JPH0747667B2 - Engineering plastics composition and molded article using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an engineering plastics composition having excellent flow properties, heat resistance and mechanical properties, and a molded product using the same.

(Prior Art) Many resins have been conventionally known as engineering plastics. These include polyetherimides, polyarylketones, polysulfones, polyarylene sulfides, polyarylates, liquid crystal polyesters, polyamideimides, polycarbonates, polyphenylene oxides and the like. These engineering plastics are used in various molded products and the like that require high performance (for example, high strength and excellent heat resistance). However, since engineering plastics generally have high melt viscosity, they have poor moldability. Therefore, it is difficult to obtain a precise molded product by using the engineering plastics. For these reasons, there is a strong demand for an engineering plastics composition having a low melt viscosity, that is, excellent flowability characteristics and excellent moldability.

Generally, as a method for reducing the melt viscosity of a polymer substance, a method of reducing the molecular weight of the polymer; a method of adding a plasticizer or a processing aid, and the like are adopted.

When the method (1) is adopted, the mechanical properties such as strength and impact resistance of the molded product made of the polymer substance are deteriorated, and the heat resistance of the molded product is also deteriorated. Among the plasticizers or processing aids used in the above method, many of the substances capable of imparting a plasticizing effect to engineering plastics have poor heat resistance and are not stable at the processing temperature of engineering plastics. Thus, until now, no effective plasticizer or processing aid has been found for engineering plastics.

Various attempts have heretofore been made to improve the moldability of engineering plastics. A conventional improvement method for each of the above engineering plastics will be described in detail below.

(A) Polyetherimide A method of blending polyetherimide with another thermoplastic resin, for example, a method of blending a low molecular weight polyaryl ether (JP-A-59-12967), polyalkyl having a specific molecular weight range. A method of blending a lactone (JP-A-60-156754), a method of blending a vinyl aromatic compound and a block copolymer of a diene compound (JP-A-60-156753), and the like have been proposed. However, all of the above thermoplastic resins have lower heat resistance than polyetherimide. Therefore, even in this method, the heat resistance of the polyetherimide is impaired.

(B) by blending a polyarylketone polyphenylene sulfide,
A method for improving the processability of polyarylketone has been proposed (JP-A-57-172954). In this method, in order to sufficiently improve the processability, it is necessary to blend a large amount (several tens% by weight) of polyphenylene sulfide. As a result, the excellent mechanical properties of the polyaryl ketone are impaired.

(C) Polysulfone A method of blending another thermoplastic resin has been proposed in order to improve the flow properties of polysulfone. For example,
Polyurethane blending method (JP-A-50-144750), polyalkylenephenylene ester or polyalkylenephenylene ether blending (JP-A-50-146648), aromatic vinyl monomer and maleimide monomer copolymerization A method of blending the polymer (JP-A-61-66750) and a method of blending an acrylonitrile-butadiene-styrene copolymer (JP-A-56-56).
167752 gazette) etc. are proposed. All of the thermoplastic resins used in the above method have poor heat resistance as compared with polysulfone. As a result, the excellent heat resistance of polysulfone is impaired.

(D) Polyarylene Sulfide A method for adding a solid ethylene polymer to polyarylene sulfide (JP-A-54-47752) and a method for adding a hydrogenated conjugated diene / monovinyl aromatic block copolymer (JP-A-59-59). No. 217760) has been proposed. However, in these techniques, the polymer used is less heat resistant than polyarylene sulfide,
The excellent heat resistance of polyarylene sulfide is impaired.

(E) Polyarylate A method for obtaining a polyarylate having a relatively low molecular weight by adding a monohydric aliphatic alcohol or an acid as a molecular weight modifier when polymerizing the polyarylate (JP-B-57-49).
No. 046), a method of using an alcohol having three or more hydroxyl groups as a branching agent during polymerization (Japanese Patent Publication No. 61-26).
No. 567) has been proposed. However, whichever method is used, the excellent properties of polyarylate such as mechanical properties are impaired.

(F) Liquid Crystal Polyester A method has been proposed in which a small amount of a low molecular weight liquid crystalline compound is mixed with liquid crystal polyester (JP-A-59-85733). However, since the low molecular weight liquid crystal compound has a relatively low liquid crystal transition temperature, the heat resistance of the liquid crystal polyester is lowered.

(G) Polyamideimide Aromatic aminocarboxylic acid or a derivative thereof, or a compound in which one of the amino groups of aromatic diamine is masked is used as a molecular weight regulator during the production of polyamideimide,
A method of adding has been proposed (Japanese Patent Laid-Open No. 61-44928). However, although the molding processability of the composition is good by this method, the excellent properties of the polyamide-imide cannot be obtained because the crosslinking density of the polyamide-imide at the time of post-cure decreases.

(H) Polycarbonate Polycarbonate has a high glass transition temperature of 140 to 150 ° C., is extremely excellent in mechanical properties and dimensional stability, and is excellent in transparency. Polycarbonate is used for mechanical parts, electric parts, optical parts, etc. that require high performance in strength and heat resistance.

