JPS63118319A - Polyester molding material - Google Patents

Abstract

PURPOSE:To obtain the titled molding material having excellent moldability and free from generation of flow mark and gate-whitening in molding, by compounding a specific thermoplastic polyester, a specific vinyl copolymer and a specific block copolymer at specific ratios. CONSTITUTION:The objective molding material is composed of (A) 94.5-50wt% thermoplastic polyester having an intrinsic viscosity of >=0.40 (measured in a mixed solvent of phenol/THF at a weight ratio of 6/4 at 35 deg.C) (preferably polyethylene terephthalate or polybutylene terephthalate), (B) 0.5-10wt%, preferably 1-8wt% vinyl copolymer containing >=5mol% (preferably 10-50mol%) glycidyl methacrylate and (C) 5-40wt% block copolymer composed of a vinyl aromatic compound polymer block (preferably styrene) and an olefin compound polymer block (preferably butadiene or isoprene).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a thermoplastic polyester molding material, and more specifically to a molding material that has excellent moldability without flow marks or gate whitening during molding. Regarding.

[Conventional technology and its problems]

Thermoplastic polyesters, such as polyethylene terephthalate and polybutylene terephthalate, are used in many products as engineering plastics because of their excellent mechanical properties and heat resistance. However, when compared to materials with excellent toughness such as polyamide and polycarbonate, its properties are not sufficient.
Attempts have been made to impart toughness using various techniques. For example, attempts have been made to add ordinary rubber such as styrene-butadiene rubber, styrene-based or olefin-based thermoplastic rubber, but mixtures of these rubbers and thermoplastic polyester cannot be mixed uniformly. This is difficult, and there are problems such as flow marks appearing during molding and peeling phenomena, and a solution to these problems has been desired. As one of these solutions, a method has been proposed in which an unsaturated carboxylic acid or its visiting compound is subjected to craft bonding to a block copolymer consisting of a vinyl aromatic compound polymer block and an olefin compound polymer block. (For example, JP-A-58-7443.

JP-A-61-106653. Japanese Patent Publication No. 61-126164
However, there is a limit to increasing the concentration of unsaturated carboxylic acid in this modification by graft bonding, which causes gelation of the block copolymer, and is limited to 2 mol%.
is approximately the upper limit, and even if more unsaturated carboxylic acid is blended than this, the amount of unsaturated carboxylic acid remaining as unreacted substances will increase, which is not preferable since it will adversely affect the processability of the final molding material.

The present invention has been studied in order to obtain a molding material free of such defects, and by using a specific vinyl copolymer in combination, a molding material with excellent moldability has been obtained.

[Means for solving problems]

That is, the present invention provides (]) 5 mol% of glycidyl methacrylate (50% by weight to thermoplastic polyester 94.5 with Al intrinsic viscosity of 0640 or higher) J1. A molding material comprising 0.5 to 10 MJir% of a vinyl copolymer containing (5 to 40% by weight of a block copolymer consisting of an O vinyl aromatic compound polymer block and an olefin compound polymer block).

Further, as an embodiment thereof, (2) (C1 component block copolymer is a block copolymer in which the degree of unsaturation of the olefin compound polymer block does not exceed 20%) molding material.

I will provide a.

In the present invention, the thermoplastic polyester used as a (to) component includes polyethylene terephthalate,
Examples include polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene inphthalate, polybutylene isophthalate, and copolymers or mixtures thereof. Among these, polyethylene terephthalate and polybutylene terephthalate are particularly preferably used in terms of moldability, mechanical properties, cost, etc.

The thermoplastic polyester used in the present invention preferably has an intrinsic viscosity of 0.40 or more as determined at 35° C. in a mixed solution of phenol/tetrachloroethane (6/4 ii ratio). If the intrinsic viscosity of the thermoplastic polyester is less than 0.40, the mechanical strength will not be sufficient.

