JPH06107927A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To provide the subject composition improved in impact resistance and flowability without deteriorating heat distortion temperature and surface characteristics, and useful for molded products, etc., by melt-kneading polybutylene terephthalate resin, an specific copolymer, a filler and a flame retardant in a specified ratio. CONSTITUTION:(A) 100 pts.wt. of polybutylene terephthalate resin, (B) 1-50 pts.wt. of a modified polyolefinec copolymer having structural units each having an amide group and one or more glycidyloxy or glycidyl groups per 4-5000 carbon atoms of a polyolefin consisting mainly of PE, (C) 2-50 pts.wt. of a filler such as neutral clay, and (D) 5-20 pts.wt. of a flame retardant such as tetrabromobisphenol A are melted and kneaded to provide the objective composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a molded article having improved impact resistance and flame retardancy without deteriorating heat distortion temperature and surface characteristics, and a thermoplastic resin composition excellent in moldability. The present invention relates to a manufacturing method thereof.

[0002]

2. Description of the Related Art Due to its excellent properties, polybutylene terephthalate is being used in a wide variety of fields. However, polybutylene terephthalate does not have sufficient mechanical properties, and therefore the mechanical strength is improved by adding a reinforcing material, but when the amount of the reinforcing material added is large, the impact strength and the surface properties are There was a problem of lowering. Further, when an impact resistance-imparting material is added to the reinforced polybutylene terephthalate in order to improve impact strength, there is a problem that molding fluidity and heat distortion temperature are lowered.

[0003]

In view of such a background, the present invention provides a molded article having improved impact resistance and flame retardancy without lowering the heat distortion temperature and surface characteristics, and at the same time, improves moldability. It is intended to provide an excellent thermoplastic resin composition.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the first aspect of the present invention includes a thermoplastic resin composition including the following components (A) to (D). (A) 100 parts by weight of polybutylene terephthalate resin,
(B) Modified polyolefin copolymer 1 having one structural unit having at least one amide group and at least one glycidyloxy group or glycidyl group per 4 to 5000 carbon atoms of a polyolefin containing polyethylene as a main component
˜50 parts by weight, (C) filler 2 to 50 parts by weight, and (D) flame retardant 5 to 20 parts by weight.

The second aspect of the present invention is to provide the following components (A) to
A method for producing a thermoplastic resin is characterized in that (D) is melt-kneaded. (A) 100 parts by weight of polybutylene terephthalate resin,
(B) Modified polyolefin copolymer 1 having one structural unit having at least one amide group and at least one glycidyloxy group or glycidyl group per 4 to 5000 carbon atoms of a polyolefin containing polyethylene as a main component
˜50 parts by weight, (C) filler 2 to 50 parts by weight, and (D) flame retardant 5 to 20 parts by weight.

As the polybutylene terephthalate (A) used in the present invention, a homopolymer or a copolymer is used, and the copolymer is composed of a dicarboxylic acid component in which at least 40 mol% is terephthalic acid and 1,4-butanediol. As the dicarboxylic acid line segment other than the terephthalate, azelaic acid, sebacic acid, adipic acid, aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as dodecanedioic acid, isophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, Alternatively, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used alone or as a mixture.

The modified polyolefin copolymer (B) used in the present invention means an amide group and a glycidyloxy group or a glycidyl group per 4 to 5000 carbon atoms of a polyolefin containing polyethylene as a main component, respectively. A modified polyolefin-based copolymer having at least one structural unit having at least one, and having 4 to 5000 carbon atoms, preferably 5 to 200 carbon atoms, of the polyolefin,
The following general formula (I)

[0008]

[Chemical 3]

(Wherein Ar represents an aromatic hydrocarbon group having at least one glycidyloxy group and having 6 to 23 carbon atoms, and R represents a hydrogen atom or a methyl group). Those having one structural unit possessed are preferred. The structural unit having a glycidyl ether group represented by the general formula (I) has the following general formula (III)

[0010]

[Chemical 4]

(Wherein Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms and at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group). The modifier is introduced by radically adding or copolymerizing the polyolefin. Such modifiers are disclosed in Japanese Patent Publication No. 2-0
It can be manufactured by the method described in Japanese Patent No. 51550. Among the above modifiers, specifically, for example, the following formula (IV)

