JPH03247652A - Polyester composition - Google Patents

Abstract

PURPOSE:To obtain a polyester composition suitable for electronics and automobile industry, having excellent mechanical, characteristics such as flexural strength, etc., by blending a polyester with a specific polyhydroxy ether, a polyfunctional oxazoline compound and an inorganic filler. CONSTITUTION:100 pts.wt. total amount of (A) a polyester (e.g. polyethylene terephthalate) having >=0.5 intrinsic viscosity and (B) a polyhydroxy ether comprising a repeating unit shown by formula I (R<1> is 6-24C arylene; p is 0-5; q and n are 1-5; m is positive integer) in a ratio of the component A:B=(99.9:0.1)-(85:15) by weight is blended with (C) 0.01-10 pts.wt. polyfunctional oxazoline compound shown by formula II (R<2> is 1-24C alkylene) n is 0 or 1, when n=1, X and Y are H or 2-oxazoline and when n=0, X and Y do not exist; etc.) and (D) 1-200 pts.wt. inorganic filler having <=50mu average particle diameter.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a thermoplastic polyester resin composition, more specifically a polyester, blended with a polyhydroxy ether, a polyvalent oxazoline compound, and an inorganic filler to improve bending strength. The present invention relates to a polyester composition having excellent mechanical properties such as tensile strength and elongation, impact strength, and heat resistance. These compositions have high strength and are useful in the electronics and automotive industries where injection molded parts require high strength properties.

(Prior Art) Polyethylene terephthalate and the like have been used in many industrial products as fibers and films due to their excellent mechanical properties, electrical properties, heat resistance, chemical resistance, and the like. When used as fibers or films, they are usually stretched, but when used in plastic applications as injection molded products, various physical property problems may occur. Are known. When an inorganic filler is blended, the surface of the inorganic filler is generally hydrophilic due to adsorbed water, etc., and has poor affinity with hydrophobic polyester resin, so simply mixing the two will result in a molded product. Does not exhibit practical strength.

Furthermore, it is known that the mechanical strength of polybutylene terephthalate can be improved by blending phenoxy resin and glass fiber (Japanese Patent Publication No. 59-359
However, there are drawbacks such as increased anisotropy and warpage of the molded product. For this reason, it is considered to incorporate an inorganic filler, and several methods have been proposed for modifying the surface of the inorganic filler to make it hydrophobic. For example, a method of increasing the affinity between an inorganic surface and a resin by adding various coupling agents (Coloring Materials, 59(3), 176-
184.1986), or a method of copolymerizing the inorganic material and resin by pulverizing the inorganic material and resin with a ball mill etc. and generating radicals on the fracture surface (Gypsum & Lime N
1189.1984) etc. are known.

(Problems to be Solved by the Invention) Usually, when a polyester resin is kneaded and filled with an inorganic material whose surface has been treated with various coupling agents, the mechanical properties of the product are improved compared to those without using a coupling agent. However, in either case, the disadvantage is that the strength is lower than that of polyester resin alone. That is, an object of the present invention is to provide a thermoplastic polyester resin composition of polyester resin/inorganic filler that has high bonding properties at the interface between the inorganic filler and the resin and has high strength.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have made extensive studies and have finally completed the present invention. That is, the present invention provides (A) a polyester, (B) a polyhydroxyether having a structure represented by the following general formula (I) as a repeating unit, (C) a polyester having the following formula (I).
A polyvalent oxazoline compound represented by [), and [wherein R2 is an alkylene group or arylene group having 1 to 24 carbon atoms, provided that, if necessary, a lower alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 19 carbon atoms; may be replaced. n represents O or an integer of 1; when n is 1, X and Y are a hydrogen atom or a 2-oxazoline group; when n is 0, X and Y are absent. In addition, the hydrogen atoms of all oxazolines are lower alkyl groups having 1 to 6 carbon atoms or 6 carbon atoms.
It may be substituted with ~19 aryl groups. ](D)
This is a polyester resin composition characterized by containing an inorganic filler having an average particle size of 50 μm or less.

