JP2000344974A - Oil-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition with high heat resistance comprising a polypropylene-based resin and a polyphenylene ether-based resin, wherein the continuous phase represents the polypropylene-based resin without raising its blend compositional ratio. SOLUTION: This composition comprises (a) a polypropylene-based resin <=800,000 in weight-average molecular weight, (b) a polyphenylene ether-based resin >=10,000 in weight-average molecular weight, and (c) an admixture; wherein the respective MFR values of the components (a) and b satisfy the relationship: MFR(a)>=MFR(b)×1.5+1.6 (g/10 min). This composition is obtained by compounding the components (a) and b and the component c together in such a blend compositional ratio as to be 5-50 vol.% in the content of the component (a) in a total of 100 vol.% of the components (a) to c followed by kneading them in a molten state to effect the continuous phase of the final composition representing the polypropylene-based resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent heat resistance and oil resistance used in the fields of automobiles, electric and electronic fields, and various other industrial materials.

[0002]

2. Description of the Related Art Many proposals have been made on polyphenylene ether-polyolefin polymer alloys. For example, US Pat. No. 3,361,851 proposes to improve the solvent resistance and impact resistance by blending polyphenylene ether with a polyolefin, and US Pat. No. 3,994,856.
In the specification, there is a description on improvement of impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and a styrene resin with a hydrogenated block copolymer.

Further, US Pat. No. 4,145,377 discloses a pre-mixture of polyphenylene ether or polyphenylene ether and a styrene resin comprising polyolefin / hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 20 parts by weight; There is a description of improving impact resistance and solvent resistance by blending with a hydrogenated block copolymer. Further, US Pat. No. 4,166,055 and US Pat. Improvements in impact resistance by blending with copolymers and polyolefins are described.

In US Pat. No. 4,383,082 and EP-A-115,712, it is described that a polyphenylene ether is blended with a polyolefin and a hydrogenated block copolymer to improve the impact resistance.

[0005]

The polymer alloy composition obtained by the above prior art is a resin composition having a good balance between the chemical resistance of polyolefin and the heat resistance of polyphenylene ether. However, since the morphology of the polymer alloy composition generally changes depending on the blend composition ratio of the component polymers,
In order to maintain the chemical resistance and oil resistance of the polyolefin, it is necessary to increase the blend composition ratio of the polyolefin, and as a result, there is a disadvantage that the heat resistance and the flame retardancy inherent to the polyphenylene ether are impaired.

An object of the present invention is to provide an oil-resistant resin composition having a heat-resistant and flame-retardant resin in which the continuous phase is a polypropylene-based resin without increasing the blending ratio of the polypropylene-based resin. It is a thing.

[0007]

Means for Solving the Problems To solve the above-mentioned problems, the present inventor has set forth the melt viscosity (MFR) of a polypropylene resin and a polyphenylene ether resin at a melt kneading temperature.
Value) difference, the blend composition ratio, and the flame retardancy, and as a result, the MF of the polyphenylene ether resin was determined.
It has been found that by using a polypropylene resin having a specific MFR value with respect to the R value and an admixture, a resin composition having excellent oil resistance can be obtained without increasing the blend composition ratio of the polypropylene resin. Further, they have found that by increasing the blend composition ratio of the polyphenylene ether-based resin, an oil-resistant resin composition excellent in heat resistance and flame retardancy, which cannot be achieved by the conventional technology, is provided.

