JPH01240549A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the present composition capable of giving molded articles outstanding in mechanical properties and free from sink mark and warpage, comprising a polyethylene terephthalate-based copolymer, an epoxy group-contg. styrene resin, an epoxy group-free styrene resin etc. CONSTITUTION:The objective composition comprising (A) pref. 10-80wt.% of polyethylene terephthalate or a copolymer containing ethylene terephthalate unit, (B) pref. 3-30wt.% of an epoxy group-contg. styrene resin, (C) pref. 5-40wt.% of an epoxy group-free styrene resin and/or (D) pref. 5-40wt.% of a thermoplastic resin compatible with the resin B (e.g., poly-2,6-dimethyl-1,4- phenylene ether). In this composition, the reaction product from the reaction between the components A and B accounts for >=5wt.% of said composition, and the intrinsic viscosity of the component A is >=0.55.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermoplastic resin composition, and more specifically, thermoplastic resins having poor compatibility are made to be compatible by blending a third component, and both resins are made to be compatible. The object of the present invention is to provide a thermoplastic resin composition which can improve the disadvantages of the invention and which can provide molded articles having excellent mechanical properties.

(Prior Art) Conventionally, many attempts have been made to solve the drawbacks of each thermoplastic resin by blending thermoplastic resins having different properties.

However, different polymers usually have poor compatibility and have the disadvantage that mechanical properties tend to be lower than that of a single polymer. On the other hand, blends of highly compatible polymers have properties [4U], so characteristic properties cannot usually be expected6. Various modifications have also been investigated, and it has been found that a blend in which modified olefin rubber is finely dispersed in a nylon matrix exhibits improved impact resistance (Japanese Patent Application Laid-Open No. 143061/1982). However, such blends also exhibit deterioration in other physical properties (showing curling and no characteristic properties other than impact resistance are obtained).

(Problems to be Solved by the Invention) The object of the present invention is to improve mechanical properties and improve surface properties, heat resistance, chemical resistance, etc. by blending thermoplastic resins with different properties and poor compatibility. That is.

(Means for Solving the Problems) The present inventors have made extensive studies to solve the above problems, and have finally completed the present invention. That is, the present invention uses polyethylene terephthalate or a copolymer containing ethylene terephthalate units (A), a styrene resin containing an epoxy group (B), and a styrenic resin not containing epoxy (C).
and/or in a thermoplastic resin composition containing a thermoplastic resin (D) having molecular compatibility with the styrenic resin (B), a reaction product generated by the reaction between component (A) and component (B). Component (A) in the composition has an intrinsic viscosity of 0.55 or more.

Component (A) in the present invention includes polyethylene terephthalate and ethylene terephthalate components and other acid components and/or glycol components, such as isophthalic acid, p-oxybenzoic acid, adipic acid, sebacic acid, geltaric acid, diphenylmethanedicarboxylic acid. , acid components such as dimer acid, naphthalene dicarboxylic acid, glycol components such as hexamethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, cyclohexane dimethylene glycol, bisphenol A1 neopentyl glycol alkylene oxide adduct, An example is polyethylene terephthalate copolymerized with an oxyacid such as oxyethoxybenzoic acid.

In the present invention, those having a melting point of 200° C. or higher are particularly preferred from the viewpoint of heat resistance.

In addition, it is essential that the component (A) of the present invention has an intrinsic viscosity of 0.55 or more in the composition measured at 30°C in a mixed solvent of phenol/tetrachloroethane (6/4 weight ratio), In particular, it is preferably 0.6 or more.

In addition, in order to make the intrinsic viscosity in the composition the above value, the intrinsic viscosity of component (A) when blending is 0.7 to 1.
．． It is preferable that it is 5.

Next, as the styrene resin (B) containing an epoxy group in the present invention, glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl ether of polyalkylene glycol (meth)acrylate , polystyrene copolymerized or graft copolymerized with epoxy group-containing copolymerizable unsaturated monomers such as glycidyl itaconate, acrylonitrile,
Examples include styrene-containing polymers such as styrene copolymers and styrene-butadiene copolymers. The content of the epoxy group-containing copolymerizable unsaturated monomer is usually 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the resin (B).

In addition, as the epoxy group-free styrene resin (C) in the present invention, homopolymers such as polystyrene, polychlorostyrene, and polyα-methylstyrene, styrene-butadiene copolymers, and styrene-acrylonitrile copolymers are used. , styrene-acrylonitrile-acrylate copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-butadiene rubber-modified polystyrene, [PD? Examples include polystyrene-based thermoplastic elastomers such as I-based rubber-modified polystyrene, acrylic rubber-modified styrene/acrylonitrile copolymer, and hydrogenated styrene/butadiene block copolymer.

