JPH01132658A - Flame-retarding highly crystallized polyethylene terephthalate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition rendered frame-retarding and decreased in finning of a molding, by mixing a specified fiber-reinforced modified PET resin with a specified inorganic compound, an ether compound, an olefin polymer, a polymeric brominated flame retardant and an Sb compound. CONSTITUTION:30-91.4wt.% modified polyethylene terephthalate resin (A) is mixed with 5-60wt.% fibrous filler (B), 0.5-40wt.% inorganic compound (C) (e.g., talc), 0.1-20wt.% ether compound (D) of the formula (wherein R1-R5 are each H or a hydrocarbon group, R6 is a 2-6C alkylene, R7 is H or a benzenoid hydrocarbon group, and m is 20-150), e.g., polyoxyethylene monononylphenyl ether, 0.5-20wt.% olefin/(meth)acrylic acid copolymer salt (E), 2-20wt.% polymeric brominated flame retardant (F), and 0.5-10wt.% antimony compound (G) (e.g., antimony trioxide) in such amounts as to give a total of 100wt.%.

Description

[Detailed Description of the Invention] [Field of Industrial Application] Glass fiber reinforced products of polyethylene terephthalate resin have excellent mechanical properties, heat resistance, and chemical resistance, so they can be used in various heating appliances (microwave ovens, It is used in electromagnetic cookers, irons, etc.), electrical parts (connectors, carp mirrors, etc.), automobile parts (reflectors), etc.

[Prior Art] The properties of crystalline polymers such as polyethylene terephthalate resin strongly depend on the degree of crystallinity. It is necessary to add a crystal nucleating agent such as an inorganic compound, and to perform molding by setting the mold temperature to a high temperature of 130°C to 140°C.

Alternatively, a molded product molded in a low-temperature mold of 100°C or less and still in a partially crystallized state may be post-heat-treated to promote crystallization, or the molded product may be immersed in a liquid that promotes crystallization. There is a method of increasing heat resistance by promoting crystallization through post-processing such as soaking the product.

[Problems to be Solved by the Invention] However, the use of high-temperature molds and post-processing have drawbacks in terms of work stability and economy.

Moreover, when molded at a low mold temperature of 100℃ or less,
Since the crystallization of the resin is sufficiently advanced, the mold releasability becomes poor. Therefore, in order to improve mold releasability, it is necessary to cool slowly and it takes a long time for cooling.

Patent Application No. 62-181968, which we previously submitted, contains polyethylene terephthalate resin, fibrous fillers, inorganic compounds, specific ether compounds, polyester elastomers, monoepoxy compounds, polymeric brominated flame retardants, and A resin composition to which antimony oxide is added is disclosed. However, although the falling weight impact strength of this composition has been greatly improved, a molded product with good appearance cannot be obtained unless molded at a mold temperature of over 90°C.

Furthermore, if the mold temperature exceeds 90° C., there is a drawback that cracks are likely to appear in the molded product.

[Means for solving problems]

The present invention solves the above-mentioned drawbacks, reduces paris, improves mechanical strength, has a high heat distortion temperature, and has high crystallinity that has excellent formability and surface appearance even when molded in a low-temperature mold. As a result of intensive studies to obtain a heat-retardant polyethylene terephthalate-based resin composition, we found that using a specific inorganic compound and a specific ether compound as a nucleating agent, a specific olefin compound, a specific flame retardant, and a specific antimony-based tallate resin. We have discovered that when incorporated into a composition, the resulting composition can produce a molded article with excellent moldability and good surface appearance at a mold temperature of 90°C or less, and that the molded article has less flakiness.
The present invention has now been completed.

That is, the gist of the present invention is as follows: A) Modified polyethylene terephthalate resin 30-9
1.4% by weight, B) fibrous filler 5-60% by weight,
C) Inorganic compound CL5-40 wt%, D
) At least one ether compound represented by the following formula [1] 0.1 to 20% by weight (in the formula, R1-
R is hydrogen or a hydrocarbon, R7 is an alkylene group having 2 to 6 carbon atoms, and R7 is hydrogen or a hydrocarbon containing a benzene ring. Moreover, m indicates the average number of curls and is in the range of 20 to 150. ), Sodium salt or potassium salt of a copolymer of phantom olefin and acrylic acid or methacrylic acid
α5~20 pitch, F) Polymer type brominated flame retardant
2 to 2oM amount (H) and G) antimony compound α5 to 10% by weight, and (Al-(Gl) total amount of each component is 100%
% by weight of a flame-retardant highly crystallized polyethylene terephthalate resin composition.