The polyester resin (A) used in the present invention includes aliphatic glycols such as ethylene glycol, propylene glycol, 14-butanediol, neopentyl glycol, and hexamethylene glycol, alicyclic glycols such as cyclohexane dimetatool, and aromatic glycols such as bisphenol. A dihydroxy compound unit selected from one or more of these group dihydroxy compounds, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid, oxalic acid, succinic acid, adipic acid, aliphatic dicarboxylic acids such as sebacic acid and undecanedicarboxylic acid;
1 of alicyclic dicarboxylic acids such as hexahydroterephthalic acid
A polyester resin formed from a species or a dicarboxylic acid unit selected from two or more of these, and as long as it exhibits thermoplasticity, a small amount of a trivalent or higher polyhydroxy compound such as triol or tricarboxylic acid, or polycarboxylic acid. It may be modified with, etc. Specifically, polyester resins containing polyethylene terephthalate or polybutylene terephthalate or at least 80 mol%, preferably 90 mol% or more of ethylene terephthalate or butylene terephthalate repeating units are preferred. Further, it is preferable that these polyester resins have an intrinsic viscosity of 0.5 or more, and more preferably 0.55 or more, as determined by measurement at 30°C with a phenol/tetrachloroethane mixed solvent (6/4 weight ratio) solution. It is particularly desirable that there be.

Linear polyhydroxyether (B) used in the present invention
is a thermoplastic resin whose main structural unit is the following structural formula (1).

In the formula, P is O~5, q and n are each integers of 1~5, R1 represents a divalent aromatic hydrocarbon group containing a P-phenylene group as a main component, and m is a positive number. It is.

The thermoplastic polyhydroxyether (B) is synthesized by a reaction between the corresponding bisphenols and shrimp chlorohydrin, a reaction between the bisphenols and butadiene dioxide, and the like.

Specific examples of such bisphenols include bisphenol F C4,4'-methylene diphenol]
, bisphenol E C4,4'-ethylidene diphenol], bisphenol A C4,4' isopropylidene diphenol], bisphenol B (4,4'
-Secondary-butylidene diphenol], bisphenol S (bis(4-hydroxyphenyl)sulfone), etc. Among these, bisphenol A is preferred in terms of easy availability.

In addition, in the general formula (I), p is 0 to 2, q is 1 to 2,
n is preferably 1 to 2, and more specifically, phenoxy resin is particularly preferred.

It is preferable that the polyhydroxy ether which is the component (B) has an intrinsic viscosity of 0.5 or more, as determined by measurement at 30°C in a phenol/tetrachloroethane mixed solvent (6/4 weight ratio) solution, and more preferably 0. It is particularly preferable that it is .55 or more.

The polyvalent oxazoline compound (C) used in the present invention is represented by the above-mentioned formula (n), and specifically includes 2,2 methylenebis(2-oxazoline), 2,2' ethylenebis(2-oxazoline), 2.2'-ethylenebis(4-methyl-2-oxazoline)2.2'-propylenebis(2-oxazoline),2.2'-tetramethylenebis(2-oxazoline),2.2'-hexazoline Methylenebis(2-oxazoline), 2.2'-octamethylenebis(2-o+tsoIJn), 2.2'
-p-phenylenebis(2-oxazoline), 2.2'
-p-phenylenebis(4-methyl-2-oxazoline), 2.2'-p-phenylenebis(4-methyl-2-oxazoline), 2.2'-p-phenylenebis(4,4
'-dimethyl-2-oxazoline), 2.2'-p-
Phenylenebis(4-phenyl-2-oxazoline),
2.2'-m-phenylenebis(2-oxazoline)
, 2.2'-m-phenylenebis(4-methyl2-oxazoline), 2.2'-m-phenylenebis(4,4'
-dimethyl-2-oxazoline), 2+2' m-phenylenebis(4-phenyl-2-oxazoline), 2
．． 2'-0-phenylenebis(2-oxazoline), 2
2'-0-phenylenebis(4-methyl-2-oxazoline), 2.2bis(2-oxazoline), 2.2
'-bis(4-methyl-2-oxazoline), 2.2
'-bis(4-ethyl-2-oxazoline), 2.2
'-Bis(4-phenyl-2-oxazoline) tri(2-oxazoline)methane, C2,2-)su(2oxazoline)ethane, 1,1.3-tri(2-oxazoline)propane, C2,3- )su(2-oxazoline)
Propane, 1,1.4-tri(2-oxazoline)butane, 1,1.4-)su(2-oxazoline)butane,
1.1.5-)li(2-oxazoline)pentane,
1.25-tri(2-oxazoline)pentane, 1,
1.6-tri(2-oxazoline)hexane, 1,2
．． 6-)su(2-oxazoline)hexane, 1.3.
Examples include 5-tri(2oxazoline)benzene.

