JPH10139984A - Resin composition - Google Patents

Abstract

(57) [Problem] To provide a novel resin composition excellent in workability, impact resistance and heat resistance. SOLUTION: An intrinsic viscosity of 95 to 5 parts by weight of a polyester resin (A) having an intrinsic viscosity of 0.5 to 2.0 dl / g and a repeating unit represented by the following general formula (1) is 0.
100 parts by weight of a resin consisting of 5 to 95 parts by weight of a polyphenylene ether resin (B) of 1 to 0.8 dl / g, a polyester resin part (a) 5 capable of undergoing an exchange reaction with the polyester resin (A) in a melt-kneading process A resin composition comprising 0.003 to 30 parts by weight of a copolymer (C) in which 80% by weight and 95 to 20% by weight of a styrene resin part (b) are chemically bonded, and this resin A resin composition obtained by melt-kneading the composition. Embedded image (Wherein, R _{1 to} R ₄ may be the same or different and represent hydrogen, halogen, a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxyl group, a phenoxy group or a nitro group)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition having a relatively balanced impact resistance, chemical resistance, moldability, heat resistance and the like.

[0002]

2. Description of the Related Art Polyphenylene ether resins have been used as high-performance resins because of their excellent properties such as excellent mechanical properties, electrical properties and heat resistance and good dimensional stability. However, because of poor moldability and impact resistance, applications have been narrowly limited.

As a method for improving the moldability of polyphenylene ether, a method of mixing polyphenylene ether and polyester is disclosed in JP-A-49-50050 and JP-A-49-756.
No. 62, JP-A-59-1594870.
Also, JP-A-63-15841, JP-A-63-20357
The publication discloses a mixture of polyphenylene ether and a polyester-vinyl polymer copolymer. WBLui et al. Eur.Polym. J Vol.32 No.1 91-99 1996
Discloses a resin composition comprising a polyphenylene ether, a polyester, and a copolymer of glycyl methacrylate and styrene. However, each of these forms a macro phase-separated structure due to poor compatibility between the polyphenylene ether-based resin and the polyester, the resulting resin composition has poor mechanical properties, and the molded product has very high impact resistance. Sex was low. Even if a rubber component was added to improve the impact resistance of the above composition, the impact resistance was hardly improved.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel resin composition having excellent workability, impact resistance and heat resistance.

[0005]

That is, the present invention relates to a polyester resin (A) having an intrinsic viscosity of 0.5 to 2.0 dl / g, 95 to 5 parts by weight, and a repeating unit represented by the following general formula (1): Intrinsic viscosity having a unit of 0.1 to 0.8 dl / g
5 to 95 parts by weight of a polyphenylene ether resin (B) and 100 to 100 parts by weight of a polyester resin (A) capable of undergoing an exchange reaction in the melt-kneading process with the polyester resin (A) in an amount of 5 to 80% by weight, and Part (b) 95-
20% by weight of a chemically bonded copolymer (C)
It is a resin composition obtained by mixing 0.003 to 30 parts by weight, and a resin composition obtained by melt-kneading this resin composition.

Embedded image (Wherein, R _{1 to} R ₄ may be the same or different and represent hydrogen, halogen, a hydrocarbon group, a substituted hydrocarbon group, a cyano group, an alkoxyl group, a phenoxy group or a nitro group)

Hereinafter, the present invention will be described in detail. The polyester resin (A) used in the present invention includes a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol residue, or a hydroxycarboxylic acid compound residue and a dicarboxylic acid residue and a diol residue as constituent units. It is a thermoplastic polyester resin. Further, a mixture thereof may be used.

Examples of the hydroxycarboxylic acid compound forming the hydroxycarboxylic acid compound residue include malic acid, citric acid, p-hydroxybenzoic acid, p-hydroxyethylbenzoic acid, and 2- (4-hydroxyphenyl)-
2- (4'carboxyphenyl) propane, etc., and these may be used alone or in combination of two or more.

Further, examples of dicarboxylic acid compounds forming a dicarboxylic acid residue include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Acid, 2,7-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as diphenic acid, and aliphatic dicarboxylic acids such as adipic acid, bimeric acid, sebacic acid, malonic acid, and succinic acid, and the like may be used alone, or two or more kinds thereof may be used. You may use together.

