JPS6143656A - Thermoplastic polyester resin - Google Patents

Abstract

PURPOSE:The titled composition having improved impact resistance, heat resistance, etc. obtained by blending a blend composition of an aromatic polyester and an aromatic polycarbonate with a styrene.butadiene block copolymer and a specific thermoplastic polyolefin elastomer in a specific ratio. CONSTITUTION:(A) 100pts.wt. composition of A1: 10-90pts.wt. aromatic polyester (e.g., PET, PBT, etc.) and A2: 10-90pts.wt. aromatic polycarbonate in a blending ratio of preferably 2/8-8/2 is blended with (B) 2-100pts.wt. styrene. butadiene block copolymer having a polystyrene chain at the end, and (C) 1- 50pts.wt. thermoplastic polyolefin elastomer (e.g., ethylene, propylene copolymer, etc.) containing no polymer chain of conjugated diene monomer in a blending ratio of the component B to C of preferably 1/4-9/1. Especially total amounts of the components B and C are 5-50pts.wt., and a blending ratio of the component B to C is 1/2-4/1.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermoplastic resin composition capable of providing molded products having excellent moldability, solvent resistance, impact resistance, heat resistance, and dimensional stability. It relates to objects, and by taking advantage of these characteristics, it is used for mechanical parts, interior and exterior parts, housings, etc. of transportation equipment, electrical and electronic equipment, etc.

Conventional technology Aromatic polyester has properties such as solvent resistance, water resistance, oxidation resistance,
It has a variety of excellent physical properties including abrasion resistance, and is used in large quantities as films and fibers.

However, as a molding material, the dimensional stability of molded products is poor,
Its use is limited due to its low impact resistance and low heat change temperature. On the other hand, aromatic polycarbonate has excellent impact resistance, molding dimensional stability, and low heat distortion temperature during WL, but it has poor solvent resistance, high melt viscosity, and poor moldability. There are drawbacks such as.

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 (for example,
6-14035, Japanese Patent Publication No. 53-12537, Japanese Patent Publication No. 57-2744). However, these blend compositions have poor molded dimensional stability, and the high impact resistance of aromatic polycarbonates is significantly impaired.

In addition, attempts were made to add polyolefin to improve the impact resistance of aromatic polyester and aromatic polycarbonate blend compositions (for example, Japanese Patent Publication No. 39-204
No. 34) is disclosed. However, polyolefins have poor compatibility with aromatic polyesters and aromatic polycarbonates, and molded products suffer from delamination, weld strength decreases, and impact resistance 7 is not sufficiently improved. In addition, attempts were made to add a diene rubber copolymer to a blend composition of aromatic polyester and aromatic polycarbonate (for example,
No. 1855-9435) is disclosed. However, in this case, although the impact resistance is improved, there are disadvantages in that the thermal stability, fluidity, oxidation resistance, and weather resistance are inferior.

The present invention has superior physical properties compared to conventional blend compositions, and can overcome the drawbacks of compositions containing a diene rubber copolymer by using a small amount of antioxidant.

Problems to be Solved by the Invention The present invention provides a molded article that maintains the excellent physical properties of aromatic polyester and aromatic polycarbonate, does not cause delamination, and has improved thermal stability and impact resistance. The present invention relates to a thermoplastic resin composition.

Means for Solving the Problems The present invention adds a thermoplastic polyolefin elastomer having no polymer chains of a styrene-fubutadiene block copolymer and a conjugated diene monomer to a blend composition of an aromatic polyester and an aromatic polycarbonate. This is based on the discovery that a thermoplastic resin composition having excellent Wi-impact resistance, heat resistance, solvent resistance, molding dimensional stability, and molding processability can be obtained by incorporating specific side compounds.

That is, the present invention comprises aromatic polyester (a) 10 to 90 parts by weight, aromatic polycarbonate (b) 10 to 90 parts by weight,
and 2 to 100 parts by weight of styrene and butadiene block copolymer (c) per 100 parts by weight in total of (a) and (b)1. : 1 to 50 parts by weight of a thermoplastic polyolefin elastomer (d) that does not have a polymer chain of a conjugated diene monomer is blended so that the blending ratio of (c) and (d) is 1/4 to 9/1. The present invention relates to a thermoplastic resin composition comprising:

The present invention will be explained in detail below.

The aromatic polyester (a) used in the present invention is a polyester having an aromatic group in the polymer chain unit, and mainly contains 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 as a component. Examples of dicarboxylic acid components include terephthalic acid,
Isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene2. Fudicarboxylic acid, diphenyl-4,4
'-dicarboxylic acid, diphenoxyethanedicarboxylic acid.

Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid or ester-forming derivatives thereof.

As the active acid component, 20 mol % or less of aliphatic dicarboxylic acids (eg, adipic acid, sebacic acid) or ester-forming recognized conductors thereof may be substituted.

Examples of diol components include ethylene glycol, 1,4-butanediol, trimethylene glycol,
Pentamethylene glycol, hexamethylene glycol, neopentyl glycol ethylene glycol, triethylene glycol.

1,1-cyclohexane dimetatool, 1,4-cyclohexane dimetatool, xylylene glycol.

2,2-bis(4-hydroxyphenyl)propane.

Bis(4-hydroxyphenyl)sulfone, bis(hydroxyethoxy)benzene, ethylene oxide adduct of 2,2-bis(4-hydroxyphenyl)propane, 2
．． Examples include propylene oxide adducts of 2-bis(4-hydroxyphenyl)propane, and ester-forming derivatives thereof.

The aromatic polyester (a) used in the present invention may be a mixture of two or more aromatic polyesters. Preferably polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene-2.6-naphthalate, polyhexamethylene-2.6-naphthalate, poly-2,2-bis(4-
hydroxyphenyl)propane inphthalate, copolymers thereof, and mixtures thereof. Particularly preferred are polybutylene terephthalate, polyethylene terephthalate, poly-2,2-bis(4-hydroxyphenyl)propane isoheptalate, copolymers thereof, and mixtures thereof.

The aromatic polycarbonate (b) used in the present invention is a homo- or copolycarbonate, or a mixture thereof, and is obtained by polymerization reaction of known bisphenols and phosgene or carbonic acid diester. Examples of bisphenols include hydroquinone, resorcinol, and hydroxydiphenyl.

Bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloartane. Bis(hydroxyphenyl) sulfide, bis(hydroxyphenyl) ether, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfoxide, bis(hydroxyphenyl)'' sulfone, and α.d-bis(hydroxyphenyl) diisopropylbenzene, etc. Particularly preferred aromatic polycarbonates are poly-2,2-bis(hydroxyphenyl)propane carbonate, polybis(4-hydroxyphenyl)sulfone carbonate, and mixtures thereof.

The styrene-butadiene block copolymer (c) used in the present invention is a polystyrene block copolymer (c). It is a linear, radial, or branched block copolymerization consisting of one or more polybutadiene blocks and one or more polybutadiene blocks, and is produced by known methods. For example, by sequentially introducing the desired monomers into the reactor using an initiator such as an alkyllithium or siliostilbene, or by coupling the two blocks with a difunctional coupling agent.
A linear block body is obtained. On the other hand, radial. The branched block copolymer can be obtained by using a trifunctional or more functional coupling agent. Examples of polyfunctional coupling agents include dihaloalkanes, dihaloalkenes, divinylbenzenes, silica halides, panxane, and esters of monohydric alcohols and polyhydric carboxylic acids. Particularly preferred styrene-butadiene block copolymers are block copolymers having polystyrene chains at the ends, such as styrene, butadiene, and styrene block copolymers. Examples of commercial products of this block copolymer include “Denka STRJ
(1!Kikagaku Kogyo), ``Califlex TRJ (Shell), etc.

The thermoplastic polyolefin elastomer (d) that does not have a polymer chain of a conjugated diene monomer used in the present invention is
It is a random, block or kraft copolymer having a constituent unit of an olefin monomer or a vinyl heptamer other than an olefin monomer, and has rubber elasticity at room temperature.

The olefin monomers used in the present invention include, for example, ethylene, propylene, 1- and 2-butene, imbutylene, 1
- and 2-pentene, 1- and 2-hexene, etc.

Furthermore, vinyl monomers other than conjugated diene monomers include, for example, vinyl fluoride.

Vinylidene fluoride, chlorotrifluoroethylene.

Tetrachloroethylene, tetrafluoroethylene.

Vinyl halide monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, and vinyl iodide. Styrene, α-methylstyrene, α-chlorostyrene, P
- Aromatic vinyl monomers such as chlorostyrene, 2,4-dichlorostyrene, P-methylstyrene, 3,4-dimethylstyrene, P-methyl-α-methylstyrene, and P-chloro-α-methylstyrene. Acrylic acid, methacrylic acid, acrylonitrile, methacrylotrile. Methyl acrylate, ethyl acrylate, n- and 1s acrylate
o-Propyl, n- and 1so-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n- and 1so-propyl methacrylate, Win- and 1so-butyl methacrylate, cyclohexyl methacrylate, acrylic acid allyl, allyl methacrylate, sodium acrylic acid or methacrylate,
Acrylic acid or methacrylic acid derivatives such as potassium, zinc, and magnesium metal salts. Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl laurate, and vinyl benzoate. Methyl vinyl ether.