That is, the present invention relates to (a) a polypropylene resin having a weight average molecular weight of 800,000 or less;
A polyphenylene ether-based resin having a weight average molecular weight of 10,000 or more and an admixture (c);
2. With respect to the MFR value of component (b) measured under a load of 2.16 kg (hereinafter abbreviated as MFR of component (b)), (a)
MFR of the components measured at 300 ° C. under a load of 2.16 kg.
The value (hereinafter abbreviated as the MFR of the component (a)) is defined as: MFR of the component (a) ≧ MFR of the component (b) × 1.5 + 1.6 (g
/ 10 min), and (a)-
An oil resistant composition in which the continuous phase obtained by blending at a blend composition ratio such that the content of the component (a) in the total 100% by volume of the component (c) is 5 to 50% by volume and melt-kneading is a polypropylene resin. Resin composition,

And (a) a weight average molecular weight of 80,000
0) or less, (b) a polyphenylene ether resin having a weight average molecular weight of 10,000 or more, (c) an admixture, and (d) a flame retardant, and (a), (b)
The MFR of the component is calculated by: MFR of component (a) ≧ M of component (b)
FR × 1.5 + 1.6 (g / 10 min), and the content of the component (a) in the total 100% by volume of the components (a) to (d) is 5 to 50. The present invention provides an oil-resistant resin composition in which a continuous phase obtained by blending at a blend composition ratio of volume% and melt-kneading is a polypropylene-based resin having flame retardancy.

The (a) polypropylene resin used in the present invention comprises a crystalline propylene homopolymer and a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and / or At least one other α-olefin (eg,
A propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing butene-1, hexene-1 and the like. Further, these crystalline propylene homopolymer and crystalline propylene- It may be a mixture of ethylene block copolymers.

[0011] Such a polypropylene-based resin is generally used at a polymerization temperature of 0 to 100 ° C in the presence of an alkylaluminum compound and a titanium halide catalyst supported on a carrier such as titanium trichloride catalyst or magnesium chloride. It is obtained by polymerization in the range of 3 to 100 atm. At this time, it is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer, and it is also possible to use a batch method or a continuous method as a polymerization method, butane, pentane, hexane, heptane A method such as solution polymerization or slurry polymerization in a solvent such as octane or octane can also be selected, and a bulk polymerization in a monomer without a solvent, a gas phase polymerization in a gaseous monomer, and the like can be applied.

In addition to the above-mentioned polymerization catalyst, an electron-donating compound can be used as an internal donor component or an external donor component as a third component in order to increase the isotacticity and polymerization activity of the obtained polypropylene. As these electron donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluate; and triphenyl phosphite and tributyl phosphite. Phosphoric acid derivatives such as phosphoric acid esters and hexamethylphosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols And / or various phenols.

The polypropylene resin used in the present invention has a polystyrene equivalent weight average molecular weight of 800,000 or less. If the weight average molecular weight exceeds 800,000, the fluidity is unpreferably reduced. This weight average molecular weight can usually be known by gel permeation chromatography or the like. Adjustment of the melt viscosity at the melt-kneading temperature is very important because it has a significant effect on the morphological form of the obtained resin composition. Melt flow rate (MFR) (300 ° C., an index indicating the melt viscosity of the polypropylene resin at the melt kneading temperature)
The load of 2.16 kg) is the MFR of the component (a) with respect to the MFR of the polyphenylene ether resin (b) described later.
≧ (FR) component MFR × 1.5 + 1.6 (g / 10 min)
Is a value derived from the equation.

When the MFR value is less than the MFR value derived from the above formula, the continuous phase of the obtained resin composition becomes a polyphenylene ether resin, and oil resistance is impaired, which is not preferable. The fact that the continuous phase is a polypropylene-based resin can be confirmed by edging the resin composition obtained by melt-kneading with chloroform or the like and observing it with a scanning electron microscope. That is, the polypropylene-based resin is observed without being edged with chloroform or the like, but the polyphenylene ether-based resin is edged with chloroform or the like, so that the continuous phase component can be specified. Also,
The morphology of the resin composition can be confirmed by ultra-thin section transmission electron microscope photography.

As the polypropylene resin of the present invention, any resin having any crystallinity or melting point can be used as long as it can be obtained by the above method.
Several kinds of polypropylenes having different molecular weights can be used in combination.

Next, the polyphenylene ether resin (b) used in the present invention is a polyphenylene ether having the following structural formula. Polyphenylene ether is a compound known per se.

[0017]

Embedded image

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, Represents an aminoalkyl group, a hydrocarbonoxy group or a group selected from the group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different from each other .