This resin is superior in heat resistance, mechanical strength and water absorption resistance to other transparent materials such as polymethylmethacrylate. However, since the melt viscosity is high, the molecules of the resin are oriented in the flow direction of the resin during molding, and as a result, birefringence easily occurs in the molded product. Therefore, for example, in a precision optical system that records and reproduces information by passing a laser through a transparent substrate, if the transparent substrate is made of polycarbonate, birefringence becomes a problem. When polycarbonate is used as a resin for mechanical parts or electrical parts, glass fibers are added to the polycarbonate in order to further improve the mechanical properties of the parts. Polycarbonate compositions containing glass fibers are increasingly poor in flow properties and require high temperatures of 300-360 ° C. for molding.
When this composition is heated to 350 ° C. or higher, the molded product may be colored.

Several methods have been proposed for obtaining a resin composition having a small birefringence by improving the fluidity of polycarbonate during processing. For this purpose, for example, a method of mixing a styrene-based copolymer (JP-A-63-90556 and JP-A-63-9).
No. 0557), and a method of mixing a polylactone and a styrene polymer (JP-A-63-90555).
Furthermore, there is also a method of adding a molecular weight regulator during the production of polycarbonate (Japanese Patent Laid-Open No. 61-123625 and Japanese Patent Laid-Open No. 123625/1986).
63-43925). As the molecular weight regulator, phenol having one specific aliphatic chain is used. However, in any of the above methods, the excellent heat resistance and mechanical strength of the polycarbonate are significantly reduced.

Furthermore, a method of adding an aromatic carboxylic acid ester (Japanese Patent Publication No. 58-13586) and a method of adding an organic carbonate (Japanese Patent Publication No. 60-34584) have been proposed.
However, the above compounds capable of acting as a plasticizer or a processing aid for polycarbonate are not stable at a high processing temperature such as 260 to 320 ° C.

(I) Polyphenylene oxide A mixture of polyphenylene oxide and polystyrene,
Mixtures of polyphenylene oxide and nylon are commercially available. However, the polyphenylene oxide composition containing a large amount of polystyrene or nylon has improved moldability, but has reduced heat resistance. When glass fibers are further added to these blended products, the resulting mixture has excellent heat resistance and mechanical properties, but has poor fluidity and poor moldability.

Also, a method of blending a copolymer of a vinyl aromatic compound and an unsaturated dicarboxylic acid anhydride (JP-A-58-42648) and a method of blending polyalkylene glycol (JP-A-59-20354). Etc. have been proposed. However, also in this case, the heat resistance and mechanical strength of the polyphenylene oxide are lowered.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks, and its objects are as follows.

To provide an engineering plastics composition having excellent processability due to its low melt viscosity, and having both the heat resistance originally possessed by engineering plastics and the excellent mechanical properties; high heat resistance and excellent mechanical properties are required. To provide useful engineering plastics compositions for electronic parts, films, sheets, pipes, etc., which are used; and paints, adhesives, fibers, etc., which require high heat resistance; when reinforcing fibers are contained. To provide an engineering plastics composition having excellent flow properties, good processability, and the excellent properties described above and above; Engineering plastics composition capable of giving a small amount of molded products (particularly polycarbonate molded products) It provides, and the engineering obtained from plastics composition, heat resistance, providing an excellent molded article to mechanical properties.

(Means for Solving the Problems) The present invention is based on the finding that when a specific p-terphenyl derivative is blended with engineering plastics, the melt viscosity of the resulting engineering plastics composition is significantly reduced. It was

The engineering plastics composition of the present invention is at least selected from the group consisting of p-terphenyl derivatives represented by the following general formulas [I], [II] and [III] per 100 parts by weight of engineering plastics. One kind is blended in an amount of 0.1 to 15 parts by weight, whereby the above object is achieved.

Examples of the engineering plastics used in the present invention include the following resins. Polyetherimides, polyarylketones, polysulfones, polyarylene sulfides, polyarylates, liquid crystal polyesters, polyamideimides, polycarbonates and polyphenylene oxides.

The polyether imide has the general formula A polymer having a unit represented by as a main constituent unit and an ether bond and an imide bond as essential bond units is preferably used. In the formula, Ar ¹ is a divalent aromatic group containing at least one carbon 6-membered ring, for example, (In the formula, X ¹ is O, S, CO, SO ₂ , SO, or a carbon number of 1 to
5 represents an alkylene group of 5) and the like.

Also, for Ar ² , (In the formula, X ² is O, S, CO, SO ₂ , SO, or a carbon number of 1 to
5 represents an alkylene group of 5) and the like.

In the present invention, the repeating unit represented by the following formula is used as a main constituent unit.
The polyether imide as the position is particularly preferably used,
For example, GE ULTEM Can be given.

The above polyarylketone has the general formula A polymer having a repeating unit represented by as a main constituent unit is preferably used.

Ar ^{3 in the} above formula is independently a divalent aromatic group containing at least one carbon 6-membered ring, for example: Etc.

X ³ is independently O, CO, or a direct bond,
n is an integer of 0-3.

In the present invention, the repeats represented by the following formulas [VI] and [VI-II] are used.
Especially the polyarylketone having a repeating unit as a constitutional unit
As a compound suitably used and represented by [VI]
Is ICI VICTREX PEEK And [V-II]
The compound represented is ULTRAPEK manufactured by BASF. Is given
It

The above polysulfone has the following formulas [VI] and [VII]
Polysulfone having a repeating unit of
As an example of [VI], for example, ICI VICTREX PES
The example of [VII] is, for example, UDEL manufactured by UCC.
Can be given.

