JP2000154290A - Stabilized resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in flowability, heat stability, and resistances to heat, impact, hot water, and chemicals by compounding a resin composition comprising a polyphenylene ether resin and a styrene resin with specified amounts of a benzofuranone compound and a metal sulfide. SOLUTION: 100 pts.wt. resin composition comprising 10-95 pts.wt. polyphenylene ether resin and 5-90 pts.wt. styrene resin is compounded with 0.01-3 pts.wt. benzofurone compound of the formula and 0.05-5 pts.wt. ingredient comprising a metal sulfide alone or together with a metal oxide and then thermally melt kneaded at 230-360 deg.C. In the formula, R1 is unsubstituted 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, hydroxyl, amino, 1-4C alkylamino, phenylamino, or a group of formula II; R2 to R5 are each H, hydroxyl, 1-25C alkyl, 7-9C phenylalkyl, unsubstituted 5-8C cycloalkyl, 1-18C alkoxy, or the like; and R6 to R9 are each H, hydroxyl, 1-18C alkyl, 1-18C alkoxy, 1-18C alkylthio, 3-4C alkynyloxy, phenyl, bonzoyl, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an excellent impact resistance,
The present invention relates to a resin composition having heat stability, hot water resistance, and chemical resistance.

[0002]

2. Description of the Related Art Polyphenylene ether resin compositions have properties such as excellent mechanical properties, electrical properties, acid resistance, alkali resistance, heat resistance, etc., and low water absorption and good dimensional stability. It is also environmentally friendly because it is easily flame-retardant without the use of halogenated compounds.
It is widely used as interior and exterior parts of automobiles, parts for water supply and drainage, OA equipment housing for computers and word processors, chassis materials, and the like.

[0003] Polyphenylene ether resin alone does not have good fluidity and impact resistance.
As shown in JP-A-83435 and JP-B-54-20537, it is used as a polymer blend composition with polystyrene, and is generally called a modified PPE.

Polyphenylene ether-based resin compositions are often processed at relatively high temperatures and used at high temperatures due to their characteristics. However, they have properties such as heat resistance during high-temperature processing and impact resistance due to acid value deterioration of practical molded products. Since the deterioration of the physical properties occurs, many stabilization techniques for improving the heat and acid value deterioration have been conventionally proposed. JP-B-54-20536 discloses inorganic sulfides and organic phosphites, JP-B-56-22909 describes alkanolamines, inorganic sulfides and metal oxides, and JP-A-2-255758 describes specific organic phosphites. A stabilized polyphenylene ether-based resin containing a specific phenolic stabilizer is disclosed.

[0005]

DISCLOSURE OF THE INVENTION The present invention is excellent in balance of fluidity, heat resistance, impact resistance, etc., and has excellent heat stability,
An object of the present invention is to obtain a stabilized polyphenylene ether-based resin composition having hot water resistance and chemical resistance.

[0006]

Means for Solving the Problems As a result of intensive studies on the technology for achieving the above-mentioned object, the present inventors have found that it becomes possible by blending a specific stabilizing agent with a polyphenylene ether-based resin. completed.

[0007] That is, the present invention relates to a method for preparing a total amount of (A) a polyphenylene ether resin and (B) a styrene-based resin.
The benzofuranone compound (C) was added in an amount of 0.1 part by weight based on 0 part by weight.
A stable resin composition comprising 0.1 to 3 parts by weight, and 0.05 to 5 parts by weight of (D) a metal sulfide or a metal sulfide and a metal oxide, and has fluidity, heat resistance, and impact resistance. Provided is a polyphenylene ether-based resin composition which is not only excellent in balance but also excellent in heat stability, hot water resistance and chemical resistance.

The polyphenylene ether resin (A) of the present invention is a homopolymer or a copolymer having a repeating unit represented by the general formula (III) and / or (IV).

