JPS61162546A - Thermoplastic polyester composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent moldability, solvent- resistance, impact-resistance, etc., by compounding an aromatic polyester and an aromatic polycarbonate with a styrenebutadiene block copolymer and a partially hydrogenated block copolymer at specific ratios. CONSTITUTION:The objective composition is produced by compounding 100 pts.(wt.) of a mixture of (A) 10-90pts. of an aromatic polyester, preferably a (co)polymer derived from terephthalic acid, etc. and ethylene glycol, etc. and (B) 10-90pts. of an aromatic carbonate, preferably poly-2,2-bis(4- hydroxyphenyl)propane carbonate, with (C) 1-100pts. of a styrene-butadiene block copolymer preferably having a polystyrene block at the terminal and (D) 1-100pts. of a partially hydrogenated block copolymer of an aromatic vinyl-conjugated diene block copolymer, wherein preferably <=25% of the aromatic double bond and >=80% of the aliphatic double bond are hydrogenated.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application e) The present invention provides a heat treatment method that can provide molded products with excellent moldability, solvent resistance, impact resistance, heat resistance, and dimensional stability. It relates to plastic compositions, and by taking advantage of these properties, it is used for mechanical parts, interior and exterior products, housings, etc. of automobiles, child devices, and other machinery.

(Conventional technology) Aromatic polyester has excellent solvent resistance, water resistance, oxidation resistance,
It has various excellent properties including abrasion resistance, and is used in large quantities as film and +a pongee.

However, as a molding material, the dimensional stability of molded products is poor,
Its applications are limited due to its low impact resistance and low heat distortion temperature.

On the other hand, aromatic polycarbonate has excellent impact resistance, molding dimensional stability, electrical properties, and high heat distortion temperature, but has the drawbacks of poor solvent resistance, high melt viscosity, and poor moldability. .

As a method to maintain the advantages of aromatic polyester and aromatic polycarbonate while at the same time compensating for the disadvantages of both polymers, a blend composition of both polymers was developed in Japanese Patent Publication No. 86-1.
It is disclosed in Japanese Patent Publication No. 4085, Japanese Patent Publication No. 58-12587, and Japanese Patent Publication No. 57-2744. However, these blend compositions have poor molding dimensional stability, and the impact resistance of the aromatic polycarbonate is significantly impaired.

In addition, a diene rubber copolymer (for example,
5-9485) and partially hydrogenated aromatic vinyl-diene block copolymerization (JP-A-58-1.98456 tS
An attempt to add > has been disclosed. However, in the former case, although the actual impact resistance is improved to some extent, it has the drawbacks of inferior thermal stability, fM dynamics, oxidation resistance, and weather resistance, while in the latter case, partially hydrogenated aromatic vinyl diene In order to form an interlocking network structure of the block copolymer and aromatic polyester and/or aromatic polycarbonate, they must be mixed in a common medium or "isoviscosity mixed" in the molten state. , complicated processes and conditions are required, and if the mutually interlocking network structure is insufficiently formed, the surface smoothness of the molded product will deteriorate, delamination will occur at the gate area, etc., and the weld strength will decrease. A drawback appears.

(Problems to be Solved by the Invention) The present invention maintains the excellent physical properties of aromatic polyester and aromatic polycarbonate, and provides thermal stability that does not cause layer separation, has a smooth molding surface, and has high weld strength. Relating to thermoplastic (fat compositions) that provide molded articles with improved impact resistance.

(Means for Solving the Problems) The present invention comprises aromatic polyester (a) 10 to 90 parts by weight, aromatic polycarbonate (b) 10 to 90 parts by weight, and a total of 100 parts by weight of (al and (b)). Styrene-butadiene block copolymer (c) 1-100 for heavy fractures
The present invention relates to a thermoplastic resin composition.

The present invention will be explained in detail below.