Examples of the polyarylene sulfide include poly
Phenylene sulfide, poly 4,4'-diphenylene sulphate
Fido, poly-2,4-tolylene sulfide, p-dichloro
Benzene, 2,4-dichlorotoluene and sodium sulfide?
Copolymers synthesized fromA polyphe whose main constituent unit is a repeating unit represented by
Nylene sulfide is preferably used. The polypheny
Examples of rensulfide include Philips Oil Co., Ltd.
Made RYTON , FORTRON manufactured by Kureha Chemical Co., Ltd. , Tosoh Sustain
Sustain made by , Topren made by Topren
Etc.

The polyarylate has the general formula [VIII] A polymer having a repeating unit represented by as a main constituent unit is preferably used.

Ar ^{4 in the} above formula is a divalent aromatic group containing at least one carbon 6-membered ring, for example, (In the formula, X ⁴ is O, S, CO, SO ₂ , SO, or 1 to 5 carbon atoms.
Represents an alkyl group. ) And the like.

In the present invention, the general formula is composed of repeating units represented by the following formula:
Polyarylate is particularly preferably used.
Nichika U Polymer , Bayer APE Made by Hooker
DUREL Etc.

The liquid crystal polyester can be obtained as follows. Aromatic dicarboxylic acid and aromatic dihydroxy compound are copolymerized. Aromatic hydroxyl carboxylic acid is polymerized. An aromatic dicarboxylic acid, an aromatic dihydroxy compound and an aromatic hydroxylcarboxylic acid are copolymerized.

Examples of the aromatic dihydroxy compound used as a constituent component of the liquid crystal polyester include resorcin, 4-acetylresorcin, hydroquinone, chlorohydroquinone, bromohydroquinone, methylhydroquinone, phenylhydroquinone (2,5-dihydroxybiphenyl), methoxyhydroquinone, phenoxyhydroquinone. , 4,4'-dihydroxybiphenyl, 3,3'-diphenyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 3,3'-diphenyl-4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, bisphenol A, 1,1-di (4-hydroxyphenyl) Yl) cyclohexane, 1,2-bis (4-hydroxyphenyl) ethane, 1,4-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene and the like. Among these aromatic dihydroxy compounds, hydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl sulfide are available as highly crystalline liquid crystalline polyesters. .

Examples of the aromatic dicarboxylic acid include isophthalic acid, 5-
Metal salts of sulfoisophthalic acid, terephthalic acid, 4,4'-
Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, 4,4'-dicarboxydiphenyl sulfone, 3,
3'-dicarboxybenzophenone, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 1,4-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and the like can be mentioned. Among these aromatic dicarboxylic acids, those capable of obtaining a highly crystalline liquid crystal polyester include terephthalic acid, 4,4′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether and 4,4′-dicarboxyl. There are diphenyl sulfide, 4,4'-dicarboxybenzophenone, 1,2-bis (4-carboxyphenoxy) ethane, 2,6-dicarboxynaphthalene.

Examples of the aromatic hydroxycarboxylic acid include salicylic acid, metahydroxybenzoic acid, p-hydroxybenzoic acid, 3-chloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid. Acid, 3-phenyl-4-hydroxybenzoic acid,
3-methoxy-4-hydroxybenzoic acid, 4-hydroxy-4'-carboxybiphenyl, 2-hydroxy-6
-Carboxynaphthalene and the like. Among these aromatic hydroxycarboxylic acids, p-hydroxybenzoic acid and 4-hydroxy-4'-carboxydiphenyl are available as the highly crystalline liquid crystalline polyesters.

In particular, a liquid crystal that is a copolymer with p-hydroxybenzoic acid
Polyester is preferred, for example Made by Sumitomo Chemical Co., Ltd. And da
Toco Zider ,Made by Hoechst Celanese Co., Ltd. whose main constituent unit is
La ,And O-CH₂CH₂-East with O as main constituent unit
Man Kodak X7G , Mitsubishi Kasei Novacure
To , Unitika Rod Run Produced by Idemitsu Petrochemical Co., Ltd.
Optical LCP Etc.

The above-mentioned polyamide-imide has the following general formula [IX] A polymer having a repeating unit represented by the formula (1) as a main constituent unit and an amide bond and an imide bond as essential bond units is preferably used.

In the formula Ar^FiveIs a divalent divalent ring containing at least one carbon six-membered ring
An aromatic group, for example, (X in the formula^FiveIs O, S, CO, SO₂, SO, C1-5 Al
(Showing a xylene group) and the like.
For example, Amoco's TORLON , Toray TI-5000 Etc.
To be

The above polycarbonate has the following general formula [X] Is a polymer having a repeating unit represented by

X ⁶ in the formula is O, S, CO, SO ₂ , SO, or a carbon number of 1 to 10.
Is an aliphatic, alicyclic or phenyl-substituted alkylene group.

In the present invention, the repeating unit represented by the following formula is a main constitutional unit.
Polycarbonate to be used particularly preferably, even if
If Mitsubishi Gas Chemical Co., Ltd. Iupilon Pandora made by Teijin Chemicals
Ito , Novalex manufactured by Mitsubishi Kasei , GE Rekizan
Marlon made by Mobay , Bayer Macrolon Etc.
can give.

