JPH1112457A - Polyphanylene ether resin composition excellent in vibration-damping performance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the vibration-damping performances of flame-retardant and non-flame-retardant resin compositions each containing a polyphenylene ether resin and a polyolefin resin. SOLUTION: There is provided a polyphenylene ether resin composition comprising 40-85 wt.% polyphenylene ether resin (A), a block copolymer (B) consisting of a styrene compound polymer having a number-average molecular weight of 2,500 or above and 5-30 wt.% isoprene polymer block having a vinyl bond content of 40% or above and having a degree of hydrogenation of the residual unsaturations of 5-30 wt.%, 0-20 wt.% polyolefin resin (C) and 0-30 wt.% aromatic phosphoric ester flame retardant, wherein components B and C form a disperse phase, and the dispersed particles having a mean particle diameter in the range of 0.2-3 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyphenylene ether-based resin composition having excellent vibration damping properties.

[0002]

2. Description of the Related Art Polyphenylene ether-based resin compositions are widely used in the fields of home appliances and office machines because of their excellent heat resistance, dimensional stability and electrical properties.

In recent years, attention has been paid to environmental problems such as noise and vibration, so that structural materials are often required to have vibration damping properties.

[0004] On the other hand, in the field of information equipment, a drive unit is required to rotate at a high speed with a large increase in information capacity and processing speed. When the drive unit rotates at a high speed, vibration is naturally likely to occur, and reading errors and malfunctions are likely to occur.

Accordingly, polyphenylene ether-based resins widely used in the fields of home electric appliances, office machines and information equipment naturally require vibration damping properties.

[0006]

Originally, polyphenylene ether-based resins have never been excellent in vibration damping properties.
As a method for improving the vibration damping properties of a polyphenylene ether-based resin, Japanese Unexamined Patent Publication (Kokai) No. Hei 3-181552 discloses an aqueous solution comprising a vinyl aromatic polymer block and isoprene or isoprene-butadiene having a main dispersion peak of tan δ at 0 ° C. or higher. A method of blending a block copolymer with an added or hydrogenated polymer block is disclosed. However, when the unhydrogenated block copolymer is blended, when molded at the molding temperature of the polyphenylene ether-based resin composition, the conjugated double bond undergoes thermal crosslinking, so that a decrease in fluidity or deterioration in appearance occurs. Not practical. Further, when the dispersed particle diameter of the block copolymer resin in the polyphenylene ether-based resin is too small, the vibration damping effect is extremely deteriorated.

JP-A-7-165998 discloses a technique relating to a resin composition containing a block copolymer of a polyphenylene ether resin, a vinyl aromatic polymer block and a hydrogenated isoprene polymer block. ing. However, this technique is intended to obtain a resin composition of a polyphenylene ether-based resin and a polyolefin, and a hydrogenated block copolymer is used for improving the compatibility between the two. . Therefore, this technique does not show an appropriate range of a resin composition having excellent vibration damping properties.

When resin materials are used in the fields of home appliances, office machines and information equipment, flame retardancy is required in most cases. In the case of flame retardation, the use of a halogen compound or antimony trioxide does not meet the demands of the times, and it is environmentally preferable if the flame retardation can be achieved with phosphoric esters. However, it is impossible to make a resin composition in which a polymer of an olefin compound forms a continuous phase flame-retardant with phosphoric esters. Therefore, the range of the technology disclosed in JP-A-7-165998 cannot be properly flame-retarded with phosphoric esters.

Accordingly, an object of the present invention is to provide a flame-retardant and non-flame-retardant resin composition having excellent vibration damping properties which can be effectively used in the fields of home appliances, office machines and information equipment.

[0010]

Means for Solving the Problems The present inventors have made it possible to achieve flame retardancy with a flame retardant that does not adversely affect the environment without reducing the fluidity or deteriorating appearance due to heat, and has excellent vibration damping properties. As a result of intensive studies aimed at obtaining a polyphenylene-based resin composition, a polyphenylene ether-based resin was added with a block copolymer of a styrene-based polymer block and a hydrogenated isoprene polymer block. In addition to having sufficient vibration damping effect and flame retardancy, there is an appropriate range of dispersed particle diameter, and the use of aromatic phosphate ester flame retardant dramatically improves the flame retardant effect. And the use of a polyolefin together to increase the temperature of the main dispersion peak of tan δ, leading to the present invention, and providing a polyphenylene ether-based resin composition having excellent vibration damping properties. It was.