Vinyl ether monomers such as ethyl vinyl ether. Allyl alcohol, allyl chloride, allyl formate.

Allyl compounds such as allyl acetate. Unsaturated dibasic acid derivatives such as maleic acid, maleic anhydride, and methyl maleate. and dicyclopentadiene, ethylidene norbornene, 1
．． 4-hexadiene, 1,4-cycloheptadiene, 1
, 5-cyclooctadiene and other non-conjugated diene monomers.

A thermoplastic polyolefin elastomer having no polymer chain of a conjugated diene monomer can be obtained by known noradical polymerization or ionic polymerization.

Among these, ethylene f propylene coelectrolyte,
Ethylene, vinyl acetate copolymer, ethylene.

Ethyl acrylate copolymer, ethylene, propylene, styrene graft copolymer, ethylene, propylene-t-styrene, acrylonitrile graft copolymer, ethylene,
Maleic acid copolymer, ethylene, vinyl chloride copolymer,
Examples include ethylene, tetrafluoroethylene copolymer, ethylene, methyl acrylate copolymer, zinc salt of ethylene and methacrylic acid copolymer, and magnesium salt of ethylene-t-methacrylic acid copolymer. Particularly preferred examples are ethylene, propylene copolymers and ethylene, vinyl acetate.

In the present invention, the blending ratio of aromatic polyester (a) and aromatic polycarbonate (b) is (a)
90 parts by weight, (b) 10 to 90 parts by weight, (a) and (b)
) and the total amount is 100 parts by weight. More particularly preferably, the blending ratio of (a) and (b) is 2/8 to 8/2.
is within the range of

If (a) is less than 10 parts by weight and (b) is more than 90 parts by weight, moldability and solvent resistance will not be sufficiently improved;
When a) is more than 90 parts by weight and (b) is less than 10 parts by weight, molding dimensional stability is poor and only a composition with low heat resistance and impact resistance can be obtained.

Furthermore, the blending ratio of the styrene and butadiene block copolymer (c) of the present invention and the thermoplastic polyolefin elastomer (d) having no polymer chain of conjugated diene monomer is the sum of (a) and (b). For 100 parts by weight, (c
) 2 to 100711 parts by weight, (d) 1 to 50 parts by weight (c
) and (d) in a blending ratio of 1/4 to 9/1.

A particularly preferable range is that the total amount of (c) and (d) is 5 to 50 parts by weight, and/or the blending ratio of (c) and (d) is 1/2 to 4/1.

If (c) is less than 2 parts by weight or/and (d) is less than 1 part by weight, the impact resistance will not be sufficiently improved and (c) will be less than 100 parts by weight.
When the heavy ffi part is added or when /' and Cd) exceeds 50 parts by weight, the heat distortion temperature 1 mechanical strength decreases significantly. Furthermore, if the blending ratio of (c) and (d) is less than 1/4, layer peeling will occur in the molded product and the smoothness of the molded surface will also deteriorate. On the other hand, if it exceeds 9/1, the thermal stability during molding and the weather resistance of the molded product will decrease.

Method for blending aromatic polyester (a), aromatic polycarbonate (b), styrene, butadiene block copolymer (c), and thermoplastic polyester elastomer (d) having no polymer chain of conjugated diene monomer of the present invention There are two methods: melt-kneading and pelletizing everything at once, a blending method during molding where everything is mixed and molded at the same time, or two or more of the components are melt-kneaded in advance to produce master pellets, and the remaining components are processed into pellets during molding. Any known method can be used, such as a method of mixing with components and molding.

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

The polyfunctional compound (e) used in the present invention has two or more epoxy groups, aryl groups, and incyanate groups.

Compounds having functional groups such as carboxyl groups, hydroxyl groups, carboxylic anhydrides, acid halides, etc. Particularly preferred examples include compounds containing 2 to 341 epoxy groups and compounds containing 2 to 3 aryl groups. It will be done. More specific examples include bisphenol A type epoxy resin, polyether type epoxy resin, and polycarboxylic acid type epoxy resin.

Triglycidyl isocyanate, N-methyl N'1y
- Diglycidyl in cyanurate, triaryl trimellitate, triaryl isocyanurate, etc.