Furthermore, the thermoplastic resin (D) in the present invention is molecularly compatible with the styrene resin (B) (a blend that is compatible with the styrene resin (B) and gives a single Tg by changing the Tg of the styrene resin (B)). A specific example is a polyphenylene ether resin. Examples of the polyphenylene ether resin include resins having a unit structure represented by the following general formula.

In Koyu, R,, R,, R, and R1 are hydrogen, halogen,
It is a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxy group, a phenoxy group, or a nitro group, and n indicates the degree of polymerization. Specific examples of RlRt, Rs and R4 include hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy, nitro, etc. The basics are given. Specifically, for example, poly-2,6-cymethyl-1,4-
Phenylene ether, poly-2,6-ethyl-1.4
-phenylene ether, poly-2,6-diprobyl-1
．． 4-phenylene ether, poly-2,6-simethoxy 1,4-phenylene ether, poly-2,6-cyclomethyl-1,4-phenylene ether, poly-2,6
-dipromemethyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether,
Poly-2,6-didryl-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether and poly-2,5-dimethyl-1,4-phenylene ether, poly-2,6- Examples include dipendyl-1,4-phenylene ether.

A preferred polyphenylene ether resin is a polymer in which R1 and R4 in the general formula have an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and n is usually preferably 50 or more.

Component (C) and component (D) may each be obtained by polymerizing the heptamer of the other component in the presence of the polymer of one component.

The blending ratio of the above components (A), (B), (C) and (D) can be changed as appropriate depending on the desired physical properties, purpose, cost, etc., but usually the components (A), (B), (C) and 5 to 95% by weight of component (A) based on the total amount of (D)
Preferably 10 to 80% by weight, component (B) 0.5 to 5%
0 weight% or 3 to 30 weight%, component (C) is 0 to 30% by weight
90% by weight, preferably 5-40% by weight, and component (D
) is 0 to 90% by weight, preferably 5 to 40% by weight,
And the total of component (C) and component (D) is 5% by weight or more.

In the present invention, the amount of the reaction product produced by the reaction between component (A) and component (B) is the amount measured by the following method, and is preferably 5% by weight or more based on the total composition, and more preferably 7% by weight or more based on the total composition. % by weight or more. If the amount of reaction product is small, the strength and elongation of the resulting composition will decrease.To increase the amount of reaction product, component (D) should be added to component (B).
The weight ratio of component (A) to component (D) is preferably in the range of 0.5 to 10, preferably 0.5 to 8.

(Amount of reaction product between component (A) and component (B) in the composition) For 3 g of the composition, 10 cc of chloroform, 10 cc of hexafluoroisopropanol, 30 cc of chlorobenzene/m-cresol (= 1/1) Dissolve the sample by adding sequentially. Next, the mixture was poured into 200 cc of benzene, 100 cc of which was evaporated and concentrated, 200 cc of benzene was added, and the mixture was left to stand for one day, and then the precipitate was filtered off.

After drying, the infrared absorption spectrum of polystyrene in the precipitate was measured by the tablet method, and assuming that component (A) and component (B') were reacting equimolarly, this was taken as the reaction product. . On the other hand, for 2111, add methanol to remove the polymer solvent while concentrating, then add methanol, repeat the same operation twice, filter the precipitate, dry it, and use the same method as above to remove the infrared absorption of polyethylene terephthalate. The spectrum was measured to determine the reaction product. The sum of these reaction products relative to the total composition is expressed as a percentage by weight.

It is important to maintain the intrinsic viscosity of component (A) in the composition at 0.55 or more, preferably 0.6 to 1.5 in order to improve the strength and elongation of the composition. ) and component (B) to lower the concentration of carboxy terminals in the system, or when blending component (A) with a high intrinsic viscosity, for example, 0.7 to 1.8. This can be achieved by using Even if the intrinsic viscosity of component (A) when blended is less than 0.7, it can be achieved by adding a thickening substance such as a jepoxy compound or an oxazoline compound.

If the amount of component (A) added is too small, heat resistance (heat distortion temperature)
In addition, if component (C) and/or component (D) is too small, molding shrinkage increases, and the molded product suffers from sink marks and warpage, resulting in deterioration of surface properties. produce shortcomings. In addition, if component (B) is too small, component (A) and component (C) and/or component (D)
The disadvantage is that the compatibility with the polymer is poor and the physical properties are deteriorated.

The composition of the present invention may further include ingredients (
A) Crystal nucleating agent such as zirco, mica, titanium oxide,
Carbon black etc. and crystallization accelerators, such as polyoxyalkylene compounds compatible with the polyester, polyhydric alcohol derivatives, higher fatty acid esters, higher fatty acid metal salts, polyvalent carboxylic acid esters, high molecular weight aliphatic polycarbons Acid salts, polyhydric alcohol esters, etc. may also be blended. Usually, the amount of crystal nucleating agent is 50% of the composition.
The amount of the crystallization accelerator is preferably up to about 10% by weight based on the composition.