[0009]

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[0010]

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(Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆
Independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen. However, R ₅ and R ₆ are not simultaneously hydrogen. A typical example of the homopolymer of the polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene).
Ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6-diethyl-1,4-
Phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) etherpoly (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, and homo (poly (2-methyl-6-chloroethyl-1,4-phenylene) ether) Polymers.

Among them, poly (2,6-dimethyl-1,1)
4-phenylene) ether is preferred.
Nos. 2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit described in JP-A-01222 and the like as a partial structure. Containing polyphenylene ethers are particularly preferred.

Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main unit. Examples thereof include copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol,
Copolymer of 2,6-dimethylphenol and o-cresol or 2,6-dimethylphenol and 2,3,6
-Copolymers with trimethylphenol and o-cresol.

In the present invention, a part or all of the polyphenylene ether resin may be used as described in JP-A-2-276823, JP-A-63-108059, and JP-A-59-5.
It can be used in place of polyphenylene ether modified with a compound having a carbon-carbon double bond described in JP-A-9724 and the like.

The styrene resin (B) of the present invention is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.

Specific examples of styrene compounds include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, pt
tert-Butylstyrene, ethylstyrene and the like can be mentioned, and styrene is most preferable. Examples of the compound copolymerizable with the styrene compound include methacrylic esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used together with styrenic compounds. The amount of the copolymerizable compound to be used is preferably 20% by weight or less, more preferably 15% by weight or less, based on the total amount with the styrene compound.

Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, and an ethylene-propylene copolymer rubber. Specifically, polybutadiene and a styrene-butadiene copolymer are particularly preferred. When an unsaturated rubbery polymer is used, it is preferable to use a partially hydrogenated rubber.

Particularly preferred as the styrene resin are polystyrene and rubber-modified polystyrene.

The benzofuranone compound (C) used in the present invention has the general formula (I):

[0020]

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Wherein R ₁ is unsubstituted or C ₁ -C 4 alkyl, C ₁ -C 4 alkoxy, C ₁ -C 4 alkylthio,
A hydroxy group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a phenylamino group, or R ₁ has the general formula (II)

[0022]

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Wherein R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 25 carbon atoms, an alkyl group having 7 to 9 carbon atoms, Phenylalkyl group, unsubstituted carbon atom 5
To 8 cycloalkyl groups, 1 to 18 carbon atoms
Represents an alkoxy group, an alkylthio group having 1 to 18 carbon atoms and an alkylamino group having 1 to 4 carbon atoms. In the general formula (II), R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms.
R ₁₀ represents an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, an alkenyloxy group having 3 to 4 carbon atoms, an alkynyloxy group having 3 to 4 carbon atoms, a phenyl group, a benzoyl group or a benzoyloxy group; Represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a phenyl group, or a cyclohexyl group. ).

The production method and specific examples of (C) the benzofuranone compound are described in JP-A-7-233160, and 5,7-di-tert-butyl-3-.
Preferred are mixtures with (3,4-di-methyl-phenyl) -3H-benzofuran-2-one and its isomers,
Commercially available from Ciba Specialty Chemicals Co., Ltd.

In the present invention, (C) the benzofuranone compound is used in an amount of 0.01 parts by weight based on 100 parts by weight of the total amount of (A) the polyphenylene ether resin and (B) the styrene resin.
About 3 parts by weight, preferably about 0.05 to 1 part by weight.

Examples of the metal sulfide (D) used in the present invention include sodium sulfide, potassium sulfide, lithium sulfide, calcium sulfide, barium sulfide, titanium sulfide, zinc sulfide, and iron sulfide. Is zinc sulfide. Generally, the range of the metal sulfide used in the composition of the present invention is about 0.05 to 5 parts by weight based on 100 parts by weight of the total amount of (A) the polyphenylene ether resin and (B) the styrene resin. 0.1 to 2 parts by weight are preferred.