The thermoplastic resin composition of the present invention can be imparted with flame retardancy by further adding a flame retardant. The flame retardant used in the present invention is a known halogenated compound, 1 elemental phosphorus, a phosphorus compound, a halogen-containing compound combined with a phosphorus compound, or a compound having a scale-nitrogen bond, or two or more of the above-mentioned compounds O. Contains mixtures. A particularly preferred example is
Red phosphorus powder coated with thermosetting resin, brominated polystyrene, tribromophenol derivative, decabromodiphenyl ether, tetrabrom-2,2-bis(4-
Examples include polycarbonate containing hydroxyphenylfuropane.

It is preferable to use such a flame retardant together with a flame retardant aid,
In addition to antimony oxide, zinc borate,
Examples include iron oxide, alumina oxide, zirconium oxide, and ammonium molybdate oxide.

The thermoplastic resin composition of the present invention further contains 1 g of a fibrous reinforcing agent, a non-fibrous filler, and a thermal and oxidative stabilizer as required.
A l-type agent, a lubricant, an ultraviolet absorber, a coloring agent, a crystallization accelerator, etc. can be added.

EXAMPLES The present invention will be explained in more detail using examples below. In addition, in the examples, parts and percentages represent MA unless otherwise specified.

Examples 1 to 9 and Comparative Examples 1 to 10 Polyethylene terephthalate (Kanebo Gosei EFG-6
), poly-2,2-bis(4-hydroxyphenyl)propane carbonate (Ondai Kasei Panlite K-130
0), styrene, butadiene, styrene block copolymer (Denka Kagaku Kogyo Denka 5TRI (302)), ethylene, vinyl acetate copolymer (Mitsui Polychemical Evaflex-150) were blended as shown in Table 1, and Antioxidant (Ciba Geigy Irganox 1010) 0.
2 parts by weight was added, and a 25 m diameter single screw extruder (
The mixture was melt-kneaded using a cylinder temperature of 260 to 270°C and extruded into strands, and pellets were produced using a pelletizer. Next, this pellet was injection molded under normal conditions for polyethylene terephthalate, and its physical properties were measured. Results Table-1 1) Polyethylene terephthalate 2) Poly-2,2-bis(4-hydroxyphenyl)propane carbonate 3) Styrene, butadiene, styrene block copolymer 4) Ethylene, vinyl acetate copolymer 5) Polyethylene ( Mitsui Petrochemical Hyzex 70
00F) 1) ASTh (D638 2) ASTM D256 (with notch 1/4") 3)
ASTM D648 (18,6Ilf/Door) 4) Visually evaluate the state of layer peeling at the gate O: No layer peeling 68 Slight layer peeling ×: Layer peeling 5) Cut a 4m summer hole, Presence/absence of cracks after immersing a bending test piece with bolts and nuts tightened to the same torque for 5 minutes in carbon tetrachloride O: No cracks △: Slight cracks ×: Cracks 6) 125 Strengthening of tensile strength after heat treatment at ℃ for 3 days compared to untreated product 7) Spiral flow test a (cut ism x 3sm) (injection pressure 660KtF/pH, cylinder temperature 265℃,
Mold temperature 110℃) s) Judgment for plate-shaped molded product of 3 cods x 200 batches x 200 cods ◎: None ○: Small △: Medium ×: Large O) ◎: Very smooth ○: Smooth △: Slightly different x
:tfL Example 1O~13 Each component was blended as shown in Table 3, and at the same time injection molded under the same conditions as ordinary polybutylene terephthalate.
Next, physical properties were measured. Examples 14 to 18 Polyethylene terephthalate (Kanebo Gosei EFG-6
) 60#, Po! 40 g of J-2.2-hyx(4-hydroxyphenyl)propane carbonate.

Styrene, butadiene, 10 parts of styrene block copolymer (Denka 5TR1602, Denki Kagaku Kogyo), 5 parts of ethylene, vinyl acetate copolymer (Mitsui Polychemical Evaflex-150), 0.3 part of Irganox 1010 (Ciba Geigy), and Table 1. Add the flame retardant and flame retardant aid shown in -5, respectively, and use a 25811 diameter axle screw extruder (
The mixture was melted and kneaded at a cylinder temperature of 265° C. to produce pellets.

Next, injection molding was performed in the same manner as in Examples 1 to 9, and physical properties were measured. The results are shown in Table-6.

Table 6 Effects of the Invention From the examples, the thermoplastic resin composition obtained by blending the four-volatile thermoplastic resin of the present invention in a specific proportion has impact resistance, heat resistance,
It is clear that solvent resistance, maximum dimensional stability, molding processability, and molding surface smoothness are also good.

