JPH07109320A - Production of modified polyphenylene ether resin - Google Patents

Abstract

PURPOSE:To obtain the resin with suppressed silver streaks and useful as printed boards, etc., by melt kneading a polyphenylene ether resin with a compound having an unsaturated bond and a functional group and a vinyl compound such as acrylic esters. CONSTITUTION:This modified polyphenylene ether resin is obtained by melt kneading (A) 100 pts.wt. polyphenylene ether resin expressed by formula I (R1 and R3 are each a 1-4C alkyl, an aryl, a halogen or H), etc., with (B) 0.1-5 pts.wt. compound simultaneously having carbon-carbon double bond or carbon- carbon triple bond and carboxylic acid group, an acid anhydride group, an acid amide group, imide group, a carboxylic acid ester group, epoxy group, amino group or hydroxyl group in the molecular structure and (C) 0.1-20 pts.wt. vinyl compound expressed by formula II [R7 is H or methyl; R8 is an (substituted)alkenyl, etc.] and/or formula III [R9 and R10 are each H or methyl; R11 is an (substituted)alkylene, etc.] such as a mono- and/or a di(meth)acrylic esters.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a modified polyphenylene ether resin and a composition of the modified polyphenylene ether resin and a thermoplastic resin.

[0002]

2. Description of the Related Art Polyphenylene ether resin is heat resistant,
It is known as an engineering resin with excellent mechanical properties, electrical properties, acid-alkali resistance, etc. In recent years, as an alloy material with polyamide, polyester, etc.,
It is widely used in a modified form with a compound having a specific functional group. As the prior art relating to the modified polyphenylene ether, styrene-maleic anhydride resin modified polyphenylene ether is disclosed in JP-B-52-19864, and free radical polymerization is performed in the presence of a radical initiator in JP-B-52-30991. A method of making polyphenylene ether modified with possible compounds (excluding styrene) is disclosed. Japanese Patent Fair 3-5248
No. 6 discloses a 1,2-substituted olefin compound having an acid anhydride structure in the presence of 0.1 to 5 parts by weight of a radical initiator relative to 100 parts by weight of polyphenylene ether.
A method for producing a modified product in which three or more are reacted is disclosed. JP-A 64-75527 discloses a compound 0.01 having a double bond or a triple bond, an acid anhydride group, etc. in the molecule, relative to 100 parts by weight of polyphenylene ether.
Disclosed is a method for producing a thermoplastic resin composition, which is characterized by allowing 0.01 to 0.1 part by weight of a radical initiator to coexist when 5 to 5 parts are melt-kneaded. Further, in Japanese Patent Publication No. 63-500803, a free radical initiator is not present when a polyphenylene ether resin is melt-kneaded with a compound having a carbon-carbon double bond or triple bond and an acid anhydride group in the molecule. A modified polyphenylene ether resin characterized by being functionalized is disclosed.
However, these modified polyphenylene ether resins have a problem that silver streaks are generated both when they are molded and processed and when they are used as a composition with other thermoplastic resins.

[0003]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that when polyphenylene ether resin is modified with a compound having a specific molecular structure, mono- and / or diacrylates And / or by using at least one vinyl compound selected from dimethacrylic acid esters in combination, the occurrence of silver streaks was significantly suppressed and the workability was also improved, and the present invention was completed. It was

That is, the present invention is as follows: 1, (A) 100 parts by weight of polyphenylene ether resin,
(B) a carbon-carbon double bond or a carbon-carbon triple bond in the molecular structure and (b) a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an epoxy group, 0.1 to 5 parts by weight of a compound having an amino group or a hydroxyl group at the same time, and (C) at least one vinyl compound selected from mono- and / or diacrylates, mono- and / or dimethacrylates 0.1-
A method for producing a modified polyphenylene ether resin, which comprises melt-kneading 20 parts by weight. 2. A composition of the modified polyphenylene ether resin obtained by the above method and (D) a thermoplastic resin. Regarding

