals are particularly preferable, and sodium or potassium is most preferable.

The amount of the metal salt (D) of the aromatic sulfonimide used is not particularly limited, and it can be used in an amount that imparts a desired flame retardancy, but (A) and ( 0.001 to 2 parts by weight, more preferably 0.00, based on 100 parts by weight of the total of B) and (C).
It is 1 to 1 part by weight.

The polytetrafluoroethylene (E) used in the present invention must be a type of polytetrafluoroethylene that forms fibrils when mechanically sheared and causes particles to stick together. . As the component (E), when polytetrafluoroethylene of a type that does not form fibrils when subjected to mechanical shearing is used, the flame retardancy is poor and it is not preferable.

The amount of the polytetrafluoroethylene (E) used is not particularly limited, and it can be used in an amount that imparts the desired flame retardancy, but preferably (A), (B) and 0.01 to 10 parts by weight, more preferably 0.01 to 100 parts by weight of (C) in total.
~ 5 parts by weight.

Metal salt of aromatic sulfonimide (D)
And / or polytetrafluoroethylene (E) is
Flame retardancy can be imparted without lowering the properties of the composition comprising (A), (B) and (C), that is, wear resistance, surface appearance, impact resistance and moldability. Is. Particularly, from the viewpoint of flame retardancy, it is preferable to use the component (D) and the component (E) together.

There is no particular limitation on the mixing method and mixing order of the components (A), (B) and (C), and further the components (D) and (E), and there are known mixers such as tumblers and ribos. It can be carried out by mixing with a blender, a high speed mixer or the like, and melt kneading. It is also possible to mix the above three components all at once or add only the specific components and then add and mix the remaining components.

Further, at the time of mixing, if necessary, tetrabromobisphenol A, chlorinated bisphenol carbonate derivative, brominated bisphenol carbonate derivative oligomer, antimony oxide, aluminum hydroxide, zinc borate, tricresyl phosphate, tris ( Flame retardant such as dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, etc., and known additives such as antistatic agent, mold release agent, antioxidant, UV absorber, dye and pigment, etc. can do.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example I] Polycarbonate (A), polytetrafluoroethylene (B), and polyvinylidene fluoride (C) were mixed in a tumbler based on the compounding ratio shown in Table 1, and then melt-kneaded in an extruder. And pellets were obtained. Using a 4 ounce injection molding machine from the obtained pellets, various test pieces were prepared at a cylinder set temperature of 280 ° C. and used for the test. The test results are shown in Table 1.

The materials obtained in this example are as follows.

P C: An aromatic polycarbonate composed of bisphenol A and phosgene and having a viscosity average molecular weight of 22,000.

B-1: polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Lubron L-5F)

C-1: Polyvinylidene fluoride (VP-850 manufactured by Daikin Industries, Ltd.) Melt flow rate (230 ° C., 5 Kg) 0.2 (g / 1
0 minutes)

C-i: polyvinylidene fluoride (VP-800 manufactured by Daikin Industries, Ltd.) Melt flow rate (230 ° C., 5 kg) 15-30 (g)
/ 10 minutes)

D-1: Potassium salt of paratolyl sulfonimide

E-1: Polytetrafluoroethylene (Teflon 6CJ manufactured by E. I. DuPont)

TBBA: Tetrabromobisphenol A
Polycarbonate oligomer (Great Lakes Chemical BC-52)

MBS: Methyl methacrylate-butadiene-acrylonitrile copolymer (Mitsubishi Rayon Co., Ltd. E-901)

Various test methods are as follows.

O Impact Strength ASTM D-256 1/8
", Notched Izod, 23 ℃

O Fluidity (melt flow index) A
STM D-1238 300 ℃, 1.2kg

O Wear resistance PV value JIS K-721
8A Slip speed 60cm / sec

O Surface appearance The appearance of the surface of the molded product (rough skin,
Flow mark) is visually determined. ◯: Good Δ: Slightly bad ×: Bad

O Flame retardance UL94 Vertical combustion test compliant (test piece thickness 1/16 ")

[Example II] Based on the components and blending ratios shown in Table 2, after mixing with a tumbler, melt kneading with an extruder was performed to obtain pellets. 4 from the obtained pellets
Use an ounce injection molding machine and set the cylinder temperature to 28.
Various test pieces were prepared at 0 ° C. and subjected to the test. The test results are shown in Table-2.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

EFFECT OF THE INVENTION The polycarbonate resin composition of the present invention is excellent in abrasion resistance, surface appearance, impact resistance and moldability, and is also excellent in flame retardancy without impairing these characteristics. is there.

Claims (2)

[Claims] 1. Polycarbonate (A), polytetrafluoroethylene (B) that does not form fibrils when subjected to mechanical shearing, and melt flow rate (230 ° C.,
5 kg) 10 or less of polyvinylidene fluoride (C), and 60 to 99 parts by weight of (A) and (B) + (C) 1 with respect to 100 parts by weight of (A), (B) and (C) in total.
A polycarbonate resin composition, characterized in that it is comprised of ˜40 parts by weight and (B) / (C) is in a weight ratio of ½ to 1 / 0.1. 2. A metal salt of aromatic sulfonimide (D) represented by the following general formula and / or polytetrafluoroethylene (E) which forms fibrils when subjected to mechanical shearing. Item 2. The polycarbonate resin composition according to item 1. [Chemical 1] (However, in the formula, Ar is an aromatic group or a substituted aromatic group, and M is a metal cation.)