JPH06256642A - Lightweight reinforced resin composition - Google Patents

Abstract

PURPOSE:To obtain a lightweight high-rigidity composition having properties such as heat resistance, low water absorptivity and electrical properties characteristics of polyphenylene ether resin (PPE resin) by mixing a resin composition comprising a PPE resin, a styrenic resin and/or a block copolymer and a flame retardant with specified microballoons. CONSTITUTION:This resin composition is obtained by adding 5-100 pts.wt. microballoons (e.g. glass balloons or pumicious balloons) having a means particle diameter of 100mum or below, a true specific gravity of 0.35g/cm<3> or above and a 10% volume contraction strength of 200kg/cm<2> or above to a resin composition comprising 5-95wt.% PPE resin, 95-5wt.% styrenic resin and/or block copolymer (e.g. a copolymer comprising at least one styrenic polymer block and at least one olefinic elastomer block) in an amount of 30wt.% or below based on the total weight of these resins and copolymer, and 0-50wt.% flame retardant (e.g. aromatic phosphoric ester or red phosphorus).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lightweight and highly rigid polyphenylene ether resin composition.

[0002]

2. Description of the Related Art Heretofore, there have been widely practiced methods of filling a hollow hollow sphere with a thermosetting resin to reduce its weight, improve its rigidity and impart heat resistance. For example, by blending with an epoxy resin or an unsaturated polyester resin, weight reduction, dimensional stability and machinability have been improved. On the other hand, when compounded with a thermoplastic resin, most of the micro hollow spheres are subjected to a large shear force in the process of extrusion and molding, so most of them are crushed, and it is difficult to achieve weight reduction and resin reinforcement in the actual situation. is there. The following techniques have been disclosed as the composition of the thermoplastic resin and the hollow microspheres. Compositions with polyvinyl chloride (JP-A-57-195761) and compositions with polyolefin resins (JP-A-60-
No. 158239, JP-A No. 01-294751), and a composition with a thermoplastic resin (polybutylene terephthalate, polyoxymethylene) (JP-A-61-2368).
59), a composition with a liquid crystal polyester (Japanese Patent Laid-Open No. Sho 6-66).
4-74258) and the like have been proposed. As a technique close to the present invention, a composition with a styrene-based resin (Japanese Patent Application Laid-Open Nos. 04-23848 and 23049) has been proposed, but since the base resin is polystyrene or ABS resin, the features other than weight reduction are unacceptable. Further, as a technique for preventing the crushing of fine hollow spheres in the extrusion step, a method of adding hollow glass spheres to a resin in a molten state using a specific extruder has been disclosed (JP-A-63-63).
278967), it is stated that the effect of the invention can be mixed without extremely destroying the hollow glass material, but there is no description of the hollow glass spheres actually used in the examples, and the specific destruction rate The effect is not clear because it is not illustrated.

On the other hand, the polyphenylene ether resin is a resin having excellent heat resistance, electrical characteristics, acid resistance, alkali resistance, etc., and also having low specific gravity and low water absorption. Known as.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors in order to achieve the above-mentioned object, the polyphenylene ether resin is blended with specific micro hollow spheres to make the polyphenylene ether resin lightweight and highly rigid. It was found that a composition was obtained, and the present invention was completed based on this finding.

That is, the present invention provides: (a) polyphenylene ether resin 5 to 95% by weight (b) styrene resin and / or block copolymer
0 to 95% by weight (however, the block copolymer is (a) +
(30% by weight or less of (b)) (c) Flame retardant relative to 100 parts by weight of a resin composed of 0 to 50% by weight (d) Average particle diameter of 100 μm or less, true specific gravity of 0.35 g /
cm ³ or more, 10% volume reduction strength is 200 kg / cm ²
A lightweight reinforced resin composition comprising 5 to 100 parts by weight of the above hollow microspheres.

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

[0007]

[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 structural unit has 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 conventionally proposed to be present in the polyphenylene ether resin may be used unless they are contrary to the gist of the present invention. It may be included as a partial structure. As an example of what is proposed to coexist in a small amount, Japanese Patent Application No. 63-1
2- (dialkylaminomethyl) -6 described in JP-A-2698 and JP-A-63-301222.
-Methylphenylene ether unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like.

Further, a polyphenylene ether resin in which a small amount of diphenoquinone or the like is bound in the main chain is also included.
Further, for example, JP-A-2-276823 and JP-A-63-
It also includes polyphenylene ether modified with a compound having a carbon-carbon double bond described in 108059, JP-A-59-59724 and the like. The amount of the polyphenylene ether-based resin of the present invention used is preferably 5 to 100% by weight of the resin component, and if it is 5% by weight or less, heat resistance and rigidity are not improved, which is not desirable.