The present invention will be described in detail below. The polyphenylene ether resin used as the component (A) of the present invention is represented by the general formula (1)

[0006]

[Chemical 1]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen or hydrogen, and R ₅ and R ₆ are not hydrogen at the same time, and the constitutional unit is represented by the general formula (1 Homopolymers or copolymers of [a] and [b] can be used. Typical examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl1,4-phenylene) ether, and poly (2 , 6-diethyl-1,4-phenylene) ether,
Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-
1,4-phenylene) ether, poly (2-methyl-6)
-N-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-Hydroxyethyl-1,4-phenylene) ether,
Homopolymers such as poly (2-methyl-6-chloroethyl-1,4-phenylene) ether may be mentioned.

The polyphenylene ether copolymer is 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure such as a copolymer with cresol.

Further, in the polyphenylene ether resin of the present invention, various other phenylene ether units, which have been proposed to be present in the polyphenylene ether resin, are proposed as long as they do not violate the gist of the present invention. It may be included as a structure. As an example of what is proposed to coexist in a small amount, Japanese Patent Application No. 63-12
6-98 and JP-A-63-301222, 2- (dialkylaminomethyl) -6-
Examples thereof include a methylphenylene ether unit and a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit. Further, a polyphenylene ether resin in which a small amount of diphenoquinone or the like is bound in the main chain is also included.

The polyphenylene ether resin used in the present invention is not particularly limited in molecular weight, but in general, an intrinsic viscosity of 0.30 to 0.70 (25 ° C. in chloroform).
If the intrinsic viscosity is less than 0.30, it becomes a very brittle resin and is not practical. If the intrinsic viscosity exceeds 0.70, the melt viscosity at the time of extrusion is high and the productivity is greatly increased. There is a problem that said it will drop to. But,
There is a case where the utility value is recognized even if it exceeds this range in a specific application, and therefore it is not particularly specified.

In the molecular structure used in the component (B) of the present invention, (a) a carbon-carbon double bond or a carbon-carbon triple bond and (b) a carboxylic acid group, an acid anhydride group, an acid amide group, Specific examples of the compound having an imide group, a carboxylic acid ester group, an epoxy group, an amino group or a hydroxyl group at the same time include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and these. Acid anhydrides, esters, half-alkyl esters, amides, imides, citric acid, malic acid, etc. of
In particular, α, β-unsaturated dicarboxylic acids and their derivatives, specifically maleic acid and maleic anhydride are preferable. These compounds may be used alone or in combination of two or more. (A) carbon-carbon double bond or carbon-carbon triple bond in the molecular structure and (b) carboxylic acid group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group, epoxy group, amino group or The addition amount of the compound having a hydroxyl group is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyphenylene ether resin. If it is less than 0.1 part by weight, the effect of transformation is insufficient, and if it exceeds 5 parts by weight, problems such as decomposition and discoloration occur, which is economically disadvantageous.

At least one vinyl compound selected from mono- and / or diacrylic acid esters and mono- and / or dimethacrylic acid esters used as the component (C) of the present invention means the following general formula (2) and

[0013]

[Chemical 2]

(In the formula, R7 represents hydrogen or a methyl group,
R8 represents a substituted and / or unsubstituted alkenyl, aralkyl or cycloalkyl group, and includes those having an ether bond inside. ) General formula (3)

[0015]

[Chemical 3]

(Wherein R9 and R10 represent hydrogen or a methyl group, R11 represents a substituted and / or unsubstituted alkylene, alkenylene, aralkylene, cycloalkylene group, including those having an ether bond therein). Refers to the compound represented. Specifically, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol. Acrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentane glycol diacrylate, tripropylene glycol diacrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl. Meta Relate, cyclohexyl methacrylate, methoxy diethylene glycol, dimethacrylate, methoxy polyethylene glycol methacrylate, 3-chloro-2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3
-Butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, etc. are mentioned, but not limited thereto.