(A known vinyl copolymer containing glycidyl methacrylate used as the Bl component can be used. For example, glycidyl methacrylate/methyl methacrylate copolymer, glycidyl methacrylate/styrene copolymer, glycidyl methacrylate/styrene/acrylonitrile copolymer glycidyl methacrylate/methyl methacrylate/styrene copolymer, glycidyl methacrylate/butyl acrylate/styrene copolymer, etc., with glycidyl methacrylate/styrene/acrylonitrile copolymer being preferred.The amount of glycidyl methacrylate in the vinyl copolymer. is required to be at least 5 mol %.If it is less than 5 mol %, the effect of improving compatibility will not be sufficient.

Preferably 5 to 70 mol%, more preferably 10 to 50
It is mole%.

The amount of the above components is 0.5 to 10% by weight in the total composition.
and preferably 1 to 8 weight percent. The blending amount is 05
If it is less than 10% by weight, the effect of improving compatibility will be obtained, but if it exceeds 10% by weight, the effect will not increase and the drop in fluidity will be too large, resulting in an adverse effect.

The block copolymer consisting of a vinyl aromatic compound polymer block and an olefin compound polymer block used as component (C) is synthesized, for example, as follows. That is, it is obtained by hydrogenating the conjugated diene portion of a block copolymer composed of a vinyl aromatic compound polymer block and a polymer block mainly composed of a conjugated diene compound.

The above block copolymer before hydrogenation contains at least one vinyl aromatic compound polymer block, preferably two or more, and at least one polymer block mainly composed of a conjugated diene compound. It is. Here, the polymer block whose living body is a conjugated diene has a weight ratio of a vinyl aromatic compound and a conjugated diene compound of O/100 to 50150.
, preferably has a composition range of 0/100S40/60, and the distribution of the vinyl aromatic compound in this block is random, Taber (monomer component increases or decreases along the molecular chain), It may be partially block-shaped or any combination thereof. In addition, in the block copolymer before hydrogenation in the present invention, 50 parts by weight of the vinyl aromatic compound is added to 0 parts of the vinyl aromatic compound polymer block and the polymer block mainly composed of a conjugated diene compound. % of a vinyl aromatic compound and a conjugated diene compound may be present, but such a polymer block shall be included in the above-mentioned polymer block whose living body is a conjugated diene compound.

In the above block copolymer, the weight ratio of the content of the vinyl aromatic compound and the content of the conjugated diene compound is 10/
The range of 90 to 90/10 is preferable, and the range is 20/80 to 85.
A range of /15 is more preferable.

As the vinyl aromatic compound constituting the block copolymer of the hydrogenated part, one or more types are selected from styrene, α-methylstyrene, vinyltoluene, etc.,
Among them, styrene is particularly preferred. Further, as the conjugated diene compound, one or more types are selected from butadiene, isoprene, 1,3-pentadiene, etc., and among them, butadiene and/or ink 1/n are particularly preferred.

The above block copolymer has a number average molecular weight of 20. OQ
The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably in the range of 1.05 to 100,000. Further, the molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. Furthermore, when butadiene is used as the conjugated diene compound in the block copolymer, the amount of 1.2 bonds in the microstructure of the butadiene moiety is preferably in the range of 10 to 80%. When the modified block copolymer needs to have rubber elasticity, the amount of 1,2 bonds is 35
A range of 55% is particularly preferred.

In the case where the above block copolymer contains two or more blocks mainly composed of vinyl aromatic compound blocks or conjugated diene compounds, each block may have the same structure, and the monomer component content and their Each structure, such as the distribution in molecular weight, the molecular weight of the block, and the microstructure, may be different.

