JPS62218436A - Thermoplastic polyester composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in mechanical properties at high temperature, appearance of a molding, heat resistance and hydrolysis resistance, by mixing a thermoplastic polyester with a reinforcement, polyphenylene sulfide and a glycidyl group-containing olefin copolymer. CONSTITUTION:Polyphenylene sulfide which is a polymer containing at least 70mol% repeating units of formula I (wherein -Ph- is a group of formula II, III or IV or the like) is heated with water by agitating to 80 deg.C or above to obtain a hot-water-treated polyphenylene sulfide (B). 100pts.wt. thermoplastic polyester (A) having an intrinsic viscosity of 0.5-1.3 (as measured in a 0.5% o-chlorophenol solution at 25 deg.C) is mixed with 1-100pts.wt. component B, 5-150 pts.wt. fibrous and/or particulate reinforcements (C) (e.g., glass fiber chopped strand) and 0.5-80pts.wt. glycidyl group-containing olefin copolymer (D) comprising an alpha-olefin and a glycidyl ester of an alpha,beta-unsaturated carboxylic acid (e.g., ethylene/glycidyl methacrylate copolymer).

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a thermoplastic polyester with an excellent balance of mechanical properties, especially mechanical properties at high temperatures, molded product appearance, heat resistance, hydrolysis resistance, and moldability. It is about the composition.

<Conventional technology> Thermoplastic polyvarnishes such as polyethylene terephthalate and polybutylene terephthalate are used in a wide range of fields due to their excellent properties, especially in applications that require high rigidity and heat resistance. In many cases, a method of modifying the material by adding a fibrous reinforcing agent such as glass fiber or a granular reinforcing agent such as talc is often used. However, thermoplastic polyester molded products obtained by blending so-called reinforcing agents are significantly inferior in appearance, including surface gloss, and their impact resistance and heat resistance are still insufficient, so further improvements are required. desired.

Therefore, as a result of studies aimed at improving these problems, the present applicants found a method (Japanese Patent Laid-Open No. 2002-120000) of blending a thermoplastic polyester, a reinforcing agent, an olefin copolymer containing a glycidyl group, and a specific amount of polyphenylene sulfite. 57-
92044).

A method of blending a thermoplastic polyester, a reinforcing agent, and high molecular weight polyphenylene sulfide (Japanese Patent Laid-Open No. 57
-137346). A method of blending a thermoplastic polyester, a reinforcing agent, a metal salt of an organic acid, and further polyphenylene sulfide (Japanese Unexamined Patent Publication No. 58-25353)
proposed that the above object could be achieved by a method of heat treating a molded article containing a thermoplastic polyester, a reinforcing agent, and polyphenylene sulfide (Japanese Unexamined Patent Publication No. 58-25353).

<Problems to be Solved by the Invention> However, although the thermal performance of thermoplastic polyester is certainly improved by the improved formulation proposed by the applicants as described above, the mechanical properties, particularly the impact resistance, are still poor. However, there remains a fatal flaw in that the mechanical properties of molded products, that is, their hydrolysis resistance, are significantly inferior when used under high temperature and high humidity conditions. found.

Therefore, the present inventors continued to study with the aim of improving these problems, and as a result, we found a composition in which a thermoplastic polyester is blended with a reinforcing agent, polyphenylene sulfide modified by specific treatment, and a glycidyl group-containing olefin copolymer. The inventors have discovered that the problem can be improved by using a product, and have arrived at the present invention.

Means for Solving the Problems> That is, the present invention provides: (A) (a) CB for 100 parts by weight of thermoplastic polyester; (b) 5 to 150 parts by weight of a fibrous and/or granular reinforcing agent; A thermoplastic polyester composition containing (c) 1 part of polyphenylene sulfide treated with hot water of 80°C or higher, and (d) 0.5 to 80 parts by weight of a glycidyl group-containing olefin copolymer. It is something that provides something.

