JPH0665497A - Modified polyphenylene ether resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Modified polyphenylene ether resin composition containing the following (a) and (b): (a) 100 parts by weight of polyphenylene ether (PPE); (b) General formula (I) [Wherein at least one of R ¹ , R ² and R ³ is
General formula (II): (In the formula, Q ¹ and Q ² are each a hydrogen atom or an alkyl group,
n and m are each an integer of 1 to 6, and at least a group represented by the general formula (III): (In the formula, T is a hydrogen atom or an alkyl group, p is an integer of 1 to 6)], a glycidyl compound 0.0
1 to 10 parts by weight A thermoplastic resin composition further comprising the modified PPE resin composition and another thermoplastic resin. [Effect] The modified PPE resin composition described above does not have an irritating odor during production, has excellent compatibility with other thermoplastic resins, and forms a resin composition having excellent mechanical strength.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified polyphenylene ether resin which has a low risk of odor generation during melt-kneading and chemical damage due to chemicals, excellent compatibility with other resins and excellent affinity with inorganic fillers. And a resin composition comprising the modified polyphenylene ether resin and another thermoplastic resin and having excellent mechanical strength.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as "PP
"E") is known as an engineering plastic that has excellent heat resistance, dimensional stability, non-hygroscopicity, and electrical properties, but it has poor melt flowability and is difficult to mold, and it is resistant to solvents and It has the drawback of poor impact resistance.

Therefore, attempts have been made to improve these drawbacks by blending with other thermoplastic resins. A typical example is a blend composition with polystyrene, which is widely used as a resin having excellent moldability and dimensional stability. However, even in this case, the drawback of poor chemical resistance remains,
When an inorganic filler such as glass fiber is added,
The drawbacks such as the poor affinity between the resin and the inorganic filler and the small reinforcing effect still remain. Further, as a resin composition having excellent chemical resistance, a blend composition with polyamide (Japanese Patent Publication No. 59-41663, etc.), a blend composition with polyester (Japanese Patent Publication No. 51-21664, Japanese Patent Publication No. 49-50050). No. 49-75662 and 59
No. 159847), and a blend composition with a polyolefin (US Pat. No. 3,361,851, Japanese Patent Publication No. 42-7069).

However, since PPE has poor compatibility with these resins, the mechanical strength of the resulting blend composition was not satisfactory at a practical level.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a modified PPE having excellent compatibility with other thermoplastic resins and the modified PPE.
It is an object of the present invention to provide a thermoplastic resin composition which comprises a thermoplastic resin and is excellent in mechanical strength.

[0006]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, modified PPE consisting of PPE and a specific glycidyl compound is compatible with other thermoplastic resins. It was found that the resin composition comprising the modified PPE and another thermoplastic resin is excellent in mechanical strength, and has reached the present invention.

That is, the present invention is a modified PPE resin composition containing the following components (a) and (b).

(A) 100 parts by weight of PPE (b) the following general formula (I)

[Chemical 4] [Wherein R ¹ , R ² and R ³ are groups represented by the following general formula (II) or (III), at least one of which is represented by the following general formula (II)

[Chemical 5] (In the formula, Q ¹ and Q ² are each a hydrogen atom or a carbon number of 1 to 6
Represents an alkyl group, and n and m each represent an integer of 1 to 6), and at least one is represented by the following general formula (III):

[Chemical 6] (Wherein T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, p represents an integer of 1 to 6)] 0.01 to 10 parts by weight of a glycidyl compound represented by the formula:

Further, it is a thermoplastic resin composition containing the modified PPE resin composition and another thermoplastic resin.

<Components> PPE used in the present invention
(A) is represented by the general formula (IV)

[0011]

[Chemical 7]

(In the formula, S ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and S ² represents Hydrogen atom, halogen atom, primary or secondary alkyl group, aryl group,
It represents a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and r represents an integer of 10 or more), and is a homopolymer or a copolymer. Suitable examples of the primary alkyl group for S ¹ and S 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, S ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and S ² is a hydrogen atom.