Next, diol compounds forming a diol residue are exemplified by 2,2'-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol A"), bis (4-hydroxyphenyl) Methane, bis (2-hydroxyphenyl) methane, o-hydroxyphenyl-p-hydroxyphenylmethane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4
-Hydroxyphenyl) diphenylmethane, bis (4-
(Hydroxyphenyl) -p-diisopropylbenzene,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl -4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-)
Hydroxyphenyl) sulfide, 1,1-bis (4-
Hydroxyphenyl) ethane, 1,1-bis (3,5-
Dimethyl-4-hydroxyphenyl) ethane, 1,1-
Bis (4-hydroxyphenyl) cyclohexane, 1,
1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylmethane, 2,2
-Bis (4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2 -Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-chloro-4-hydroxyphenyl)
Propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-hydroxyphenyl) propane, 4,4 '-Biphenol, 3,3', 5,5 '
-Tetramethyl-4,4'-dihydroxybiphenyl,
Aromatic diols such as 4,4'-dihydroxybenzophenone, ethylene glycol, propylene glycol,
1,4-butanediol, pentamethylene glycol,
Examples thereof include aliphatic diols such as hydrogenated bisphenol A, and these may be used alone or in combination of two or more. Further, the polyester resins obtained therefrom may be used alone or in combination of two or more.

The polyester resin (A) used in the present invention
May be composed of a combination of these residues, and among them, a polyester resin composed of an aromatic dicarboxylic acid residue and a diol residue is preferred.

Examples of the preferred polyester resin (A) used in the present invention include polyethylene terephthalate,
Examples thereof include polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and polyethylene-2,6-naphthalate. Of these, polyethylene terephthalate and polybutylene terephthalate having appropriate mechanical properties are most preferable.

The polyester resin (A) used in the present invention
Has an intrinsic viscosity of 0.5 to 2.0 dl / g, preferably 0.65 to 1.7 dl / g, more preferably 0.8 to 2.0 dl / g.
1.5 dl / g. If the intrinsic viscosity is lower than 0.5 dl / g, the mechanical strength is low because it does not mix uniformly with the polyphenylene ether resin (B), and if it exceeds 2 dl / g, the moldability is poor, and neither of the poly is preferable.

The intrinsic viscosity is measured at a concentration of 0.5% in orthochlorophenol at 25 ° C.
Ask by. In the formula, C is the concentration expressed in g of resin per 100 ml of the solution, t ₀ is the flow time of the solvent, t is
Represents the flow time of the solution.

(Equation 1)

The polyphenylene ether resin (B) used in the present invention has a repeating unit represented by the general formula (1) and has an intrinsic viscosity of 0.1 to 0.8 dl / g. Specific examples of R _{1 to} R _{4 in} the general formula (1) are as follows:
Hydrogen, methyl, ethyl, propyl, isopropyl, allyl, butyl, phenyl, benzene, methylbenzene, chloromethyl, cyanoethyl, cyanomethoxy, ethoxy, phenoxy, nitro, etc. Groups, which may be the same or different.

Specific examples of the polyphenylene ether resin (B) include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,
4-phenylene) ether, poly (2,6-diethyl-)
1,4 phenylene) ether, poly (2-ethyl-6-
n-propyl-1,4-phenylene) ether, poly (2
-Ethyl-6-isoprene-1,4-phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether And a copolymer composed of repeating units thereof. Above all, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-) which are copolymerized with 2,3,6-trimethyl-1,4-phenyleneether units.
(1,4-phenylene) ether is most preferred.

The intrinsic viscosity of the polyphenylene ether resin used in the present invention, measured at 1% in chloroform at 25 ° C. and determined by the above equation (1), is preferably from 0.1 to 0.1.
0.8 dl / g, more preferably 0.15 to 0.8 dl
/ G, most preferably 0.2 to 0.6 d / g. If the intrinsic viscosity of the polyphenylene ether is lower than 0.1 dl / g, the mechanical strength of the resin composition becomes poor, and 0.8 g
If it exceeds 1 / g, the mechanical properties decrease due to poor dispersion, and the object of the present invention cannot be achieved.

The polyphenylene ether resin used in the present invention can be produced by various methods and is not particularly limited.
For example, there is a method in which phenol that gives a desired polyphenylene ether resin is oxidized and polymerized by introducing an oxygen-containing gas in the presence of a catalyst containing a metal species such as Fe, Mn, Co, and Cu.

The mixing ratio (A) of the polyester resin (A) of the present invention and the polyphenylene ether resin (B)
(B) is 95/5 to 5/95 by weight, preferably 85
/ 15-15 / 85, more preferably 70 / 30-30
/ 70. If the content of the polyphenylene ether resin is less than 5 parts by weight, only a resin composition having a low heat distortion temperature can be obtained, while if it exceeds 95 parts by weight, chemical resistance and moldability will be poor.