In addition, we also use antioxidants, ultraviolet absorbers, stabilizers such as hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, colorants, conductivity imparting agents, and adhesives. Mobility improver (
solid lubricants, liquid lubricants), polyfunctional crosslinking agents, impact modifiers (for example, Tg is 0°C or less, preferably -20°C
'C or less rubber-like substances, more preferably reactive group-containing rubbers), inorganic fillers other than the above, fibrous reinforcing agents (for example, glass fibers, carbon fibers, graphite fibers, silicon carbide fibers, silicon nitride fibers, nitrided Additives such as boron fibers, potassium titanate whiskers, heat-resistant organic fibers) and conductivity imparting agents (for example, metal fibers, polyacetylene fibers, metal powders, iron phosphorus, carbon black, organic conductive polymers, etc.) can also be blended. When blending inorganic fillers and inorganic fibers, silane couplers, titanium couplers, zircoaluminum 2-1 type couplers, etc. may be used in combination.

Additionally, it is possible to blend resins of any degree and type without detracting from the objectives of the present invention.

The method for producing the composition of the present invention is not particularly limited, and any method may be used. For example, it may be blended by mechanical kneading with an extruder, roll mill, Banbury mixer, etc., or multi-stage kneading such as kneading components (A) and (B) again. Good too.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Note that the percentages in the examples are based on weight.

Example 1. ~5. Comparative example 1. ~5° Polyethylene terephthalate with [η] of 1.0 or 0.63, styrenic resin containing epoxy groups, styrenic resin without epoxy groups and [η] of 0.58 (measured in chloroform at 30°C) ) of poly-2,6-dimethylphenylene-1,4-ether powders were mixed in a blender, and heated to a cylinder temperature of 300°C using a 30mm diameter twin-screw extruder (Ikegai Tekko Co., Ltd. PCM-30). The mixture was kneaded and extruded at °C to form pellets.

The obtained pellets were dried in a vacuum dryer at 120° C. for 5 hours, and then molded into a molded product using an injection molding machine (Metsuki Jushi Kogyo Co., Ltd., model FS-75). The cylinder temperature at this time was 295°C. Moreover, the mold temperature was 90°C.

Table 1 shows the physical property values of each of the obtained compositions.

In addition, various measurements in the examples were carried out by the following methods.

(1) Tensile strength and elongation Measured according to ASTM D-638.

(2) Izotsu impact strength Measured with a notch according to ASTM D-256.

(3) Heat distortion temperature Load: 18.6 for a 1/16 inch thick test piece molded at a mold temperature of 90'C according to ASTM D-648
Measured under kg/c-.

(4) Surface properties The molded product was visually evaluated for sink marks, surface gloss, etc.

(5) When measuring the amount of the intrinsic viscosity reaction product of component (A) in the ffl product, in order to remove the reaction product of the separated precipitate, after dissolving the precipitate with hexafluoroisopropanol, It was reprecipitated into chloroform and dried. After repeating this twice, the intrinsic viscosity of component (A) was determined to be 30% in a mixed solvent of phenol/tetrachloroethane (674 weight ratio).
Measured at °C.

In Table 1 *1) Intrinsic viscosity 1.0 *2) Intrinsic viscosity 0.63 *3) Styrene copolymer copolymerized with 7.5% by weight of glycidyl methacrylate *4) Copolymerized with 15.4% by weight of glycidyl methacrylate Styrene copolymer *5) Hydrogenated styrene-butadiene copolymer *6) Polyphenylene ether (Effects of the invention) The composition of the present invention can be used in various molded parts, films, temporary sheet-like materials, fibrous materials, and tubular materials. Widely used for forming molded products such as objects and containers (in addition to being used as a coating agent, adhesive, sealant, and modifier for other resins, etc.) It is also possible to further perform stretching molding or to form a secondary molded product.

Due to the presence of component (B), the composition of the present invention
is modified and the compatibility between component (A) and component (C) and/or component (D) is improved, resulting in a uniformly dispersed state and providing a molded product with excellent mechanical properties. , to solve problems such as sink marks and warpage by reducing molding shrinkage of component (A), and to provide molded products with excellent surface properties; and also to provide molded products with excellent surface properties.
It has features such as improved heat resistance and chemical resistance.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] (1) Polyethylene terephthalate or a copolymer containing ethylene terephthalate units (A), a styrene resin containing an epoxy group (B), a styrenic resin not containing an epoxy group (C), and/or the styrenic resin (B).
) in a thermoplastic composition containing a thermoplastic resin (D) having molecular compatibility with component (A) and component (B).
1. A thermoplastic resin composition characterized in that the reaction product produced by the reaction with the component (A) accounts for 5% by weight or more, and the intrinsic viscosity of component (A) in the composition is 0.55 or more.