JPH0559273A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in impact resistance, etc., by mixing a specified amount of a specified polyhydroxyphenylene ether with a specified amount of a specified saturated polyester. CONSTITUTION:The title composition comprises a specified amount of a polyhydroxyphenylene ether comprising p structural units of formula I [wherein m is 1-4; n is 0-3; and m+n <=4; J is-R<1>-(OH) (wherein R<1> is a 1-20C aliphatic polyvalent hydrocarbon group or an aromatic polyvalent hydrocarbon group); K is H, halogen, 1-20C prim, or sec. alkyl, 1-20C alkenyl, phenyl, 1-20C aminoalkyl, 1-20C haloalkyl or 1-20C (halo)hydrocarbonoxy] and q structural units of formula II (wherein Q<1> to Q<4> are each K (except for phenyl) or an aromatic group), having a specified number-average degree of polymerization and satisfying a specified relationship between p and q-and a specified amount of a saturated polyester (e.g. polybutylene terephthalate).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition containing polyhydroxyphenylene ether and saturated polyester. This is an engineering plastic that provides industrial materials such as connectors, ignition manifolds, coil sealing materials, gears, crankshafts, etc., which are excellent in solvent resistance and heat resistance, such as automobile parts and electric parts.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as PPE) is used as an engineering plastic having excellent heat resistance, dimensional stability, non-hygroscopicity, and electrical characteristics, but it is used for injection molding or extrusion molding. There is a drawback that the melt fluidity is poor and the molding process is difficult, and the molded product has poor solvent resistance and impact resistance.

On the other hand, saturated polyester represented by polybutylene terephthalate is widely used as an engineering plastic excellent in moldability, solvent resistance and mechanical strength in the fields of automobile parts and electric / electronic equipment parts. There is. However, the molded body of this resin is
It has the drawbacks that the molding shrinkage and linear expansion are large, and that the reduction in rigidity at high temperatures is large.

Therefore, if a resin or compound (composition) having both the good properties of PPE and saturated polyester and complementing the undesired properties can be obtained, it becomes possible to provide an excellent resin material with a wide range of fields of use, and its industry. The meaning is very big. Therefore, for the purpose of providing a molding material that complements the drawbacks without impairing the advantages of both, for example, a composition obtained by simply melt-mixing both resins is disclosed in Japanese Patent Publication No.
1-216664, JP-A-49-50050, 49
-75662 and 59-159847. However, in such a simple blend system, the PPE and the saturated polyester are inherently poor in compatibility, so that the adhesiveness at the interface of this two-phase structure is not good, and the two phases have a uniform and fine morphology. When it is subjected to shear stress during molding processing such as injection molding, delamination is likely to occur, the appearance of the obtained molded product deteriorates, and the two-phase interface becomes a defective part, resulting in dimensional accuracy. A composition having excellent mechanical properties such as heat resistance and rigidity and physical properties such as solvent resistance cannot be obtained.

[0005]

SUMMARY OF THE INVENTION The present invention improves the compatibility of PPE and saturated polyester by using polyhydroxyphenylene ether, and by melt-kneading, a stable fine particle which cannot be reached by the conventional technique is obtained. An object is to provide a resin composition having a dispersed structure.

[0006]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that PPE having an arbitrary number of hydroxyl groups in the substituent, that is, polyhydroxyphenylene ether and saturated polyester. It was found that and have extremely good compatibility, and the present invention has been completed.

That is, the present invention comprises 10 to 90% by weight of polyhydroxyphenylene ether of the following component (A),
The present invention provides a resin composition containing 90 to 10% by weight of saturated polyester as the component (B). Component (A): a copolymer composed of p structural units represented by the following general formula (I) and q structural units represented by the following general formula (II), wherein p and q are , 0.2 ≦ 100
P / (p + q) ≦ 100 is satisfied, and the number average degree of polymerization is 25.
~ 400 polyhydroxyphenylene ether

[0008]

[Chemical 3]

[In the formula, m represents an integer of 1 to 4 and n represents an integer of 0 to 3, and m + n ≦ 4. J is -R ^1- (O
H) (wherein R ¹ is an aliphatic polyvalent hydrocarbon group having 1 to 20 carbon atoms, which may be interrupted by an oxygen atom or may have a substituent in the side chain, or an aromatic polyvalent hydrocarbon group). Represents a valent hydrocarbon group), and m and n are each 2 or more, J and K may be different from each other.