Further, the copolymer (C) used in the present invention
Is a polyester resin part (a) capable of undergoing an exchange reaction with the polyester resin (A) during the melt-kneading process, from 5 to 80% by weight,
It is a copolymer in which 95 to 20 parts by weight of the styrene resin part (b) is chemically bonded.

[0020] Polyester resin (A) and copolymer (C)
The exchange reaction in the process of melt-kneading the polyester-based resin portion (a) is an exchange reaction between bonds such as an ester exchange reaction and an ester-carbonate exchange reaction. This exchange reaction is performed at 500 ° C. or higher at the highest temperature among the melting points and glass transition temperatures of the polyester resin (A) and the copolymer (C).
It can be carried out by melt-kneading these at the following temperatures using various known mixers. The exchange reaction may be an exchange reaction in which the reaction proceeds under a suitable catalyst such as a known esterification catalyst. The reaction between the polyester resin (A) and the polyester resin portion (a) of the copolymer (C) is determined by melting and mixing an appropriate amount of the polyester resin (A) and the copolymer (C) at an appropriate temperature. , The copolymer (C) or the polyester resin (A) is extracted with a solvent that dissolves it, and the weight change and components of the solvent-soluble component are analyzed by a known analysis method such as nuclear magnetic resonance or infrared spectroscopy. Can be determined. Specifically, it can be considered that the reaction is possible when the ratio by weight of the soluble component / the charged weight part is 99% or less, or when the soluble component contains 1% or more of the insoluble component.

The polyester-based resin portion (a) of the copolymer (C) may contain the above-described hydroxycarboxylic acid compound residue, dicarboxylic acid residue and diol residue, or hydroxycarboxylic acid compound residue and dicarboxylic acid residue and A thermoplastic polyester having a diol compound residue as a constituent unit, a thermoplastic polycarbonate having a diol residue as a constituent unit, or a polyester carbonate which is a copolymer of these polyesters and a polycarbonate, among which bisphenol A residue and terephthalic acid Most preferred are polyesters having a structural unit of phthalocyanine and isophthalic acid residues or polycarbonates having a bisphenol A skeleton. The copolymer having the polyester moiety can easily excite transesterification with the polyester resin (A), and functions as a highly reactive reactive compatibilizer. Further, the polyester resin portion (a) of the copolymer (C) may be a copolymer with polyamide or polyimide as long as polyester is the main component. Here, the main component means that the constituent unit is 50 parts by weight or more.

Styrene resin part (b) of copolymer (C)
Is, in addition to the styrene monomer, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, t
And repeating units appearing when addition-polymerization of alkylated styrenes such as -butylstyrene, halogenated styrenes such as monochlorostyrene, and styrene-based monomers such as α-methylstyrene. Further, these may be copolymerized with other vinyl monomers as a main component. here,
The main component is 50 parts by weight or more. Among them, a styrene monomer or an α-methylstyrene unit is most preferred because of its good compatibility with polyphenylene ether.

The weight ratio of the polyester resin part (a) to the styrene resin part (b) of the copolymer (C) used in the present invention is 5 to 80% by weight for the former and 95 to 20% by weight for the latter. %. When the content of the polyester resin part (a) is lower than 5% by weight, it is difficult to use this as a reaction part with the resin (A). On the other hand, if the amount of the styrene resin part (b) is less than 20% by weight, the copolymer formed by the reaction is difficult to be fixed on the phase separation interface, and cannot be used as a suitable compatibilizer. Further preferably, the polyester resin part (a)
And the weight ratio of the polystyrene-based resin part (b) to 5 / 95-
The ratio is preferably 50/50, more preferably 5/95 to 30/70. When the weight ratio of the polyester resin part (a) increases, as shown in Takashi Inoue Polymer Vol.45 No.7 450 1996, the copolymer (C) independently forms a microphase-separated structure and becomes compatible. Difficult to function as an agent. This is 5/9
In the range of 5 to 30/70, it is difficult to form a phase separation structure, and the copolymer (C) can easily function as a reactive compatibilizer using the polyester resin part (a) as a reaction part.

In the copolymer (C) used in the present invention, it is important that the polyester-based resin part (a) and the styrene-based resin part (b) are chemically bonded. Or bonded to a side chain. Preferably, a polyester-based resin part (a) is added to the end of the styrene resin part (b).
Is a block copolymer bonded. E. Helfand J. Che
As disclosed in m.Phys. vol. 57 1812 (1970), the probability that the terminal of the molecular chain exists at the polymer-polymer interface increases, and the polyester resin part (a) and the polyester resin (A ) Tends to increase.