The styrene resin used as the component (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. Is. The styrene compound is represented by the general formula (2),

[0013]

[Chemical 2]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5). Means a compound. Specific examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like. The compounds copolymerizable with styrene compounds include "methacrylic acid esters such as methyl methacrylate and ethyl methacrylate", "unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile", and acid anhydrides such as maleic anhydride. And the like, which are used together with the styrene compound. The rubbery polymer that can coexist during the polymerization is a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, a partially hydrogenated product of these, or ethylene-
Examples thereof include propylene copolymer rubber.

The method for producing the styrene resin of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization well known to those skilled in the art may be used. The block copolymer used in accordance with the component (b) of the present invention is a block copolymer composed of at least one styrene block polymer and at least one olefin elastomer block. The styrene-based polymer block referred to in the present invention is specifically represented by the general formula (3),

[0016]

[Chemical 3]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5) Is a polymer or copolymer block derived from The olefin elastomer block referred to in the present invention includes monoolefins such as ethylene, propylene, 1-butene and isobutylene, conjugated diolefins such as butadiene, isoprene and 1,3-pentadiene, 1,4-hexadiene and norbornene derivatives. A polymer block having a form in which one or more olefin compounds selected from non-conjugated diolefins are polymerized or copolymerized, and the unsaturation degree of the block is 20% or less. Therefore, when the above diolefins are used as the constituent monomers of the olefin elastomer block, the degree of unsaturation of the block portion is 2
Measures to reduce the degree of unsaturation, such as hydrogenation, must be taken to the extent that it does not exceed 0%. Further, a styrene compound may be randomly copolymerized with the olefin elastomer block.

As the flame retardant used in the component (d) of the present invention, aromatic phosphates, red phosphorus, aromatic halides, nitrogen compounds typified by melamine, antimony trioxide and the like are effective. Aromatic phosphate esters and red phosphorus are preferred. Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris (isopropylphenyl) phosphate, octyl diphenyl phosphate, and high molecular weight aromatic phosphorus described in JP-A-54-23493. Acid esters and Japanese Patent Application No. 4-22958
Examples thereof include bisphenol-A-polyphosphate described in No. 1. The amount of these used is preferably in the range of 0 to 50% by weight. If it is used in an amount exceeding 50% by weight, the heat resistance will be impaired, which is not preferable.

The hollow microspheres used in the component (d) of the present invention are generally shirasu balloons, glass balloons,
Known as carbon balloons and the like. Of these, glass balloons are the most excellent in terms of strength and economy.
Known glass balloons include "Scotchlight (trademark)" Glass Bubbles manufactured by Sumitomo 3M Co., Ltd., Cellstar (trademark) manufactured by Asahi Glass Co., Ltd., and glass microballoon manufactured by Fuji Devison Chemical Co., Ltd. Although these glass balloons have various properties, in the present invention, the average particle diameter is 100 μm or less and the true specific gravity is 0.35 g / cm ³
As described above, a material having a 10% volume reduction strength of 200 Kg / cm ² or more is preferable. The reason is that the average particle size and the true specific gravity are closely related to the fracture strength, and those that deviate from this specification are preferable because the strength is insufficient and stable physical properties cannot be obtained even when used for injection molding applications. Absent. Further, these glass balloons may be treated with a coupling agent such as an aminosilane type, a glycidsilane type and an acrylsilane type, and it is rather preferable. The fine hollow spheres in the present invention are preferably blended in an amount of 5 to 100 parts by weight when the resin component is 100 parts by weight. If the amount is less than 5 parts by weight, the weight is insufficient and the reinforcing effect is insufficient. If the amount exceeds 100 parts by weight, the volume of the dispersed phase increases and the fluidity is significantly reduced, which is not preferable.

Other additives to the composition of the present invention, such as:
A plasticizer, a stabilizer, an ultraviolet absorber, a colorant, a release agent and a fibrous reinforcing agent such as glass fiber and carbon fiber, and a filler such as glass beads, calcium carbonate and talc can be added. As the stabilizer, phosphites,
The hindered phenols, sulfur-containing antioxidants, alkanolamines, acid amides, metal salts of dithiocarbamic acid, inorganic sulfides and metal oxides can be used alone or in combination.

Any method may be used for mixing the components constituting the present invention, and for example, an extruder, a heating roll, a Banbury mixer, a kneader or the like may be used. However, as is generally carried out in the step of blending the resin and the glass fiber, the method of blending with the resin in the molten state is a preferable method in that the crushing of the hollow microspheres is minimized.