In addition, among these polyvalent oxazoline compounds, especially
2.2'-(1,3phenylene)-bis(2oxazoline) and 2.2'-methylenebis(2oxazoline) are preferred.

The inorganic filler (D) used in the present invention refers to fibrous, acicular, and granular fillers, including wollastonite, talc, clay, mica, sericite, kaolin, potassium titanate, calcium carbonate, and carbonate. Examples include magnesium and aluminum silicate, and the average particle size is 50 μm or less. These can be used in combination of two or more types, and can also be used in combination with glass fiber. Among these fillers, wollastonite, talc, mica, clay, and calcium carbonate are particularly preferred.

The inorganic filler used in the present invention must have an average particle size of 50 μm or less, preferably 45 μm or less. Furthermore, the thickness is particularly preferably 30μ or less.

If the average particle size exceeds 50 μm, not only is there little effect of improving mechanical strength, but also the surface properties of the molded product are deteriorated.

In the composition of the present invention, it is desirable to incorporate an additive that increases the crystallization rate of the polyester resin, that is, a crystallization promoter. The crystallization accelerator mentioned here is
For example, carbon powder, talc, neutral clays, and periodic table ■
Examples of the metal oxides selected from the group include sulfates, phosphates, silicates, oxalates, stearates, benzoates, salicylates, and tartrates.

In order for the composition of the present invention to exhibit good effects, the blending ratio of each component is preferably such that the weight ratio of polyester resin (A) and thermoplastic poly(hydroxy ether) (B) is (A): (B) -99,9: 0.1~
85:15, and "':) Polyvalent oxazoline compound (C
) component is in the range of 0.01 to 10 parts by weight, and the inorganic filler (D) has an average particle size of 5 μm or less. Department.

(A) :(B) = From 99.10.1, (B)
If the amount of the ingredient is small, no improvement effect can be expected; (
If the blending amount of component (B) is larger than A):(B) -85:1s, it is not preferable because heat resistance, rigidity, etc. will decrease.

Moreover, the amount of component (C) is 0.01 to 10 parts by weight, preferably 0.5 to 5.0 parts by weight. If component (C) is less than 0.01 parts by weight, both the heat distortion temperature and mechanical strength will decrease, while if it exceeds 10 parts by weight, the heat distortion temperature will not change, but the mixture will not be uniform and the quality will deteriorate. This is not desirable because it is not constant.

If the amount of component (D) is less than 1 part by weight, there will be no improvement effect, and if it exceeds 200 parts by weight, not only will the mechanical strength drop significantly, but the surface of the molded product will deteriorate, and moldability and fluidity will deteriorate. happens.