That is, the present invention relates to (A) a polyphenylene ether resin or a polyphenylene ether resin and a polystyrene resin thereof.
Parts by weight, (B) a polymer block of a styrene-based compound and a polymer block of hydrogenated isoprene in which the total content of vinyl bonds is at least 40% and at least 70% of the remaining unsaturated bonds are hydrogenated Block copolymer resin 5
To 30 parts by weight, (C) 0 to 20 parts by weight of a polyolefin resin, and (D) 0 to 30 parts of an aromatic phosphate ester flame retardant
A polyphenylene ether having excellent vibration damping properties, wherein the polyphenylene ether is composed of parts by weight, the component (B) + (C) forms a dispersed phase, and the average diameter of the dispersed particles is in the range of 0.2 to 3 μm. The present invention provides a resin composition.

The present invention will be described in more detail. In the present invention, when the component (C) is not contained, the dispersed particle diameter tends to be small. The addition of the component (C) increases the size of the dispersed particles and also increases the temperature of the main dispersion peak of tan δ, so that the effect of improving the vibration damping property is large. However, if the component (C) is added more than necessary, the dispersed particles become too large to make it flame-retardant, and the rigidity of the molded product decreases.
The range of the dispersed particle diameter in which the effect of improving the vibration damping property is sufficiently exerted and which can be made flame-retardant by using an aromatic phosphate ester-based flame retardant is in the range of 0.2 to 3 μm. The particle diameter of the dispersed phase is represented by an arithmetic mean of the major axis and the minor axis of the dispersed phase obtained from an electron micrograph.

When the components (B) and (C) form a continuous phase, the characteristics of the polyphenylene ether-based resin cannot be exhibited, and even if an aromatic phosphate ester-based flame retardant is used, the flame retardant reaches a required level. It is difficult to convert.

[0014] In the case of flame retardation, even if the components (B) and (C) form a dispersed phase, the purpose of the present invention is to use a phosphoric ester flame retardant other than the aromatic phosphoric ester flame retardant because the flame retardant effect is poor. Cannot be achieved. Only when an aromatic phosphate ester-based flame retardant is used, the flame retardant effect is large because the polyphenylene ether-based resin component tends to be charred, and this char forms a protective film and burns the components (B) + (C). It is presumed to make it difficult to do. It is considered that as the diameter of the dispersed particles composed of the components (B) and (C) increases, the particles cannot be fully protected by the char, so that the flame retardant effect is reduced.

The polyphenylene ether resin as the component (A) of the present invention is represented by the following general formula (1):

[0016]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, hydrogen, etc. ₍₅ and R ₆ are not hydrogen at the same time) as a repeating unit, and a homopolymer or a copolymer having a structural unit of [a] and [b] of the general formula (1) can be used.

A typical example of the homopolymer of the polyphenylene ether resin is poly (2,6-dimethyl-1,4).
-Phenylene) ether, poly (2-methyl-6-ethyl1,4-phenylene) ether, 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, poly ( Homopolymers such as 2-methyl-6-chloroethyl-1,4-phenylene) ether are exemplified.

The polyphenylene ether copolymer is 2,2
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-cresol
Includes polyphenylene ether copolymers having a polyphenylene ether structure as a main component, such as copolymers with cresol.

In the polyphenylene ether resin of the present invention, various other phenylene ether units which have been proposed to be allowed to exist in the polyphenylene ether resin so far as they do not contradict the gist of the present invention are used. It may be included as a partial structure. Japanese Patent Application Laid-Open No. 63-31988 discloses an example of a proposal for coexistence in a small amount.
Examples thereof include a 2- (dialkylaminomethyl) -6-methylphenylene ether unit and a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit described in JP-A-01222.

The polyphenylene ether resins also include those in which a small amount of diphenoquinone or the like is bonded in the main chain.

Further, for example, Japanese Patent Application Laid-Open No. 2-276823,
Also included are polyphenylene ethers modified with compounds having a carbon-carbon double bond described in JP-A-63-108059 and JP-A-59-59724.

The component (A) may contain a polystyrene resin in an arbitrary ratio in addition to the polyphenylene ether resin. The polystyrene-based resin is a polymer obtained by polymerizing a styrene-based compound or a compound copolymerizable with the styrene-based compound in the presence or absence of a rubbery polymer.