The thermoplastic polyester used in the present invention includes polyethylene terephthalate, polybutylene terephthalate, polyethylene-α, β-bisphenoxyethane-4,
These thermoplastic poly-3-esters include aliphatic dicarboxylic acids such as azelaic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid, isophthalic acid, orthophthalic acid, and naphthalene dicarboxylic acid. , other dicarboxylic acid components such as aromatic dicarboxylic acids such as diphenylethane-4°4'-dicarboxylic acid and cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, and propylene glycol, neopentyl glycol, l,
Aliphatic glycols such as 5-bentanediol, l,6-hexanediol, decamethylene glycol, cyclohexane dimetatool, cyclohexanediol, and long glycols such as polyethylene glycol, poly-1,3-7'ropylene glycol, polytetramethylene glycol, etc. at least one other diol component such as a chain glycol
It may also be one in which a small proportion of seeds are copolymerized. When polyethylene terephthalate is used as the thermoplastic polyester, it is preferable to add a crystallization promoter such as talc, mica, barium stearate, sodium stearate, potassium benzoate, sodium terephthalate, and sodium monomethylisophthalate.

In addition, if the degree of polymerization of these thermoplastic polyesters is too small, sufficient mechanical properties cannot be obtained, and if the degree of polymerization is too large, molded products with good surface gloss cannot be obtained. The intrinsic viscosity of the orthochlorophenol solution measured at 25°C is 0.5 to 1.3, especially 0.6 to 1.3.
It is preferably in the range of Ll.

The reinforcing agent used in the present invention can preferably be fibrous and/or granular. Examples of fibrous reinforcing agents include inorganic fibers such as glass fibers, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers (such as stainless steel fibers), and carbon fibers. . In addition, granular reinforcing agents include wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, and metal oxides such as alumina, silicon oxide, magnesium oxide, zirconium oxide, and titanium oxide. carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as barium sulfate, glass beads, boron nitride, silicon carbide, and saroyan, and these may be hollow ( For example, hollow glass fibers, glass microballoons, glass balloons, carbon balloons (fxt).

The above-mentioned reinforcing agents may be used after being pretreated with a coupling agent such as a silane type or a titanium type, if necessary.

Moreover, two or more kinds of these can also be used as a mixture.

The blending amount of these reinforcing agents is 100% of thermoplastic polyester.
5 to 150 parts by weight, preferably 10 to 1 parts by weight
It is 30 parts by weight. If the amount is less than 5 parts by weight, sufficient mechanical strength cannot be obtained, and if it is more than 150 parts by weight, there is a marked tendency to impair surface gloss, which is not preferable.

Polyphenylene sulfide (hereinafter referred to as PPS) used in the present invention
(abbreviated as) is not particularly limited to, but is
Structural formula polymerized by the method disclosed in the official publication ÷ph
A polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by -s+ (In the above general formula, -Ph- is etc., and Q is F, CI, Br or CH3, (m3 represents an integer of 1 to 4) Furthermore, more preferably, the PPS is produced without curing after polymerization in order to further enhance the effect of the following hot water treatment.

In order to treat PPS with hot water in the present invention, it is important to set the temperature of the hot water to 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher, particularly preferably 170°C or higher, and 80°C or higher. If it is less than this, the desirable modification effect of PPS will be small and the hydrolysis resistance of the thermoplastic polyester will be greatly reduced, which is not preferable. Further, the water used in the hydrothermal treatment is preferably distilled water or deionized water in order to enhance the effect. Further, the treatment time is usually preferably 5 minutes or more. The operation of hot water treatment is not particularly limited, but it can usually be carried out by placing a predetermined amount of PPS and a predetermined amount of water in a pressure-resistant container, heating and stirring.

As for the ratio of water to PPS, the more water the better, but usually a bath ratio of 200 f or less PPS to water IAt is selected. The atmosphere for the hydrothermal treatment is not particularly limited, but may be carried out under an inert gas atmosphere in order to avoid decomposition of the terminal groups of PPS.

It is preferable that the PPS after the operation is further washed with water several times to remove remaining components.