Examples of the metal oxide used together with the metal sulfide (D) used in the present invention include calcium oxide, magnesium oxide, barium oxide, zinc oxide, titanium dioxide, etc., and preferably zinc oxide. It is. In general, the range of the metal sulfide used in the composition of the present invention is 0.05 to 100 parts by weight of the total amount of (A) the polyphenylene ether resin and (B) the styrene resin.
It is about 5 parts by weight, preferably 0.1 to 2 parts by weight.

The stabilized resin composition of the present invention can provide a flame-retardant resin having excellent thermal oxidation stability by appropriately containing a generally used flame retardant. As the flame retardant, a halogen-based flame retardant can be used, but a phosphate ester-based flame retardant is preferably used from an environmental point of view. Here, the phosphoric ester-based flame retardant refers to all phosphoric ester compounds effective for improving flame retardancy. For example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, Phosphoric acid esters such as dimethylethyl phosphate, methyldibutylphosphate, ethyldipropylphosphate, hydroxyphenyldiphenylphosphate, compounds modified with these various substituents, and various condensed type phosphoric acid ester compounds. Ester compounds are preferred.

Of these, the phosphate compound represented by the general formula (V) is particularly preferred.

[0030]

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(Wherein Q1, Q2, Q3, and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen;
2, R3 and R4 represent a methyl group or hydrogen. n is 1
N1 and n2 represent integers from 0 to 2;
1, m2, m3, and m4 each represent an integer of 1 to 3. )
Is represented by

In the general formula (V), Q1, Q2, Q3,
Particularly preferred among Q4 is hydrogen or a methyl group.

In formula (V), R1 and R2 are preferably hydrogen, and R3 and R4 are preferably a methyl group.

In the general formula (V), n is an integer of 1 or more, and heat resistance and workability vary depending on the number. The preferred range of n is 1-5. Further, the phosphoric ester may be a mixture of n-mers.

A preferred phosphate compound has a bonding structure with “specific bifunctional phenol” and a terminal structure with “specific monofunctional phenol”.

"Specific bifunctional phenols" include:
2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy- 3,5-
Bisphenols such as, but not limited to, dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane. Particularly, bisphenol A is preferable.

As the “specific monofunctional phenol”, unsubstituted phenol, monoalkylphenol, dialkylphenol, and trialkylphenol can be used alone or as a mixture of two or more. Especially phenol, cresol, dimethylphenol (mixed xylenol),
2,6-dimethylphenol and trimethylphenol are preferred.

These phosphorus compounds can be used alone or in combination of two or more. It is also effective to use a flame retardant other than the phosphoric acid ester compound, and a combination of polytetrafluoroethylene, a silicone resin, a phenol resin, glass fiber, carbon fiber, and the like as a dripping inhibitor.

The amount of the phosphate ester flame retardant is as follows:
It is used in an amount of about 2 to 30 parts by weight, preferably about 4 to 15 parts by weight, based on 100 parts by weight of the total of (A) polyphenylene ether resin and (B) styrene resin.

The stabilized resin composition of the present invention is blended with an inorganic filler such as glass fiber, glass flake, kaolin clay, talc and the like, and other fibrous reinforcing agents, etc. to provide a high flowability and a high heat resistance. A strength composite can be obtained. Also,
Styrene-based thermoplastic elastomer as impact modifier,
For example, styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated elastomers thereof are preferably used.

To the stabilizer resin composition of the present invention, other additives, for example, a plasticizer, an antioxidant other than the above, and the like, for imparting other properties or within the range not impairing the effects of the present invention. Stabilizers such as ultraviolet absorbers, antistatic agents, release agents, dyes and pigments, and other resins can be added.

The method for producing the composition of the present invention is not particularly limited, and the composition can be kneaded and manufactured using a kneader such as an extruder, a heating roll, a kneader, and a Banbury mixer. Among them, kneading with an extruder is preferable in terms of productivity. The kneading temperature is in the range of 230 to 360 ° C,
Preferably it is the range of 240-320 degreeC.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

The physical properties of the obtained resin composition were evaluated by the following methods and conditions.