The molecular weights of the polyester resin portion (a) and the styrene resin portion (b) of the copolymer (C) are not particularly limited, but the number average molecular weight of the polyester resin portion (a) is not limited. Is preferably 10,000 or less. If it exceeds 10,000, the polyester resin portion often forms a domain in the resin (B) phase, and it is difficult to excite the reaction at the phase separation interface. Also,
As for the styrene resin part (b), it is desirable that the number average molecular weight is 1,000 or more. This is 1,00
If it is smaller than 0, the copolymer (C) is hardly fixed to the phase separation interface, and cannot be used as a suitable compatibilizer.

The method for producing the copolymer (C) is as follows:
Known methods can be adopted, and there is no particular limitation.
For example, the styrene-based monomer is polymerized using a functional group-containing polymerization initiator such as valeric acid to prepare a styrene-based resin having a functional group introduced into a terminal. There is a known polycondensation reaction method using an appropriate polycondensation catalyst together with an acid, a dicarboxylic acid and a diol. Alternatively, an appropriate amount of oxycarboxylic acid, dicarboxylic acid, diol and a monohydroxy compound having a vinyl bond such as paraisopropeniphenol are polycondensed under a suitable polycondensation catalyst to form a vinyl group terminal. There is a known method of producing a polyester resin and subjecting it to a known addition polymerization together with an appropriate amount of the styrene-based monomer described above. In any case, the copolymer (C) of the present invention comprises:
It is sufficient that the polyester resin part (a) 5 to 80% by weight and the styrene resin part (b) 95 to 20 parts by weight are chemically bonded, and the production method is not limited to the above method.

The resin composition of the present invention contains the copolymer (C) in an amount of 0.003 to 3 based on 100 parts by weight of the total weight of the polyester resin (A) and the polyphenylene ether (B).
It is necessary that it is added in an amount of 0 parts by weight. If the amount is less than 0.003 parts by weight, the resin (A) and the resin (B)
Cannot be sufficiently improved. Also, 3
When the amount exceeds 0 parts by weight, the reaction between the polyester resin (A) and the ester resin part (a) of the copolymer (C) proceeds too much, and the physical properties of the resin composition are easily impaired.

Further, the polyphenylene ether resin (A) used in the present invention may be blended or grafted with another polymer in the range of up to 50 parts by weight based on 100 parts by weight of the resin composition of the present invention. Good. Examples of such a polymer include polycarbonate, polysulfone, polyamide, olefin-based resin, styrene-based polymer, rubber-based polymer, and thermoplastic elastomer. Among them, rubber-based polymer and thermoplastic elastomer are used for impact-resistant reinforcement. It is preferable because it functions as an agent.

Examples of rubbery polymers include diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyisoprene, ethylene-α-olefin copolymer, ethylene-α-olefin- Non-diene rubbers such as polyene copolymers and polyacrylates may be used, and these may be used alone or in combination of two or more. Also,
Examples of the thermoplastic elastomer include a styrene-butadiene block copolymer, a hydrogenated styrene-butadiene block copolymer, an ethylene-propylene elastomer, a styrene-grafted ethylene-propylene elastomer, an ethylene-based ionomer resin, a styrene-isoprene block copolymer, Examples thereof include a hydrogenated styrene-isoprene copolymer, and these may be used alone or in combination of two or more. Further, these rubbery polymers and thermoplastic elastomers can be used in combination.

Preferred rubbery polymers and thermoplastic elastomers from the viewpoint of impact resistance are styrene-butadiene copolymer, ethylene-α-olefin copolymer, polyacrylate, styrene-butadiene block copolymer,
A hydrogenated styrene-butadiene block copolymer,
More preferred are styrene-butadiene copolymer, ethylene-α-olefin copolymer and styrene-butadiene block copolymer, and more preferred are ethylene-α-olefin copolymers from the viewpoint of thermal stability. More specifically, in the ethylene-α-olefin copolymer, the weight ratio of ethylene to α-olefin is 85/15 to 70/3.
It is particularly desirable that the α-olefin is an unsaturated hydrocarbon having 3 to 20 carbon atoms.

Further, when a rubbery polymer or a thermoplastic elastomer is added as an impact resistance reinforcing agent, a specific polymer is added to improve the compatibility between the rubbery polymer or the thermoplastic elastomer and the resin (A). An unsaturated compound having a functional group or a polar bond and a known radical initiator or chain transfer agent can also be added.

