JP3159776B2 - Method for producing thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermoplastic resin composition having an improved balance between impact resistance and heat resistance, excellent dimensional stability and excellent appearance of a molded product.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as PPE)
Is abbreviated as engineering plastics having excellent heat resistance, dimensional stability, non-hygroscopicity, electrical properties, etc., but has poor melt fluidity, is difficult to mold, and has solvent resistance, There is a disadvantage that the impact resistance is poor.

[0003] On the other hand, the saturated polyester has a moldability,
It is widely used as an engineering plastic with excellent solvent resistance and mechanical strength in the fields of automobile parts and electric / electronic equipment parts, but has a large molding shrinkage and linear expansion coefficient, and has high rigidity at high temperatures. It has the disadvantage that the drop is large. In order to improve this, a method of filling a reinforcing agent such as glass fiber has been proposed. However, since the appearance of a molded article is deteriorated, there is a problem that its use is restricted depending on the required field.

[0004] For this reason, if a composition having both the good properties of PPE and saturated polyester and complementing the undesired properties can be obtained, it is possible to provide an excellent resin material having a wide range of applications and its industrial significance is very high. It can be said that it is big. For the purpose of providing a molding material with the disadvantages complemented without impairing the advantages of both, for example, a composition obtained by simply melting and mixing both resins is disclosed in JP-B-51-21664, JP-A-5-21664.
Nos. 9-5050, 49-75662 and 59-
It is disclosed in each publication of 159847.

However, in such a simple blend system, since the PPE and the saturated polyester have essentially poor compatibility, the adhesion at the interface of the two-phase structure is not good, and the two phases are uniform and uniform. It is difficult to form a fine form, and when subjected to shear stress during molding processing such as injection molding, it tends to cause delamination (delamination), the appearance of the obtained molded product deteriorates, and the two-phase interface becomes a defect, A composition having excellent mechanical properties such as dimensional accuracy, heat resistance and rigidity and physical properties such as solvent resistance cannot be obtained.

[0006] For this reason, several techniques for improving the compatibility of both have been proposed. For example, the molecule has (i) a carbon-carbon double bond or a carbon-carbon triple bond and (ii) one or more groups selected from carboxylic acids, acid anhydrides, acid amides, epoxy groups, hydroxyl groups, and the like at the same time. Method using a modified PPE obtained by reacting a compound (JP-A-62-2
No. 57958, No. 63-54427 and Tokuyo Sho 63-
No. 500803, etc.), alkoxysilyl group-modified P
A method using PE (JP-A-63-503392) and a method using oxazoline-modified PPE (Japanese Unexamined Patent Publication No.
JP-A-187453), a method using a polyester modified with a polystyrene terminated with a hydroxyl group or a carboxyl group (JP-A-2-170852), and a method of blending oxycarboxylic acids (JP-A-2-12952).
No. 59) is disclosed. However, these methods are often insufficient to improve the compatibility of both the PPE and the saturated polyester, and the mechanical properties of the resulting composition are still not sufficient. There is a need for improvements.

[0007]

DISCLOSURE OF THE INVENTION The present invention has an excellent miscibility between PPE and a saturated polyester, and both components show a homogeneous and finely miscible state, thereby reducing shear stress during molding such as injection molding. A method for producing a thermoplastic resin composition which suppresses laminar peeling upon receiving, has a fine PPE dispersed particle diameter, has excellent appearance gloss of the obtained molded article, and has excellent impact resistance, heat resistance and rigidity. The purpose is to provide.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, they have found that PPE, a saturated polyester, an impact resistance improving material, and a compatibilizer are blended in a specific ratio. When the kneaded resin and the organic solvent are melted and kneaded, in order to reduce the organic solvent content of the final composition to less than 1.0% by weight, a kneading machine is provided with a vent port and a vacuum device at each vent port. Is maintained under reduced pressure, and the resin composition produced so that the organic solvent content of the final composition is less than 1.0% by weight has a fine PPE-dispersed particle diameter, excellent appearance gloss, impact resistance, and heat resistance. And found that the composition had excellent rigidity, and reached the present invention.

