JPH07331054A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having improved chemical resistance without impairing excellent mechanical properties of an aromatic polycarbonate. CONSTITUTION:This thermoplastic resin composition comprises (A) an aromatic polycarbonate, (B) a polyester composed of an aromatic dicarboxylic acid and an aliphatic dihydric alcohol and (C) a diamine and is constituted of 60-99wt.% of the component A and 40-1wt.% of the component B based on 100 pts.wt. of the total amount of the components A and B and 0.0001-3 pts.wt. of the component C based on 100 pts.wt. of the total amount of the components A and B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing aromatic polycarbonate and polyester as main components.

[0002]

2. Description of the Related Art Aromatic polycarbonates are widely used in the industrial field due to their excellent mechanical properties, but on the other hand, they have the drawback of poor chemical resistance. As an attempt to improve the chemical resistance of an aromatic polycarbonate, for example, JP-A-61-225245 discloses a resin composition obtained by adding a polyester and / or a modified polyolefin to the aromatic polycarbonate. Japanese Patent No. 3431224 discloses a resin composition prepared by mixing polycarbonate with at least one kind of general-purpose engineering plastic such as polyester, polyolefin, and the like, and Japanese Patent Publication No. 3-74267 discloses aromatic polycarbonate with polyvinyl acetal. However, the chemical resistance of the aromatic polycarbonate has not been sufficiently improved.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition having improved chemical resistance without impairing the excellent mechanical properties of aromatic polycarbonate, especially impact resistance. It is in.

[0004]

The present inventors have arrived at the present invention as a result of intensive studies. That is, the present invention comprises the inventions described below. (1) Aromatic polycarbonate (A), (B) Polyester consisting of aromatic dicarboxylic acid and aliphatic dihydric alcohol, and (C) Diamine are included, and the component is added to the total amount of component (A) and component (B). (A) is 60 to 99% by weight,
Thermoplastic resin composition in which the component (B) is 40 to 1% by weight, and the component (C) is 0.0001 to 3 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). object.

The present invention will be described in detail below. The aromatic polycarbonate as the component (A) of the thermoplastic resin composition of the present invention is represented by the general formula (I) obtained by reacting a dihydric phenol with a carbonate precursor such as phosgene, a haloformate or a carbonic acid ester. Aromatic polycarbonates having repeating structural units

[0006]

[Chemical 1] (In the formula, A represents a divalent aromatic group derived from a dihydric phenol.) If the Fe content in the aromatic polycarbonate is 1 ppm or less and the Cl content is 50 ppm or less, decomposition and foaming of the resin during heating, etc. Is less likely to occur, and a Cl content of 10 ppm or less is more preferable. Fe in resin
The content and Cl content can be determined by a usual analytical method such as an atomic absorption method and a fluorescent X-ray method.

The dihydric phenol used herein is a monocyclic or polycyclic aromatic compound, and has two hydroxyl groups directly bonded to carbon in the aromatic ring. Specific examples of these dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), hydroquinone, resorcin, 2,2-bis (hydroxyphenyl) pentane, and 2,4'-dihydroxy-diphenylmethane. , Bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1-bis (4
-Hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-dihydroxydiphenyl, 2,6-dihydroxy-naphthalene, bis (4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl Sulfone, 5-chloro-2,4'-
Dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) diphenyldisulfone, 4,4-dihydroxydiphenyl ether, 4,4'-dihydroxy-
3,3'-dichlorodiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether and the like. Preferably, bisphenol A and its nuclear substitution derivative are mentioned. These dihydric phenols are used alone or as a mixture.

The aromatic polycarbonate of the component (A) in the thermoplastic resin composition of the present invention is a known method using the dihydric phenol represented by the above general formula (I) as a raw material, that is, a transesterification method and a solution. Method, interfacial polycondensation method, etc., preferably viscosity average molecular weight 1500
It is 0 or more, more preferably 25000 or more. These specific polymerization methods include, for example, "ENCYC
LOPEDIA OF POLYMER SCIENC
E AND TECHNOLOGY "Volume 10 (Jho
n Wiley & Sons, Inc. , 1969
Year) 710 to 764, “Polycarbonate” section. Further, as these polycarbonates, copolymers exemplified by the polycarbonate-styrene block copolymers disclosed in JP-B-48-25076 can also be used.