The modified polyethylene terephthalate (A) of the present invention is
Refers to a block copolymer of a polyethylene terephthalate component and a polyalkylene glycol component.

The polyethylene terephthalate component referred to herein refers to a polyethylene terephthalate component that is obtained by directly esterifying or transesterifying a carbonic acid component containing at least 90 mo/l/% of terephthalic acid and a yosiolic acid component containing at least 90 mo/l/% of ethylene glycol. It is obtained by polycondensation.

The 0 to 1 o moyvsrtc of the cicatric acid component is, for example, phthalic acid, isophthalic acid, adipic acid, sebacic acid,
naphthalene-1,4-4L< is -λ6-dicarboxylic acid,
Examples include acid components such as diphenyl ether A/-4,4'-dicabonic acid.

Examples of the diol component from 0 to 10 mo/%/ls include propylene glyco-〃, butylene glyco-μ, neobentyl glycol, cyclohexane dimetatool, 2.
Glyco-μ components such as 2-bis(4-hydroxyphenylv)propane: Oxy acids such as p-oxybenzoic acid, p-hydroxybenzoic acid, and p-hydroxyethoxybenzoic acid are mentioned.

The boria μ xylene glycol μ component mentioned here is, for example, polyethylene glyco μ, polypropylene glyco! ,
Polytetramethylene glycol, ethylene oxide
Examples include propylene oxide copolymers, but those with an average molecular weight of 100 or more are preferred.

The weight ratio of these polyethylene terephthalate components/boria μ-kylene glyco-μ components is 50/5.
0-99/1, preferably 70/30-97
/3.

Further, as an example of a method for producing this block copolymer, there is the following method. For example, dimethyterephthalate
and ethylene glyco-μ are mixed at a ratio of 1/1.4 (7μ ratio), and after raising the temperature, polyethylene glyco-μ is added to obtain the above-mentioned block copolymer.

The above block copolymer polymer (A) is 3 in the total resin composition.
It is blended in a range of 0 weight to 91.4 weight. If it is less than 30% by weight, the flowability deteriorates, and if it exceeds 91.4% by weight, the intended purpose cannot be achieved, which is not preferable.

Examples of the fibrous filler (B) include glass fibers, inorganic fibers other than glass fibers, carbon fibers, and heat-resistant organic fibers. Specifically, yR fiber diameter is 1 to 20 μm, fiber length is 10 cm or less. Examples include chopped strands of glass fiber or carbon fiber, glass fiber medium fiber, pitch-based secondary fiber, aromatic polyamide fiber, aromatic polyimide fiber, aromatic polyamide-imide fiber, and combinations thereof.

Among these, chopped strands of glass fiber are particularly preferred. The blending amount of the fibrous filler is 5 to 60% by weight in the total polyethylene terephthalate resin composition. 5
If the weight is less than -, the reinforcing effect of the fiber filler is insufficient;
If the blending amount exceeds 60 weight tS, the flow processability decreases.

Inorganic compounds (0) include neutral clays, zinc oxide,
Examples include oxides, sulfates, and silicates of Group I metals in the periodic table, such as magnesium oxide, μsium silicate, magnesium silicate, sium sulfate, and barium sulfate. These nucleating agents may be used alone or in combination, and are blended in an amount of α5 to 40% by weight in the total resin composition. If it is added in an amount less than 15% by weight, it is not effective as a nucleating agent, and if it exceeds 40% by weight, the moldability deteriorates, which is not preferable.

Further, the ether compound (D) constituting the fiber-reinforced polyethylene terephthalate resin composition of the present invention has the formula (11
In the formula, R1 to R are hydrogen or hydrocarbon. In the case of hydrocarbons, the number of carbon atoms is not particularly limited, but those having 5 to 30 carbon atoms are particularly preferred.