That is, the present invention relates to (a) 4-95% by weight of PPE, (b) 4-95% by weight of a saturated polyester, (c) 0.5-40% by weight of an impact resistance modifier, and (d) a compatibilizer. When melt-kneading 100 parts by weight of a total of 100 parts by weight of 0.11 to 50% by weight and (e) 1.0 parts by weight or more of an organic solvent, the kneading machine has a vent port and a vacuum device is provided at each vent port. And a method for producing a thermoplastic resin composition, wherein the organic solvent content of the final composition is less than 1.0% by weight by maintaining each vent port under reduced pressure.

Hereinafter, the present invention will be described in detail.

<PPE (a)> PPE used in the present invention
(A) is a compound represented by the general formula (I)

[0012]

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Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents Each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and m represents a number of 10 or more)

A homopolymer or a copolymer having the structure represented by the following formula: Preferred examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n
-Hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, particularly an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

A preferred homopolymer of PPE is, for example, one composed of 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer comprising a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in patents and literature. Also suitable are, for example, PPEs containing molecular constituents that improve properties such as molecular weight, melt viscosity and / or impact strength.

The PPE (a) used here has an intrinsic viscosity of 0.2 to 0.8 dl at 30 ° C. measured in chloroform.
/ g is preferred. More preferably, the intrinsic viscosity is 0.2 to 0.5 dl / g, and particularly preferably, the intrinsic viscosity is 0.25 to 0.4 dl / g. If the intrinsic viscosity is less than 0.2 dl / g, the impact resistance of the composition is insufficient,
If it exceeds 0.8 dl / g, there will be difficulties in the moldability of the composition and the appearance of the molded article.

<Saturated polyester (b)> As the saturated polyester (b) used in the present invention, various polyesters can be used.

For example, one of them is a thermoplastic polyester produced by condensing a dicarboxylic acid or a lower alkyl ester, an acid halide or an acid anhydride derivative thereof with glycol or a dihydric phenol according to a conventional method. Can be

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

The aliphatic glycols suitable for the production of polyesters include linear alkylene glycols having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol. , 1,12-dodecamethylene glycol and the like. Examples of the aromatic glycol compound include p-xylylene glycol, and examples of the dihydric phenol include pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other suitable glycols also include 1,4-dichlorohexanedimethanol.

Other preferable polyesters include polyesters obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone)
And so on.

Still another preferred polyester is a polymer which forms a liquid crystal in a molten state (Thermotrope).
It is a polyester that is ic Liquid Crystal Polymer (TLCP). Representative polyesters that fall into these categories include X7G from Eastman Kodak, Xydar from Dartco, Econol from Sumitomo Chemical, Vectra from Celanese, and the like.

Among the above-mentioned saturated polyesters (b), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polynaphthalene terephthalate (PEN), poly (1,4-cyclohexane dimethylene terephthalate) (PCT) or Liquid crystalline polyesters and the like are preferred saturated polyesters for the thermoplastic resin composition of the present invention.

The saturated polyester used here (b)
Is preferably in the range of 0.5 to 5.0 dl / g in intrinsic viscosity measured at 20 ° C. in a phenol / 1,1,2,2-tetrachloroethane = 60/40% by weight mixed solution. More preferably, 1.0 to 4.0 dl / g, particularly preferably 2.0 to 4.0 dl / g.
It is 3.5 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, the impact resistance is insufficient, and when the intrinsic viscosity is 5.0 dl / g or more, the moldability is poor.

<Impact resistance improving material (c)> As the impact resistance improving material (c), an elastomer is used. If the tensile modulus of this elastomer is too high,
Since it does not function well, the tensile modulus of the elastomer is 5,0
00 kg / cm ² (ASTM D882) or less,
More preferably, it is 3,500 kg / cm ² or less. Elastomers include natural rubbers or diene-based synthetic rubbers such as polybutadiene, polyisoprene or copolymers of such dienes with vinyl monomers such as vinyl aromatic monomers such as styrene.