The component (B) polyester in the thermoplastic resin composition of the present invention comprises an aromatic dicarboxylic acid and an aliphatic dihydric alcohol. The polyester does not exhibit anisotropy when melted. Examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate (polytetramethylene terephthalate), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethylol terephthalate, and polyneopentyl terephthalate. Of these, polyethylene terephthalate and polybutylene terephthalate are particularly preferable.

The polyester preferably has an intrinsic viscosity [η] of 0.30 to 1.8. Here, the intrinsic viscosity [η] (dl / g) is obtained from the solution viscosity measured at 25 ° C in an o-chlorophenol solvent.
If the intrinsic viscosity [η] of the polyester is less than 0.30, the effect of improving the compatibility is insufficient, and if it exceeds 1.80, the melt viscosity of the reaction product becomes high and it becomes difficult to process it. Not preferable.

Examples of the diamine as the component (C) in the thermoplastic resin composition of the present invention include those represented by the following formula.

[Chemical 2] (In the formula, R ₁ is a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms, or one containing oxygen of an ether bond; divalent heterocyclic group; substituted or unsubstituted A monocyclic aromatic hydrocarbon group; or a substituted or unsubstituted polycyclic aromatic hydrocarbon group, R ₂ , R
₃ represents hydrogen, an alkyl group, a cycloalkyl group, or an aromatic group. )

The diamine is specifically 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10. -Diaminodecane, 1,12-
Diaminododecane, 1,4-diaminocyclohexane,
Bis (methylamino) hexane, bis (3-aminopropyl) ether, 1,2-bis (3-aminopropoxy) ethane, ethylaminoethylamine, methylaminopropylamine, N, N'-di-t-butylethylenediamine, Examples thereof include bis (2-aminoethyl) benzene. Among them, it is preferable that one or both of R ₂ and R ₃ be hydrogen. Specific examples thereof include 1,3-diaminopropane, 1,6-diaminohexane, 1,10-diaminodecane, 1,12-diaminododecane, methylaminopropylamine and bis (3-aminopropyl) ether.

In the thermoplastic resin composition of the present invention,
When the composition ratio of the component (A), the component (B) and the component (C) takes a value within a specific range, the intended thermoplastic resin composition can be obtained. The ratio of the component (A) to the component (B) in the present invention is 60 to 99% by weight of the component (A) and 40 to 1% by weight of the component (B), preferably 80 to 95% by weight of the component (A). %, Component (B) is 20 to 5
% By weight.

When the amount of the component (A) is less than 60% by weight, the mechanical properties of the molded article formed from the composition are particularly insufficient in impact resistance, and when it exceeds 99% by weight, the chemical resistance of the composition is high. Is insufficient, which is not preferable.

In the thermoplastic resin composition of the present invention,
The amount of the diamine as the component (C) is 0.001 to 3 parts by weight, preferably 0.03 to 2.0 parts by weight, based on 100 parts by weight of the total weight of the components (A) and (B). When the amount of diamine is less than 0.001 part by weight, the effect of improving the chemical resistance of the composition is small, and when it exceeds 3 parts by weight, the heat resistance of the composition is significantly reduced, which is not preferable.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and known methods can be used. For example, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned.
From an industrial point of view, a method of kneading each component in a molten state is preferable. For melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.

Upon kneading, the respective components may be mixed in advance by an apparatus such as a tumbler or a Henschel mixer, or if necessary, the mixing is omitted and the respective amounts are separately fed to the kneading apparatus. Methods can also be used.

For example, the aromatic polycarbonate and the polyester may be previously solution-blended or melt-kneaded to obtain a mixture, and then this and diamine may be melt-kneaded to obtain a thermoplastic resin composition. Alternatively, the aromatic polycarbonate, the polyester and the diamine may be charged from the first charging port of the kneading machine, and the polyester or the aromatic polycarbonate may be charged from the second charging port to obtain a thermoplastic resin composition by kneading once. .

It is also possible to obtain a thermoplastic resin composition by melt-kneading the aromatic polycarbonate, polyester and diamine, blending the kneaded product with the aromatic polycarbonate and polyester, and further melt-kneading.