Further, R in the formula is composed of an alkylene group having 2 to 6 carbon atoms, and specifically, ethylene group, propylene group, butylene group, neobenzene group, etc. are preferable. In the present invention, the alkylene oxide represented by +Rs'i in formula [1] includes an alkylene oxide structure composed of a single alkylene group and an alkylene oxide structure composed of different alkylene groups. Ashi, the total number of those average repetitions m
must be in the range of 20 to 150. m is 2
If it is less than 0, it is not preferable because the mechanical strength of the resulting resin composition decreases and the effect of improving the appearance is insufficient. On the other hand, if m exceeds 150, the heat resistance of the resulting resin composition will decrease, which is not preferable. Further, R7 is a hydrocarbon containing a hydrogen-bridged benzene ring. The ether compound used in the present invention is one in which at least one terminal of the polyalkylene oxide is an aromatic hydrocarbon as shown in formula [I], and the ether compound has such a special structure. By blending the compound, it has excellent heat resistance and mechanical strength, and has well-balanced performance. On the other hand, even if the repeat chain of the same polyalkylene oxide is compounded with a structure consisting of an aliphatic hydrocarbon, a hydroxyl group, or a combination thereof at both ends, the improvement in heat resistance is insufficient. This results in a composition with a large decrease in mechanical strength, making it extremely difficult to balance performance.

As a specific example of the ether compound used in the present invention, the total number of repeating units of alkylene oxide is 20
-150 polyoxyethylene mono(μ) phenylene μ ether μ, holoxyethylene monoocty-fee=˜ether μ, polyoxyethylene dinonylphenyl ether, polyoxyethylene diocty μ phenyl ether, and the like.

In the present invention, the ether compounds represented by the above formula CI] can be used alone or in combination, but (A)
~(In the resin composition composed of each component of Gl [11~
It is necessary that it is blended in a range of 20% by weight,
If the amount is less than α1% by weight, there is almost no effect on improving the heat resistance and appearance of the molded article. Moreover, if the amount exceeds 20% by weight, the mechanical strength of the molded article will decrease, which is not preferable.

In the present invention, the component (2) is a sodium salt or potassium salt of a copolymer of an olefin and acrylic acid or methacrylic acid, and the olefin is usually a 50-9% copolymer.
8% by weight, preferably 80-98% by weight, full force
30% or more of the ponic acid residues must be neutralized with sodium or potassium, and particularly preferred substances are ethylene/
It is a sodium salt of methacrylic acid copolymer. The copolymer of such olefin and acrylic acid or methacrylic acid contains 0 IJium salt or potassium salt in the entire resin composition.
．． It is blended in a range of 5 to 20% by weight. If the CL is less than 5% by weight, the effect of suppressing flaking is small, and if it exceeds 20% by weight, the fluidity decreases, which is not preferable.

Furthermore, the polymeric brominated flame retardants (specifically, pentabromobenzyl polyacrylate,
Pentabromobenzyl polymethacrylate, polytethopromoxylylene bisacrylate, polytethopromoxylylene bismethacrylate, brominated polycarbonate, poly(2,4,6-)ligromo)styrene, poly(
2,4,5-)! Examples include J dibromostyrene, brominated crosslinked polystyrene, and the like.

The polymeric flame retardant is blended in an amount of 2 to 20% by weight in the total resin composition. If it is less than 2 times #, -, almost no flame retardant effect can be expected. Moreover, if it exceeds 20% by weight, the mechanical strength of the molded product obtained will decrease.

The antimony-based compounds (Gl is a component) that functions as a flame retardant aid for flame retardants, and specific examples thereof include antimony trioxide, antimony pentoxide, and sodium antimonate.

In order to exhibit the effect as a flame retardant aid in the entire resin composition, it is necessary to add more than 5% by weight of a, and in order not to reduce the mechanical strength of the resulting molded product, 1c is 10% by weight.
It is necessary to use the following amount.

The flammable highly crystallized polyethylene terephthalate resin composition of the present invention may optionally contain wollastonite,
It is also possible to add various additives, such as fillers such as mica, glass foil, clay or kaolin; stabilizers against light or heat; dyes or pigments.

When manufacturing a molded article from the resin composition of the present invention,
As in the past, a predetermined amount of the components are put into an appropriate mixing machine such as an extruder, and after the mixture is mixed and mixed into pellets,
A molded article can be obtained by injection molding or pressure molding. At this time, it is characterized in that it can be molded at a mold temperature of 90° C. or less and in that it reduces flash.

Next, the present invention will be explained using examples.

[Embodiments of the invention]

Examples 1 to 10 Modified polyethylene terephthalate polymer (A), 3
Chopped strand gaff fiber (abbreviated as GIF in the table) and the above (C) (D) (E) (
Fl and (Gl components are blended in the proportions shown in the table, and this is
Mix in a mold blender for 5 minutes to homogenize. The obtained mixture was put into a vent type melt extruder having a diameter of 40 cm and extruded at a cylinder temperature of 260 to 280°C to obtain pellets of the resin composition of the present invention.