The polyphenylene ether is a homopolymer and / or copolymer having a weight average molecular weight in terms of polystyrene of 10,000 or more. Weight average molecular weight of 1000
If it is less than 0, the fluidity is excellent but the productivity and the color tone are lowered, which is not preferable. This weight average molecular weight is usually
It can be known by gel permeation chromatography or the like.

Specific examples of the polyphenylene ether include, for example, poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-
1,4-phenylene ether), poly (2-methyl-6)
-Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like. Further, 2,6-dimethylphenol and other phenols (for example, 2,3 Polyphenylene ether copolymers such as copolymers with 6-trimethylphenol and 2-methyl-6-butylphenol) are also included. Among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3
A copolymer with 6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

The method for producing the polyphenylene ether is not particularly limited as long as it can be obtained by a known method. For example, a complex of a cuprous salt and an amine by Hay described in US Pat. No. 3,308,874 may be used as a catalyst. For example, it can be easily produced by oxidative polymerization of 2,6-xylenol. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, and JP-A-50-1985. It can be easily produced by the method described in 51197 and 63-152628 and the like.

The polyphenylene ether-based resin used in the present invention may be prepared by combining the above-mentioned polyphenylene ether with an α, β-unsaturated dicarboxylic acid and its derivative in the presence of a radical generator.
It may be a known modified polyphenylene ether obtained by reacting at 80 to 350 ° C. in a molten state or a solution state in the absence of the polyphenylene ether, or a mixture of the above-mentioned polyphenylene ether and the modified polyphenylene ether in any ratio. It doesn't matter.

Further, the polyphenylene ether resin used in the present invention, in addition to the above-mentioned polyphenylene ether, exceeds 400 parts by weight of polystyrene (including syndiotactic polystyrene) or high-impact polystyrene with respect to 100 parts by weight of the polyphenylene ether. Those added to the extent that they do not exist can also be suitably used.

The (c) admixture used in the present invention is obtained by melting (a) a polypropylene resin and (b) a polyphenylene ether resin, and then mixing (b) the polyphenylene ether resin with the (a) polypropylene resin. It can be used without any limitation as long as it has the ability to disperse it suitably.

For example, a block copolymer or a graft copolymer (hereinafter abbreviated as a polypropylene-polystyrene block copolymer) in which a styrene polymer chain is linked to a propylene polymer in a block shape, and a propylene polymer is a polyphenylene ether polymer It is obtained by hydrogenating a block copolymer or a graft copolymer (hereinafter abbreviated as a polypropylene-polyphenylene ether block copolymer) in which chains are linked in a block shape, a styrene-butadiene and / or isoprene copolymer. Preferred are hydrogenated block copolymers and the like.

Among them, (c) the block copolymer which can be suitably used as an admixture in the present invention is a vinyl aromatic compound-conjugated diene compound which also has an effect of imparting impact strength to the obtained resin composition. A hydrogenated product of at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. The hydrogenated block copolymer is more preferable, for example, AB, ABAA, ABAB,
A hydrogenated block copolymer having a structure such as (A-B-) 4-Si or ABABA is preferred.

As the vinyl aromatic compound constituting the block copolymer, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like can be used. It can be selected, and among them, styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3.
-One or more of butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

The total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (hereinafter abbreviated as vinyl bonds) of the polymer block mainly composed of a conjugated diene compound is 4
It is preferably 0% or more, and more preferably, in the polymer block mainly composed of butadiene, the vinyl bond content is 65 to 90%, more preferably 70 to 85%. In the polymer block mainly composed of isoprene, the vinyl bond content is preferably 45% or more, more preferably 45 to 90%.

Further, in a polymer block composed of a conjugated diene compound such as a random, tapered (a monomer component increases or decreases along a molecular chain) composed of a combination of butadiene and isoprene, or a block copolymer, preferably The vinyl bond content is 45% or more, and more preferably 45 to 90%. If the vinyl bond content is less than 40% by weight, the miscibility of the polypropylene resin and the polyphenylene ether resin decreases, and the impact resistance and tensile elongation decrease, which is not preferable. The amount of these vinyl bonds can usually be known by an infrared spectrophotometer or NMR.