Such a functional group may be any functional group capable of reacting with the terminal residual group of the polyester resin (A).
Specific examples include an epoxy group, a carboxyl group, an acid anhydride group, and a hydroxyl group. The polar bond is a bond that excites an exchange reaction or a hydrogen bond with an ester bond of the polyester resin (A), and examples thereof include an ester bond, an amide bond, and a carbonate bond.

The amount of the unsaturated compound having a specific functional group or a polar bond is desirably not more than 2 to 3 times the molar amount of the rubbery polymer or the thermoplastic elastomer. The amount of the radical initiator or the chain transfer agent to be added is 0.01 to 5 with respect to the rubbery polymer or the thermoplastic elastomer.
0% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight. When the amount of the radical initiator or the chain transfer agent exceeds 50% by weight, the depolymerization reaction is excited, and the function as an impact-resistant reinforcing agent is reduced. On the other hand, if it is less than 0.01, the radical-generating function is weak and the compound cannot be introduced into a rubbery polymer or a thermoplastic elastomer.

The resin composition of the present invention is melt-kneaded at a predetermined temperature, for example, 200 to 350 ° C., using a known various extruder or various mixers such as a Brabender, kneader, and Banbury mixer. Can be manufactured. In order to improve the reactivity between the polyester resin (A) and the copolymer (C) at the time of melt-kneading, an appropriate catalyst can be added. The amount of the catalyst to be added is desirably 3 parts by weight or less based on the total weight of the resin composition. If the catalyst exceeds 3 parts by weight, the copolymer (C)
Decomposition reaction may be accelerated.

The resin composition of the present invention may contain various fillers, for example, fiber reinforcing agents such as glass fiber, metal fiber, potassium whisker, carbon fiber, etc., for the purpose of improving rigidity and linear expansion characteristics. For example, a filler-based reinforcing agent such as talc, calcium carbonate, mica, glass flake, milled fiber, metal flake, and metal powder may be mixed.
Among these fillers, the shape of the glass fiber and the carbon fiber preferably has a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. The amount of these additives is preferably 5 to 15 parts by weight based on the total weight of the resin composition.

Further, according to the purpose, the present resin composition may contain
It is also possible to add appropriate amounts of heat stabilizers, antioxidants, light stabilizers, mold release agents, lubricants, pigments, flame retardants, plasticizers, antistatic agents, antibacterial and antifungal agents.

When the above resin composition of the present invention is melt-kneaded, a reaction occurs between the polyester resin (A) and the polyester resin portion (a) of the copolymer (C), and the styrene resin (B) ) Is compatible with the styrene resin portion (b) of the copolymer (C). Therefore, after melt-kneading, another resin composition in which the polyester resin (A), the styrene-based resin (B), and the copolymer (C) of the resin composition of the present invention are integrated is formed. Thereby, it is considered that moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, and the like are improved as compared with a conventionally known resin composition of a polyester resin and a styrene-based resin.

[0038]

The present invention will be described below in more detail with reference to examples and comparative examples. In the following, the molecular weight refers to a number average molecular weight (Mn) and a weight average molecular weight (Mw) measured using a gel permeation gas chromatograph (GPC) (corrected with a monodispersed PS). The composition of the aromatic polyester resin-polystyrene polymer was calculated from the ratio of NMR proton spectra. The intrinsic viscosity of (2,6-dimethyl-1,4-phenylene) ether (PPE) used in this example and the comparative example is 0.45, and polybutylene terephthalate (PBT) is 1401-X0 manufactured by Toray Industries, Inc.
4. Polyethylene terephthalate (PET) has an intrinsic viscosity of 0.65 dl / g (0.
Styrene-ethylene-butylene-styrene block copolymer (SEBS) has a molecular weight of PS: EB: PS = 2900: 11600:
At 2900, the PS weight ratio is 33%. The heat distortion temperature, tensile strength, and Izod impact value are ASTM-D
648 (0.455 MPa), ASTM-D638, A
It measured according to STM-D-256.

Reference Examples 1 to 3 [Production of polystyrene having a terminal carboxylate] Radical polymerization was carried out using 4,4'-azobiscyanovaleric acid as a polymerization initiator and a styrene monomer as a monomer. (Mn = 70,000,
20,000, 6,000). PS-COOH obtained
Was subjected to neutralization titration, and the equivalent of COOH groups was measured (in each case, COOH equivalent = 2.00 / molecule).