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

The PPE (a) used here has an intrinsic viscosity of 0.2 to 0.8 dl / 30 ° C. measured in chloroform.
Those with g are preferred. The intrinsic viscosity is more preferably 0.2 to 0.7 dl / g, and most preferably the intrinsic viscosity is 0.25 to 0.6 dl / g.
If the intrinsic viscosity is less than 0.2 dl / g, the impact resistance of the composition will be insufficient, and if it exceeds 0.8 dl / g, the moldability of the composition and the appearance of the molded article will be poor.

Next, the glycidyl compound of the component (b) is represented by the following general formula (I)

[0016]

[Chemical 8]

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

Preferred glycidyl compounds are:
The following general formula:

[0019]

[Chemical 9]

Or

[0021]

[Chemical 10]

(In the formula, Q ¹ is the same as the above).

Next, another thermoplastic resin used in the present invention is
Any material that can be melt-kneaded may be used and is not particularly limited. Examples thereof include alkenyl aromatic compound polymers, polyesters, polyamides, polyolefins, polyphenylene sulfides and polycarbonates.

The alkenyl aromatic compound polymer is a known material based on styrene. Examples include polystyrene, poly (α-methylstyrene), polystyrene modified with rubber, styrene-maleic anhydride copolymer or its imidized product, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-
Styrene copolymers and the like.

Examples of the above-mentioned polycarbonate include aromatic polycarbonate, aliphatic polycarbonate, and aliphatic-aromatic polycarbonate. Among them, 2,2-bis (4-oxyphenyl) alkane-based, bis (4-oxyphenyl) ether-based, bis (4
Aromatic polycarbonates composed of bisphenols such as -oxyphenyl) sulfone, sulfide or sulfoxide type are preferred. Further, a polycarbonate composed of bisphenols substituted with halogen as required can also be used.

The molecular weight of the polycarbonate used is not particularly limited, but it is generally 10,000 or more, preferably 20,000 to 40,000.

Further, as the above polyester, for example, one of them is produced by condensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative and a glycol or a dihydric phenol according to a usual method. The thermoplastic polyester is used.

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

As the aliphatic glycol suitable for producing polyester, linear alkylene glycol having 2 to 12 carbon atoms such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol. , 1,12-dodecamethylene glycol and the like. Further, the aromatic glycol compound is exemplified by p-xylene glycol, and the dihydric phenol is exemplified by pyrocatechol, resorcinol, hydroquinone or alkyl-substituted derivatives of these compounds. Other suitable glycols also include 1,4-cyclohexanedimethanol.

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

Still another preferred polyester is a polymer (Thermotrop) which forms a liquid crystal in a molten state.
There is polyester as ic Liquid Crystal Polymer (TLCP). For polyesters that fall into these categories,
Representative products include Eastman Kodak's X7G, Dartco's Xydar, Sumitomo Chemical's Econoll, and Celanese's Vectra.

Among the saturated polyesters listed above,
Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly (1,4-cyclohexanedimethylene terephthalate) (PCT), liquid crystalline polyester, or the like is the crystalline thermoplastic resin of the present invention. It is a saturated polyester suitable for the composition.

The viscosity of the saturated polyester used here is such that the intrinsic viscosity measured at 20 ° C. in a phenol / 1,1,2,2-tetrachloroethane = 60/40 wt% mixed solution is 0.5 to 5. A range of 0 dl / g is preferred. More preferably 1.0 to 4.0 dl / g, particularly preferably 2.
It is 0 to 3.5 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, the impact resistance will be insufficient, and if it exceeds 5.0 dl / g, the moldability will be poor.

Further, the above polyamide has a --CO--NH-- bond in the polymer main chain and can be melted by heating. Nylon-
4, nylon-6, nylon-6,6, nylon-4,
6, Nylon-12, Nylon-6, 10 and the like, and in addition, low crystalline polyamides containing a known aromatic diamine, aromatic dicarboxylic acid and other monomer components can also be used.

Preferred polyamides are nylon-6 or nylon-6,6, with nylon-6 being particularly preferred and having a relative viscosity of 2.0 to 8.0 (98 at 25 ° C.).
% Measurement in concentrated sulfuric acid) is preferred.