Procedural amendment dated November 6, 1980 1, Indication of the case Patent Application No. 165910 of 1988 2, Name of the invention Thermoplastic polyester composition 8, Person making the amendment Relationship to the case Patent applicant address Tokyo 584 Sumida 5-17-4, Sumida-ku
Contents of the amendment (1) Contents of the amendment (1) In the column of "Claims" and "Detailed Description of the Invention" of the specification No. 5-90 Tomobuchi-cho, Bejima-ku, Osaka City The description in the scope section will be corrected as shown in the attached sheet.

(2) The description in the detailed description of the invention section of the specification shall be amended as shown in the following table.

'A detailed book! ! Table 5 on page 26, "Red Burnt Powder" in Example 14 was replaced with "
Red phosphorus powder” is corrected.

"Flame resistance" in the first row of Table 6 on page 27 of the Monthly Specification is corrected to "1 Flammability."

Claims (1) Aromatic polyester (a) 10 to 90 parts,
Aromatic polycarbonate (b) 10-90! jt part, and styrene-butadiene block copolymer (c) 2 to ioozg parts based on a total of 100 parts by weight of (a) and (b), a thermoplastic polyolefin elastomer that does not have a polymer chain of a conjugated diene monomer. (d) 1 to 50 parts by weight, and a thermoplastic resin composition characterized in that the blending ratio of (c) and (d) is 174 to 9/1.

(2) Aromatic polyester (a) is polyethylene terephthalate, polybutylene terephthalate, poly-2,2
- His(4-1)'roxyphenyl)propane inphthalate and copolymers thereof
Compositions as described in Section.

(3) Aromatic polycarbonate (b) is poly-2,2
The composition according to claim 1, which is -bis(4-hydroxyphenyl)propane carbonate or polybis(4-hydroxyphenyl)sulfone carbonate.

(4) Styrene-butadiene block copolymer (c
) is a polystyrene chain.
Compositions as described in Section.

(5) Thermoplastic polyolefin elastomer (d)
The composition according to claim 1, wherein is an ethylene-propylene copolymer or an ethylene-vinyl acetate copolymer.

(6) The composition according to claim 1, wherein the blending ratio of aromatic polyester (a) and aromatic polycarbonate (b) is 2/8 to 8/2.

(7) The total amount of the styrene-butadiene block copolymer (c) and thermoplastic polyolefin elastomer (d) is 5 to 5 parts by weight based on 100 parts by weight of the aromatic polyester (a) and the aromatic polycarbonate. A composition according to claim 1.

(8) Styrene-butadiene block copolymer (c
2. The composition according to claim 1, wherein the blending ratio of ) and the thermoplastic polyolefin elastomer (d) is 1/2 to 4/1.

−, anp

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:butadiene block copolymer (c) 2 to 100 parts by weight, thermoplastic polyolefin elastomer (d) having no polymer chain of conjugated diene monomer (d) 1 to 100 parts by weight, based on a total of 100 parts by weight of a) and (b). 50 parts by weight of a thermoplastic resin composition, characterized in that the blending ratio of (c) and (d) is 1/4 to 9/1. (2) Aromatic polyester (a) is polyethylene terephthalate, polybutylene terephthalate, poly-2,2
-bis(4-hydroxyphenylpropane isophthalate) and copolymers thereof. (3) Aromatic polycarbonate (b) is poly-2,2
The composition according to claim 1, which is -bis(4-hydroxyphenyl)propane carbonate or polybis(4-hydroxyphenyl)sulfone carbonate. (4) The composition according to claim 1, wherein the terminal of the styrene-butadiene block copolymer (c) is a polystyrene chain. (5) The composition according to claim 1, wherein the thermoplastic polyolefin elastomer (d) is an ethylene-propylene copolymer or an ethylene-vinyl acetate copolymer. (6) The composition according to claim 1, wherein the blending ratio of aromatic polyester (a) and aromatic polycarbonate (b) is 2/8 to 8/2. (7) A patent in which the total amount of the styrene-butadiene block copolymer (c) and thermoplastic polyolefin elastomer (d) is 5 to 50 parts by weight based on 100 parts by weight of the aromatic polyester (a) and aromatic polycarbonate. A composition according to claim 1. (8) The composition according to claim 1, wherein the blending ratio of the styrene-butadiene block copolymer (c) and the thermoplastic polyolefin elastomer (d) is 1/2 to 4/1.