Moreover, various compounds can be added to the inorganic filler (D) having an average particle size of 50 μm or less, as necessary, for the purpose of improving the interfacial adhesive force with the resin and increasing the reinforcing effect. For example, vinyltriethoxysilane, T-methacryloxypropylmethoxysilane, β-(3,4-evoquincyclohexyl)ethyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, T-aminopropyltriethoxysilane, T- -Those treated with a silane-based treatment agent such as -chloropropylmethoxysilane, T-mercaptopropyltrimethoxysilane, or a chromium-based treatment agent such as methacrylate chromic chloride are used.

In the present invention, thermoplastic poly(hydroxy ether) and polyhydric oxazoline compounds are added to the mineral-filled subcompound polyester resin in several ways. A typical method is (1) adding thermoplastic poly(hydroxy ether), component (B), to inorganic filler, component ([1)], and then adding a polyvalent oxazoline compound, component (C). (A) A method of sufficiently kneading the polyester resin as the component, (2) A method of thoroughly kneading the polyester resin (
A method of thoroughly kneading thermoplastic poly(hydroxy ether) (B) and inorganic filler (D) after mixing in addition to A), (3)
) Polyester resin (A), thermoplastic poly(hydroxy ether) (B), and polyvalent oxazoline compound (
A method of sufficiently kneading the inorganic filler (D) after kneading C),
(4) This is a method of thoroughly mixing the components (A) to (D) described above at the same time. Other methods of mixing may also be used satisfactorily.

A conventionally known device can be used for the above mixing. For example, a mixing device such as a reaction device with stirring blades, a shaft or two-wheel screw extruder, a Banbury mixer, a kneader, and a mixing roll can be used alone or in combination. The heating and mixing temperature is preferably higher than the melting point of the polyester resin and thermoplastic poly(hydroxy ether).

Depending on the purpose and use, the composition of the present invention may further include stabilizers such as antioxidants, ultraviolet absorbers, etc., as well as plasticizers, lubricants, etc.
Various additives such as a flame retardant, an antistatic agent, a coloring agent, a mold release agent, and a metal powder can be blended.

The composition of the present invention does not require special molding methods or molding conditions, and can be molded under normal molding conditions for crystalline thermoplastic resins, giving molded products with excellent heat resistance, dimensional accuracy, and mechanical properties. Therefore, in addition to molding various molded parts, films, sheet-like objects such as plates, fibrous objects, tubular objects, containers, etc., it can also be used as coating materials, coating agents, and adhesives.

(Function) In the composition of the present invention, it is not clear how the polyhydroxy ether and the polyvalent oxazoline compound act, but the polyvalent oxazoline compound is a stabilizer for the polyester resin and a stabilizer for the polyhydroxy ether and the polyester resin. It is thought that it acts as a coupling agent with. This composition has been found to be useful in practical applications, such as significantly improved mechanical properties such as bending strength and tensile elongation at break, compared to compositions consisting only of two components, polyester resin and inorganic filler. The value is extremely high.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. still,
Parts and percentages in the examples are by weight. Also,
Characteristics of the test pieces in the examples were evaluated using the following test method.

(1) Heat deformation temperature: According to ASTM D-648, a test piece with a thickness of 174 inches molded at a mold temperature of 90°C was subjected to a load of 4.6
Measured under kg/cd.

(2) Bending strength: Measured according to ASTM D-790.

(3) Tensile strength and tensile elongation: Measured according to ASTM D-638.

(4) Crystallinity: Crystallinity was determined by measuring the melting point and crystallization initiation temperature using a differential calorimeter (temperature increase and peak speed 20°C/min).

(5) Surface properties: The surface properties were determined based on the surface gloss and flow pattern of the disc.