[0022]

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) Polyphenylene ether resin a-1: Intrinsic viscosity 0.50 (measured in chloroform at 30 ° C.) poly (2,6-dimethyl-1.4-phenylene) ether a-2: Intrinsic viscosity 0.40 Poly (2,6-dimethyl-1.4-phenylene) ether (measured in chloroform at 30 ° C.) (b) Styrene resin, block copolymer b-1: Asahi Kasei Polystyrene 685 Asahi Kasei Kogyo KK b-2: Asahi Kasei Polystyrene H8117 manufactured by Asahi Kasei Kogyo Co., Ltd. b-3: Tuftec H1271 manufactured by Asahi Kasei Kogyo Co., Ltd. (c) Flame retardant c-1: CR733S manufactured by Daihachi Chemical Co., Ltd. c-2: CR741C Daihachi. Chemical Industry Co., Ltd. (d) Micro hollow spheres are shown in Table 1.

The physical property evaluation conditions and methods are as follows. (1) Heat distortion temperature Based on ASTM D648, a load of 18.6 Kg / cm
Measured at ² . (2) Melt flow rate Based on JIS K-7210, temperature 250 ° C, load 1
Measured at 0 kg.

(3) Izod impact strength Measured according to ASTM D256 at a temperature of 23 ° C. and with a notch. (4) Flexural modulus Measured at a temperature of 23 ° C. based on ASTM D790. (5) Flame retardance Based on UL standard 94, measured with a 1/16 inch test piece.

(6) Density An electron specific gravity meter ED-120T (marketed by Mirage Trading Co., Ltd.) was used for measurement. (7) Fragmentation rate of micro hollow spheres The ratio of the weight of the crushed micro hollow spheres to the weight of the added micro hollow spheres was shown (% by weight), and was calculated from the density and the content of the micro hollow spheres. .

[0026]

Example 1 Intrinsic viscosity 0.50 (in chloroform, 30
35 parts of poly (2,6-dimethyl-1.4-phenylene) ether (hereinafter abbreviated as PPE) (measured at C), polystyrene (Asahi Kasei Co., Ltd., trade name: Asahi Kasei Polystyrene 685) 45 parts, And 0.1 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer and tris (2,4-
0.2 parts of di-t-butylphenyl) phosphite were mixed. This mixture was added to a ZSK-25 twin screw extruder [W & P
8kg / hr from the main feeder
And at the same time, 2 Kg / Hr of fine hollow glass spheres (Table 1, d-1) were fed from a side feeder and melt-kneaded at a temperature of 330 ° C. to obtain a resin composition.
A molding test piece was prepared from the obtained resin composition using an injection molding machine IS-80C (manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 330 ° C and a mold temperature of 90 ° C. The physical properties were evaluated using this test piece. The results and the examples shown below,
The results of the comparative examples are also shown in Table 2.

[0027]

Example 2 A resin composition was obtained by repeating Example 1 except that the micro hollow glass spheres in Example 1 were changed to (Table 1, d-2).

[0028]

Example 3 A resin composition was obtained by repeating Example 1 except that the fine hollow glass spheres in Example 1 were changed to (Table 1, d-3).

[0029]

[Example 4] The resin fed from the main feeder in Example 3 was fed at 7 kg / hr, and the minute hollow glass spheres fed from the side feeder were fed at 3 kg.
Example 3 was repeated, except that the resin composition was changed to / Hr.

[0030]

Example 5 A resin composition was obtained by repeating Example 1 except that the micro hollow glass spheres in Example 1 were changed to (Table 1, d-4).

[0031]

Example 6 The resin fed from the main feeder in Example 5 was fed at 7 kg / hr, and the fine hollow glass spheres fed from the side feeder were fed at 3 kg.
Example 5 was repeated except that / Hr was changed to obtain a resin composition.

[0032]

Comparative Example 1 A resin composition was obtained by repeating Example 1 except that the micro hollow glass spheres in Example 1 were changed to (Table 1, d-5).

[0033]

Comparative Example 2 A resin composition was obtained by repeating Example 1 except that the fine hollow glass spheres in Example 1 were changed to (Table 1, d-6).

[0034]

Comparative Example 3 A resin composition was obtained by repeating Example 1 except that the micro hollow glass spheres in Example 1 were changed to (Table 1, d-7).

[0035]

Comparative Example 4 A resin composition was obtained by carrying out Example 1 without adding the fine hollow glass spheres of Example 1.