The amount used is polyphenylene ether 10
0.1 to 15 parts by weight with respect to 0 parts by weight,
10 parts by weight is more preferable. If the addition amount is less than 0.1 part, the improvement effect is insufficient, and if it is used in excess of 15 parts by weight, the heat resistance of the resin is impaired, which is not preferable. The thermoplastic resin used in the component (D) of the present invention includes polymers of polyethylene, polypropylene, butene-1, butene-2, poly-4-methylpentene-1, ethylene and propylene, ethylene and butene, ethylene and 4 -Polyolefin such as methylpentene-1, copolymer mainly composed of polyolefin, polyvinyl chloride, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene -Vinyl compounds such as acrylonitrile copolymer, polymethylmethacrylate resin, methylmethacrylate-styrene copolymer, copolymers thereof, polycarbonate resin, polyacetal resin, polyethylene terephthalate, polypropylene terephthalate, polybutylene Polyalkylene terephthalates such as terephthalate, aromatic polyester resins, fluorine resins,
Examples include various polyamide resins, polyphenylene sulfide resins, polyether sulfone resins, polyetherimide resins, polyarylate resins and the like.

The amount of the thermoplastic resin used is preferably 95 to 5 parts by weight based on 5 to 95 parts by weight of the modified polyphenylene ether resin. When the amount of the thermoplastic resin is less than 5 parts by weight, the moldability is remarkably deteriorated, and when it exceeds 95 parts by weight, the effect of adding the modified polyphenylene ether resin cannot be recognized, which is not preferable. The modified polyphenylene ether resin of the present invention and the composition of the modified polyphenylene ether resin and the thermoplastic resin may optionally contain other additives such as a plasticizer, a flame retardant, various stabilizers, an ultraviolet absorber, a colorant, and a release agent. Molding agents and fibrous reinforcing agents such as glass fibers and carbon fibers, and fillers such as glass beads, calcium carbonate and talc can be added.

The modified polyphenylene ether resin of the present invention and the respective components constituting the composition of the modified polyphenylene ether resin and the thermoplastic resin may be melt-kneaded by any method, for example, an extruder, a heating roll, a Banbury. A mixer, a kneader or the like can be used. Of these, an extruder is preferable in terms of productivity.

[0020]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
Hereinafter,% and parts represent% by weight and parts by weight, respectively. The resin components used in Examples and Comparative Examples are as follows. A-1: Polyphenylene ether resin Intrinsic viscosity 0.50 (measured in chloroform at 25 ° C.)
Poly (2,6-dimethyl-1.4-phenylene) ether A-2: Polyphenylene ether resin Intrinsic viscosity 0.65 (measured in chloroform at 25 ° C.)
Poly (2,6-dimethyl-1.4-phenylene) ether A-3: Polyphenylene ether resin, intrinsic viscosity 0.40 (measured in chloroform at 25 ° C.)
Poly (2,6-dimethyl-1.4-phenylene) ether A-4: Polyphenylene ether resin, intrinsic viscosity 0.32 (measured in chloroform at 25 ° C.)
Poly (2,6-dimethyl-1.4-phenylene) ether B-1: maleic anhydride C-1: stearyl acrylate D-1: polystyrene resin Asahi Kasei polystyrene H8117 (manufactured by Asahi Kasei Kogyo KK) D-2: Acrylonitrile-butadiene-styrene copolymer Stylak (trademark) ABS200 (manufactured by Asahi Kasei Kogyo KK) D-3: Polyamide resin Leona (trademark) 1300S (manufactured by Asahi Kasei Kogyo KK)

[0021]

Example 1 Intrinsic viscosity 0.50 (in chloroform, 25
100 parts by weight of poly (2,6-dimethyl-1.4-phenylene) ether (A-1) (measured at C), 2 parts by weight of maleic anhydride (B-1) and stearyl acrylate (C-1) 2 A mixture of parts by weight was melt-kneaded using a ZSK-25 twin-screw extruder [manufactured by W & P Co., Ltd.] and extruded to obtain pellets. The basic conditions for extrusion are barrel temperature =
330 ° C, screw rotation speed = 300 rpm, discharge amount =
Evacuated under reduced pressure at the vent portion at 15 kg / hr. Table 1 shows the evaluation results and the extrusion results of the obtained resin.