K is independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, a alkenyl group having 1 to 20 carbon atoms, a phenyl group, an amino group having 1 to 20 carbon atoms. Represents an alkyl group, a haloalkyl group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms or a halohydrocarbon oxy group, and when n is 2 or more, K
May be different from each other. ]

[0011]

[Chemical 4]

[In the formula, Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Alkenyl group, aromatic group, C1-C20 aminoalkyl group, C1-C20 haloalkyl group, C1-C20
Represents a hydrocarbon oxy group or a halohydrocarbon oxy. ]
Hereinafter, the present invention will be described in detail. (A) Polyhydroxyphenylene ether The polyhydroxyphenylene ether of the component (A) of the present invention contains 0.2 to 100 mol% of one or more phenol derivatives having a hydroxyl group represented by the general formula (III) and one or two. It is a resin having a polyphenylene ether skeleton obtained by polymerizing or copolymerizing 99.8 to 0 mol% of the phenol-substituted compound represented by the general formula (IV).

[0013]

[Chemical 5]

[Definition of K, J, m and n in the formula is the same as in formula (I). ]

[0015]

[Chemical 6]

[Definition of Q ¹ , Q ² , Q ³ and Q ^{4 in} the formula is the same as in formula (II). ] Preferable specific examples of the phenol derivative having a hydroxyl group represented by the formula (III) include 2- (2-hydroxyethyl) -6-methylphenol, 2- (3-hydroxypropyl) -6-methylphenol, 2- (4-Hydroxybutyl) -6-methylphenol, 2- (2-hydroxypropyl) -6-methylphenol, 2- (2,3-dihydroxypropyl) -6-methylphenol and the like can be mentioned.

Further, preferred specific examples of the phenol derivative represented by the formula (IV) include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-dipropylphenol, 2,3,6. -Trimethylphenol, 2,6-benzylphenol, 2-chlorophenol, 2-allyl-6-methylphenol, etc. or mixtures thereof.

The production of polyhydroxyphenylene ether can be carried out in the same manner as the usual oxidative polymerization of PPE. For example, US Pat. No. 3422062 and US Pat.
No. 306874, No. 3306875, No. 3257
No. 257 and No. 3257358. The catalyst used for the oxidative polymerization is not particularly limited, and any catalyst capable of obtaining a desired degree of polymerization may be used. Many catalyst systems are known in the art consisting of cuprous salt-amine, cupric salt-amine-alkali metal hydroxide, manganese salt-primary amine, and the like.

Further, this polyhydroxyphenylene ether is obtained by metallizing polyphenylene ether with a metal alkyl or alkali metal hydride or amide, and adding ethylene oxide to this, as disclosed in JP-A-2-107634. Can also be manufactured by. The polyhydroxyphenylene ether as the component (A) may be a homopolymer, a random polymer or a block polymer. The number average degree of polymerization is 25 to 400. If it is less than 25, the mechanical properties of the composition are not good, and if it exceeds 400, it is not easy to handle such as deterioration of molding processability due to increase of melt viscosity.

Among them, preferred are 2- (3-hydroxypropyl) -6-methylphenol 0.5 to 50 mol%, preferably 1 to 40 mol% and 2,6-xylenol 99.5 to 50 mol%. , Preferably from 99 to 60 mol% of a copolymer. The number average molecular weight is 3,000.
0 to 50,000 is preferable, and further 5,000 to 3
10,000 is preferable. This polymer is composed of the number x of structural units of the formula (V) and the number y of structural units of the formula (VI), and x and y satisfy the following formula.

0.5 ≦ 100x / (x + y) ≦ 50

[0022]

[Chemical 7]

[0023]

[Chemical 8]

(B) Saturated Polyester Various polyesters can be used as the saturated polyester of the component (B) used in the present invention. For example, one of them is a thermoplastic polyester produced by condensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative thereof, and a glycol according to a usual method.

Specific examples of the aromatic or aliphatic dicarboxylic acid suitable for producing this polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and terephthalic acid. acid,
Isophthalic acid, p, p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2,6-naphthalene dicarboxylic acid or 2,7 -Naphthalene dicarboxylic acid and the like or a mixture of these carboxylic acids.