81 The PPS to be subjected to hot water treatment in the present invention is preferably in the form of powder or granules, and particularly preferably in the form of fine granules from the viewpoint of cleaning efficiency. Since PPS produced by a generally known method is obtained in the form of powder or granules, it is preferable to use and wash them without pelletizing them.

The amount of the PPS treated with hot water thus obtained is 1-100 parts by weight, preferably 5 to 80 parts by weight, per 100 parts by weight of the thermoplastic polyester. The effect of improving physical properties is insufficient, and if it exceeds 100 parts by weight, moldability decreases and the appearance of the molded product is also poor, which is not preferable.

The glycidyl group-containing olefin copolymer used in the present invention is an olefin copolymer consisting of an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid. The α-olefin referred to herein includes ethylene, propylene, butene-1, etc., and ethylene is preferably used.

In addition, glycidyl ester of α,β-unsaturated carboxylic acid is a compound represented by the general formula (R in the formula represents a hydrogen atom or a lower alkyl group), and specifically, glycidyl acrylate, glycidyl methacrylate, , glycidyl acrylate, etc., among which glycidyl methacrylate is preferably used.

α in olefin copolymer with glycidyl group
The copolymerization amount of glycidyl ester of β-unsaturated carboxylic acid is preferably 0.5 to 50% by weight. Furthermore, unsaturated monomers that can be copolymerized with the above copolymer at 40% by weight or less, such as vinyl ether M, vinyl esters such as vinyl acid and vinyl propionate, acrylic acids such as methyl, ethyl, and propyl; Methacrylic acid esters, acrylonitrile, styrene, etc. may be copolymerized.

Specific examples of the olefin copolymer having a glycidyl group include ethylene/glycidyl methacrylate copolymer and ethylene/glycidyl methacrylate-1/vinyl acetate copolymer. These can be used in combination of two or more types.

When using a glycidyl group-containing olefin copolymer, organic sulfonic acid metal salts such as sodium dodecylbenzenesulfonate and sodium dodecylsulfonate, and alcohol sulfate ester salts such as lauryl sulfate sodium salt should be used. They can be added together in small amounts, and the effect of improving impact resistance is further exhibited by the addition of these.

The blending amount of the glycidyl group-containing olefin copolymer is 0.5 parts by weight per 100 parts by weight of the thermoplastic polyester.
~80 parts by weight, particularly preferably 5 to 50 parts by weight. 0,
If it is less than 5 parts by weight, a molded product with insufficient mechanical properties, particularly toughness, is obtained, and the moldability is also poor, and if it is more than 80 parts by weight, the elastic modulus of the molded product is undesirably lowered.

-II The composition of the present invention may further contain antioxidants and heat stabilizers (for example, hindered phenols, hydroquino/, thioethers, phosphites, substituted products thereof, and combinations thereof) to the extent that the objects of the present invention are not impaired. ), UV absorbers (e.g. various resorcinols, salicylates, benzotriazoles, benzophenones, etc.), lubricants and mold release agents (e.g. stearic acid and its salts, montanic acid and its salts, esters, halfesters, stearyl alcohol, stearic acid), colorants, including dyes (e.g. nitrosine) and pigments (e.g. cadmium sulfide, phthalocyanine, carbon black, etc.), flame retardants (e.g. decabromodiphenyl ether, halogen-based such as brominated polycarbonates, melamine or cyanuric acid-based) , phosphorus-based, etc.), flame retardant aids (e.g., antimony oxide, etc.), antistatic agents (e.g., sodium dodecylbenzenesulfonate, polyalkylene glycol, sodium alkylsulfonate, etc.), and crystallization promoters. One or more types can be added. In addition, small amounts of other thermoplastic resins (e.g. polyethylene, polypropylene, acrylic resins, fluorine resins, polyamides, polyacetals, polycarbonates, polysulfones, polyphenylene oxides, etc.), thermosetting resins (e.g. phenolic resins, melamine resins, polyester resins, silicone resins) , epoxy resin, etc.) and soft thermoplastic resins (for example, ethylene/vinyl acetate co-M combination, polyester elastomer, ethylene/propylene terpolymer, etc.) can also be added.