[0012]

[Chemical 5]

Compounds represented by are preferably used.
A modified polyolefin-based copolymer using this modifier is
Formula (II) below

[0014]

[Chemical 6]

It has a glycidyl ether group represented by: The amide bond in the structural unit of general formula (I) improves the surface properties of the polyolefin as well as its affinity for polybutylene terephthalate. The glycidyl group contributes to the improvement of mechanical strength and compatibility of the resin composition by reacting with a carboxyl group and a hydroxyl group at the terminal of polybutylene terephthalate. The proportion of the structural unit of the general formula (I) contained in the polyolefin-based copolymer is important for balancing various properties, and if it is less than the above, the characteristics of the resin composition cannot be sufficiently improved. On the other hand, if the amount is too large, the original properties of the resin composition are lost, such as the thermoplasticity being impaired. The amount of the above modifier in the modified polyolefin copolymer is preferably in the range of 1 to 10% by weight, particularly preferably 2
Is in the range of up to 5% by weight.

The modified polyolefin used in the present invention is a copolymer of ethylene and propylene, a monomer selected from ethylene and propylene and dienes such as ethylidene norbornene, 1,4-hexadiene, 1,4-butadiene and dicyclopentadiene. A copolymer in which at least one of the above is copolymerized is exemplified. These may be used alone or in combination of two or more. The molecular weight of the modified polyolefin-based copolymer used in the present invention is preferably in the range of 0.01 to 100 in terms of melt index. Outside of the above range, the mechanical strength is lowered, which is not preferable. Here, the melt index is a value measured according to JIS K6758 (measured at 230 ° C.), and the unit is g / 10 minutes. The method for producing the modified polyolefin copolymer (B) is not particularly limited, but the polyolefin and the modifier are melt-kneaded by using various blenders such as an extruder, a heat roll, a Brabender, and a Banbury mixer. Method, olefin monomer and the modifier, a general polymerization method, for example, a radical polymerization method, a cationic polymerization method, an anionic polymerization method,
It is also possible to copolymerize by a coordination polymerization method. The modified polyolefin copolymer (B) is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of polybutylene terephthalate (A).
It is preferably 5 to 20 parts by weight. If it is less than 1 part by weight, the impact resistance is lowered, and if it exceeds 50 parts by weight, the heat distortion temperature is lowered.

Examples of the filler (C) used in the present invention include neutral clays, silica, talc, mica, glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers and titanic acid fibers. Are used alone or in combination of two or more. The blending amount of the filler (C) is 2 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the polybutylene terephthalate (A). If it is less than 2 parts by weight, the heat distortion temperature is lowered, and if it exceeds 50 parts by weight, the surface property is lowered.

Examples of the flame retardant (D) used in the present invention include tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, hexabromobenzene and tris (2,3). -Dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, halogen such as chlorinated paraffin Flame retardants; ammonium phosphate, tricresyl phosphate, triethyl phosphate,
Phosphorus flame retardants such as trischloroethylphosphate, tris (β-chloroethyl) phosphate, trisdichloropropylphosphate, cresylphenylphosphate, xylenyldiphenylphosphate, acidic phosphates, nitrogen-containing phosphorus compounds and the like; Inorganic flame retardants such as red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide; brominated polystyrene, brominated poly α
-Polymer flame retardants such as methyl styrene, brominated polycarbonate, brominated epoxy resin, chlorinated polystyrene, chlorinated poly α-methyl styrene, chlorinated polycarbonate, chlorinated epoxy resin and the like, and these may be used alone or in combination of two or more. Used in combination. The amount of the flame retardant (D) compounded is 5 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the polybutylene terephthalate (A). If it is less than 5 parts by weight, the flame retardancy is lowered, and if it exceeds 20 parts by weight, the surface properties are lowered.

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, but it is most preferable to use the melt mixing method. For example, various blenders such as an extruder, a heat roll, a Brabender, and a Banbury mixer are used. It may be melt mixed. When mixed, a glycidyl group and a carboxylic acid group,
A reaction catalyst having a hydroxyl group or an ester group may be added. The catalyst is not particularly limited and is selected from a combination of compounds accelerating the above reaction, but is preferably an amine compound such as a tertiary amine or a quaternary ammonium salt, a phosphonium salt or a phosphine. Phosphorus compounds or imidazole compounds, etc. are used, and these may be used alone or in combination of two or more.