The styrene compound is represented by the general formula [2]

[0025]

Embedded image

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 0-5. Means a compound.

Specific examples thereof include styrene, α-
Examples thereof include methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Examples of the compound copolymerizable with the styrene compound include methacrylates 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. Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, a hydrogenated product thereof, and an ethylene-propylene copolymer rubber. Preferred styrenic resins for the present invention are polystyrene and rubber reinforced polystyrene.

The block copolymer as the component (B) of the present invention is a block copolymer comprising at least one styrene-based compound polymer block and at least one polyisoprene block. The total vinyl content of 3,4- and 1,2-bonds in the polyisoprene block must be at least 40%. When the total vinyl content is less than 40%, the temperature of the main dispersion peak of tan δ is low, and it is not preferable because the temperature cannot be increased to a sufficient level to exhibit the vibration damping property even when a polyolefin resin is used in combination.

It is necessary that at least 70% of the unsaturated bonds in the polyisoprene block be hydrogenated. If more than 30% of the unsaturated bonds remain, it is not preferable because the heat causes a decrease in the fluidity of the composition and a deterioration in the appearance of the molded product. The molecular weights of the styrene-based compound polymer block and the polyisoprene block are not particularly limited, but if the molecular weight of the styrene-based compound polymer block decreases, the compatibility between the component (A) and the block copolymer deteriorates. Therefore, it is preferable to use a molded article having a number average molecular weight of 2,500 or more. When the molecular weight of the polyisoprene block is reduced, the performance as an elastic body is reduced and the vibration damping property is impaired.

The preferred range of the content of the polymer block of the styrenic compound in the block copolymer is not particularly limited because it varies depending on the molecular weight of the block copolymer. % Range. If the content of the polymer block of the styrenic compound is less than 10% by weight, the compatibility with the component (A) is insufficient, so that the molded article is easily delaminated. Is not preferable because the dispersed particles are less than 0.2 μm even if the component (C) is added, so that a sufficient damping effect cannot be obtained. When the component (C) is not added, if the content exceeds 35% by weight, the dispersed particles become 0.2 μm or less, so the range of 10 to 35% by weight is preferable.

The polyolefin resin which is the component (C) of the present invention is known per se, for example, polyethylene,
Examples include homopolymers of olefin monomers such as polypropylene, polybutylene, and polyisobutylene, and copolymers containing olefin monomers such as ethylene-propylene copolymer and ethylene-ethyl acrylate copolymer. Preferred polyolefin resins for the present invention are low crystalline polypropylene and ethylene-propylene copolymers.

The aromatic phosphate ester flame retardant which is the component (D) of the present invention is not particularly limited. For example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylate Renyl diphenyl phosphate, dixylenyl phenyl phosphate, hydroquinone bisphosphate, resorcinol bisphosphate, bisphenol A bisphosphate, etc., may be used alone or in combination of two or more. A particularly suitable aromatic phosphate ester flame retardant for the present invention is triphenyl phosphate. Triphenyl phosphate is preferable because it has an excellent flame retarding effect as compared with other aromatic phosphate ester-based flame retardants and increases the effect of improving the vibration damping effect of the component (B) + (C) for any reason.

In the present invention, the addition amount of the polyphenylene ether resin or the polystyrene resin as the component (A) is selected from the range of 40 to 85 parts by weight.
If the amount of the component (A) is less than 40 parts by weight, the characteristics of the polyphenylene ether resin are not exhibited, and the component (B) + (C) cannot form a dispersed phase, which is not preferable. When the added amount of the component (A) exceeds 85 parts by weight, the components (B) and (C) sufficient to impart the vibration damping property and the component (D) sufficient to impart the flame retardancy are added. It is not preferable because it cannot be done.

In the present invention, the amount of the block copolymer (B) added is selected from the range of 5 to 30 parts by weight. If the amount of component (B) is less than 5 parts by weight, sufficient vibration damping effect cannot be obtained, which is not preferable. If it exceeds 30 parts by weight, component (C) should be added in the form of forming dispersed particles. This is not preferable because it is not possible to perform flame retardation with an aromatic phosphate ester-based flame retardant, and the molded product is easily delaminated.