The method for producing the composition of the present invention is not particularly limited, but preferably a thermoplastic polyester, a reinforcing agent, a glycidyl group-containing olefin copolymer, and hot water-treated PPS are melted and mixed in an extruder, and then pelletized. An example of this method is to cut the material into shapes.

The resin composition of the present invention can be easily molded by conventional methods such as injection molding and extrusion molding, and the resulting molded product exhibits the excellent properties described above. - The present invention will be explained below with reference to Examples.

<Example> Each abbreviation in the examples means the following.

PP5-1: Sodium sulfide 3.26# (25 mol, containing 40% crystal water) and sodium hydroxide 41. 4 (approximately 10 mol) and 7.9 and 9 of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were added to 1.36 of sodium acetate trihydrate, and the temperature was gradually raised to 205°C while stirring. , about 1.51 kg of distillate containing 1.36 kg of water was removed.

1.4-dichlorobenzene 3.75# (2
5.5 mol) and NMP2ky were added and heated at 265°C for 4 hours. The obtained reaction product was washed 5 times with warm water at 70°C and dried under reduced pressure at 80°C for 24 hours to obtain powdered PPS of about 2
I got kg.

The same operation was repeated to provide the examples described below.

PP5-2: Philips +1 Rydon PR-
06” E/GMA: Ethylene/glycidyl methacrylate copolymer (copolymerization weight ratio 88) Hot water treatment of PPS: Approximately 2 k of PPS in an autoclave
y and deionized water 101 were prepared, heated to the temperature listed in Table 1, kept warm for about 30 minutes while stirring, and then cooled. Take out the contents and add it to 50℃ deionized water.
After washing with water 5 times, the product was dried under reduced pressure at 120° C. for 24 hours to obtain hot water-treated PPS.

Examples 1-3 Polyethylene terephthalate 100 with an intrinsic viscosity of 0.65
50 parts by weight of chopped glass fiber strands having a length of 3 m and 2 parts by weight of barium stearate as a nucleating agent were blended with the parts by weight, and the mixture was further treated with hot water at the treatment temperature shown in Table 1 in the proportions shown in Table 1. PPS and 5 parts by weight of ethylene/glycidyl methacrylate copolymer (E/GMA) were triblended. Next, this was melt-mixed and pelletized using an extruder having a screw of 40 jffφ set at 280 to 290°C.

The pellets were then placed in a 5 oz screw in-line injection molding machine set at 280-290°C, with a mold temperature of 1
An Izot impact test piece (l/!!'X station' x 2 pieces') and a tensile test piece (ASTM No. L dumbbell test piece) were molded at 20°C. Using the obtained Izot impact test piece, Izot impact strength (ASTM D256) was measured to evaluate impact resistance.

In addition, hydrolysis resistance was determined by subjecting a tensile test piece to deterioration treatment in hot water at 80°C and then measuring the tensile strength according to ASTM D-638. It was evaluated based on the time taken. The results are shown in Table 1.

Comparative Examples 1 to 4 Example 1 except that PPS without hot water treatment or PPS treated with hot water under conditions outside the scope of the present invention was used.
Melt kneading, injection molding, and performance evaluation were performed in the same manner as above. The results are shown in Table 1.

It is recognized that the compositions of the Examples in Table 1 all have superior impact resistance and hydrolysis resistance compared to the Comparative Examples.

<Effects of the Invention> The thermoplastic polyester resin molded article obtained from the composition of the present invention has extremely excellent heat resistance, impact resistance, and hydrolysis resistance.

Patent application Daitoshi Co., Ltd. 19 (complete)

Claims (1)

Scope of Claims: (A) (a) 5 to 1 part by weight of (b) fibrous and/or granular reinforcing agent per 100 parts by weight of thermoplastic polyester;
50 parts by weight, (C) 1 to 100 parts by weight of polyphenylene sulfide treated with hot water at 80°C or higher, (d) 0.5 to 100 parts by weight of glycidyl group-containing olefin copolymer
A thermoplastic polyester composition containing 80 parts by weight.