If necessary, a phosphorus-based or phenol-based stabilizer, a flame retardant aid such as antimony trioxide, an ultraviolet absorber, a pigment, etc. may be added to the composition of the present invention to provide a new function. May be imparted to the resin composition. The thermoplastic resin composition of the present invention has excellent fluidity at the time of molding, and a molded product obtained from the composition has excellent surface properties, mechanical properties such as heat distortion temperature, impact strength and flame retardancy. It is possible to provide a molding material that has properties and is suitable for, for example, automobile parts, machine parts, electric / electronic device parts, and the like.

[0021]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples, but various modifications can be made without departing from the scope of the invention. The present invention also includes these. Reference example: Synthesis of modified polyolefin copolymer Ethylene propylene rubber 1 having an average molecular weight of 100,000
00 parts by weight, 1 part by weight of the modifier of the above formula (IV) and 0.1 part by weight of benzoyl peroxide were put in an extruder to obtain 20 parts by weight.
The mixture was melt-kneaded at 0 ° C. for 1 minute. A film was formed from the obtained pellets, and the infrared absorption spectrum was measured.
Absorption due to amide group near 300 cm ^-1 , 910 cm ^-1
Absorption due to the epoxy group was observed in the vicinity, and it was confirmed that the modifier was introduced. The modified polyolefin copolymer had one structural unit having a glycidyl ether group per 1600 carbon atoms.

Examples 1 to 10 1. Production of resin composition Polybutylene terephthalate (manufactured by Polyplastics Co., Ltd .:
Duranex 2002) and the modified polyolefin-based copolymer obtained in Reference Example, talc, mica, ammonium phosphate, tetrabromobisphenol A, and antimony trioxide were blended in predetermined parts by weight to prepare a twin-screw extruder (Japan A resin composition in the form of pellets was produced by extruding at a temperature of 240 ° C. using TEX44 or LABOTEX manufactured by Steel Works.

Comparative Example 1 A reinforced polybutylene terephthalate resin was molded as it was and evaluated.

Comparative Examples 2 to 6 Polybutylene terephthalate (manufactured by Polyplastics Co .:
Duranex 2002) and the modified polyolefin-based copolymer obtained in Reference Example, talc, mica, ammonium phosphate, tetrabromobisphenol A, and antimony trioxide were blended in predetermined amounts by weight to prepare a twin-screw extruder (( Made by Japan Steel Works, TEX44 or LABOTEX)
Was extruded at a temperature of 240 ° C. to produce a pellet-shaped resin composition.

2. Measurement of heat distortion temperature, Izod impact strength, flame retardancy and evaluation of surface characteristics The pelletized resin composition prepared in
After drying under reduced pressure at a temperature of 15 ° C. for 15 hours, injection molding was performed to prepare test pieces, and each test piece was measured or evaluated by the method shown below. The results are shown in Table 1. (1) Heat distortion temperature It was measured using a 1/4 inch bar according to the measuring method defined in ASTM D648. (2) Izod impact strength The Izod impact strength was measured using a 1/4 inch bar according to the measuring method defined in ASTM D256. (3) Flame Retardancy Test A vertical combustion test according to UL-94 standard was performed using a test piece of 1/8 inch × 1/2 inch × 5 inch. (4) Surface property test Using a JISI type dumbbell test piece, its surface was visually evaluated in three levels according to the following evaluation criteria. ◯: Surface gloss is uniform Δ: Surface gloss is partially uneven x: No surface gloss or uneven gloss over the entire surface

[0026]

[Table 1]

As shown in Table 1, it is a surprising fact that the resin composition of the present invention gives a molded article having improved impact resistance and flame retardancy without lowering the heat distortion temperature and surface characteristics. .

[0028]

As described in detail above, the resin composition of the present invention gives a molded article having improved impact resistance and flame retardancy without deteriorating the heat distortion temperature and surface characteristics, and at the time of molding. It has excellent fluidity.