Further, as the above-mentioned polyolefin,
Homopolymers of α-olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, heptene-1, octene-1, and these α-olefins Random or block copolymers of each other, random with other unsaturated monomers with a majority weight of these α- olefins, copolymers such as graft or block or olefinic polymers thereof, halogenated, It has been subjected to a treatment such as sulfonation, and exhibits crystallinity derived at least partially from polyolefin. These may be used alone or in combination of two or more. Examples of other unsaturated monomers here are: acrylic acid, methacrylic acid, maleic acid,
Unsaturated carboxylic acids or their derivatives such as itaconic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic anhydride, aryl maleic acid imides, alkyl maleic acid imides; bisesters such as vinyl acetate, vinyl butyrate; styrene , Aromatic vinyl compounds such as methylstyrene; vinylsilanes such as vinyltrimethylmethoxysilane and γ-methacryloyloxypropyltrimethoxysilane; dicyclopentadiene, 4-ethylidene-2
And non-conjugated dienes such as norbornene.

The polyolefin can be obtained by polymerization or modification by a known method, but may be appropriately selected from commercially available products.

Among these, propylene and butene-
A homopolymer of 1,3-methylbutene-1,4-methylpentene-1 or a copolymer containing a majority of these is preferable, and among them, a crystalline propylene-based polymer, that is, a crystalline propylene homopolymer, a crystalline propylene. -Α-olefin block or random copolymer, these crystalline propylene polymers and α-olefin-based rubber, that is, a copolymer composed of a plurality of rubber-like α-olefins or a plurality of α-olefins and non-conjugated diene A mixture of
It is preferable in terms of balance of mechanical properties.

The melt flow rate (MFR) (230 ° C., load 2.16 kg) of these crystalline propylene polymers or a mixture containing them and α-olefin rubber is in the range of 0.01 to 300 g / 10 minutes. Preferably 0.0
The range of 5 to 200 g / 10 minutes is more preferable, and the range of 0.1 to 100 g / 10 minutes is particularly preferable. When the MFR value is lower than this range, molding processability becomes difficult, and when the MFR value is higher than this range, the level of mechanical property balance is low, which is not preferable.

Among these, those of higher molecular weight,
Also included are those in which the molecular weight is changed by heat treatment in the presence of a radical generator, such as an organic peroxide, so that the MFR falls within this range.

Further, as the polyphenylene sulfide (hereinafter referred to as "PPS"), the following general (V)

[0042]

[Chemical 11]

A crystalline resin containing a repeating unit represented by as a main constituent element.

In the present invention, the repeating unit (V) is the main constituent, that is, the repeating unit (V), or the main component thereof is preferably 80 mol% or more, more preferably 90 mol% or more. The inclusion is preferable from the viewpoint of physical properties such as heat resistance.

When the substantial total amount does not consist of the component consisting of the repeating unit (V), the rest (for example, up to 20 mol%) is filled with a copolymerizable component such as the following repeating unit. be able to.

[0046]

[Chemical 12]

(Wherein R is an alkyl group, preferably a lower alkyl group)

The PPS used here preferably has a substantially linear structure from the viewpoint of the physical properties of the molded product.
However, as long as the physical properties are not substantially deteriorated, for example, a polymerized crosslinked product obtained by using an effective amount of a crosslinking agent (for example, trihalobenzene) at the time of polymerization, or a polymer is crosslinked by heat treatment in the presence of oxygen. The heat-crosslinked product can also be used.

The PPS has a melt viscosity of 1 at 300 ° C.
00-20,000P, more preferably 500-10,
Those in the range of 000P are preferable. Melt viscosity is 100P
When it is less than 1, the fluidity is too high and molding is difficult, which is not preferable. Moreover, even if the melt viscosity exceeds 20.000 P,
On the other hand, the fluidity is too low and molding is difficult.

The PPS used here can be produced by any method as long as it does not violate the object of the present invention, but a preferable PPS satisfying the above conditions is disclosed in, for example, Japanese Patent Publication No. 45-3368. For producing a polymer having a relatively small molecular weight as described above, JP-B-52-122
According to the method for producing a linear polymer having a relatively high molecular weight or the method for obtaining a crosslinked product obtained by heating a low molecular weight polymer in the presence of oxygen as disclosed in JP-A-40, or by adding necessary modifications thereto. , Can be manufactured.

Further, PPS can be treated with hot water or the like, if necessary, when a fibrous feller is used.