[0036]

Example 7 Intrinsic viscosity 0.50 (in chloroform, 30
35 parts of poly (2,6-dimethyl-1.4-phenylene) ether (hereinafter abbreviated as PPE) (measured at C), polystyrene (Asahi Kasei Kogyo KK, trade name: Asahi Kasei Polystyrene 685) 15 parts, Ha Impact Polystyrene (Asahi Kasei Kogyo Co., Ltd., trade name: Asahi Kasei Polystyrene H
8117) 30 parts and octadecyl-3 as stabilizer
0.1 part of-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-t)
0.2 parts of -butylphenyl) phosphite were mixed. This mixture was added to a ZSK-25 twin screw extruder [W & P
8kg / hr from the main feeder
And at the same time, 2 Kg / Hr of fine hollow glass spheres (Table 1, d-1) were fed from a side feeder and melt-kneaded at a temperature of 330 ° C. to obtain a resin composition.
A molding test piece was prepared from the obtained resin composition using an injection molding machine IS-80C (manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 330 ° C and a mold temperature of 90 ° C. The physical properties were evaluated using this test piece.

[0037]

[Example 8] The high impact polystyrene (produced by Asahi Kasei Kogyo Co., Ltd., trade name: Asahi Kasei Polystyrene H8117) in Example 7 was changed to 25 parts, and a block copolymer (produced by Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec) was changed. H12711)
Example 1 was repeated except that 5 parts of was added to obtain a resin composition.

[0038]

Example 9 Intrinsic viscosity 0.50 (in chloroform, 30
48 parts of poly (2,6-dimethyl-1.4-phenylene) ether (hereinafter abbreviated as PPE) (measured at C), polystyrene (Asahi Kasei Kogyo KK, trade name: Asahi Kasei Polystyrene 685) 24 parts, Flame retardant (Dahachi Chemical Industry Co., Ltd.)
Made by trade name: CR733S) 8 parts and as a stabilizer octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 0.1 part, tris (2,4-di-t-butyl). 0.2 parts of phenyl) phosphite were mixed. This mixture was fed at 8 Kg / Hr from the main feeder using a ZSK-25 twin-screw extruder [manufactured by W & P Co., Ltd.], and at the same time, 2 Kg / H from the side feeder to the micro hollow glass spheres (Table 1, d-2).
It was fed at r and melt-kneaded at a temperature of 330 ° C. to obtain a resin composition. The obtained resin composition is injected into an injection molding machine IS-8.
0C (manufactured by Toshiba Machine Co., Ltd.), cylinder temperature 3
Molding test pieces were prepared at 30 ° C and a mold temperature of 90 ° C. The physical properties were evaluated using this test piece.

[0039]

[Example 10] CR741C was used as the flame retardant in Example 9.
Example 9 was repeated except that the resin composition was changed to (Daihachi Chemical Industry Co., Ltd.) to obtain a resin composition.

[0040]

Example 11 Intrinsic viscosity 0.40 (3 in chloroform
10 parts of poly (2,6-dimethyl-1.4-phenylene) ether (measured at 0 ° C.) (hereinafter abbreviated as PPE),
Polystyrene (Asahi Kasei Kogyo KK, trade name: Asahi Kasei Polystyrene 685) 25 parts, Ha impact polystyrene (Asahi Kasei Kogyo KK, trade name: Asahi Kasei Polystyrene H
8117) 45 parts and octadecyl-3 as stabilizer
0.1 part of-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, tris (2,4-di-t)
0.2 parts of -butylphenyl) phosphite were mixed. This mixture was added to a ZSK-25 twin screw extruder [W & P
8kg / hr from the main feeder
At the same time, the fine hollow glass spheres (Table 1, d-2) were fed at 2 Kg / Hr from the side feeder, and melt-kneaded at a temperature of 300 ° C. to obtain a resin composition.
Using the obtained resin composition, an injection molding machine IS-80C (manufactured by Toshiba Machine Co., Ltd.) was used to prepare molding test pieces at a cylinder temperature of 300 ° C and a mold temperature of 90 ° C. The physical properties were evaluated using this test piece.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

The lightweight reinforced resin composition of the present invention is lightweight,
A material that has high rigidity and features such as heat resistance, low water absorption, electrical characteristics, etc., which are the characteristics of polyphenylene ether resin,
It will greatly contribute to the weight reduction of office machines, home appliances, and automobiles.

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Claims (1)

[Claims] 1. A polyphenylene ether resin (a)
5 to 95% by weight, (b) styrene resin and / or block copolymer 95 to 5% by weight (however, the block copolymer is 30% by weight or less of (a) + (b)), (c) difficult (D) Average particle diameter of 100 μm or less, true specific gravity of 0.35 with respect to 100 parts by weight of a resin composed of 0 to 50% by weight of a combustion agent.
g / cm ³ or more, 10% volume reduction strength is 200 kg / c
A lightweight reinforced resin composition comprising 5 to 100 parts by weight of hollow microspheres having a size of m ² or more.