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Claims (13)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) to (D): (A) 100 parts by weight of a polybutylene terephthalate resin, (B) a polyolefin containing polyethylene as a main component, and having 4 to 5000 carbon atoms. Modified polyolefin copolymer 1 having one structural unit having at least one amide group and at least one glycidyloxy group or glycidyl group per unit
˜50 parts by weight, (C) filler 2 to 50 parts by weight, and (D) flame retardant 5 to 20 parts by weight. 2. A modified polyolefin-based copolymer (B)
Is the following general formula (I) per 4 to 5000 carbon atoms: (In the formula, Ar represents an aromatic hydrocarbon group having 6 to 23 carbon atoms having at least one glycidyloxy group, and R represents a hydrogen atom or a methyl group.) A structural unit having a glycidyl ether group The resin composition according to claim 1, which has one. 3. A structural unit having a glycidyl ether group has the following formula (II): The resin composition according to claim 2, represented by: 4. The resin composition according to claim 2, wherein the content of the structural unit of the general formula (I) in the modified polyolefin copolymer (B) is 1 to 10% by weight. 5. The repeating unit contained in the modified polyolefin-based copolymer (B) is a copolymer of ethylene and propylene, ethylene and propylene, 1,4-butadiene, ethylidene norbornene, 1,4-hexadiene,
The resin composition according to claim 1, which comprises a copolymer obtained by copolymerizing at least one kind of a monomer selected from diene such as dicyclopentadiene, or a mixture of the copolymers. 6. The resin composition according to claim 5, wherein the ethylene component of the copolymer of ethylene and propylene is 50 to 90% by weight and the propylene component is 50 to 10% by weight. 7. The ethylene and propylene components of a copolymer of ethylene, propylene and a diene monomer are 99 to 9
The resin composition according to claim 5, which is 0% by weight and the diene component is 1 to 10% by weight. 8. The modified polyolefin has a melt index (JIS K6758, 230 ° C.) of 0.01 to 10.
The resin composition according to claim 1, which is 0 g / 10 minutes. 9. The resin composition according to claim 1, wherein the structural unit having a glycidyl ether group represented by the formula (II) is grafted to a polyolefin. 10. The resin composition according to claim 1, wherein the structural unit having a glycidyl ether group represented by the formula (II) is random or block copolymerized with the polyolefin. 11. The filler (C) comprises at least one kind of neutral clay, silica, talc, mica, glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber and titanic acid fiber. The resin composition according to 10. 12. The flame retardant (D) is tetrabromobisphenol A, 2,2-bis (4-hydroxy-3,5-).
Dibromophenyl) propane, hexabromobenzene,
Tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-
Dibromophenyl) propane, decabromodiphenyl oxide, brominated polyphosphate, chlorinated polyphosphate, chlorinated paraffin, and other halogen-based flame retardants;
Ammonium phosphate, tricresyl phosphate, triethyl phosphate, trischloroethyl phosphate, tris (B-chloroethyl) phosphate,
Phosphorus flame retardants such as trisdichloropropyl phosphate, cresyl phenyl phosphate, xylenyl diphenyl phosphate, acidic phosphoric acid esters, nitrogen-containing phosphorus compounds; red phosphorus, tin oxide, antimony trioxide, zirconium hydroxide, meta Inorganic flame retardants such as barium borate, aluminum hydroxide, magnesium hydroxide; brominated polystyrene, brominated poly α-methylstyrene, brominated polycarbonate, brominated epoxy resin, chlorinated polystyrene, chlorinated poly α-methylstyrene, 2. At least one selected from the group consisting of polymer flame retardants such as chlorinated polycarbonate and chlorinated epoxy resin.
The resin composition according to 1. 13. A method for producing a thermoplastic resin, which comprises melt-kneading the following components (A) to (D): (A) 100 parts by weight of polybutylene terephthalate resin, and (B) polyethylene as a main component. Modified polyolefin copolymer 1 having one structural unit having at least one amide group and at least one glycidyloxy group or glycidyl group per 4 to 5000 carbon atoms of the polyolefin
˜50 parts by weight, (C) filler 2 to 50 parts by weight, and (D) flame retardant 5 to 20 parts by weight.