In the present invention, the addition amount of the polyolefin resin as the component (C) is selected from the range of 0 to 20 parts by weight, preferably the range of 2 to 20 parts by weight. It is more preferable to add the component (C) in an amount of 2 parts by weight or more, since it becomes easy to make the dispersed particles composed of the component (B) and the component (C) into 0.2 μm or more. If the amount is more than 3 parts by weight, the dispersed particles composed of the component (B) and the component (C) exceed 3 μm, so that the flame retardation by the aromatic phosphate ester-based flame retardant cannot be achieved, which is not preferable.

In the present invention, the addition amount of the aromatic phosphate ester flame retardant as the component (D) is selected from the range of 0 to 30 parts by weight. Must be at least 5 parts by weight. When the amount is less than 5 parts by weight, the flame retarding effect becomes insufficient, and when it exceeds 30 parts by weight, the heat resistance of the composition is unpreferably decreased.

Various additives may be added to the resin composition of the present invention, if necessary. In order to increase rigidity and dimensional performance, an inorganic filler is added at an arbitrary ratio.
In the case of blending an inorganic filler, it is particularly preferable to use a flaky filler such as glass flake, mica, flaky talc, or flaky graphite because the vibration damping property is improved.

[0038] Stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers and the like, colorants, release agents and the like for increasing the stability of the resin composition can also be added.

The method for preparing the composition of the present invention is not particularly limited, but an extruder is generally used to control the diameter of the dispersed particles. It is easiest to control the dispersed particle size by the shear stress during extrusion. The shear stress at the time of extrusion can be changed by the extrusion temperature, screw pattern, screw rotation speed, and the like.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples. The parts used below are parts by weight and% is% by weight.

The polystyrene-polyisoprene block copolymer used in the following Examples and Comparative Examples is as follows.

(1) Hybra-VS-1 (polystyrene block amount: 20%, vinyl bond amount: 70%, non-hydrogenated), manufactured by Kuraray Co., Ltd. (2) Hybra-HVS-3 (polystyrene block amount: 20) %, Vinyl bond amount: 55%, hydrogenation ratio: 85
%), Manufactured by Kuraray Co., Ltd. (3) Hibra-HVS-429 (polystyrene block amount: 40%, vinyl bond amount: 55%, hydrogenation ratio: 85)
%), Manufactured by Kuraray Co., Ltd. The respective measured values in Examples and Comparative Examples were determined by the following methods.

(1) Tan δ characteristics The viscoelastic spectrum was measured using Leo Vibron manufactured by Orientec, and the tan δ at peak temperature and 23 ° C. was measured.
The value was determined.

(2) Average Particle Diameter of Dispersed Phase An electron micrograph of an ultrathin section of the resin composition was taken, and the arithmetic average of the major axis and the minor axis of the dispersed phase particles was taken as the particle diameter. The average was determined.

(3) Vibration Suppression Property (Loss Coefficient η) Using a two-channel fast Fourier transform apparatus, measurement was performed by the cantilever method using non-contact random excitation, and the result was expressed in%. The measurement temperature is 23 ° C.

(4) Flammability A 1.6 mm thick test piece was measured in accordance with the UL-94 test method.

(5) Fluidity Using a melt indexer P-111 manufactured by Toyo Seiki Co., Ltd., the melt index (M
I) was measured.

Example 1 The intrinsic viscosity (measured at 30 ° C. in a chloroform solvent) was 0.
30 parts of 43 dl / g poly (2,6-dimethyl-1,4-phenylene) ether, 49 parts of polystyrene 685 from Asahi Kasei Corporation, 20 parts of Hybra-HVS-3 and 2,6-di-tert A screw having kneading disc L: 2, kneading disc R: 3, sealing: 1 using a PCM30 twin screw extruder manufactured by Ikegai Iron Works, Ltd. with 1 part of -butyl-4-methylphenol. In a pattern, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C. and a screw rotation speed of 100 rpm.
Table 1 shows the physical property test results of the composition.

Comparative Example 1 Hybra-HVS was used to adjust the amount of the isoprene component.
-3 and 7 parts of polystyrene were replaced with Hybra-HVS-4
Example 1 was repeated in place of 29 to obtain a resin composition.
Table 1 shows the physical property test results of the composition.