<Composition Ratio of Constituent Components> The composition ratio of the components (a) and (b) described above is 0.01 to 10 parts by weight, preferably 100 parts by weight of the component (b). 0.05 to 10 parts by weight, particularly preferably 0.1 to
80 parts by weight.

When the amount of the component (b) is less than 0.01 parts by weight, the compatibility with other thermoplastic resins and the mechanical strength of the obtained resin composition are unsatisfactory, and when it exceeds 10 parts by weight, the appearance of the molded product is unsatisfactory. Is.

The ratio of the modified PPE resin composition to the other thermoplastic resin is preferably 5:95 to 95: 5 by weight, more preferably 10:90 to 90: 1.
0, particularly preferably 15:85 to 85:15.

If the modified PPE resin composition is less than 5% by weight, the heat resistance of PPE is impaired, and if the modified PPE resin composition exceeds 95% by weight, moldability is unsatisfactory.

Further, other additional components may be added to the thermoplastic resin composition of the present invention. For example, impact resistance improvers, radical generators, antioxidants, weather resistance improvers, nucleating agents, additives such as flame retardants, plasticizers, fluidity improvers and the like can be used as additional components. Further, addition of organic / inorganic fillers and reinforcing agents such as glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like is effective for improving rigidity, heat resistance, dimensional accuracy and the like. For practical use, various colorants and dispersants thereof may be known ones.

<Manufacturing and Molding Method of Composition> As a melt-kneading machine for obtaining a thermoplastic resin composition containing the modified PPE resin composition of the present invention, a kneading machine generally used for thermoplastic resins is applied. it can. For example, it is a single-screw or multi-screw kneading extruder, and may be a roll, a Banbury mixer, or the like.

The kneading is carried out by blending all components and then melt-kneading, melt-kneading using a pre-kneaded blend, and providing several feed ports in the middle of the extruder, Examples include a method of feeding each component. Particularly preferably, PPE (a)
And the glycidyl compound (b) are pre-kneaded, or two or more feed ports are provided in the middle of the extruder, and PPE (a) and the glycidyl compound (b) are fed from the first feed port, This is a method of feeding another thermoplastic resin from a feed port after the eyes.

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

[0060]

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

Example 1 PPE [Poly (2,6-dimethyl-1,4-phenylene ether) manufactured by Nippon Polyether Co., intrinsic viscosity measured in chloroform at 30 ° C .: 0.41 dl / g]
(A) 100 parts by weight, glycidyl compound of the following formula as a modifier (manufactured by Nissan Kagaku) (b)

[0062]

[Chemical 13]

2 parts by weight were thoroughly mixed and stirred with a super mixer. Next, this is a twin-screw extruder TE manufactured by Japan Steel Works
X44 (trade name) was melt-kneaded at a set temperature of 250 ° C. and a screw rotation speed of 250 rpm to prepare a composition,
Pelletization was performed to obtain a modified PPE resin composition. This is designated as (a-1).

Further, the grafting amount of the resulting modifier (a-1) was determined by dissolving this in boiling xylene, reprecipitating with methanol, and then drying under reduced pressure, followed by press molding, and its IR spectrum. The results are shown in Table 1.

[0065]

[Table 1]

Example 2 The same as Example 1 except that α, α′-bis (t-butylperoxyisopropyl) benzene (trade name: Percadox 14, manufactured by Kayaku Akzo Co., Ltd.) was blended as a radical generator. A modified PPE resin composition was obtained. This is (a-
2). The results are shown in Table 1.

Comparative Example 1 An unmodified PPE was obtained in the same manner as in Example 1 except that nothing was added as a modifier. This is designated as (b-1). The results are shown in Table 1.

Comparative Example 2 A modified PPE resin composition was obtained in the same manner as in Example 1 except that 2 parts by weight of maleic anhydride (Manh, commercially available product) was used as a modifier. This is designated as (b-2). The results are shown in Table 1.

Comparative Example 3 A modified PPE resin composition was obtained in the same manner as in Example 1 except that 2 parts by weight of glycidyl methacrylate (GMA, a commercial product) was used as a modifier. This is designated as (b-3).
The results are shown in Table 1.

Examples 3 to 6 and Comparative Examples 4 to 7 The components used are as follows.