Reference Examples 4 to 8 [Production of Aromatic Polyester-Polystyrene Block Copolymer (PS-b-PAr)] The PS-COOH of Reference Examples 1 to 3 was added to a 5-fold equivalent of triphenyl based on the terminal carboxyl group. By reacting with 5-fold equivalent of bisphenol A in the presence of phosphine, hexachloroethane and triethylamine, a phenolic terminal styrene resin (PS-OH) was produced. This PS-OH, bisphenol A and iso / terephthalic acid dichloride were added according to the ratio of SAN to PAr, and solution condensation polymerization was carried out in the presence of triethylamine and calcium hydroxide.
After the completion of the polymerization, a large amount of an aqueous acetic acid solution was added to the reaction solution to remove the unreacted substances to make the reaction solution acidic. After removing the aqueous layer from the acidified reaction solution, a large amount of methanol was added to recover the polymer. Table 1 shows the molecular weight (Mn, Mw) and SAN / PAr of the obtained aromatic polyester-polystyrene block copolymer (PS-b-PAr).

[0041]

[Table 1]

Reference Example 9 [Production of Aromatic Polyester-Polystyrene Graft Copolymer (PS-g-PAr)] According to Example 1 of JP-A-3-11,413, a vinyl-terminated aromatic polyester ( Vinyl PAr) and a styrene monomer are radically polymerized at 60 ° C. in the presence of a radical polymerization initiator (azobisisobutyronitrile) to obtain an aromatic polyester-polystyrene graft copolymer (P
Sg-PAr). Vinyl PAr part (Mn = 5,000, Mw = 18,000)
00) PS-g-PAr (Mn = 6,000, Mw = 20,000)
00, PS / PAr = 85/15)

Reference Example 10 [Production of a Styrene Resin Containing One Terminal Amino Group (PS-NH ₂ )] A styrene monomer and an acrylonitrile monomer were reacted with a radical polymerization initiator (azo) according to the examples in JP-A-5-9,354. Radical polymerization in the presence of bisisobutyronitrile) and a chain transfer agent (2-aminoethanethiol) results in a styrene resin containing one terminal amino group (PS-N
H ₂₎ was obtained. Amino equivalent was calculated by neutralization titration with an aqueous hydrochloric acid solution (Mn = 25,000, amine equivalent =
1.01).

REFERENCE EXAMPLE 11 [Production of PS-b-PAr] PS-NH ₂ of Reference Example 10, bisphenol A and iso / terephthalic acid dichloride were added according to the ratio of SAN to PAr, and triethylamine and water were added. Solution condensation polymerization was carried out in the presence of calcium oxide. After the completion of the polymerization, a large amount of an aqueous acetic acid solution was added to the reaction solution to remove the unreacted substances to make the reaction solution acidic. After removing the aqueous layer from the acidified reaction solution, a large amount of methanol was added to recover the polymer. An aromatic polyester-polystyrene block copolymer (PS-b-PAr) shown in Table 2 was obtained. This PS-g-PAr
Means n is 35,000, Mw is 80,000, PS / P
Ar was 70/30.

Reference Example 12 [Production of copolymer of PBT and PS] According to Reference Example 1 of JP-A-63-15,841, terephthalic acid, 1,4-butanediol, tetra-n-butyl titanate Was used to polymerize the PBT. This PBT and PS having an alcohol group at the terminal (Mn = 6,000)
Were melt-kneaded at 250 ° C. under vacuum in the presence of tetra-n-butyl titanate to produce a copolymer of PBT and PS.

Examples 1 to 7 85 parts by weight of PBT and PS of Reference Examples 4 to 9 and Reference Example 11
Each of 15 parts by weight of the -PAr copolymer was added, and the mixture was kneaded with two batch-type closed rolls at 260 ° C and 80 rotations for 7 minutes. After kneading, the kneaded product was collected, pulverized with a coffee mill, extracted with tetrahydrofuran (soluble only in the copolymer of Reference Example) for 48 hours, and the extract was dried. As a result, Example 1 was 1.5 parts by weight, Example 2 was 1.8 parts by weight, Example 3 was 1.5 parts by weight, Example 4 was 1.7 parts by weight, and Example 5 was 3 parts by weight. , Example 6 was 4 parts by weight, and Example 7 was 0.3 parts by weight, and all the polymers were able to react with PBT.

Examples 8 to 12 8.4 g of PPE and PS-b-PAr of Reference Examples 4 to 8 1.
4 g were kneaded with two batch-type closed rolls at 260 ° C. and 80 rotations for 3 minutes. After kneading, 19.6 g of PBT was added and kneaded under the same kneading conditions for 7 minutes. The kneaded material was recovered, cooled to liquid nitrogen temperature and cut, and the section was ultrasonically washed with chloroform for 30 minutes to dissolve the PPE dispersed phase. After cleaning, gold deposition and scanning electron microscope (SEM)
Was used to measure the average diameter of the PPE dispersed phase. Table 2 shows the results.