The above-mentioned block copolymers are usually produced by using a vinyl aromatic compound and a conjugated diene compound as monomers in an inert hydrocarbon solvent such as benzene, toluene, hexane, or cyclohexane, using an organic lithium compound such as butyllithium as a catalyst. Obtained by anionic living polymerization method. Furthermore, by reacting the block copolymer having lithium active terminals obtained by the above method with a polyfunctional coupling agent such as carbon tetrachloride, silicon tetrachloride, etc., branched or radial block copolymers can be obtained. It is also possible to combine them. In the present invention, any polymer produced by any polymerization method can be used as long as it falls within the above range. Furthermore, the block copolymer can be used not only as a single type but also as a mixture of two or more types.

By hydrogenating the above block copolymer by a known method, for example, the method described in Japanese Patent Publication No. 42-8704, the aromatic double bonds of the vinyl aromatic compound block are
A partially hydrogenated block copolymer is synthesized in which not more than 0% and at least 80% of the aliphatic double bonds of the conjugated diene compound block are hydrogenated.

The degree of unsaturation of the olefin compound polymer block as used in the present invention refers to the proportion of urea-carbon double bonds contained in the olefin compound polymer block, and this is determined by nuclear magnetic resonance absorption spectrum (NMR), infrared rays It is measured by horizontal instrument analysis such as absorption spectrum (IR), and chemical analysis such as E-de titration.

The degree of unsaturation of the olefin compound polymer block is preferably 20% or less from the viewpoint of processing stability of the molding material.

In the molding material of the present invention, the content of the ((?) component is 5 to 40% by weight. If it is less than 5% by weight, no improvement in toughness is observed, and if it exceeds 40% by weight, the heat resistance is significantly reduced. , not practical.

The molding material of the present invention further contains fillers, crystal nucleating agents, sintering agents, and other additives, such as heat stabilizers, lubricants, antioxidants, ultraviolet absorbers, and colorants, for the purpose of improving various properties. additives, flame retardants, etc. can be added.

Filling materials include glass fibers, carbon fibers, aramid fibers, asbestos, metal fibers, inorganic and organic fibrous materials such as whiskers, and granular materials such as mica, Merck, clay, silica, calcium carbonate, calcium silicate, and carbon black. Substances can be used. Especially glass fiber, mica,
Merck is preferred~ゝO As the crystal nucleating agent, an inorganic compound with a particle size of 2μ or less, an alkali metal salt of an organic carboxylic acid, an alkali metal salt of an organic sulfonic acid, an alkali metal salt of an organic phosphoric acid or phosphorous acid, Polymers having an alkali metal salt of carboxylic acid in the chain can be used.

Further, it is possible to use a polyester modified by blending an alkali metal salt of phenolsulfonic acid during polymerization. In the case of polyester blended with a crystal nucleating agent in this manner, particularly polyethylene terephthalate, impact resistance tends to decrease, and the present invention is effective.

Flame retardants include decabromodiphenyl ether, brominated epoxy resin, brominated polycarbonate, brominated polyphenylene ether, brominated polystyrene, brominated crosslinked polystyrene, brominated polybenzyl acrylate, melamine, melamine cyanurate, triphenyl phosphite. etc. can be used.

(Example) Examples will be shown below, but these are intended to explain the present invention more specifically, and are not intended to limit the scope of the present invention.

Reference Example 1 (zl Preparation of hydrogenated block copolymer Anionic block copolymerization of butadiene and styrene using n-butyllithium as a polymerization catalyst and tetrahydrofuran as a vinyl content regulator in n-hexane or cyclohexane solvent. From the above steps, block copolymers as shown in Table 1 were synthesized.

Table 1 The vinyl content of the butadiene portion of the styrene-butadiene block copolymer was measured by the Hampton method.

Next, the block copolymer shown in Table 1 was prepared in a mixed solvent of n-hexane and cyclohexane using cobalt naphthenate and triethylaluminum as a catalyst under hydrogen pressure of 7.
When hydrogenation was carried out at 50°C for 5 hours, about 90% of the double bonds in the butadiene block were hydrogenated, and the benzene ring in the styrene block remained almost unhydrogenated. A hydrogenated block copolymer was synthesized.The metal of light remaining on the catalyst was removed by washing with an aqueous hydrochloric acid solution and methanol.