Specifically, a terpolymer of styrene-butadiene-styrene or a hydride thereof; polybutadiene, polychlorobutadiene such as neoprene; a copolymer of isobutylene and butadiene or isoprene; polyisoprene; ethylene and propylene And a copolymer with butadiene; thiocol rubber; polysulfide rubber; acrylic rubber; and polyurethane rubber.

Further, maleic acid, maleic acid monomethyl ester, maleic anhydride,
Α, β-unsaturated dicarboxylic acids such as itaconic acid, itaconic acid monomethyl ester, itaconic anhydride and fumaric acid;
Alternatively, graft polymerization of an alicyclic carboxylic acid such as endo-bicyclo [2.2.1] -5-heptene-2,3-carboxylic acid or a derivative thereof using peroxide, ionizing radiation, ultraviolet light, or the like. You may use what was done.

<Compatibilizing agent (d)> The "compatibilizing agent" used in the present invention is chemically, for example, by a grafting or blocking reaction, and physically, for example, for changing the interfacial properties of a dispersed phase. And / or by increasing its dispersion, thereby interacting with the PPE, the saturated polyester or both, thereby resulting in the phase of the resin mixture as evidenced by, inter alia, increased impact resistance, elongation, and weld line strength. Polyfunctional, non-rubbery compounds that improve solubility and / or
Or a polymer. Many compatibilizers suitable for PPE-saturated polyester blends are well known as described above, and additional compatibilizers will be identified as more is known about PPE-saturated polyester systems. Have been. All such compatibilizers are considered to be within the scope of the present invention.

Examples of various compatibilizers that can be used in the practice of the present invention include the following, described below.

(A) Hydroxyalkylated PPE

(B) Compound having both an unsaturated group and a polar group in the same molecule

The hydroxyalkylated PPE (a) is
PPE in which an alcoholic hydroxyl group is added to a terminal phenolic hydroxyl group by a modifying agent, for example, the following (A) invented by a part of the present inventors and already applied for a patent
To (E), specifically, PPE and a modifier
It can be obtained by a method in which a reaction is performed at a temperature of 50 to 200 ° C. using a basic catalyst in the presence or absence of an organic solvent capable of dissolving PE.

(A) Formula (III _A ) is added to PPE (I).

[0034]

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Glycidol represented by the following formula (II _A )

[0036]

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(Wherein Q ¹ , Q ² and m are the same as above, and n represents a number from 1 to 10)

(JP-A-3-250025).

(B) The PPE (I) has the general formula (III _B )

[0040]

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(Wherein, X represents a halogen atom)

An epihalohydrin represented by, for example, epichlorohydrin is reacted, and the obtained terminal glycidyl-modified PPE is hydrolyzed to obtain a compound represented by the general formula (II _B )

[0043]

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(Wherein Q ¹ , Q ² and m are the same as above)

(JP-A-3-250025).

(C) PPE (I) has the general formula (III _C )

X—R ¹ —OH (III _C )

(In the formula, R ¹ represents an alkylene group having 1 to 10 carbon atoms. X is the same as described above.)

Halogenated alkyl alcohols such as 2-chloroethanol or 3-chloro-1-
Reaction with propanol, etc., the general formula (II _C )

[0050]

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(Wherein Q ¹ , Q ² , m and R ¹ are the same as above)

A method for producing a hydroxyalkylated PPE represented by the following formula (JP-A-3-292326).

(D) PPE (I) has the general formula (III _D )

[0054]

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(Wherein R ² is a hydrogen atom or a carbon atom having 1 to 8 carbon atoms)
Represents an alkyl group)

An alkylene carbonate represented by the general formula (II _D ) is reacted with, for example, ethylene carbonate or propylene carbonate.