[0048]

[Table 2]

Example 13 8.4 g of PPE and 1.4 g of PS-g-PAr of Reference Example 9
And 2 batch-type closed rolls at 260 ° C and 3 revolutions at 80 rotations.
Kneaded for minutes. After kneading, 19.6 g of PBT was added, and 7
The mixture was kneaded under the same kneading conditions for minutes. When the diameter of the PPE dispersed phase of the kneaded product was measured in the same manner as in Examples 8 to 12, the average diameter was 1050 nm.

Example 14 8.4 g of PPE and 1.4 of PS-b-PAr of Reference Example 11
g was kneaded with two batch-type closed rolls at 260 ° C. and 80 rotations for 3 minutes. After kneading, 19.6 g of PBT was added,
Kneading was performed for 7 minutes under the same kneading conditions. When the diameter of the PPE dispersed phase of the kneaded product was measured in the same manner as in Examples 8 to 12, the average diameter was 400 nm.

Comparative Example 1 8.4 g of PPE and 19.6 g of PBT were kneaded with two batch-type closed rolls at 260 ° C. and 80 rotations for 7 minutes, and the PPE dispersed phase was dissolved in the same manner as in Examples 1 to 4, followed by SEM. When the diameter of the dispersed phase was measured, the average diameter was 10 μm.

Comparative Example 2 According to WBLui Eur. Polym. J Vol.
Polystyrene having 5% glycyl methacrylate (GMA) (PSGMA: Nippon Yushi MAPROOF G10)
05S) 1.4 g of PPE and 8.4 of batch-type closed mold 2
The mixture was kneaded with a roll at 260 ° C. and 80 rpm for 3 minutes. After kneading, 19.6 g of PBT and 0.014 g of n-tetrabutyl orthotitanate were added and kneaded under the same kneading conditions for 7 minutes. After kneading, the PPE dispersed phase was dissolved in the same manner as in Example 1, and the dispersed phase diameter was measured by SEM.
700 nm.

Comparative Example 3 19.6 g of the PS-PBT copolymer produced in Reference Example 12
And 8.4 g of PPE in a batch-type closed-type 2 roll
The mixture was kneaded at 80 ° C. and 80 rpm for 7 minutes. After kneading, Examples 1 to 7
The PPE dispersed phase was dissolved in the same manner as described above, and the dispersed phase diameter was measured by SEM. The average diameter was 9 μm.

From the comparison between Examples 8 to 14 and Comparative Examples 1 to 3, the average diameter of the PPE dispersed phase in Examples 8 to 14 was as follows:
Both are 1500 nm or less, and are known PBT / PP
E (Comparative Example 1), PBT / PPE / PSGMA (Comparative Example 2), and better compatibility than PS-PBT copolymer / PPE (Comparative Example 3).

Examples 15 to 19 50 parts by weight of PPE, 50 parts by weight of PBT and Reference Examples 4 to 8
Of PS-b-PAr was added in an amount of 5 parts by weight based on the total weight of PPE and PBT, followed by dry blending. This blend was converted to 26 mm by a 30 mm φ twin screw extruder (L / D = 28).
The mixture was kneaded at 0 ° C. and 150 rpm and cooled with water to obtain resin pellets. Using this pellet, a test piece was formed at 260 ° C., and the heat distortion temperature, tensile strength, tensile elongation, and Izod impact test (with a ８ inch notch) were measured.
Table 3 shows the results.

[0056]

[Table 3]

Example 20 PS-b-PAr of Reference Example 11 was added instead of PS-b-PAr of Examples 15 to 19, and kneaded under the same conditions.
The test was molded, and the heat distortion temperature, tensile strength, tensile elongation, and Izod impact test (with a 1/8 inch notch) were measured. The heat distortion temperature was 147 ° C, the tensile strength was 50 MPa, the tensile elongation was 40%, and Izod. Is 30K
g-cm / cm ² .

Comparative Example 4 50 parts by weight of PPE and 50 parts by weight of PBT were added and dry blended. This blend was kneaded in the same manner as in Examples 7 to 11. The kneaded material was very brittle and could not be formed into chips.

From the comparison between Examples 15 to 20 and Comparative Example 4, the compositions of Examples 15 to 20 are of known PBT / PPE.
It has better mechanical strength and toughness than (Comparative Example 4).