The hydrogenated block copolymer thus obtained was C-Ic-n
shall be.

Examples 1-6. Comparative Examples 1 to 4 After weighing the composition shown in Table 1, it was mixed for 10 minutes in a rotary drum blender, and then put into the hopper of a 70mm diameter pent type single screw extruder, and the barrel temperature was 260-280-2.
After melting and mixing at 80°C, the pellets were made into K.

The obtained pellets were dried in a vacuum dryer at 140°C for 5 hours.
-90B (manufactured by Toshiba Machine) injection molding machine, 90X66X2
m flat plate at a cylinder temperature of 250-260-270-
It was molded at 270°C, a mold temperature of 80°C, and a molding cycle of 30 seconds, and the appearance was checked. Further, a short shelf was molded using the same molding machine, and the notched Izo impact stiffness was measured according to ASTM D256, and the heat distortion temperature was measured according to ASTM D638. The results of the same evaluation are shown in Table 1 together with comparative examples.

(Remarks) Appearance was evaluated in the following three stages.

A: There are no flow marks or peeling.

B: There is no peeling, but flow marks appear.

C: Peeling occurs.

1st polyethylene terephthalate with surface intrinsic viscosity 0.75 2)
Table 1 shows that the molding material of the present invention has a good balance in terms of moldability, impact resistance, and heat resistance. I can see that

Example 7 and Comparative Example 5 Example 3 was prepared as Example 7 by the same method as Example 3.
A molding material was manufactured and evaluated by blending 20 parts by weight of glass fibers with a diameter of 10 μm into 100 parts by weight of the polymer composition mixture.

On the other hand, as Comparative Example 5, Polymer Composition Mixture 1 of Comparative Example 3
A molding material containing 20 parts by weight of the same glass fiber was produced and evaluated. The results are shown in Table 2.

Table 2 Example 8 and Comparative Example 6 Modified polyethylene terephthalate with an intrinsic viscosity of 0.75 was polymerized by blending 0, s% of disodium P-phenolsulfonate as Example 8 by the same method as in Example 3. The results are shown in Table 3 together with Comparative Example 6 when the compound was used as the prisoner component.

Table 3 1) Bremmer CP 20 SA Examples 9 to 10 Table 4 shows the results obtained by using the same method as in Example 3 but changing the type of vinyl copolymer.

, - person 1; remainder b) Table 4 1) Polyethylene terephthalate 2 with intrinsic viscosity 0.75
) Blenmar 〇PIO8AC glycidyl methacrylate/styrene/acrylonitrile copolymer] (manufactured by NOF Corporation) 8) Blenmar CP50S (glycidyl methacrylate/styrene copolymer) (manufactured by NOF Corporation) Patent applicant Asahi Kasei Corporation Commissioner of the Patent Office Black 1) Mr. Akio 1. Description of the case 1985 Patent Application No. 262834 2 Name of the invention Polyester molding material 3 Person making the amendment Relationship to the case: Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture, Amendment Contents of amendment (1) Description, page 10, line 12, “Urea-carbon” Column 5 of “Detailed Description of the Invention” of the subject specification, contents of amendment as shown in attached sheet
is corrected to "carbon-carbon".

(2) Same, page 13, in the second line from the bottom, ``remained.'' is corrected to ``remained.''

that's all -1 to 4

Claims (2)

[Claims] (1), (A) 94.5 to 50% by weight of thermoplastic polyester with an intrinsic viscosity of 0.40 or more (B) 0.5 to 10% by weight of a vinyl copolymer containing 5 mol% or more of glycidyl methacrylate (C) Block copolymer 5 consisting of a vinyl aromatic compound polymer block and an olefin compound polymer block
Molding material consisting of 40% by weight The molding material according to claim 1, wherein the block copolymer of components (2) and (C) is a block copolymer in which the degree of unsaturation of the olefin compound polymer block does not exceed 20%.