The kneaded resin composition is molded by various molding methods such as injection molding, extrusion molding and the like, but it is dry-blended at the time of injection molding or extrusion molding without undergoing a kneading process in advance and melt processing operation is carried out. It is also possible to directly knead into the resin composition of the present invention to obtain a molded product.

The reason why the thermoplastic resin composition of the present invention exhibits excellent chemical resistance, mechanical properties, etc. is not necessarily clear, but a polymer in which an aromatic polycarbonate and a polyester are bonded via a diamine is aromatic. It is considered that this is due to the effect of improving the compatibility between the group polycarbonate and the polyester.

In the thermoplastic resin composition of the present invention,
Inorganic fillers are used if desired. Such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass fiber, carbon fiber, alumina fiber,
Examples include silica-alumina fibers, aluminum borate whiskers, potassium titanate fibers, and the like.

If necessary, the thermoplastic resin composition of the present invention may further include an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic coloring agent. Add various additives such as agents, rust preventives, cross-linking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss modifiers, release modifiers such as fluororesin, etc. during the manufacturing process or subsequent processing processes. be able to.

[0024]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited to these. The aromatic polycarbonate may be abbreviated as PC. [1] Physical property measurement method The physical properties of the obtained composition were measured by Toshiba Machine Co., Ltd.
Molding temperature 2 using IS150E-V type injection molding machine
The molding was carried out on a molded product injection-molded at 00 ° C to 290 ° C and a mold temperature of 80 ° C. Chemical resistance: The critical strain was determined by the 1/4 ellipse method described in Coloring Material, Vol. 39, page 455 (1966). The chemicals used at that time were gasoline [Nippon Oil Co., Ltd., trade name Nisseki Dash G], detergent [Kao Co., Ltd., trade name Mypet,
20% solution]. Izod impact strength: 3.2 mm thickness The test piece was notched and measured according to JIS K7110.

[2] Component in Resin Composition (1) Aromatic Polycarbonate of Component (A) The aromatic polycarbonate used as the component (A) of the thermoplastic resin composition of the present invention is as follows. A-1 (abbreviation): Sumitomo Dow Co., Ltd. product name CALI
BRE 300-6 [MFR (300 ° C, 1.2 kg load) = 6]. (2) Aromatic Polyester of Component (B) The polyester used as the component (B) of the present invention is as follows. B-1 (abbreviation): Teijin Ltd. polyethylene terephthalate, trade name TR4500) Intrinsic viscosity [η] =
0.7. B-2 (abbreviation): manufactured by Teijin Ltd. polybutylene terephthalate, trade name TRB-K, intrinsic viscosity [η] = 0.7
3. (3) Component (C) Diamine The diamine used for the component (C) of the present invention is as follows. C-1 (abbreviation): diaminododecane.

Examples 1 to 3 and Comparative Examples 1 to 4 Each component having the composition shown in Table 1 was mixed with a Henschel mixer, and then a cylinder set temperature 282 was set using a PCM-30 type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. After kneading at a temperature of 80 rpm, the mixture was molded and the physical properties were measured. The results obtained are shown in Table 1. It can be seen that the thermoplastic resin composition of the present invention is a resin composition having excellent chemical resistance without impairing impact resistance.

[0027]

[Table 1]

[0028]

The thermoplastic resin composition of the present invention has excellent mechanical properties of aromatic polycarbonate, particularly impact resistance, and improved chemical resistance. The thermoplastic resin composition is used for molded products, sheets, tubes, films, fibers, laminates, coating materials and the like by injection molding or extrusion molding by taking advantage of such characteristics.

Claims (1)

[Claims] (1) An aromatic polycarbonate (A), a polyester (B) comprising an aromatic dicarboxylic acid and an aliphatic dihydric alcohol, and a diamine (C) are contained, and the total amount of the component (A) and the component (B) is increased. On the other hand, the component (A) is 60 to 99% by weight, the component (B) is 40 to 1% by weight, and the component (C) is 0 with respect to 100 parts by weight of the total amount of the component (A) and the component (B). A thermoplastic resin composition which is 0.0001 to 3 parts by weight.