In the hydrogenated block copolymer, the content of the vinyl aromatic compound bound to the block copolymer before hydrogenation is preferably 20 to 80% by weight, more preferably 30 to 80% by weight. Is preferred. The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating an aliphatic double bond of a polymer block B mainly comprising a conjugated diene compound of the above block copolymer according to the present invention. Can be used as the component (c).

The hydrogenation rate of such an aliphatic double bond is at least over 50%, preferably at least 80%. The hydrogenated block copolymer having the above structure has a number average molecular weight of 40,000 to 500,000, preferably 500,000.
00 to 300,000, more preferably 60000 to 2
000, and the molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography) is 10 or less. Furthermore, the molecular structure of the block copolymer is linear,
It may be branched, radial or any combination thereof.

These hydrogenated block copolymers may be obtained by any production method as long as they have the above-mentioned structure. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, and JP-A-54-126255. 56-
10542, JP-A-56-62847, JP-A-56-100840, and JP-A-2-30021.
No. 8, No. 1,130,770 and U.S. Pat. Nos. 3,281,383 and 3,639,517 and methods described in U.S. Pat. No. 1,020,720, U.S. Pat. Nos. 3,333,024 and 4,501,857.

Further, the hydrogenated block copolymer used in the present invention may comprise, in addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or a derivative thereof. A known modification (the α, β-unsaturated carboxylic acid or a derivative thereof) obtained by reacting in the presence, absence, or absence of a radical generator in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. Is 0.01
(10% by weight graft or addition) hydrogenated block copolymer, or a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer in any ratio. .

Next, the flame retardant (d) used for imparting flame retardancy to the oil-resistant resin composition obtained in the present invention is not particularly limited to components and shapes as long as it is a flame retardant. Can be used. That is, (d) inorganic flame retardants (antimony, aluminum hydroxide, magnesium hydroxide, etc.), halogen-containing flame retardants, phosphoric esters, aromatic condensed phosphoric esters, polyphosphoric acids, triazine derivatives, red phosphorus A flame retardant or the like is used. Among these, phosphate esters, aromatic condensed phosphate esters, polyphosphates, triazine derivatives, red phosphorus-based flame retardants and the like are preferably used alone or in combination in consideration of the balance between safety and other physical properties during combustion, Further, it is more preferable to use a red phosphorus-based flame retardant as a main component.

The resin composition of the present invention comprises the above (a) to
The component (d) is configured as a basic component. In the present invention, in order to obtain a resin composition having excellent heat resistance and oil resistance, which is the object of the present invention, the content of the (a) polypropylene-based resin in the total 100% by volume of the components (a) to (c) is required. Is 5
It is essential that the mixture be blended at a blend composition ratio of ５０50% by volume and that the continuous phase be a polypropylene resin.
If the content of the polypropylene resin exceeds 50% by volume, oil resistance is excellent but heat resistance is not improved, which is not preferable. If the content is less than 5% by volume, the heat resistance is excellent, but the polypropylene resin cannot form a continuous phase and the oil resistance is impaired, which is not preferable.

In order to obtain an oil-resistant resin composition having excellent flame retardancy and heat resistance, a total of 100% of the components (a) to (d) is required.
The content of the (a) polypropylene-based resin is 5 to 50% by volume, preferably 5 to 40% by volume, more preferably 5 to 35% by volume. It is essential that the resin is a polypropylene resin. Content of polypropylene resin is 50% by volume
If it exceeds, a large amount of a flame retardant is required, so that mechanical strength is impaired, which is not preferable. If the content is less than 5% by volume, the heat resistance is excellent, but the polypropylene resin cannot form a continuous phase and the oil resistance is impaired, which is not preferable.