◎: Extremely good ○: Good △: Fairly good ×: Poor
XX: Extremely poor Examples 1 to 6, Comparative Examples 1 to 8 (A) As the polyester resin of the component, polyethylene terephthalate resin (RE530 manufactured by Toyobo ■ [[η]
= 0.62 to 0.63], as the linear polyhydroxy ether of component (B), union carbide (UCC
) manufactured by Co., Ltd., 7-hydroxy resin (PKHC), as the (C) component, ■2.2'-(1,3 phenylene)-bis(
2-oxazoline) or ■2,2'-methylenebis(
2-oxazoline), as component (D) ■wollastonite (NYCOA Division of Pro
NYAD manufactured by cessed Minerals Inc.
325), ■Talc (Talcan PK manufactured by Kasei Co., Ltd.), ■
Calcined (anhydrous) kaolin clay (Burgess Pigment Co., USA, Burgess No. 30), mica (Suzolite [Kuraray Co., Ltd.] Mica ■4O-3 (weight average flake diameter 2)
80μ, weight average aspect ratio 90μ), ■325-
3 (also 40μ, 30μ)) in the proportions shown in Table 1, the mixture was charged into the hopper of a twin-screw extruder PCM 30, and melt-kneaded at a cylinder temperature of 265 to 275°C to form a compound chimney. After drying the chips at 140°C for 4 hours, the cylinder temperature was 265~
A test piece was molded by injection molding 11L (Metsuki Jushi Kogyo Co., Ltd. FS-75) with a mold temperature of 265-275°C and a mold temperature of 90°C.

The physical properties of the obtained molded article were evaluated and the results are shown in Table 1.

The following margins are shown in Table 1: 2,2'-(1,3phenylene)-bis(2-
oxazoline) ■72.2'-methylenebis(2-oxazoline)■:
Wallastonite (NYCOA Division of
NYAD325 manufactured by Processed Minerals Inc.) ■: Talc (Talcan PK manufactured by Kasei Co., Ltd.)
) ■: Calcined (anhydrous) kaolin clay (Burgess Pigment Co., USA, Burgess NCL30) ■: Mica: Kuraray Suzolite 0 Mica 4O-8 (weight average flake diameter 280 μ, weight average aspect ratio 9)
0μ) ■: Mica: Suzolite manufactured by Kuraray ■Mica 325S (same, 40μ, 30μ) As is clear from Table 1 above, Comparative Examples 1 to 3 are (B)
Since the component thermoplastic polyhydroxy ether is not blended, physical properties such as strength and elongation are insufficient. Comparative example 4
In Comparative Examples 5 to 7, the average particle size of the inorganic filler of component (D) was as large as 280 μm, resulting in insufficient strength and elongation, and the surface of the molded product was poor. Comparative Example 8, which does not have sufficient strength and elongation because no valent oxazoline compound is blended, is a mixture of only components (^) and (D),
It is clear that the physical properties are poor.

In addition, Examples 1 to 6 have very well-balanced mechanical properties such as tensile strength and elongation, bending breaking strength, and thermal deformation in order to satisfy the requirements described in the claims. It can be seen that a fully satisfactory thermoplastic polyester composition has been obtained.

(Effects of the Invention) The composition of the present invention has good moldability and excellent mechanical properties such as bending properties and heat deformation temperature, and is used for OA, connectors in the secondary field, coil bobbins, CI? It is possible to provide molded products that pass through T-sockets, etc., making a great contribution to industry.

Claims (1)

[Scope of Claims] (A) Polyester, (B) Polyhydroxyether having a structure represented by the following general formula (I) as a repeating unit, ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 is carbon Arylene group of numbers 6 to 24, p is 0 to
5, q and n are each integers of 1 to 5, and m is a positive integer. (C) A polyvalent oxazoline compound represented by the general formula (II) below, and ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R^2 is an alkylene group or arylene group having 1 to 24 carbon atoms, However, if necessary, a lower alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 19 carbon atoms may be substituted. n represents an integer of 0 or 1, and when n is 1, X and Y are a hydrogen atom or a 2-oxazoline group, and n
When is 0, X and Y do not exist. In addition, all the hydrogen atoms of the oxazoline may be substituted with a lower alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 19 carbon atoms. (D) A polyester resin composition containing an inorganic filler having an average particle size of 50 μm or less.