The aromatic polyester (a) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is a polyester containing an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymer obtained by a condensation reaction in which the main component is a condensation reaction. Examples of dicarboxylic acid components include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4
, 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether dicarboxylic acid, etc., or an ester-forming transparent conductor thereof. Further, as the acid component, 20 mol % or less of aliphatic dicarboxylic acids (eg, adipic acid, sebacic acid) or ester-forming derivatives thereof may be substituted. Examples of diol components include ethylene glycol, 1,4-butanediol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentylene gellicol, diethylene glycol, triethylene glycol, 1,1-cyclohexane dimetatool, l,4-cyclohexane dimetatool.

Xylylene glycol, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)
Sulfone, bis(hydroxyethoxy)benzene, 2,
Examples include ethylene oxide adducts of 2-bis(4-hydroxyphenyl)propane, propylene oxide adducts of 2°2-bis(4-hydroxyphenyl)propane, and ester-forming derivatives thereof.

The aromatic polyester (al) used in the present invention may be a mixture of two or more aromatic polyesters. Particularly preferably, terephthalic acid, isophthalic acid, or an ester-forming derivative thereof, ethylene glycol, 1.
The polymer is one or more selected from polymers and copolymers obtained with 4-"jl-enthiol, 2-bis(4-hydroxyphenyl)propane, or ester-forming derivatives thereof.

The aromatic polycarbonate (b) used in the present invention is
It is a homo- or copolycarbonate, or a mixture thereof, and is obtained by the polycondensation reaction of known bisphenols and phosgene or carbonic acid diester. Bisphenols include, for example, hydroquinone, resorcinol,
Dihydroxydiphenyl, bis(hydroxyphenyl)
Alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfoxides,
Bis(hydroxyphenyl)sulfone, α,l-bis(hydroxyphenyl)diisopropylbenzene, and the like. A particularly preferred aromatic polycarbonate is poly-
2,2-bis(hydroxyphenyl)propane)car#
t*-t, polybis(4-hydroxyphenyl)sulfone carbonate, and mixtures thereof.

The styrene-butadiene block copolymer used in the present invention (c1 is a linear, radial, or branched block copolymer consisting of one or more polystyrene blocks and one or more polybutadiene blocks, and is a known For example, by sequentially introducing a given heptad into a reactor using an initiator such as an alkyl lithium or dilithiostilbene, or by combining two types of block chains with a difunctional coupling agent. A linear block copolymer can be obtained by coupling.On the other hand, a radial or branched block copolymer can be obtained by using a coupling agent with 8 or more functionalities. A method of introducing polystyrene blocks can also be used. Examples of the above-mentioned polyfunctional coupling agents include dihaloalkanes, dihaloalkenes, divinylbenzenes, silicon halides, siloxanes, and esters of monohydric alcohols and polycarboxylic acids. .

Particularly preferred styrene-butadiene block copolymerization is
For example, it is a block copolymer in which the terminal block is a polystyrene chain, such as a styrene-butadiene-styrene block copolymer. Examples of commercial products of this block copolymer include "Denka 8TRJ" (manufactured by W1 Ki Kagaku Kogyo ■) and "Califlex '1" RJ (manufactured by Shell Kagaku ■).

The partially hydrogenated aromatic vinyl-conjugated diene block copolymer (d) used in the present invention is composed of an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, butadiene,
Various aromatic vinyl-conjugated diene block copolymers were produced from conjugated diene compounds such as isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene in the same manner as the styrene-butadiene block copolymer described above. (
7) Obtained by hydrogenation using a hydrogenation catalyst (alkylaluminium, Raney nickel, chromate steel, molybdenum sulfide, etc.) under conditions in which substantially mainly aliphatic double bonds are converted into rings. Note that each block of the aromatic vinyl-conjugated diene block copolymer may be a copolymer composed of two or more types of monomers. Preferred structures before hydrogenation are styrene or/and α-methylstyrene-butadiene or/and isoprene block copolymers, particularly preferably block copolymers with polystyrene end blocks or/and polybutadiene intermediate blocks. . Further, the preferable partial hydrogenation ratio is 25% or less of the aromatic double bonds and 80% or more of the aliphatic double bonds contained in the aromatic vinyl-conjugated diene block copolymer, and more preferably 5% or less of the double bonds and 95% or more of the III aliphatic double bonds. An example of this partially hydrogenated block copolymer is "Krayton GJ" (manufactured by Shell Chemical Co., Ltd.).