With respect to the compounding amount of the other components in the total of 100% by volume of the components (a) to (d), the compounding amount of the admixture (c) is 0.1 to 20% by volume, and (d) ) When the flame retardant is used, the compounding amount is 0.1 to 20% by volume. The blending amount of the polyphenylene ether-based resin (b) is the remaining amount obtained by subtracting the sum (a + c + d) of the blending amounts of the above (a), (c), and (d) from 100% by volume, that is, 10 to 94.
8% by volume.

In the present invention, in addition to the above-mentioned components, if necessary, other additional components such as a styrene-butadiene block having a bound styrene content of 10 to 90% may be used as long as the characteristics and effects of the present invention are not impaired. Polymer, bound styrene content 1
0-90% styrene-isoprene block copolymer,
Antioxidants, metal deactivators, fluoropolymers, plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.),
Weather (light) resistance improver, nucleating agent for polyolefin, slip agent, inorganic or organic filler or reinforcing material (glass fiber,
Glass flake, carbon fiber, polyacrylonitrile fiber, whisker, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate,
Wollastonite, conductive metal fibers, conductive carbon black, etc.), various coloring agents, release agents, and the like.

The method for producing the resin composition of the present invention is not particularly limited. Examples of these methods include a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, and a hot-melt kneading method using a Banbury mixer, but a melt-kneading method using a twin-screw extruder is particularly preferred. Most preferred. The melting and kneading temperature at this time is not particularly limited, but is preferably selected arbitrarily from 250 to 350 ° C. in order to suppress decomposition and deterioration of each resin component and obtain a sufficient kneading effect.

As a specific melt-kneading method, for example, using each of the above-mentioned components, (a) a polypropylene-based resin and (b) a polyphenylene ether-based resin, (c) an admixture, and (D) a method in which a flame retardant is supplied and melt-kneading is performed, (a) a polypropylene resin and (b) a polyphenylene ether resin, and (c) an admixture are supplied from a first raw material supply port, (D) a method of supplying a flame retardant as required from a supply port, (b) supply of a polyphenylene ether-based resin and (c) an admixture, and (d) a flame retardant as necessary from a first raw material supply port And (a) a method of supplying a polypropylene resin from the second raw material supply port,

(B) Polyphenylene ether-based resin and (c) an admixture are supplied from a first raw material supply port, and (a) a polypropylene-based resin and (d) a flame retardant, if necessary, from a second raw material supply port. A method of supplying, wherein (b) a polyphenylene ether-based resin is supplied from a first raw material supply port, and (a) a polypropylene-based resin and (c) an admixture and, if necessary, (d) a flame retardant, from a second raw material supply port. How to supply the
(A) a part of the polypropylene resin, (b) a polyphenylene ether resin and (c) an admixture are supplied from the first raw material supply port, and the remaining (a) polypropylene resin and the necessary (D) supplying a flame retardant according to

(A) a part of the polypropylene resin and (b) a polyphenylene ether resin are supplied from the first raw material supply port, and the remaining (a) polypropylene resin and (c) the admixture are supplied from the second raw material supply port. And if necessary, it can be produced by a method such as (d) a method of supplying a flame retardant.
The screw rotation speed at this time is not particularly limited, but can be arbitrarily selected from 100 to 1200 rpm.

The resin composition of the present invention thus obtained can be prepared by various known methods, for example, injection molding,
It can be molded as a molded body of various parts by extrusion molding and hollow molding. These various parts include, for example, automobile parts,
Interior and exterior parts of electrical equipment, and various other industrial material parts.