The polyphenylene oxide has the following general formula [XI] A polymer having a repeating unit represented by as a main constituent unit is preferably used.

In the formula, X ⁷ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or halogen.

In the present invention, polyphenylene oxide having a repeating unit represented by the following formula as a main constituent unit is particularly preferably used.

Polyphenylene oxide is commercially available by itself.
No polystyrene, styrene-acrylonitrile
Polymer, styrene-acrylonitrile-butadiene copolymer
Polymer, styrene-methyl methacrylate copolymer, etc.
Mixtures with ethylene resin and nylon are commercially available.
It Such commercially available products include GE's Noryl , Nori
Le GTX , Asahi Kasei Zylon Manufactured by Diamar
Piece Styrene resin or nylon
Generally, 20 to 400 per 100 parts by weight of polyphenylene oxide
It is added by weight.

The p-terphenyl derivative used in the present invention is at least one selected from the compounds represented by the general formulas [I], [II] and [III].

In the formula, R ¹ and R ² are each independently --H, --COCH ₃ ,
_{-CH 2 CH 2 OH, -CH 2} CH 2 OCOCH 3, -CH 2 CH (CH 3) OH, -CH 2 CH
(CH ₃ ) represents OCOCH ₃ or an alkyl group having 1 to 15 carbon atoms. The alkyl group may or may not be branched.

Examples of the p-terphenyl derivative represented by the above formula [I] include, for example, 4,4 ″ -dihydroxy-p-terphenyl, 4,4 ″ -di (2-hydroxyethoxy) -p-terphenyl, 4, 4 ″ -diacetoxy-p-terphenyl,
4,4 "-di (2-acetoxyethoxy) -p-terphenyl, 4,4" -di (2-hydroxyisopropoxy)-
p-terphenyl, 4,4 "-di (2-acetoxyisopropoxy) -p-terphenyl, 4,4" -dimethoxy-
p-terphenyl, 4,4 "-diethoxy-p-terphenyl, 4,4" -dipropoxy-p-terphenyl, 4,4 "
-Dibutoxy-p-terphenyl, 4,4 "-dipentyloxy-p-terphenyl, 4,4" -dihexyloxy-p-terphenyl, 4,4 "-diheptyloxy-p-
Terphenyl, 4,4 "-dioctyloxy-p-terphenyl, 4,4" -dinonyloxy-p-terphenyl,
4,4 "-didecyloxy-p-tatterphenyl, 4,4"-
Diundecyloxy-p-terphenyl, 4,4 "-didodecyloxy-p-terphenyl, 4,4" -ditridecyloxy-p-terphenyl, 4,4 "-ditetradecyloxy-p-ter Examples thereof include phenyl and 4,4 ″ -dipentadecyloxy-p-terphenyl.

Examples of the p-terphenyl derivative represented by the formula [II] include 4-hydroxy-p-terphenyl,
4- (2-hydroxyethoxy) -p-terphenyl,
4-acetoxy-p-terphenyl, 4- (2-acetoxyethoxy) -p-terphenyl, 4- (2-hydroxyisopropoxy) -p-terphenyl, 4- (2-
Acetoxyisopropoxy) -p-terphenyl, 4-
Methoxy-p-terphenyl, 4-ethoxy-p-terphenyl, 4-propoxy-p-terphenyl, 4-butoxy-p-terphenyl, 4-pentyloxy-p-
Terphenyl, 4-hexyloxy-p-terphenyl, 4-heptyloxy-p-terphenyl, 4-octyloxy-p-terphenyl, 4-nonyloxy-p
-Terphenyl, 4-decyloxy-p-terphenyl, 4-undecyloxy-p-terphenyl, 4-dodecyloxy-p-terphenyl, 4-tridecyloxy-p-terphenyl, 4-tetradecyloxy -P-
Examples thereof include terphenyl and 4-pentadecyloxy-p-terphenyl. The p-terphenyl derivative of the formula [III] is p-terphenyl.

Next, a method for producing the p-terphenyl derivative represented by the general formulas [I] and [II] will be described.

(A) 4,4 ″ -dihydroxy-p-terphenyl (in the formula [I], R ¹ and R ² are —H): 4-methoxy-4′-bromobiphenyl was used to prepare a Grignard reagent using Mg. ,
This can be obtained by coupling with 4-bromoanisole and NiCl ₂ (dppe) as a catalyst to synthesize 4,4 ″ -dimethoxy-p-terphenyl and then treating with PBr _3. .

(B) 4,4 ″ -diacetoxy-p-terphenyl (in the formula [I], R ¹ and R ² are —COCH ₃ ): 4,4 ″ -dihydroxy-p-terphenyl (hereinafter referred to as DHT) It can be obtained by an acetoxylation reaction.

(C) 4,4 ″ -di (2-hydroxyethoxy) -p-terphenyl (in the formula [I], R ¹ and R ² are —CH ₂ CH ₂ OH): obtained by adding ethylene oxide to the above DHT. be able to.

(D) 4,4 ″ -di (2-acetoxyethoxy) -p-terphenyl (in the formula [I], R ¹ and R ² are —CH ₂ CH ₂ OCOC.
H ₃ ): It can be obtained by an acetoxylation reaction of the compound shown in (c) above.