[0022]

[Example 2] The stearyl acrylate of Example 1 was mixed with 0.
The same procedure as in Example 1 was carried out except that the amount was changed to 5 parts by weight. The evaluation results of the obtained resin are shown in Table 1.

[0023]

Example 3 The stearyl acrylate of Example 1 was added to 5.
The same procedure as in Example 1 was carried out except that the amount was changed to 0 part by weight. The evaluation results of the obtained resin are shown in Table 1.

[0024]

Comparative Example 1 The procedure of Example 1 was repeated except that the stearyl acrylate of Example 1 was changed to non-added. The evaluation results of the obtained resin are shown in Table 1.

[0025]

Example 4 The procedure of Example 1 was repeated, except that the amount of maleic anhydride used in Example 1 was changed to 0.5 part by weight. The evaluation results of the obtained resin are shown in Table 1.

[0026]

Example 5 The procedure of Example 1 was repeated except that the amount of maleic anhydride used in Example 1 was changed to 1.0 part by weight. The evaluation results of the obtained resin are shown in Table 1.

[0027]

Example 6 The procedure of Example 1 was repeated except that the amount of maleic anhydride used in Example 1 was changed to 4.0 parts by weight. The evaluation results of the obtained resin are shown in Table 1.

[0028]

Example 7 The PPE of Example 1 was treated with A-2: intrinsic viscosity of 0.
Except for changing to 65 (measured in chloroform at 25 ° C.), the same procedure as in Example 1 was carried out, and the evaluation results of the obtained resin are shown in Table 1.

[0029]

Example 8 The procedure of Example 7 was repeated except that the amount of stearyl acrylate in Example 7 was changed to 5 parts by weight.
The evaluation results of the obtained resin are shown in Table 1.

[0030]

Example 9 The stearyl acrylate of Example 7 was used in 10 parts.
The same procedure as in Example 7 was carried out except that the amount was changed to parts by weight. The evaluation results of the obtained resin are shown in Table 1.

[0031]

Comparative Example 2 The procedure of Example 7 was repeated except that the stearyl acrylate of Example 7 was changed to non-added. The evaluation results of the obtained resin are shown in Table 1.

[0032]

Example 10 The procedure of Example 2 was repeated except that the PPE of Example 2 was changed to A-3: intrinsic viscosity 0.40 (measured in chloroform at 25 ° C.). The evaluation results of the resin are shown in Table 2.

[0033]

Example 11 The procedure of Example 10 was repeated except that the amount of stearyl acrylate in Example 10 was changed to 2.0 parts by weight. The evaluation results of the obtained resin are shown in Table 2.

[0034]

Example 12 The procedure of Example 10 was repeated except that the PPE of Example 10 was changed to A-4: intrinsic viscosity 0.32 (measured in chloroform at 25 ° C.). The evaluation results of the resin are shown in Table 2.

[0035]

Example 13 The procedure of Example 12 was repeated except that the amount of stearyl acrylate in Example 12 was changed to 2.0 parts by weight. The evaluation results of the obtained resin are shown in Table 2.

[0036]

Example 14 40 parts by weight of the modified polyphenylene ether resin obtained in Example 1 and a polystyrene resin (D-1:
Asahi Kasei Polystyrene H8117) 60 parts by weight, ZSK
A resin composition was obtained by melt-kneading with a -25 twin-screw extruder (manufactured by W & P Co., Ltd.). The basic conditions of extrusion are as follows: barrel temperature = 280 ° C., screw rotation speed = 300 rpm, discharge rate = 20 Kg / Hr, and degassing under reduced pressure at the vent. Table 3 shows the evaluation results of the obtained resin composition.