Example 21 42.5 parts by weight of PPE, 42.5 parts by weight of PBT, SEB
S15 parts by weight and PS-b-PAr of Reference Example 4 by PPE
And 5 parts by weight based on the total weight of PBT and SEBS. A test piece was molded by kneading in the same manner as in Examples 7 to 11, and the Izod impact test (with a ８ inch notch) was measured. As a result, it was 100 kg-cm / cm ² .

Example 22 Instead of PS-b-PAr of Example 13, kneading was performed using PS-b-PAr of Reference Example 11, a test piece was molded, and the Izod impact test was measured. cm
/ Cm ² .

Comparative Example 5 PSGMA was used in place of PS-b-PAr in Example 14,
Further, n-tetrabutyl orthotitanate is added to PPE, PB
T, kneading by adding 0.05% to the total amount of SEBS,
The test piece was molded and measured for an Izod impact test (with a 1 / 8-inch notch) to find that it was 25 kg-cm / cm ² .

From the comparison between Examples 21 to 22 and Comparative Example 5, the resin composition of the present invention was found to be of the known PPE / PBT / SE
Better impact resistance than BS / PSGMA.

Example 23 PET was used in place of PBT of Examples 1 to 7, kneaded with the PS-PAr copolymer of Reference Example 6, and solvent extraction was carried out in the same manner. It was 1% by weight.

Example 24 PET was used in place of the PBT of Examples 8 to 12, kneaded with the PS-PAr copolymer of Reference Example 6, and the dispersed phase diameter was measured. The average diameter was 750 nm. there were.

Comparative Example 6 Kneading was performed by using PET instead of PBT of Comparative Example 1,
When the particle diameter of the PPE dispersed phase was measured, the average diameter was 15 μm.
Met.

From the comparison between Example 24 and Comparative Example 6, it was found that PPE / PS-b-PAr / PET of the present invention was obtained from a known PP.
Compatibility is better than E / PET.

[0068]

The resin composition of the present invention is prepared by melting and kneading the polyester resin (A) and the polyphenylene ether resin (B) having a repeating unit represented by the general formula (1) with the polyester resin (A). Exchangeable polyester-based resin part (a) 5-80% and styrene-based resin part (b)
It consists of a resin composition in which an appropriate amount of a copolymer (C) chemically bonded to 95 to 20 parts by weight is blended. Therefore, the reaction between the polyester resin part (a) and the polyester resin (A) of the copolymer (C) and the compatibility between the styrene resin part (b) and the polyphenylene ether resin (B) are utilized. It became possible to make the polyester resin (A) and the polyphenylene ether resin (B) compatible. As a result, the resin composition of the present invention has higher compatibility than known polyester-polyphenylene ether resin compositions, and is excellent in moldability, heat resistance, impact resistance, chemical resistance, mechanical strength, etc. Instead, it can be suitably used for industrial parts, electronic equipment, general housing equipment, miscellaneous goods, and the like.

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁶ identifications FI C08L 23:08)

Claims (6)

[Claims] 1. A polyester resin (A) having an intrinsic viscosity of 0.5 to 2.0 dl / g, having an intrinsic viscosity of 95 to 5 parts by weight and a repeating unit having a repeating unit represented by the following general formula (1):
100 parts by weight of a resin composed of 5 to 95 parts by weight of a polyphenylene ether resin (B) of 1 to 0.8 dl / g, and a polyester resin part (a) 5 capable of undergoing an exchange reaction with the polyester resin (A) in a melt kneading process. A resin composition comprising 0.003 to 30 parts by weight of a copolymer (C) in which 80% by weight and 95 to 20% by weight of a styrene resin part (b) are chemically bonded. Embedded image (Wherein, R _{1 to} R ₄ represent the same or different hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, cyano group, alkoxyl group, phenoxy group or nitro group) 2. The resin composition according to claim 1, wherein the polyester resin part (a) of the copolymer (C) comprises an aromatic diol residue and an aromatic dicarboxylic acid residue. 3. The weight ratio of the polyester resin part (a) to the styrene resin part (b) of the copolymer (C) is 5/95.
The resin composition according to claim 1, wherein the ratio is from 30 to 70/70. 4. A resin composition comprising 100 parts by weight of the resin composition according to claim 1 and 1 to 50 parts by weight of an impact-resistant reinforcing agent. 5. The impact-resistant reinforcing agent is an ethylene / α-olefin copolymer having a weight ratio of ethylene to α-olefin of from 95/5 to 5/95 and a Mooney viscosity of from 5 to 200. Item 6. The resin composition according to Item 4. 6. A resin composition obtained by melt-kneading the resin composition according to claim 1.