(E) 4,4 "-di (2-hydroxyisopropoxy)-
p-terphenyl (in the formula [I], R ¹ and R ² are —CH ₂ CH (C
H ₃ ) OH): It can be obtained by adding propylene oxide to the above DHT.

(F) 4,4 "-di (2-acetoxyisopropoxy)-
p-terphenyl (in the formula [I], R ¹ and R ² are —CH ₂ CH (C
H ₃ ) OCOCH ₃ ): It can be obtained by an acetoxylation reaction of the compound shown in (e) above.

(G) p-quaterphenyl dialkoxy compound (in the formula [I], R ¹ and R ² are alkyl groups having 1 to 15 carbon atoms): It can be obtained by a known etherification reaction of the above DHT.

Here, if the number of carbon atoms exceeds 15, the liquid crystal transition temperature of this compound becomes low, so that when the compound is blended with engineering plastics, the heat resistance of the engineering plastics composition is lowered.

(H) 4-hydroxy-p-terphenyl (formula [II]
R ¹ is —H): It can be obtained by demethylating the compound (n) described below.

(I) 4-acetoxy-p-terphenyl (formula [II]
In the above, R ¹ can be obtained by an acetoxylation reaction of —COCH ₃ ): 4-hydroxy-p-terphenyl (hereinafter referred to as DHT).

(J) 4- (2-hydroxyethoxy) -p-quaterphenyl (in the formula [II], R ¹ is —CH ₂ CH ₂ OH): It can be obtained by adding ethylene oxide to the above HT.

(K) 4- (2-acetoxyethoxy) -p-terphenyl (in the formula [II], R ¹ is —CH ₂ CH ₂ OCOCH ₃ ): the above (j)
It can be obtained by the acetoxylation reaction of the compound shown in.

(L) 4- (2-hydroxyisopropoxy) -p-quaterphenyl (in the formula [II], R ¹ is —CH ₂ CH (CH ₃ ) O
H): It can be obtained by adding propylene oxide to the above HT.

(M) 4- (2-acetoxyisopropoxy) -p-terphenyl (in the formula [II], R ¹ is —CH ₂ CH (CH ₃ ) OCOC.
H ₃ ): It can be obtained by an acetoxylation reaction of the compound shown in (l) above.

(N) p-terphenyl monoalkoxy compound (in the formula [II], R ¹ is an alkyl group having 1 to 15 carbon atoms): It can be obtained by a known etherification reaction of the above HT.

When the carbon number is more than 15, the liquid crystal transition temperature of this compound becomes low.

(O) p-terphenyl: 4-bromobiphenyl was obtained by preparing a Grignard reagent using Mg and coupling it with bromobenzene using NiCl ₂ (dppe) as a catalyst.

The engineering plastics composition of the present invention can be produced by a generally known method. For example, a method of fixing the p-terphenyl derivative to the engineering plastics particles by mixing the engineering plastics particles with the p-terphenyl derivative particles, the engineering plastics and the p-terphenyl derivative
-A method of melt-mixing with a terphenyl derivative can be mentioned. Particularly, as a method for uniformly mixing the engineering plastics and the p-terphenyl derivative, a melt-kneading method using an extruder, a kneader, a Banbury mixer or the like can be mentioned.

In the present invention, the p-terphenyl derivative is blended in a proportion of 0.1 to 15 parts by weight, preferably 0.5 to 12 parts by weight, and more preferably 0.7 to 10 parts by weight, based on 100 parts by weight of engineering plastics. It is mixed in a ratio of 10 parts by weight. The amount of the above p-terphenyl derivative blended is 0.1 with respect to 100 parts by weight of engineering plastics.
When the amount is less than the weight part, there is almost no decrease in melt viscosity of the obtained engineering plastics composition.
Even if the content of the p-terphenyl derivative is more than 15 parts by weight based on 100 parts by weight of engineering plastics, the effect of decreasing the melt viscosity of the engineering plastics composition does not become large, and the characteristics peculiar to engineering plastics, for example, heat resistance , The mechanical properties, etc. are reduced. Therefore, the blending amount of the p-terphenyl derivative with respect to 100 parts by weight of engineering plastics is 0.1 to 15
Limited to the range of parts by weight. The above p-quaterphenyl derivatives may be used alone or a plurality of p-quaterphenyl derivatives may be used.
-A terphenyl derivative may be used in combination.

The composition of the present invention contains engineering plastics and the above p-terphenyl derivative. The composition may further contain a reinforcing fiber for the purpose of improving heat resistance and mechanical properties as long as its practicality is not impaired. When the composition contains reinforcing fibers, the reinforcing fibers are added in a proportion of 1.0 to 400 parts by weight, preferably 5 to 200 parts by weight, based on 100 parts by weight of the engineering plastics. When the content of the reinforcing fiber relative to 100 parts by weight of engineering plastics is less than 1.0 part by weight, the effect of increasing the mechanical strength of the composition is small, and when it exceeds 400 parts by weight, the melt viscosity of the composition is high. Inferior in moldability.