As the aliphatic diol suitable for producing polyester, linear alkylene glycol having 2 to 12 carbon atoms such as ethylene glycol, 1,3-trimethylene diol, 1,4-tetramethylene diol, 1,
6-hexamethylene diol, 1,12-todecamethylene diol, etc. are mentioned. Further, as the aromatic diol compound, p-xylene diol, pyrocatechol,
There are resorcinols, hydroquinones or alkyl-substituted derivatives of these compounds. Other suitable diols also include 1,4-cyclohexanedimethanol.

Other preferable polyesters include polyesters obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone)
Etc. In addition, as another preferable polyester, a polymer that forms liquid crystals in a molten state (Thermotropic
There is polyester as Liquid Crystal Polymer (TLCP). For polyesters that fall into these categories,
Eastman Kodak X 7G, Dartco Xy
Typical products are dar (Zider), Sumitomo Chemical's Econor, and Celanese's Vectra.

Among the polyesters listed above, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene terephthalate (PEN), poly (1,4-cyclohexanedimethylene terephthalate) (PCT), liquid crystalline polyester, etc. Is a saturated polyester suitable for the thermoplastic resin composition of the present invention.

Additional Components Other additional components can be added to the thermoplastic resin component according to the present invention. For example, well-known antioxidants, weather resistance improvers, nucleating agents, flame retardants, and other additives are added to saturated polyester; well-known antioxidants, weather resistance improvers, plasticizers, flow improvers, etc. are added to PPE. Can be used as an active ingredient. Further, addition of organic / inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonide, potassium titanate, calcium carbonate, silka, etc. is effective in improving rigidity, heat resistance, dimensional accuracy and the like. For practical use, various known colorants and their dispersants can be used.

Further, an impact strength improver is added, especially styrene-butadiene copolymer rubber and its hydride, ethylene-propylene- (diene) copolymer rubber, and their α, β-unsaturated carboxylic acid anhydrides. Addition of a modified product and a modified product with an unsaturated glycidyl ester or an unsaturated glycidyl ether and a copolymer composed of an unsaturated epoxy compound and ethylene or an unsaturated epoxy compound, a copolymer composed of ethylene and an ethylenically unsaturated compound, etc. It is effective for improving the impact strength of the composition. The above impact strength improvers may be used alone or in combination of two or more. The blending amount of the impact strength improver varies depending on the target physical property value. For example, in the case of improving the balance between the rigidity and the impact strength of the composition, it is 5 to 30 parts by weight per 100 parts by weight of the resin component of the composition. is there.

Composition Ratio of Constituents The composition ratio of (A) polyhydroxyphenylene ether to (B) saturated polyester in the resin composition of the present invention is such that mechanical strength, moldability and solvent resistance are two-component system. From the viewpoint of harmony, the weight ratio of component (A) and component (B) is 10
The range is 90 to 90 to 10, preferably 20 to 80 to 80 to 20, more preferably 30 to 70 to 70 to 30. When the content of the component (A) polyhydroxyphenylene ether is less than 10% by weight, the effect of improving dimensional stability and absorbability is small as compared with the saturated polyester,
If it exceeds 90% by weight, the effect of improving moldability and solvent resistance is small.

The thermoplastic resin composition of the present invention may contain components other than the above components (A) and (B). For example, part (up to 80% by weight) of the component (A) polyhydroxyphenylene ether may be replaced with unmodified polyphenylene ether. Further, an antioxidant, a weather resistance improver, a nucleating agent, a flame retardant, a plasticizer, a fluidity improver and the like may be contained in the resin composition in an amount of 20% by weight or less. Furthermore, organic and inorganic fillers such as glass fibers, mica,
50% by weight or less of talc, wollastonite, potassium titanate, calcium carbonate, silica and the like, and 5% by weight or less of a colorant dispersant may be contained. Further, addition of impact strength improver, for example, styrene-butadiene copolymer rubber and its hydride, ethylene-propylene-
(Diene) copolymer rubber, further modified products thereof with α, β-unsaturated carboxylic acid anhydride and modified products thereof with unsaturated glycidyl ester or unsaturated glycidyl ether, or copolymers composed of unsaturated epoxy compound and ethylene, or 5 to 30% by weight of an unsaturated epoxy compound, a copolymer of ethylene and an ethylenically unsaturated compound, and the like may be contained.