[0044]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to examples, but the present invention is not limited to these examples. (A) Polypropylene resin used in Examples (a-1): Homo-polypropylene MFR = 2.4 g / 10 min Weight average molecular weight (Mw) 763,000, Mw / Mn =
5.0 (a-2): Homo-polypropylene MFR = 5.6 g / 10 min Weight average molecular weight (Mw) 634000, Mw / Mn =
4.3 (a-3): Homo-polypropylene MFR = 9.4 g / 10 min Weight average molecular weight (Mw) 519000, Mw / Mn =
4.9

(A-4): Homo-polypropylene MFR = 20 g / 10 min Weight average molecular weight (Mw) 441,000, Mw / Mn =
4.8 (a-5): Homo-polypropylene MFR = 36 g / 10 min Weight average molecular weight (Mw) 374000, Mw / Mn =
4.1 (a-6): Homo-polypropylene MFR = 60 g / 10 min Weight average molecular weight (Mw) 311000, Mw / Mn =
4.3 (a-7): Homo-polypropylene MFR = 81 g / 10 min Weight average molecular weight (Mw) 260,000, Mw / Mn =
4.0 MFR (melt flow rate) of polypropylene is AS
It was measured at 300 ° C. under a load of 2.16 Kg in accordance with TM D1238.

(B) Polyphenylene ether resin (b-1) used in Examples: Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 9.1 g / 10 min Weight average molecular weight (Mw) 13500 , Mw / Mn = 2.
0 (b-2): polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 3.7 g / 10 min Weight average molecular weight (Mw) 33700, Mw / Mn = 2.
2 (b-3): Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 2.0 g / 10 min Weight average molecular weight (Mw) 48000, Mw / Mn = 2.
0 (b-4): polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 1.3 g / 10 min Weight average molecular weight (Mw) 56900, Mw / Mn = 2.
4

(B-5): Polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 0.7 g / 10 min Weight average molecular weight (Mw) 65300, Mw / Mn = 2.
3 (b-6): polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 0.3 g / 10 min Weight average molecular weight (Mw) 86200, Mw / Mn = 2.
9 (b-7): polyphenylene ether obtained by oxidative polymerization of 2,6-xylenol MFR = 0.06 g / 10 min Weight average molecular weight (Mw) 127800, Mw / Mn =
3.3 MFR (melt flow rate) of polyphenylene ether is 300 ° C. in accordance with ASTM D1238.
It was measured at a load of 16 kg.

(C) Admixture used in the examples (c-1): having the structure of polystyrene (1) -hydrogenated polyisoprene-polystyrene (2), and having a number average molecular weight of 8
6,300, molecular weight distribution 1.10, polyisoprene before hydrogenation had a vinyl bond content of 54%, polystyrene (1)
A hydrogenated block copolymer having a number average molecular weight of 20,200, a polystyrene (2) having a number average molecular weight of 20,000, and a hydrogenation rate of a polyisoprene portion of 83.5% was synthesized. ).

(D) Flame retardant used in Examples (d-1): Red phosphorus flame retardant Nova Red 140 (manufactured by Rin Kagaku Co., Ltd.) (d-2): Organic phosphoric ester compound triphenyl phosphate (large) (D-3): Aromatic condensed phosphate CR741 (produced by Daihachi Chemical Co., Ltd.) (d-4): Ammonium polyphosphate Terage C60
(Manufactured by Chisso Corporation) (d-5): 1,3,5-triazine derivative 2-piperazinylene-4-morpholino-1,3,3 using cyanuric chloride, morpholine and piperazine.
Polymer of 5-triazine (n = 11, molecular weight about 277)
0) was synthesized.

[0050]

EXAMPLES Examples 1 to 27 and Comparative Examples 1 to 9 Examples 1 to 17 are oil-resistant resin compositions of the present invention. A polypropylene-based resin, a polyphenylene ether-based resin, and an admixture were blended and melt-kneaded according to the blend composition ratios and melt-kneading methods shown in Tables 1 and 2 to obtain pellets. In Comparative Examples 1 to 6, the relationship between the MFR of the polypropylene-based resin and the polyphenylene ether-based resin is out of the claims of the present invention, and Comparative Example 7 is out of the claims of the present invention because no admixture is used. . In each case, the continuous phase is a polyphenylene ether-based resin in which oil resistance is impaired. A polypropylene-based resin, a polyphenylene ether-based resin, and an admixture were blended and melt-kneaded according to the blend composition ratios and melt-kneading methods shown in Table 3 to obtain pellets.