[0057]

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(Wherein Q ¹ , Q ² , m and R ² are the same as above)

A method for producing a hydroxyalkylated PPE represented by the formula (JP-A-3-250027).

(E) PPE (I) has the general formula (III _E )

[0061]

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(Wherein R ³ is a hydrogen atom or a carbon number of 1 to 8)
Represents an alkyl group)

By reacting an alkylene oxide represented by, for example, ethylene oxide or propylene oxide,
General formula (II _E )

[0064]

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(Wherein Q ¹ , Q ² , m and R ³ are the same as above)

(JP-A-63-128021).

The organic solvents used here are aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform and carbon tetrachloride; halogenated aromatic solvents such as chlorobenzene and dichlorobenzene. Hydrocarbon; N-methyl-2-pyrrolodone, 1,3-dimethyl-
And heterocyclic compounds such as 2-imidazolidinone.

Examples of the basic catalyst include alcoholates such as sodium methoxide and sodium ethoxide; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate. No.

The reaction ratio of the PPE and the modifier used in these reactions is 1 to 50 mol of the modifier with respect to 1 mol of the terminal phenolic hydroxyl group of the PPE, and the amount of the basic catalyst used is 100 parts by weight of the PPE. To 50 to 50 parts by weight.

Among the hydroxyalkylated PPEs (II _A ) to (II _E ) obtained by the methods shown in the above (A) to (E), the present invention relates to the group having two or more (II _a) or (II _B) is preferably, (II _a) is particularly preferred.

The compound (b) having both an unsaturated group and a polar group in the same molecule includes an unsaturated group, ie, a carbon-carbon double bond or a carbon-carbon triple bond, and a polar group, ie, a saturated polyester. It is a compound having, in the same molecule, a carboxyl group or a hydroxyl group present at an ester bond or a chain terminal contained therein and a functional group having affinity or chemical reactivity. Examples of such functional groups include epoxy groups,
Examples include carboxyl groups, various salts or acid anhydrides derived from carboxyl groups, hydroxyl groups, oxazolines, amino groups, nitriles, esters, imides, acid azides and the like.

Specifically, glycidyl methacrylate,
Glycidyl acrylate and the like are preferable, and more preferably a compound having both a glycidyloxy group and a (meth) acrylamide group in the same molecule, or an epoxidized liquid polybutadiene having 0.07% by weight or more of oxirane oxygen or a mixture of ethylene and glycidyl methacrylate Binary copolymers or ternary copolymers with a third component copolymerizable with ethylene.

Compounds having both a glycidyloxy group and a (meth) acrylamide group in the same molecule are represented by the general formula (IV)

[0074]

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(Wherein, Ar represents an aromatic hydrocarbon group having at least one glycidyloxy group and having 6 to 20 carbon atoms, R represents a hydrogen atom or a methyl group, and s represents 1 to 1)
Is an integer of 4)

Is shown. Examples of such compounds include compounds of formula (V)

[0077]

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(Wherein R is as defined above)

A compound represented by the formula (VI)

[0080]

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Wherein R is the same as above, and p is 1 or 2.

Formula (VII)

[0083]

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(Wherein R is as defined above, and q and r
Represents an integer of 0 to 2, and at least one of q and r is 1 or more.

And the like. Among them, a compound represented by the formula (V), wherein R in the formula is a hydrogen atom, is preferable.

The epoxidized liquid polybutadiene is epoxidized by adding an oxygen atom to the ethylene bond of the liquid polybutadiene, and has an oxirane oxygen content of 0.07% by weight or more and a molecular weight of 500 to 1%.
Those in the range of 000 are preferred.

The oxirane oxygen refers to oxygen added to the ethylene bond, and the oxirane oxygen amount is the weight percent of oxirane oxygen in the epoxidized liquid polybutadiene. Any microstructure of the double bonds of the epoxidized liquid polybutadiene, ie, the ratio of vinyl groups, trans-1,4 structure, and cis-1,4 structure, is included in the present invention. The oxirane oxygen content of the epoxidized liquid polybutadiene used in the present invention is preferably 0.07% by weight or more. Below this, the impact strength becomes unsatisfactory.