The crystallization rate of the resin composition obtained here was measured using a differential calorimeter (DC), and 8 ounces (2279
), using a screw type injection molding machine with a diameter of 45 m, cylinder temperature 280°C, mold temperature 80°C, molding cycle A/
An ASTMI dumbbell test piece was formed from the pellet in 30 seconds and subjected to a tensile test using A8TMD638ic.

Note that the measurement of the crystallization rate using a differential calorimeter is carried out in advance by melting and
Using a sample obtained by performing a rapid cooling operation, the temperature was raised in a nitrogen stream at a heating rate of 10°C/min, held at 280°C for 3 minutes, and a cooling rate of 10°C/min.
The crystallization temperature Tc- at the time of cooling was measured.

Incidentally, the lower the value of Tc, the higher the value of Tc-, the higher the crystallization rate.

In addition, to determine the size of the mold, a Mu8TM No. 1 dumbbell specimen was molded under the same molding conditions, and the appearance of the mold was observed.

Comparative Examples 1 to 6 Resin compositions were produced in the same manner as in the above Examples, except that the compounds shown in the table were used, and the same tests as in the above Examples were conducted. The results obtained are also listed in the table.

<Type of (A) component> @: Polyethylene terephthalate/Polyethylene glyco-A/ (9575 weight ratio) Copolymerized polymer Molecular weight of Polyethylene glyco-〃 = 4,000 (Engineering): Polyethylene terephthalate/Polytetramethylene glyco-A/ (90740 weight ratio) Molecular weight of copolymer polytetophmethylene glycol = 1.
OOO (of: polyethylene terephthalate homopolymer <(D
) Type of component〉 Polyoxyethylene monononi~phenyl ether Agoyama 8o-(C!H OH, O)g-H polyoxyethylene dino 2μ phenyl ether〃C mountain (Xo-(OH,OH OH,O) eo+osH+s<(Type of El component) (K): Ethylene/methacrylic acid (weight ratio 85/15)
Copolymer 60% of the methacrylic acid was neutralized with sodium.

(-Diethylene/acrylic acid (weight ratio 85/15) copolymer 65% of acrylic acid was neutralized with potassium.

<Types of (F') components> Pyrocheck 68PB: Brominated polystyrene, manufactured by Nippon Ferro ■ InBR370PK: Brominated cross-linked polystyrene, manufactured by Matsunaga Chemical ■ 1FG7000: Brominated polycarbonate, manufactured by Teijin Kasei ■ As is clear from the table results , modified polyethylene terephthalate resin (a1 minute, (Dl component, (m component, (-
It has been found that by blending component (G) with K, flame retardance is imparted (Tc+ is lowered, the crystallization rate is improved, and the flakiness of the molded article is reduced).

〔Effect of the invention〕

As detailed above, the flame-retardant highly crystallized polyethylene terephthalate resin composition of the present invention contains inorganic compounds (0, specific ether μ compounds (D
i. When a specific olefin compound (type, specific flame retardant), and a specific antimony compound (Gl) are combined with a specific fiber-reinforced modified polyethylene terephthalate resin, it imparts flame retardancy. Furthermore, it is possible to maintain a high degree of crystallinity and reduce the flakiness of the molded product.

Patent applicant: Mitsubishi Rayon Co., Ltd. Agent: Patent Attorney Toshio Yoshizawa

Claims (1)

[Scope of Claims] A) 30 to 91.4% by weight of a modified polyethylene terephthalate resin, B) 5 to 60% by weight of a fibrous filler, C) 0.5 to 40% by weight of an inorganic compound, D) at least one of the following: Ether compound represented by formula [I] 0.1 to 20% by weight ▲Mathematical formulas, chemical formulas, tables, etc. are available▼[I] (In the formula, R_1 to R_5 are hydrogen or hydrocarbons, and R_6 is a carbon number of 2 to 6. The alkylene group, R_7, is hydrogen or a hydrocarbon containing a benzene ring. m indicates the average repeating number, ranging from 20 to 150.), E) Copolymer of olefin and acrylic acid or methacrylic acid. consisting of 0.5 to 20% by weight of a sodium salt or potassium salt, F) 2 to 20% by weight of a polymeric brominated flame retardant, and G) 0.5 to 10% by weight of an antimony compound,
The flame retardant highly crystallized polyethylene terephthalate resin composition is characterized in that the total amount of (A) to (G) is 100% by weight.