Examples 18 to 27 are the oil-resistant resin compositions provided with the flame retardancy of the present invention. A polypropylene-based resin, a polyphenylene ether-based resin, an admixture, and a flame retardant were blended and melt-kneaded according to the blend composition ratios and melt-kneading methods shown in Tables 4 and 5, to obtain pellets. Comparative Examples 8 and 9 are examples in which the content of the polypropylene-based resin is out of the claims of the present invention, and flame retardancy is not provided. A polypropylene-based resin, a polyphenylene ether-based resin, an admixture, and a flame retardant were blended and melt-kneaded according to the blend composition ratios and the melt-kneading methods shown in Table 5, to obtain pellets.

The melt-kneading is carried out first in the upstream with respect to the resin flow direction.
A twin screw extruder (ZSK-25; WERNER & PFLEIDE) having a supply port and a second supply port downstream and a vacuum vent port upstream of the second supply port and between the second supply port and the die.
RER Co., Germany), the front barrel setting temperature is 290-330 ° C., the rear barrel setting temperature is 250-290.
° C, screw rotation speed 250 rpm, discharge rate 15 kg /
It was melt-kneaded under the conditions of time to obtain pellets.

The plane parallel to the cut surface of the obtained pellet is
After smoothing using an ultramicrotome (Ultracut E manufactured by Reichert), the sample was immersed in chloroform for about 30 minutes and vacuum-dried at 80 ° C. for 60 minutes. A sample was taken with a scanning electron microscope (JSM manufactured by JEOL Ltd.). -T2
00) and photograph observation. The continuous phase component was confirmed from this photograph. In addition, a plane parallel to the cut surface of the obtained pellet was prepared with an ultramicrotome (Ultracut E manufactured by Reichert), and an ultrathin section was prepared and stained with ruthenic acid. Observation and photography were performed using 1200EX). The morphology was confirmed from this photograph.

Further, 260 to 3
The test piece is supplied to a screw in-line injection molding machine set within a temperature range of 30 ° C., and a test piece for a bending test, a test piece for an Izod impact test, and a mold temperature of 80 ° C.
A test piece for measuring heat distortion temperature, an oil resistance test piece and a combustion test piece were injection molded. The physical properties, oil resistance, and flame retardancy of these test pieces were measured, and the results are shown in Tables 1 to 5. The evaluation of physical properties was performed as follows.

(1) Heat deformation temperature Measured under a load of 4.6 kg / cm 2 according to ASTM D-648. (2) Izod (notched) impact strength Measured at 23 ° C. according to ASTM D-256. (3) Flexural modulus test Flexural modulus was measured at 23 ° C. according to ASTM D-790. (4) Oil resistance test A dumbbell test piece (total length: 215 mm, thickness: 2 mm) was molded using an injection molding machine, and this dumbbell test piece was subjected to 1% strain using a bending foam.
It was immersed in gasoline and salad oil for a time, and the state of crack generation and the presence or absence of breakage after immersion were visually observed. (5) Combustion test A combustion test was performed using a sample having a thickness of 1/16 inch according to the UL94 standard.

According to Examples 1 to 17 and Comparative Examples 1 to 6, the resin composition comprising a polypropylene resin having a weight average molecular weight of 800,000 or less, a polyphenylene ether resin having a weight average molecular weight of 10,000 or more, and an admixture has an X-axis. MFR of polyphenylene ether resin
And the XY graph showing the MFR of the polypropylene-based resin on the Y-axis, the result of oil resistance is described as: (MFR of polypropylene-based resin) ≧ (MFR of polyphenylene ether-based resin)
FR) × 1.5 + 1.6, the content of the polypropylene resin is 5 to 50% by volume.
Even when blended in such a blend composition ratio as described above, an oil-resistant resin composition having excellent heat resistance, in which the continuous phase intended for the present invention is a polypropylene resin, can be obtained.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