In the present invention, the blending ratio of aromatic polyester (a) and aromatic polycarbonate (b) is (a) I
0 to 90 parts by weight, (b) l O to 90 parts by weight (a)
and (b) totaling 100 parts by weight. More particularly preferably, the blending ratio of (a) and (b) is 1/4 to 1/4.
It is in the range of 4/1.

Is (a) less than 10 parts by weight? If (b) exceeds 90 weighted parts in 4, the improvement in moldability and solvent resistance is insufficient;
When (a) is more than 90 parts by weight and (b) is less than 10 parts by weight, the molding dimensional stability is poor and only a composition with low heat resistance and impact resistance can be obtained.

Further, the blending ratio of the styrene-butadiene block copolymer (c) and the partially hydrogenated polymer (d) of the aromatic vinyl-conjugated diene block copolymer of the present invention is (al and (b)
Total of 100! For Ryube, (c) 1-100N11
Parts, fd) 1 to 100 weight ft s (D Range) A particularly preferable range for teal o sara is that the blending ratio of (c) and (d) is 1/8 to 8/1.

(If c1 and (d) are less than 1 part by weight, # impact resistance will not be sufficiently improved, and if only (c) is less than 1 part by weight,
Layer peeling occurs in the molded product, the smoothness of the molding surface deteriorates, and the weld strength also decreases. If only (d) is used in an amount less than 11 parts, the thermal stability during molding and the weather resistance of the molded product will decrease. On the other hand, if (c) or/and support (d) exceeds 100 M, the thermal deformation temperature and mechanical strength are significantly reduced.

Blend of aromatic polyester (a) of the present invention, aromatic polycarbonate (b), styrene-butadiene block copolymer (c), and partially hydrogenated polymer (d) of aromatic vinyl-conjugated diene block copolymer Methods include melt-kneading and pelletizing everything at once, blending during molding where everything is mixed and molded at the same time, or mixing 2 to 8 of the ingredients.
Any known method can be used, such as a method in which a master pellet is prepared by melt-kneading M or above in advance, and then mixed with the remaining components during molding.

From the viewpoint of improving mechanical strength and heat resistance, it is preferable to blend nine bottles of a polyfunctional compound into the thermoplastic resin composition of the present invention within a range that does not impair fluidity during molding.

The polyfunctional compound used in the present invention is a compound having two or more functional groups such as an epoxy group, an aryl group, an incyanate group, a carboxy group, a hydroxyl group, a carboxylic anhydride, or an acid halide, and is preferred by samurai. Examples include compounds containing 2 to 3 epoxy groups and compounds containing 2 to 8 aryl groups. More specific examples include bisphenol type epoxy resin, polyether type epoxy resin, polyhydric carboxylic acid type epoxy resin,
Triaryl isocyanurate, N-methyl-, N'
- diglycidyl isocyanurate, triaryl trimellitate, triaryl isocyanurate and the like.

The thermoplastic resin composition of the present invention can be easily imparted with flame retardancy by further adding a flame retardant. The flame retardant used is a known halogenated compound, a halogen-containing compound combined with an elemental groove, an adjacent compound, a compound, or a compound having a phosphorus-nitrogen bond, or a compound containing 2M'M or more of each of the above compounds. Contains mixtures.

Preferred examples include red phosphorus powder coated with a thermosetting resin, brominated polystyrene, tribromophenol derivatives, decabromodiphenyl ether, and polycarbonate containing tetrafrom-2°2-bis(4-hydroxyphenyl)propane. .

It is preferable to use such a flame retardant together with a flame retardant aid,
FD1 combustion aids include antimony oxide, zinc borate, iron oxide, alumina oxide, zirconium oxide, ammonium molybdate oxide, and the like.

The thermoplastic sphere lipid composition of the present invention may further include J.
A: Pongee-like reinforcing agent Non-fibrous filler, heat stabilizer, antioxidant, mold release agent, lubricant, ultraviolet absorber, coloring agent, crystallization accelerator, etc. can be added.