Preparation Method and Molding Method of Composition As a melt-kneading method for obtaining the thermoplastic resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, powdery or granular components, if necessary, together with the additives and the like described in the section of additional components, Henschel mixer, ribbon blender,
After uniform mixing with a V-type blender or the like, the mixture can be kneaded with a uniaxial or multiaxial kneading extruder, a roll, a Banbury mixer, or the like.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, that is, injection molding,
Molding methods such as hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding and press molding can be applied.

[0035]

The alcoholic hydroxyl group of the component (A) polyhydroxyphenylene ether and the component (B) saturated polyester are highly compatible.

[0036]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, parts and percentages are based on weight.

Unmodified polyphenylene ether: manufactured by Nippon Polyether Co., Ltd., poly (2,6-dimethyl-1,4-)
(Phenylene ether) with an intrinsic viscosity of 0.31 dl / g measured in chloroform at 30 ° C. (In the table, abbreviated as PPE.)

2- (3-hydroxypropyl) -6-me
Anhydrous tetrahydrofuran under butylphenol nitrogen gas atmosphere (abbreviated as THF) in 266 parts of 2-allyl-6-methylphenol 5
0 part was dissolved, 300 parts of a THF solution of borane having a concentration of 1 mol / liter was added dropwise at 5 ° C., and the mixture was further reacted at 20 ° C. for 1 hour. 20 parts of pure water was added, and 200 parts of 10% sodium hydroxide aqueous solution was further added. 34 parts of 30% hydrogen peroxide solution was added dropwise at 40 ° C., and the mixture was further reacted at 50 ° C. for 1 hour. 2-diethyl ether extraction followed by vacuum distillation
(3-Hydroxypropyl) -6-methylphenol was obtained. The yield based on 2-allyl-6-methylphenol was 84%.

Synthesis of polyhydroxyphenylene ether
Example 1 98 parts of 2- (3-hydroxypropyl) -6-methylphenol, 94.2 parts of 2,6-xylenol and 9.1 parts of sodium hydroxide were dissolved in 2890 parts of xylene and 766 parts of methanol.

Next, 20.5 parts of diethanolamine, 12.6 parts of dibutylamine, 0.4 parts of manganese chloride tetrahydrate.
What melt | dissolved 8 parts in 316 parts of methanol was added in this order. The polymerization reaction was carried out in two stages, and in the former stage, the temperature was kept at 40 ° C. and oxygen gas was introduced at a flow rate of 0.8 liter / min to carry out the reaction until a solid was deposited. In the latter stage, the temperature was maintained at 30 ° C. and oxygen gas was introduced at a flow rate of 0.8 liter / min and nitrogen gas at 8 liter / min until the precipitation of the polymer stopped.

After washing the polymer with hydrochloric acid-methanol to deactivate the catalyst, the target polyhydroxyphenylene ether resin was obtained. Yield: 94% Hydroxyl content: 5.4 mol% Mn; 13,900 Mw; 34,880 Here, the content of the hydroxyl group in the polyphenylene ether is shown in mol% with respect to the number of repeating main chain phenylene rings. , ¹ H-NMR, and calculated from the integrated intensity of a signal derived from a methylene group to which a hydroxyl group was bound at about 3.6 ppm. The number average molecular weight (denoted by Mn) and the weight average molecular weight (denoted by Mw) are polystyrene-converted values measured by GPC. The resin thus obtained is modified with P
PE-1. Synthesis example 2 of polyhydroxyphenylene ether

66 parts of 2- (3-hydroxypropyl) -6-methylphenol and 95 parts of 2,6-xylenol
The reaction was carried out under the same conditions as in Synthesis Example 1 except that 2 parts were used. Yield: 95% Hydroxyl content: 3.6 mol% Mn; 14,000 Mw; 36,600

Synthesis of polyhydroxyphenylene ether
Example 3 The reaction was carried out under the same conditions as in Synthesis Example 1 except that 80 parts of 2- (3-hydroxypropyl) -6-methylphenol and 942 parts of 2,6-xylenol were used. Yield: 94% Hydroxyl content: 4.4 mol% Mn; 10,200 Mw; 18,380 The resin thus obtained is referred to as modified PPE-3.