Ethylene and glycidyl methacrylate 2
An terpolymer or a terpolymer with a third component copolymerizable with ethylene can also be used. Particularly, those having a glycidyl group of 1% by weight or more are preferable.

The compatibilizer (d) used in the present invention may be used alone or in combination of two or more.

<Organic Solvent (e)> The organic solvent (e) used in the present invention is not particularly limited as long as it is inert to the nucleus-substituted phenols. For example, aromatic hydrocarbons such as benzene, toluene and xylene; linear or cyclic aliphatic hydrocarbons such as heptane and cyclohexane; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene and dichloromethane; dioxane, diethyl ether and the like Ethers; ketones such as cyclohexanone and acetophenone; esters such as ethyl acetate and propiolactone; nitriles such as acetonitrile and benzonitrile; methanol, ethanol, n-
Propanol, isopropanol, n-butanol, se
Alcohols such as c-butanol; nitrobenzene, sulfolane and the like. These may be used alone or as a mixture. Preferably, a good solvent for PPE, an organic solvent having a solvent solubility parameter in the range of 7 to 12,
More preferably aromatic hydrocarbons, halogenated hydrocarbons,
Alcohols, and particularly preferred are organic solvents such as xylene, toluene, dichlorobenzene, and trichlorobenzene.

<Composition Ratio of Constituent Components> The composition ratio of the components (a) to (d) described above is as follows, assuming that the total weight of (a), (b), (c) and (d) is 100% by weight. It is as follows.

Component (a): 4 to 95% by weight, preferably 5 to 70% by weight, particularly preferably 10 to 55% by weight. If the component (a) is less than 4% by weight, the heat stiffness is unsatisfactory, and if it exceeds 95% by weight, the solvent resistance and the impact resistance are unsatisfactory.

Component (b): 4 to 95% by weight, preferably 30 to 95% by weight, particularly preferably 45 to 90% by weight. If the component (b) is less than 4% by weight, the solvent resistance and the impact resistance are unsatisfactory, and if it exceeds 95% by weight, the heat resistance is insufficient.

Component (c): 0.5 to 40% by weight, preferably 3 to 30% by weight, particularly preferably 7 to 20% by weight. If component (c) exceeds 40% by weight, heat resistance is unsatisfactory.

Component (d): 0.01 to 50% by weight, preferably 0.5 to 40% by weight, particularly preferably 1 to 3%
5% by weight. If component (d) exceeds 50% by weight, the solvent resistance, impact resistance and appearance are unsatisfactory.

The mixing ratio of the component (e) is as follows:
The total amount of (d) is 100 parts by weight, and the amount added as an external number is 1.0 part by weight or more, preferably 1.5 to
It is in the range of 50 parts by weight, particularly preferably 2 to 30 parts by weight. The organic solvent content of the final composition is below 1.0% by weight, preferably below 0.8% by weight, particularly preferably below 0.5% by weight. If the component (e) is less than 1.0 part by weight, the compatibility, impact resistance and appearance are unsatisfactory. When the content of the organic solvent in the final composition is 1.0% by weight or more, heat resistance and appearance are unsatisfactory.

<Additional Components> Other additional components can be added to the thermoplastic resin composition according to the present invention.
For example, well-known additives such as antioxidants, weather resistance improvers, nucleating agents, and flame retardants for saturated polyesters; and antioxidants, weather resistance improvers, plasticizers, flow improvers, etc. for PPE. Can be used as an additional component. Further, as a compatibilizer for the saturated polyester and PPE, a phase transfer catalyst such as tetrabutylammonium bromide and tetrabutylphosphonium bromide, or an organic metal catalyst such as titanium tetra (2-ethylhexyl oxide) and titanium tetrabutoxide can be used. Furthermore, the addition of organic / inorganic fillers and reinforcing agents, especially glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc.
It is effective for improving heat resistance and dimensional accuracy. For practical use, various colorants and their dispersants can be used well-known ones.