Thermoplastic resin: polystyrene Rubber-modified polystyrene (trade name: HT7 manufactured by Mitsubishi Kasei Co., Ltd.)
6) was used. Polyamide Kanebo nylon-6 (trade name: MC112L) was used. Polyester Kanebo Polybutylene Terephthalate (Product name: PBT
128) was used. Polyolefin An ethylene-propylene copolymer manufactured by Mitsubishi Petrochemical Co., Ltd. (ethylene content: 5.5% by weight, trade name: BC8DQ) was used.

The respective components shown in Table 2 were sufficiently mixed and stirred with a super mixer at the compounding ratio shown in the same table. Then, using a twin screw extruder TE × 44 manufactured by Japan Steel Works,
Set temperature 230-300 ℃, screw rotation speed 250rp
The mixture was melt-kneaded at m to obtain a resin composition and then pelletized.

From the pellets of each of the above resin compositions, using an in-line screw type injection molding machine (molding force of 100T manufactured by Japan Steel Works, Ltd.), a cylinder temperature of 260 to 300 is obtained.
Injection molding at a mold cooling temperature of 60 to 120 ° C.,
A test piece was prepared.

In the injection molding, a vacuum dryer was used immediately before the injection molding under the conditions of 0.1 mmHg and 80 ° C. for 48 hours. 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 evaluated, and the results are shown in Table 2.

Each physical property value was measured by the following methods. (1) Flexural modulus and flexural strength ISO R178-1974 Procedure 12 (JIS
In accordance with K7203), using an Instron tester,
It was measured.

(2) Izod impact strength ISO R180-1969 (JIS K 7110)
According to the notched Izod impact strength, it was measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho.

(3) Heat distortion temperature Using an HDT tester manufactured by Toyo Seiki Seisakusho, JIS
Examples 3-6 and Comparative Examples 4-7 according to K 7207
Is 4.6 kg, and Examples 7 to 10 and Comparative Example 8 described later are used.
In the case of -11, the load was evaluated with a load of 18.6 kg.

[0078]

[Table 2]

Examples 7-10 and Comparative Examples 8-11 In addition to the components used in Examples 3-6, the following components were also used. Thermoplastic resin: Polyphenylene sulfide manufactured by Topren Co., Ltd. (trade name: Topren T-7) was used. Glass fiber: Chopped strands (diameter 10 μm, length 3 mm) manufactured by Asahi Fiber Glass Co., Ltd. were used.

Of the components shown in Table 3, components other than glass fiber were mixed and stirred sufficiently with a super mixer at the compounding ratio shown in the table. Then, using a twin-screw extruder TE × 44 manufactured by Japan Steel Works, these are set at a temperature of 230 to 300 ° C.,
While melt-kneading at a screw rotation speed of 250 rpm, glass fiber was supplied from a feed port provided in the middle of the extruder,
After forming the reinforcing composition, it was pelletized.

Molding and evaluation were carried out in the same manner as in Examples 3 to 6, and the results are shown in Table 3.

[0082]

[Table 3]

[0083]

From the results of the above evaluation test, the modified PPE resin composition of the present invention has no irritating odor upon modification, has a high graft ratio, and has excellent compatibility with other thermoplastic resins. It can be seen that the resin composition comprising the composition and another thermoplastic resin has excellent mechanical strength. Therefore, the modified PPE resin composition of the present invention has a wide range of uses and can be an industrially useful material.

Claims (2)

[Claims] 1. A modified polyphenylene ether resin composition comprising the following components (a) and (b): (A) 100 parts by weight of polyphenylene ether (b) The following general formula (I): [Wherein R ¹ , R ² and R ³ are groups represented by the following general formula (II) or (III), at least one of which is represented by the following general formula (II): (In the formula, Q ¹ and Q ² are each a hydrogen atom or a carbon number of 1 to 6
In which n and m each represent an integer of 1 to 6), and at least one is represented by the following general formula (III): (Wherein T represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, p represents an integer of 1 to 6)] 0.01 to 10 parts by weight of a glycidyl compound represented by the formula: 2. A thermoplastic resin composition comprising the modified polyphenylene ether resin composition according to claim 1 and another thermoplastic resin.