Synthesis of polyhydroxyphenylene ether
Example 4 2,6-xylenol and 2-allyl-6 in the presence of manganese chloride / diethanolamine / dibutylamine catalyst
-Polyphenylene ether having an allyl group in the side chain was obtained by oxidative polymerization of methylphenol. Next, 50 parts of this polyphenylene ether having an allyl group was dissolved in 449 parts of anhydrous THF under a nitrogen gas atmosphere, and the solution was stirred at 50 ° C. for 9 hours.
-74 parts of a THF solution containing 0.5 mol / l of borabicyclo- (3,3,1) nonane was added dropwise and reacted for 2 hours. 24 parts of a 10% aqueous sodium hydroxide solution was added, 20 parts of a 30% aqueous hydrogen peroxide solution was added dropwise, and the mixture was reacted at 50 ° C. for 2 hours. Precipitate the resin in a large amount of methanol,
Polyhydroxyphenylene ether was obtained. Yield: 95% Hydroxyl content: 5.0 mol% Mn; 25,500 Mw; 54,290 The resin thus obtained is referred to as modified PPE-4.

Saturated polyester polybutylene terephthalate [trade name: Novador 5010 manufactured by Mitsubishi Kasei Co., Ltd.] (hereinafter abbreviated as PBT) was vacuum-dried at 100 ° C. for 24 hours in advance.

Examples 1 to 7 and Comparative Example 1 Using the polyhydroxyphenylene ether and polybutylene terephthalate obtained in Synthetic Examples 1 to 4, each component was blended according to the composition ratio shown in Table 1 by Toyo Seiki Seisakusho Labo Plastomill. Using a machine, the mixture was kneaded at 250 ° C. and 180 rpm for 10 minutes and then pulverized to obtain a granular resin composition.

The characteristics of the obtained resin composition were measured and evaluated by the following methods. The measurement results are shown in Table 1. (1) Bending elastic modulus: Using a hydraulic press molding machine manufactured by Toyo Seiki Seisakusho, pressure molding was performed at 280 ° C. to obtain a sheet having a heat of 2 mm, and then a test piece having a width of 15 mm and a length of 80 mm was cut out, and JIS K was used. According to -7106, the cantilever bending elastic modulus was measured at 23 ° C. and a bending angle of 10 °. (2) Impact strength: Using a CS-183MMX minimax injection molding machine manufactured by Custom Scientific Co., at a temperature of 280 ° C. and a length of 31.
A 5 mm wide, 6.2 mm wide, 3.2 mm thick test piece was injection-molded and a custom scientific Minimax Izod impact tester model CS-138TI was used to obtain a notched Izod impact strength at 23 ° C. Was measured. (3) Evaluation of mixed state: A part of the test piece of the above (2) was cut out, immersed in toluene at room temperature for 5 seconds, and selectively subjected to PP.
After the E particles were dissolved, the dispersed particle diameter was observed with a scanning electron microscope (Hitachi, S-2400).

[0048]

[Table 1]

[0049]

EFFECT OF THE INVENTION A thermoplastic resin composition comprising a component (A) polyhydroxyphenylene ether and a component (B) saturated polyester gives a molded article excellent in impact resistance in addition to mechanical strength. Therefore, it can be used in a wide range of fields such as automobile parts and electric parts.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Tsukahara 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (1)

[Claims] 1. A resin composition containing 10 to 90% by weight of a polyhydroxyphenylene ether as a component (A) and 90 to 10% by weight of a saturated polyester as a component (B). Component (A): a copolymer composed of p structural units represented by the following general formula (I) and q structural units represented by the following general formula (II), wherein p and q are , 0.2 ≦ 100
P / (p + q) ≦ 100 is satisfied, and the number average degree of polymerization is 25.
~ 400 polyhydroxyphenylene ethers [In the formula, m represents an integer of 1 to 4 and n represents an integer of 0 to 3, and m + n ≦ 4. J is —R ¹ — (OH) (wherein R ¹ may be interrupted by an oxygen atom or may have a substituent on the side chain and has 1 to 20 carbon atoms; Represents a hydrocarbon group or an aromatic polyvalent hydrocarbon group),
When m and n are 2 or more, J and K may be different from each other. K is each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a phenyl group, an aminoalkyl group having 1 to 20 carbon atoms, Represents a haloalkyl group having 1 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms or a halohydrocarbonoxy group, and when n is 2 or more,
Each K may be different. ] [Chemical 2] [Wherein Q ¹ , Q ² , Q ³ and Q ⁴ are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 1 to 20 carbon atoms. , Aromatic groups, C1-C20 aminoalkyl groups, C1
Represents a haloalkyl group having 20 to 20 carbon atoms, a hydrocarbon oxy group having 1 to 20 carbon atoms, or a halohydrocarbonoxy. ]