One example of the morphology of the resin composition is shown in FIGS. FIG. 1 is a photograph of a transmission electron microscope obtained by observing the pellet of Example 1 at a magnification of 10,000 times by the above method. In the figure, a dispersed phase spherically dispersed is a polyphenylene ether-based resin, and a continuous phase is polypropylene. The black block at the interface is a hydrogenated block copolymer which is an admixture. FIG. 2 is a transmission electron microscope photograph of the pellet of Comparative Example 1 observed at a magnification of 10,000 times by the above method. In the figure, the dispersed phase elliptically dispersed is a polypropylene resin, and the continuous phase is polyphenylene. The ether-based resin is a hydrogenated block copolymer in which the black portion at the interface is an admixture.

Further, in addition to the above-mentioned properties, from Examples 18 to 27, a flame retardant was added to the above composition, and the blending ratio was such that the content of the polypropylene resin was 5 to 50% by volume. In addition, it is possible to provide an oil-resistant resin composition in which the continuous phase is a polypropylene resin and has excellent flame retardancy and heat resistance. Comparative Examples 8 and 9 are Examples 18 to 27
In Table 2, the composition was changed as shown in Table 5. As a result, it is an example in which it is difficult to impart flame retardancy. When the amount of the flame retardant is increased, heat resistance and rigidity are reduced, and the effect of the present invention is lost, which is not appropriate.

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

The weight average molecular weight of the present invention is 800,000.
The following polypropylene resin has a weight average molecular weight of 100
The resin composition comprising a polyphenylene ether-based resin and an admixture of at least 00 has a continuous phase of a polypropylene-based resin, and has an effect of being excellent in heat resistance and oil resistance,
Further, the addition of the flame retardant has the effect of providing a resin composition having excellent flame retardancy in addition to the above properties.

[Brief description of the drawings]

FIG. 1 is a transmission electron microscope (magnification: 10,000 times) photograph of a cut surface of a pellet of Example 1 (a photograph substituted for a drawing).

FIG. 2 is a transmission electron microscope (magnification: 10,000 times) photograph of a cut surface of the pellet of Comparative Example 1 (a photograph substituted for a drawing).

Claims (5)

[Claims] 1. A polypropylene resin having a weight average molecular weight of 800,000 or less and (b) a weight average molecular weight of 1
0000 or more polyphenylene ether resin and (c)
3 of the component (a) with respect to the MFR value of the component (b) measured at 300 ° C. under a load of 2.16 kg.
The MFR value measured at a load of 2.16 Kg at 00 ° C.
MFR value of component (a) ≧ MFR value of component (b) × 1.5
+1.6 (g / 10 minutes), and the content of the component (a) in the total 100% by volume of the components (a) to (c) is 5 to 50% by volume. An oil-resistant resin composition in which the continuous phase obtained by blending at such a blend composition ratio and melt-kneading is a polypropylene resin. 2. A (a) polypropylene resin having a weight average molecular weight of 800,000 or less and (b) a weight average molecular weight of 1
0000 or more polyphenylene ether resin and (c)
The MFR value of the components (a) and (b), which is composed of the admixture and the flame retardant and is measured at 300 ° C. under a load of 2.16 kg, is calculated by dividing the MFR value of the component (a) by the MFR value of the component (b). Value x
1.5 + 1.6 (g / 10 min), and the content of the component (a) in the total 100% by volume of the components (a) to (d) is 5 to 50% by volume. An oil-resistant resin composition in which the continuous phase obtained by blending and melt-kneading is a polypropylene-based resin imparted with flame retardancy, such that (C) a block copolymer comprising at least one polymer block A mainly composed of at least one vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound; 2. A hydrogenated block copolymer obtained by hydrogenating a polymer.
Or the oil-resistant resin composition according to 2. 4. The oil-resistant resin composition according to claim 2, wherein the flame retardant (d) is a flame retardant mainly composed of a red phosphorus flame retardant. 5. The oil-resistant resin composition according to claim 1, wherein the melt-kneading temperature is from 250 to 350 ° C.