As the reinforcing fiber, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, graphite fiber, alumina fiber, amorphous metal fiber, silicon / titanium / carbon-based inorganic fiber, aramid fiber, etc. are preferably used for reinforced plastics. A fibrous glass fiber having a thickness of 1 to 50 μm and a length of 0.1 mm to 5 cm is particularly preferably used. The engineering plastics composition of the present invention contains a stabilizer, a flame retardant, an antistatic agent, a release agent, a pigment, etc., if necessary, for the purpose of improving heat resistance and mechanical properties within a range not impairing its practicality. can do.

In order to obtain a molded product from the obtained engineering plastics composition, a melt molding method such as press molding, extrusion molding, injection molding or blow molding is adopted. Molded products have excellent heat resistance and mechanical properties, and are used for machine parts, electronic parts, films, pipes and the like.

In the case of the polycarbonate composition, a transparent optical molded product having a small birefringence (for example, an optical disk substrate or various lenses) can be obtained.

(Example) Below, this invention is demonstrated based on an Example.

The physical properties of the engineering plastics compositions obtained in the following examples were measured according to the following methods.

<Measurement of Physical Properties> (A) Liquid Crystal Transition Temperature The initial endothermic peak was measured as a liquid crystal transition temperature by measurement with a differential thermal analysis device.

(B) Melt viscosity Using a Koka type flow tester, measurement was performed 3 times in accordance with JIS K 7210 (flow test method-reference test), and the average value was used as the measured value. The measurement conditions were a cross-sectional area of the plunger of 1 cm ² , a die diameter of 1 mm, a die length of 10 mm, and a load of 100 kg. The heating temperatures are shown in the table of each example.

(C) Mechanical Properties (Tensile Modulus, Tensile Strength, Elongation at Break) Based on ASTM D638, it was measured by pulling at a speed of 25 mm / min.

(D) Heat distortion temperature According to ASTM D648, a load of 18.6 kg / cm ² was applied for measurement.

(E) Spiral flow Injection pressure 2200 kg / cm ² , molding temperature 340-350 ℃, mold temperature 200 ℃ in a mold having a spiral groove with a width of 5 mm and a depth of 2.5 mm
Injection molding was carried out under the conditions of, and the flow length was measured.

(F) Birefringence and light transmittance From the center of an injection molded disk with a diameter of 130 mm and a thickness of 1.2 mm
The birefringence at the position of 40 mm was measured with a polarizing microscope, and the light transmittance at the same position was measured with a haze meter.

<Synthesis of p-terphenyl derivative> (A) 4,4 ″ -dihydroxy-p-terphenyl 4-methoxy-4′-bromobiphenyl was prepared from Mg in tetrahydrofuran to prepare a Grignard reagent, which was treated with 4-bromo. Anisole was coupled with NiCl ₂ (dppe) as a catalyst to synthesize 4,4 ″ -dimethoxy-p-terphenyl, then 4,4 ″ -dihydroxy-p- was used with BBr ₃ in methylene chloride. Terphenyl (hereinafter DHT
I got). The liquid crystal transition temperature of DHT was 270 ° C.

(B) 4,4 ″ -diacetoxy-p-terphenyl By reacting the DHT obtained in the above (A) with acetic anhydride, 4,4 ″ -diacetoxy-p-terphenyl (hereinafter referred to as DAT) ) Got. The liquid crystal transition temperature of DAT is 267
It was ℃.

(C) 4,4 "-di (2-hydroxyethoxy) -p-terphenyl By reacting the DHT obtained in the above (A) with ethylene oxide in the presence of sodium carbonate, 4,4"-
Di (2-hydroxyethoxy) -p-terphenyl (hereinafter referred to as DHET) was obtained. Liquid crystal transition temperature of DHET is 300 ℃
Met.

(D) 4,4 ″ -di (2-acetoxyethoxy) -p-terphenyl By reacting the DHET obtained in the above (C) with acetic anhydride, 4,4 ″ -di (2-acetoxyethoxy) is obtained. ) -P
-Terphenyl (hereinafter referred to as DAET) was obtained. The liquid crystal transition temperature of DAET was 266 ° C.

(E) 4,4 ″ -diethoxy-p-terphenyl By reacting the DHT obtained in the above (A) with ethyl bromide in the presence of potassium carbonate, 4,4 ″-
Diethoxy-p-terphenyl (hereinafter referred to as DET) was obtained. The liquid crystal transition temperature of DET was 268 ° C.

(F) 4,4 ″ -dibutoxy-p-terphenyl By reacting the DHT obtained in the above (A) with butyl bromide in the presence of potassium carbonate, 4,4 ″-
Dibutoxy-p-terphenyl (hereinafter referred to as DBT) was obtained. The liquid crystal transition temperature of DBT was 260 ° C.

<Polyetherimide Composition> Examples 1 to 3 and Comparative Examples 1 to 3 100 parts by weight of polyetherimide (GE company, ULTEM1000),
A predetermined amount of DHT shown in Table 1 was supplied to a plastograph and melt-mixed at 360 ° C. for 3 minutes to obtain a polyetherimide composition.

The melt viscosity of the polyetherimide composition was measured at 340 ° C. and the results are shown in Table 1.

The polyetherimide composition was press-molded at 340 ° C. and 150 kg / cm ² for 2 minutes to obtain sheets having thicknesses of 1 mm and 4 mm. The mechanical properties of the obtained sheet having a thickness of 1 mm and the heat distortion temperature of the sheet having a thickness of 4 mm were measured. The results are shown in Table 1.