<Production and Molding Method of Composition> As a melt kneading machine for obtaining the thermoplastic resin composition of the present invention, if it is a melt kneading machine provided with a vent port, it is generally used for thermoplastic resins. Kneading machine can be applied. For example,
It may be a single-screw or multi-screw kneading extruder, or a roll, a Banbury mixer, or the like.

Since the vent port must be kept under reduced pressure, at least a part of the resin in the kneader should be melted at the front part of the vent port so that the resin can be sealed under reduced pressure. Further, if the resin in the kneader is kept in a molten state for a long time before reaching the vent port, the impact resistance is reduced. Therefore, it is preferable that the resin be melted immediately before reaching the vent port as far as possible. The capacity of the vacuum device directly connected to the vent port may be selected according to the degree of pressure reduction of the vent port, and the type and the like are arbitrary.

It is preferable that the degree of pressure reduction at the vent port is maintained at 200 Torr or less.
The compatibility between PE and the saturated polyester becomes poor (domain dispersed particle size: large), and the impact resistance becomes unsatisfactory. It is more preferably at most 100 Torr, particularly preferably at most 50 Torr.

The order of kneading may be such that all components may be kneaded at the same time or may be kneaded using a preliminarily kneaded blend. Further, each component may be sequentially fed and kneaded from some feed ports in the middle of the extruder. The organic solvent may be directly added to the extruder using a pump.

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

[0103]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 7 The components used are as follows.

PPE of component (a): (a-1): Poly (2,6-dimethyl-1,4-phenylene ether) prototyped by Japan Polyether Company
(Intrinsic viscosity measured in chloroform at 30 ° C .:
0.30 dl / g). (A-2): Poly (2,6-dimethyl-1,4-phenylene ether) prototyped by Japan Polyether Company
(Intrinsic viscosity measured in chloroform at 30 ° C .:
0.40 dl / g).

Saturated polyester of component (b): Polybutylene terephthalate (PBT) manufactured by Kanebo Co. (trade name: PB
T128) was used.

Component (c) for improving impact resistance: hydrogenated styrene-butadiene block copolymer (S
EBS) (trade name: Clayton G1651: styrene content 33% by weight, and Clayton G1652: styrene content 28% by weight).

Component (d) compatibilizer: hydroxyalkylated PPE: 500 g of PPE having an intrinsic viscosity of 0.41 dl / g
Was added with 5 liters of toluene, and 100
Stirred at 0 ° C. to completely dissolve. To this solution was added 500 ml of ethanol in which 75 g of sodium ethoxide as a catalyst had been previously dissolved, and 250 g of glycidol was added dropwise. Further, stirring was continued at 100 ° C. for 5 hours. The reaction mixture was poured into 25 liters of methanol to precipitate the product hydroxyalkylated PPE. The product was separated by filtration, washed twice with methanol, and dried by heating under reduced pressure at 80 ° C. The obtained hydroxyalkylated PPE was used.

The hydroxyalkylated PPE exhibited an absorption derived from a hydroxyl group at around 3,380 cm ^{-1 in the} infrared absorption spectrum. When the phenolic hydroxyl group in the terminal group was quantified, 74% reacted and unreacted P
It was found to contain 26% PE.

Incidentally, the reaction rate of the terminal phenolic hydroxyl group of PPE was determined by the Journal of Applied Polymer.
Science: Applied Polymer Symposium (Jo
urnal of Applied Polymer Science: Applied Polymer
Symposium), 34, (1987), 103-117
According to the method described on page 3, the terminal phenolic hydroxyl groups before and after the reaction were quantified and calculated.

Further, an epoxidized acrylamide compound (trade name: Kaneka AXE) manufactured by Kanegafuchi Chemical Industry Co., Ltd. was used.