[0050]

[Table 1]

Example 2 45 parts of the poly (2,6-dimethyl-1,4-phenylene) ether of Example 1, 27 parts of polystyrene, 15 parts of Hybra-HVS-3, 12 parts of bisphenol A bisphosphate and 2 parts , 6-Di-tert-butyl-4-
PCM3 of Ikegai Iron Works Co., Ltd.
0 Using a twin screw extruder, kneading disc L: 2
, Kneading disc R: 3 and sealing: 1 with screw pattern, cylinder temperature 300
The mixture was melt-kneaded at 100 ° C. and a screw rotation speed of 100 rpm to obtain a resin composition. Table 2 shows the physical property test results of the composition.

Comparative Example 2 A resin composition was obtained by repeating Example 1 except that Hybra-VS-3 was replaced with Hybra-VS-1. Table 2 shows the physical property test results of the composition.

Comparative Example 3 Hybra-HVS was used to adjust the amount of the isoprene component.
-5 and 5 parts of polystyrene were replaced with Hybra-HVS-4
Example 2 was repeated in place of 29 to obtain a resin composition.
Table 2 shows the physical property test results of the composition.

Example 3 A resin composition was obtained by repeating Comparative Example 3 by replacing 10 parts of Hibra-HVS-429 with polypropylene SA510 of Nippon Polyolefin Co., Ltd. Table 2 shows the physical property test results of the composition.

Comparative Example 4 A resin composition was obtained by repeating Example 3 except that HVS-429 and SA510 were obtained.
10 parts each, Thermoplastics Industry Co., Ltd.
Was melt-kneaded in a full flight screw pattern at a cylinder temperature of 280 ° C. and a screw rotation speed of 100 rpm to obtain a resin composition. Table 2 shows the physical property test results of the composition.

[0056]

[Table 2]

Example 4 40 parts of poly (2,6-dimethyl-1,4-phenylene) ether of Example 1, 13 parts of polystyrene, HVS-3
7 parts, SA510 7 parts, triphenyl phosphate 12 parts, 13 μm diameter glass fiber 10 parts, Kuraray Co., Ltd.
10 parts of mica 200K1 and 2,6-di-ter
One part of t-butyl-4-methylphenol was melt-kneaded under the same extrusion conditions as in Example 1 to obtain a resin composition. Table 3 shows the physical property test results of the composition.

Comparative Example 5 A resin composition was obtained by repeating Example 4 with the exception that triphenyl phosphate was replaced with ethyl acid phosphate. Table 3 shows the physical property test results of the composition.

Comparative Example 6 A resin composition was obtained by repeating Example 4 with the exception that triphenyl phosphate was replaced with ethyne glycol acid phosphate. Table 3 shows the physical property test results of the composition.

Example 5 45 parts of the poly (2,6-dimethyl-1,4-phenylene) ether of Example 1, 9 parts of polystyrene, 15 parts of HVS-3, 15 parts of SA510, 15 parts of triphenyl phosphate and One part of 2,6-di-tert-butyl-4-methylphenol was melt-kneaded under the same extrusion conditions as in Example 1 to obtain a resin composition. Table 3 shows the physical property test results of the composition.

Comparative Example 7 HVS-3 was reduced from 15 parts to 5 parts, and SA510 was reduced to 1 part.
Example 5 was repeated except that the amount was increased from 5 parts to 25 parts to obtain a resin composition. Table 3 shows the physical property test results of the composition.

[0062]

[Table 3]

[0063]

The resin composition of the present invention comprises a polyphenylene ether-based resin, a hydrogenated block copolymer, a polyolefin-based resin or / and an aromatic phosphate-based flame retardant, and has a hydrogenated block copolymer having a specified structure. The use of coalescing improves the flame retardancy of the flame-retardant and non-flame-retardant resin compositions of a resin composition containing a polyphenylene ether-based resin and a polyolefin-based resin, which were difficult with the prior art.

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Claims (1)

[Claims] (A) a polyphenylene ether-based resin or 40 to 85 parts by weight of a polystyrene-based resin and a polystyrene-based resin;
(B) a block copolymer composed of a polymer block of a styrene-based compound and a polymer block of isoprene in which the total content of vinyl bonds is at least 40% and at least 70% of the remaining unsaturated bonds are hydrogenated. 5 to 30 parts by weight of a combined resin, 0 to 20 parts by weight of a polyolefin resin (C) and 0 to 30 parts by weight of an aromatic phosphate ester flame retardant, and the component (B) + (C) is a dispersed phase. Wherein the average particle size of the dispersed particles is in the range of 0.2 to 3 μm.