Examples 4 to 6 and Comparative Examples 4 and 5 Instead of the above DHT, DET having the number of parts shown in Table 2 was used.
A polyetherimide composition was obtained in the same manner as in Example 1 except that the melt mixing temperature was 420 ° C. The physical properties of the composition were measured in the same manner as in Example 1. The results are shown in Table 2.

<Polyarylketone Compositions> Examples 7 to 9 and Comparative Examples 6 to 8 Polyetheretherketone (ICI, VICTREX PEEK 15
100 parts by weight of PF) and a predetermined amount of DHT shown in Table 3 were supplied to a plastograph and melt-mixed at 370 ° C. for 3 minutes to obtain a polyether ether ketone composition. The melt viscosity was measured at a measurement temperature of 360 ° C. Further, the polyether ether ketone composition was press-molded at 360 ° C. and 150 kg / cm ² for 2 minutes to obtain a 4 mm sheet having a thickness of 1 mm, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

Examples 10 to 12 and Comparative Examples 9 to 10 Polyetheretherketone compositions were obtained in the same manner as in Example 7, except that DBT in the number shown in Table 4 was used instead of the above DHT. Physical properties of the polyether ether ketone composition were measured in the same manner as in Example 7. The results are shown in Table 4.

<Polysulfone Compositions> Examples 13 to 15 and Comparative Examples 11 to 13 100 parts by weight of polysulfone (ICT, VICTREX PES 4800G) and a predetermined amount of DHT shown in Table 5 were supplied to a plastograph at 360 ° C. A polysulfone composition was obtained by melt mixing for 3 minutes. The melt viscosity was measured at a measurement temperature of 350 ° C. The physical properties of the sheet were measured in the same manner as in Example 1 except that the polysulfone composition was press-molded at 360 ° C. and 150 kg / cm ² for 2 minutes to obtain sheets having thicknesses of 1 mm and 4 mm. The results are shown in Table 5.

Examples 16 to 18 and Comparative Examples 14 and 15 Polysulfone compositions were obtained in the same manner as in Example 13 except that DAT in the number of parts shown in Table 6 was used instead of the above DHT. A sheet was obtained in the same manner as in Example 13, and the physical properties of the sheet were measured. The results are shown in Table 6.

Example 19, Comparative Example 16 Example 13 except that 100 parts by weight of polysulfone (UCC, Udel P-1700) and the predetermined amount of DHT shown in Table 7 were used.
A polysulfone composition was obtained in the same manner as. A sheet was obtained in the same manner as in Example 13, and the physical properties of the sheet were measured. The results are shown in Table 7.

<Polyphenylene sulfide composition> Examples 20-22, Comparative Examples 17-19 100 parts by weight of polyphenylene sulfide (Toprene T-4, Toprene Co., Ltd.) and a predetermined amount of DHT shown in Table 8 were supplied to a plastograph. A polyphenylene sulfide composition was obtained by melt mixing at 350 ° C. for 3 minutes.
Melt viscosity was measured at 340 ° C. The polyphenylene sulfide composition was press-molded at 350 ° C. and 150 kg / cm ² for 2 minutes to obtain sheets having a thickness of 1 mm and 4 mm, and the physical properties of the sheet were measured in the same manner as in Example 1. The results are shown in Table 8.

Examples 23 to 25, Comparative Examples 20 and 21 Polyphenylene sulfide compositions were obtained in the same manner as in Example 20 except that DHET in the number of parts shown in Table 9 was used instead of the above DHT. A sheet was obtained in the same manner as in Example 20,
The physical properties of the sheet were measured. The results are shown in Table 9.

<Polyarylate Compositions> Examples 26 to 28, Comparative Examples 22 to 24 Polyarylate (Unitika Co., U Polymer, U-100) 1
A polyarylate composition was obtained by supplying 00 parts by weight and a predetermined amount of DHT shown in Table 10 to a plastograph and melting and mixing at 350 ° C. for 3 minutes. Melt viscosity 360 ° C
It was measured at. The composition was press-molded at 360 ° C. and 150 kg / cm ² for 2 minutes to obtain sheets having thicknesses of 1 mm and 4 mm. Sheet physical properties were measured in the same manner as in Example 1. The results are shown in Table 10.

Examples 29 to 31, Comparative Examples 25 and 26 Polyarylate compositions were obtained in the same manner as in Example 26 except that DAT in the number shown in Table 11 was used instead of the above DHT. A sheet was obtained in the same manner as in Example 26, and the physical properties of the sheet were measured. The results are shown in Table 11.

<Polyamide-imide composition> Examples 32-34, Comparative Examples 27-29 100 parts by weight of polyamide-imide (TORLON-4203L, Amoco, Inc.) and a predetermined amount of DHT shown in Table 12 were mixed, and the mixture was heated at 120 ° C for 8 hours.
A polyamideimide composition was obtained by drying for an hour. The resulting polyamide-imide composition was injection-molded and the spiral flow was measured.