Compatibilizing Aid: Commercially available tetrabutylphosphonium bromide (Aldrich) was used. Also,
Titanium tetra (2-ethylhexyl oxide) (TO
The commercial product (Wako) of T) was used.

Organic solvent of component (e): Commercial xylene (reagent grade) was used.

All the above-mentioned components except the component (e) were sufficiently mixed and stirred by a super mixer at the mixing ratio shown in Table 1.
Then, using a TEX44 twin screw extruder manufactured by Nippon Steel Works, set temperature 230 ° C., screw rotation speed 350 rp
m, under the kneading conditions, the organic solvent of component (e) was directly added to the first kneading section by using a pump, and the pressure was reduced from the vent port provided downstream of the first kneading section as shown in Table 1. After melt-kneading to obtain a composition, the mixture was pelletized.

From the pellets of the above resin composition, an in-line screw type injection molding machine (IS Toshiba Machine Co., Ltd.)
(-90B type), injection molding was performed at a cylinder temperature of 260 ° C. and a mold cooling temperature of 80 ° C. to prepare test pieces.

At the time of injection molding, drying was performed for 48 hours under conditions of 0.1 Torr and 80 ° C. using a reduced pressure drier until immediately before the injection molding. The injection-molded test piece was placed in a desiccator immediately after molding, allowed to stand at 23 ° C. for 4 to 6 days, and then subjected to an evaluation test. The results are shown in Table 1.

The physical properties and various properties were measured by the following methods.

(1) Flexural modulus ISO R178-1974 Procedure 12 (JIS
K 7203), using an Instron tester.

(2) Izod impact strength ISO R180-1969 (JIS K 7110)
According to the notched Izod impact strength, the measurement was performed using an Izod impact tester manufactured by Toyo Seiki Seisaku-sho.

(3) Heat deformation temperature Using an HDT tester manufactured by Tokyo Seiki Seisakusho, JIS
It was evaluated at a load of 4.6 kg according to K 7207.

(4) Solvent Content in Final Composition The final composition was subjected to Soxhlet extraction using n-heptane, and the obtained extract was subjected to quantitative analysis by gas chromatography.

(5) Dispersion Form A part of the test piece was cut out, immersed in toluene at room temperature for 5 seconds to selectively dissolve the PPE particles, and then subjected to scanning electron microscope Model S-2400 manufactured by Hitachi, Ltd. The dispersed particle size was observed.

[0123]

[Table 1]

Comparative Example 1 The procedure of Example 1 was repeated, except that the impact modifier (c) and the compatibilizer (d) were not added. Table 1 shows the results.

Comparative Example 2 The operation was performed in the same manner as in Example 2 except that the compatibilizing agent (d) was not blended.
Table 1 shows the results.

Comparative Example 3 The same operation as in Example 3 was carried out without blending the organic solvent (e).
Table 1 shows the results.

Comparative Example 4 Example 4 was repeated except that the vent pressure was released (atmospheric pressure).
The same was done. Table 1 shows the results.

[0128]

From the results of the above evaluation tests, according to the production method of the present invention, a thermoplastic resin composition having an excellent balance between impact resistance and heat resistance can be obtained, and its use is wide and industrially useful. Material can be obtained.

Continuation of the front page (72) Inventor Toshio Ito 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Co., Ltd. Yokkaichi Research Laboratory (56) References JP-A-63-128076 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 3/20 C08L 67/00-67/04 C08L 71/10-71/12

Claims (1)

(57) [Claims] 1. A polyphenylene ether (a)
4 to 95% by weight (b) Saturated polyester
4 to 95% by weight (c) Impact resistance improving material
0.5 to 40% by weight (d) Compatibilizer
100 parts by weight of a resin comprising a total of 100% by weight of 0.01 to 50% by weight;
In melting and kneading 1.0 part by weight or more, the kneading machine is provided with a vent port and a vacuum device at each vent port, and each vent port is maintained at a reduced pressure, so that the organic solvent content of the final composition is 1. A method for producing a thermoplastic resin composition, wherein the content is less than 0% by weight.