[0037]

COMPARATIVE EXAMPLE 3 The procedure of Example 14 was repeated, except that the modified polyphenylene ether resin used in Example 14 was changed to that obtained in Comparative Example 1. Table 3 shows the evaluation results of the obtained resin composition.

[0038]

Comparative Example 4 The same procedure as in Example 14 was repeated except that the modified polyphenylene ether resin used in Example 14 was changed to that obtained in Comparative Example 1 and 2.0 parts by weight of stearyl acrylate was newly added. did. Table 3 shows the evaluation results of the obtained resin composition.

[0039]

Example 15 40 parts by weight of the modified polyphenylene ether resin obtained in Example 1 and an acrylonitrile-butadiene-styrene copolymer (D-2: styrac ABS2
00) 60 parts by weight of ZSK-25 twin-screw extruder [W & P
Manufactured by Co., Ltd.] was used to obtain a resin composition.
The basic conditions of extrusion are as follows: barrel temperature = 280 ° C., screw rotation speed = 300 rpm, discharge rate = 20 Kg / Hr, and degassing under reduced pressure at the vent. Table 3 shows the evaluation results and the extrusion results of the obtained resin composition.

[0040]

Comparative Example 5 The procedure of Example 15 was repeated, except that the modified polyphenylene ether resin used in Example 15 was changed to that obtained in Comparative Example 1. Table 3 shows the evaluation results of the obtained resin composition.

[0041]

Comparative Example 6 The same procedure as in Example 15 was carried out except that the modified polyphenylene ether resin used in Example 15 was changed to that obtained in Comparative Example 1 and 2.0 parts by weight of stearyl acrylate was newly added. did. Table 3 shows the evaluation results of the obtained resin composition.

[0042]

Example 16 50 parts by weight of the modified polyphenylene ether resin obtained in Example 1 and a polyamide resin (Leona 13
00S) 50 parts by weight of ZSK-25 twin screw extruder [W &
P Co., Ltd.] was used for melt kneading to obtain a resin composition. The basic conditions of extrusion are as follows: barrel temperature = 280 ° C., screw rotation speed = 300 rpm, discharge rate = 20 Kg / Hr, and degassing under reduced pressure at the vent. Table 3 shows the extrusion results of the obtained resin composition.

[0043]

Comparative Example 7 The procedure of Example 16 was repeated except that the modified polyphenylene ether resin used in Example 16 was changed to that obtained in Comparative Example 1. Table 3 shows the extrusion results of the obtained resin composition.

[0044]

Comparative Example 8 The same procedure as in Example 16 was repeated except that the modified polyphenylene ether resin used in Example 16 was changed to that obtained in Comparative Example 1 and 2.0 parts by weight of stearyl acrylate was newly added. did. Table 3 shows the evaluation results of the obtained resin composition.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

INDUSTRIAL APPLICABILITY The modified polyphenylene ether resin of the present invention has significantly suppressed silver streaks as compared with the conventional ones, and is not only an important material as a raw material for polymer alloys, but also excellent in its electrical conductivity. It is also a useful material for E & E applications such as printed circuit boards due to its mechanical characteristics.

Claims (2)

[Claims] 1. A polyphenylene ether resin (A) 10
0 parts by weight, (B) carbon-carbon double bond or carbon-carbon triple bond in the molecular structure and (b) carboxylic acid group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group 0.1 to 5 parts by weight of a compound having an epoxy group, an amino group or a hydroxyl group at the same time, and (C) at least one vinyl compound selected from mono- and / or diacrylic acid esters, mono- and / or dimethacrylic acid esters A method for producing a modified polyphenylene ether resin, which comprises melt-kneading 0.1 to 20 parts by weight. 2. A composition of a modified polyphenylene ether resin obtained by the method according to claim 1 and a thermoplastic resin (D).