Sheets with thicknesses of 1 mm and 4 mm were prepared under the injection molding conditions of injection pressure 2200 kg / cm ² , molding temperature 340 to 350 ° C, and mold temperature 200 ° C. This sheet at 165 ℃ for 24 hours, 245 ℃ for 24 hours,
After post-curing at 260 ° C. for 24 hours, the physical properties were measured in the same manner as in Example 1. The results are shown in Table 12.

<Polycarbonate Composition> Examples 35 to 37, Comparative Examples 30 to 32 Polycarbonate (Teijin Kasei, Panlite L-1225
L) 100 parts by weight and a predetermined amount of DHT shown in Table 13 were supplied to a plastograph and melt-mixed at 340 ° C for 3 minutes to obtain a polycarbonate composition. The measurement temperature of the melt viscosity was 300 ° C.

Using an injection molding machine, the above composition was injected at a pressure of 1400 kg / cm ² , a molding temperature of 340 ° C., a mold temperature of 100 ° C., a diameter of 130 mm, and a thickness of 1.2 mm.
A disc was prepared, and the birefringence and the light transmittance were measured at a position 40 mm from the center of the disc.

The composition mixed in the above plastograph is 340 ° C, 150 kg
The physical properties of sheets having a thickness of 1 mm and 4 mm obtained by press molding at / cm ² for 2 minutes were measured in the same manner as in Example 1. Result first
It is shown in Table 13.

Examples 38-40, Comparative Examples 33-35 100 parts by weight of glass fiber reinforced polycarbonate (Teijin Kasei Co., Panlite G-3130, glass fiber content 30% by weight, glass fiber thickness 20 μm, length 0.2-1.0 mm) Then, a predetermined amount of DHT shown in Table 14 was supplied to the plastograph and melt-mixed at 340 ° C. for 3 minutes to obtain a polycarbonate composition. The measurement temperature of the melt viscosity was 260 ° C. Example 35
The sheet was pressed in the same manner as in 1. to obtain sheets having a thickness of 1 mm and 4 mm, and the physical properties of the sheet were measured. The results are shown in Table 14.

<Polyphenylene oxide composition> Examples 41 to 43, Comparative Examples 36 to 38 Modified polyphenylene oxide (GE company, Noryl-PP0534
J) 100 parts by weight and a predetermined amount of DHT shown in Table 15 were supplied to a plastograph and melt-mixed at 300 ° C. for 3 minutes to obtain a polyphenylene oxide composition. The melt viscosity was measured at a measurement temperature of 300 ° C. Composition at 320 ° C, 150 kg /
Sheets having a thickness of 1 mm and 4 mm were obtained by press molding at cm ² for 2 minutes, and the physical properties of the sheet were measured in the same manner as in Example 1.
The results are shown in Table 15.

Examples 44 to 46, Comparative Examples 39 to 41 Glass fiber reinforced modified polyphenylene oxide (GE,
Noryl-GFN3J, glass fiber content 30% by weight, glass fiber thickness 20 μm, length 0.2 to 1.0 mm) 100 parts by weight, and the same amount of DHT as shown in Table 16 and using the same method as in Example 41 Thus, a polyphenylene oxide composition was obtained. A sheet was obtained in the same manner as in Example 41, and the physical properties of the sheet were measured. The results are shown in Table 16.

(Effect of the Invention) As described above, in the engineering plastics composition of the present invention, since the above compound is blended with the engineering plastics in a predetermined ratio, the excellent heat resistance and mechanical properties of the engineering plastics are impaired. In addition, the melt viscosity of the engineering plastics composition can be reduced to improve the moldability.
Therefore, the engineering plastics composition of the present invention is extremely useful for electronic parts with high requirements for heat resistance and mechanical properties, molded articles such as films, sheets and pipes, paints with high heat resistance, adhesives, fibers, etc. is there. Furthermore, since the flow characteristics can be improved even in the composition containing the reinforcing fiber, a molded article having excellent heat resistance and mechanical characteristics can be obtained with good moldability. The polycarbonate composition eliminates the possibility of molecules being oriented in the resin flow direction during molding, and an optical molded article with reduced birefringence can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 71/12 LQM 79/08 LRB 81/02 LRG 81/06 LRF 101/00 (72) Inventor Tonosuke Saito 5-17-21 Yamatedai, Ibaraki-shi, Osaka (72) Inventor Hiroki Kadomachi 7-20 Otemachi, Ibaraki-shi, Osaka (72) Daishiro Kishimoto 2--11, Mishimaoka, Ibaraki, Osaka No. 20 Umeyama Mansion 102 (56) Reference JP-A-50-143844 (JP, A) JP-A-56-116729 (JP, A) JP-A-54-47752 (JP, A) JP-A-59-217760 (JP, A)

Claims (3)

[Claims] 1. At least one selected from the group consisting of p-terphenyl derivatives represented by the following general formulas [I], [II] and [III] per 0.1 part by weight of engineering plastics is 0.1 to 15. An engineering plastics composition containing 1 part by weight. 2. The engineering plastics composition according to claim 1, further comprising a reinforcing fiber, wherein 100 parts by weight of the engineering plastics is used.
The composition according to claim 1, wherein 0.1 to 15 parts by weight of the terphenyl derivative and 0.1 to 400 parts by weight of the reinforcing fiber are blended. 3. A molded article obtained by melt-molding the engineering plastics composition according to claim 1 or 2.