(1) Izod Impact Strength According to ASTM D256, 23 notched test pieces were used.
Measured in ° C.

(2) Heat Exposure Property A 3.2 mm thick notched Izod impact test piece based on ASTM D256 was placed in a hot air circulating thermostat at 120 ° C. and exposed. After exposure for 500 hours, the test piece was taken out, and after conditioning for 24 hours at 23 ° C., the Izod impact strength was measured, and the retention rate (expressed in%) with respect to the Izod impact strength before exposure was calculated.

(3) Hot water After being kept in hot water at 90 ° C. for 1000 hours,
After adjusting the condition for 4 hours, measure the Izod impact strength,
The retention rate (expressed in%) with respect to the Izod impact strength before exposure was calculated.

(4) Chemical Resistance Tensile strength based on ASTM D638 was measured.
Further, the test piece is set on a bending bar having a curvature of 1% strain, and immersed in a mixed solution of isopropyl alcohol and cyclohexane (weight ratio 60/40) at 23 ° C. for 30 minutes. Next, the tensile strength of the test piece removed from the bending bar was measured, and the strength retention was calculated.

(5) Flame retardancy Based on the UL-94 vertical flame test, the flame retardancy was measured using a 1/16 inch thick injection molded test piece. As for the flame retardancy level, V-0 is the best, and becomes worse as the rank becomes V-1 or V-2.

The main components used in Examples and Comparative Examples were as follows.

(1) Polyphenylene ether resin PPE-1: ηs measured with a chloroform solution at 30 ° C.
poly-2,6-dimethyl-1,4- having a p / c of 0.54
Phenylene ether (2) Styrene resin PS-1: Asahi Kasei Kogyo Co., Ltd. high impact polystyrene, Asahi Kasei Polystyrene H8117 PS-2: Asahi Kasei Kogyo Co., Ltd. homopolystyrene, Asahi Kasei Polystyrene 685 PS-3: Asahi Kasei Kogyo Co., Ltd. Homopolystyrene, Asahi Kasei polystyrene G8102 (3) As a benzofuranone compound, HP-136 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Was used.

Example 1 With respect to 100 parts by weight of a resin component containing 45 parts by weight of PPE-1, 45 parts by weight of PS-1 and 10 parts by weight of PS-2, 0.1 part of HP-136 as a stabilizer was added. 15 parts by weight,
A heating cylinder having a composition of 0.6 parts by weight of organic phosphite (trade name: IRGAFOS 168, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.2 parts by weight of zinc sulfide, and 0.2 parts by weight of zinc oxide Was supplied to a twin-screw extruder having a screw diameter of 25 mm and the maximum temperature was set to 320 ° C., and was melt-kneaded at a screw rotation speed of 300 rpm to obtain resin composition pellets. Next, the resin composition pellets were subjected to a cylinder temperature of 290 ° C. and a mold temperature of 8
Injection molding was performed using an injection molding machine set at 0 ° C. and a mold clamping pressure of 80 tons, and evaluation of molding fluidity and physical properties were performed using the obtained molded pieces. The results are shown in Table 1.

[0053]

Comparative Example 1 Melting and kneading were performed in the same manner as in Example 1 except that zinc sulfide and zinc oxide were not used, and the physical properties were evaluated. The results shown in Table 1 were obtained.

[0054]

Comparative Example 2 In Example 1, except that HP-136 was not contained, the mixture was melted and kneaded in the same manner as in Example 1, and the physical properties were evaluated. The results shown in Table 1 were obtained.

[0055]

COMPARATIVE EXAMPLE 3 Melting and kneading were carried out in the same manner as in Example 1 except that HP-136 and organic phosphite were not used, and the physical properties were evaluated. The results shown in Table 1 were obtained.