(Example) The present invention will be described in more detail below using Examples and Comparative Examples.

Examples 1 to 7 and Comparative Examples 1 to 7 Polyethylene terephthalate (Belpezut EFG-6 manufactured by Kanebo Gosen ■) and styrene-butadiene block copolymer (Denka 8T manufactured by Denki Kagaku Kogyo ■) having the compositions shown in Table 1.
R1602), partially hydrogenated block copolymer (Krayton G1652 manufactured by Shell Chemical Co., Ltd.) and 0.2 for the above resins.
Weight percent of antioxidant (Irganox TOIO manufactured by Ciba Geigy) was added to a 25 mm diameter single screw extruder (nozzle diameter 3 m, cylinder temperature 260 to 290°C).
The mixture was melt-kneaded to produce pellets. Next, Table-1
The pellets were tri-blended with poly 2,2-bis-(4-hydroxyphenyl)propane carbonate (Kijin Kasei Panlite -1800) to give the following composition, and injection molded under normal conditions for polyethylene phthalate to determine the physical properties. Table 1: Polyethylene terephthalate 2) Poly-2,2-bis(4-hydroxyphenyl)propane carbonate 8) Styrene-butadiene block copolymer 4) Partially hydrogenated block copolymer 7) Plate-shaped molded product (8MX2001allX200111
g) Condition of warping ◎: None, ○: 4\△: Medium, ×: Large 8) Visual evaluation of the state of layer peeling at the gate ○: No layer peeling, △: Slightly present, ×: Yes 9) Visual inspection Evaluation ◎: Very smooth, ○: Smooth, △: Slightly rough, X: @
to) NB: Fractured break (effect of the invention) As is clear from the examples, specific proportions of the styrene-butadiene block copolymer and partially hydrogenated block copolymer are added to the aromatic polyester and aromatic polycarbonate of the present invention. The thermoplastic resin composition made by blending has excellent heat resistance,
Compositions that have properties such as solvent resistance, molding dimensional stability, molding processability, and surface smoothness, and that contain only a styrene-butadiene block copolymer or a partially hydrogenated block copolymer, It also has unexpectedly excellent impact resistance.

Claims (8)

[Claims] (1) 10 to 90 parts by weight of aromatic polyester (a), 10 to 90 parts by weight of aromatic polycarbonate (b), and (
Styrene based on a total of 100 parts by weight of a) and (b)
A thermoplastic polyester composition comprising 1 to 100 parts by weight of a butadiene block copolymer (c) and 1 to 100 parts by weight of a partially hydrogenated block copolymer (d) of an aromatic vinyl-conjugated diene block copolymer. (2) Aromatic polyester (a) is terephthalic acid, isophthalic acid, or an ester-forming derivative thereof, and ethylene glycol, 1,4-butanediol, 2,2-bis(4-hydroxyphenyl)propane, or an ester thereof. The composition according to claim 1, which is selected from polymers and copolymers obtained from formable derivatives. (3) Aromatic polycarbonate (b) is poly-2,2-
The composition according to claim 1, which is bis(4-hydroxyphenyl)propane carbonate and/or polybis(4-hydroxyphenyl)sulfone carbonate. (4) The composition according to claim 1, wherein the styrene-butadiene block copolymer (c) has a polystyrene block at the end. (5) In the partially hydrogenated block copolymer (d), 25% or less of the aromatic double bonds and 80% or more of the aliphatic double bonds contained in the aromatic vinyl-conjugated diene block copolymer are water. A composition according to claim 1. (6) The composition according to claim 1, wherein the structure of the partially hydrogenated block copolymer (d) before hydrogenation has a polystyrene end block and/or a polybutadiene intermediate block. (7) The composition according to claim 1, wherein the blending ratio of aromatic polyester (a) and aromatic polycarbonate (b) is 1/4 to 4/1. (8) The blending ratio of styrene-butadiene block copolymer (c) and partially hydrogenated block copolymer (d) is 1/8 to 8
1. The composition according to claim 1, wherein