[0056]

Example 2 40 parts by weight of PPE-1 and 40 parts by weight of PS-1
10 parts by weight of the resin component and 20 parts by weight of PS-3
19 parts by weight of a phosphate ester-based flame retardant (CR741C, manufactured by Daihachi Chemical Co., Ltd.), 0.15 parts by weight of HP-136 as a stabilizer, and organic phosphite (Ciba Special) The composition of 0.6 parts by weight of trade name (IRGAFOS 168, manufactured by Tea Chemicals Co., Ltd.), 0.2 parts by weight of zinc sulfide and 0.2 parts by weight of zinc oxide. The mixture was supplied to a twin screw extruder having a set screw diameter of 25 mm, and was melt-kneaded at a screw rotation speed of 300 rpm to obtain a resin composition pellet. Next, the resin composition pellets were subjected to injection molding using an injection molding machine with a mold clamping pressure of 80 tons set at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. The physical properties were evaluated. The results are shown in Table 1.

[0057]

Comparative Example 4 In Example 2, the stabilizer was changed to organic phosphite (Ciba Specialty Chemicals Co., Ltd.)
(Trade name: IRGAFOS 168) and 0.6 parts by weight of a phenolic stabilizer (Ciba Specialty Co., Ltd.)
Chemicals Co., Ltd., trade name IRGANOX 565)
Except that the amount was changed to 0.4 part by weight, melt kneading was performed in the same manner as in Example 1 to evaluate the physical properties, and the results in Table 1 were obtained.

[0058]

[Table 1]

[0059]

The resin composition of the present invention provides a material which is remarkably superior in stability as compared with conventional polyphenylene ether-based resins, and which has excellent moldability, mechanical properties and heat resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5:15 3:30) (C08K 13/02 5:15 3:30 3:22)

Claims (5)

[Claims] 1. A total of 100 parts by weight of (A) a polyphenylene ether resin and (B) a styrene-based resin, and (C) a compound represented by the following general formula (I): (Wherein R ₁ is unsubstituted or has 1 to 4 carbon atoms)
An alkyl group, an alkoxy group having 1 to 4 carbon atoms,
An alkylthio group having 1 to 4 carbon atoms, a hydroxy group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a phenylamino group, or R ₁ has the general formula (II): Wherein R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 25 carbon atoms, or a phenylalkyl having 7 to 9 carbon atoms. Group, an unsubstituted cycloalkyl group having 5 to 8 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, and an alkylamino group having 1 to 4 carbon atoms. In the general formula (II), R ₆ , R ₇ , R ₈ , and R ₉ each independently represent a hydrogen atom, a hydroxy group, a carbon atom of 1 to 18;
Alkyl group having 1 to 18 carbon atoms, alkylthio group having 1 to 18 carbon atoms, alkenyloxy group having 3 to 4 carbon atoms, alkynyloxy group having 3 to 4 carbon atoms, phenyl group, benzoyl R ₁₀ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkylthio group having 1 to 18 carbon atoms, a phenyl group, or a cyclohexyl group. The benzofuranone compound represented by
And (D) 0.05 to 5 parts by weight of a metal sulfide or a metal sulfide and a metal oxide. 2. (A) Polyphenylene ether resin 10
2. The stabilized resin composition according to claim 1, comprising from about 95 parts by weight to about 95 parts by weight of the styrene resin (B). 3. The method according to claim 1, wherein (A) the polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene) ether, and (B) the styrene resin is polystyrene. Resin composition. 4. The method according to claim 1, wherein the benzofuranone compound (C) is 5,7-
Di-tert-butyl-3- (3,4-di-methyl-
The stabilized resin composition according to claim 1, which is (phenyl) -3H-benzofuran-2-one. 5. The stabilized resin composition according to claim 1, wherein (D) the metal sulfide and the metal oxide are zinc sulfide and zinc oxide, respectively.