JPH0912800A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To produce a thermoplastic resin composition having low orientation in the dispersed phase in injection molding, hardly causing delamination and good in heat resistance, rigidity and toughness after thermal hysteresis by blending a polyphenylene ether with two specific types of polypropylene-based resins and a hydrogenated block copolymer. CONSTITUTION: This thermoplastic resin composition comprises 100 pts.wt. in total of a blend of (A) 70-10wt.% polyphenylene ether with (B) 30-90wt.% polypropylene-based resin in which the weight ratio of a highly crystalline resin component to a moderately crystalline resin component ranges from (95/5) to (10/90), and (C) 5-30 pts.wt. copolymer obtained by hydrogenating, in a range of 65 to <80%, a copolymer of polymer blocks composed mainly of an aromatic vinyl compound and other polymer blocks composed mainly of a conjugated diene compound having 65-75% contents of 1, 2 or 3,4-vinyl bonds. The ratio of the crystalline phase of homopolypropylene parts determined by free induced attenuation of pulse NMR is >=96% and the melting point of the crystalline phase is >=163 deg.C for the highly crystalline component, while those for the moderately crystalline component are 93 to <96% and 114 deg.C to <163 deg.C, respectively.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention relates to oil resistance, which can be used in electric / electronic fields, automobile fields, and various other industrial material fields.
The present invention relates to a resin composition having excellent chemical resistance, heat resistance, impact resistance and rigidity, and further to a thermoplastic resin composition having excellent toughness (elongation) after heat history and excellent durability as a heat resistant material. is there.

[0002]

2. Description of the Related Art Polyphenylene ether has low mechanical properties, electrical properties, heat resistance, low temperature properties, low water absorption, and excellent dimensional stability, but has the drawbacks of poor moldability and impact resistance. These problems are improved by blending with polystyrene and high-impact polystyrene, and they are widely used as resin compositions for, for example, electric / electronic parts, office equipment housings, automobile parts, precision parts and various industrial parts.

However, a classical polyphenylene ether resin composition composed of this polyphenylene ether and high-impact polystyrene (US Pat. No. 33834).
No. 35) has improved impact resistance, but has a drawback of poor chemical resistance.

For this reason, for example, US Pat.
In the specification of Japanese Laid-Open Patent Publication No. 51, it has been proposed to blend polyphenylene ether with polyolefin to improve solvent resistance and impact resistance, and US Pat. No. 3,994,485.
No. 6 discloses the improvement of impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and styrene resin with a hydrogenated block copolymer, and US Pat. No. 4,145,377.
In the specification, a polyphenylene ether or a polyphenylene ether and a styrene resin are used as a polyolefin / hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 2
There is a disclosure regarding improvement of impact resistance and solvent resistance by blending with 0 parts by weight of a premixture and a hydrogenated block copolymer, and further, there is disclosed in US Pat. No. 4,166,055.
U.S. Pat. No. 4,239,673 and U.S. Pat. No. 4,239,673 disclose improved impact resistance by blending polyphenylene ether with hydrogenated block copolymers and polyolefins.

And US Pat. No. 4,383,082 and EP-A-115712 disclose that impact resistance is improved by blending polyphenylene ether with a polyolefin and a hydrogenated block copolymer. . In addition, Japanese Unexamined Patent Publication
3-113058, JP-A-63-225642, US Pat. No. 4,863,997, JP-A-3-72512, JP-A-4-183748, and JP-A-5-320471 disclose polyolefins. It has been proposed to blend a specific hydrogenated block copolymer into the modification of a resin composition comprising a resin and a polyphenylene ether resin to obtain a resin composition having excellent chemical resistance and processability.

[0006] The applicant of the present invention is also disclosed in JP-A-62-2055.
1, JP-A-62-25149, JP-A-62-62
-48757, JP-A-62-48758,
Japanese Patent Laid-Open No. 62-199637 and US Pat. No. 4
In the specification of 772657, a rubber composition comprising a polyphenylene ether, a polyolefin and a hydrogenated block copolymer, which is excellent in rubber elasticity, is proposed.
25563, Japanese Unexamined Patent Publication No. 3-185058, Japanese Unexamined Patent Publication No. 5-70679, Japanese Unexamined Patent Publication No. 5-295184, Japanese Unexamined Patent Publication No. 6-9828, Japanese Unexamined Patent Publication No. 6-1692
No. 4, JP-A-6-57130, and JP-A 6-1.
In Japanese Patent No. 36202, a resin composition composed of polyphenylene ether, polyolefin and a specific hydrogenated block copolymer, which is excellent in compatibility, rigidity and heat resistance, and solvent resistance is proposed.

[0007]

DISCLOSURE OF THE INVENTION The prior art disclosed herein provides a resin composition having dramatically improved solvent resistance and is excellent in heat resistance as compared with a classical polyphenylene ether resin composition. To provide an elastomer composition. In addition, such advance of the conventional technology is surely a significant improvement in terms of compatibility (presence or absence of delamination of the composition when both components are mixed) in mixing the polyolefin resin and the polyphenylene ether. However, it has been revealed that they do not necessarily have sufficient compatibility when used in complicated molding processes accompanying the progress of molding technology in recent years.

That is, in the resin composition obtained by the above-mentioned prior art, extreme orientation of the dispersed phase is observed during injection molding, and in the case of various molded articles, the proof stress against external pressure and internal pressure decreases and the orientation direction becomes At present, the delamination phenomenon is observed along the line. However, a resin composition in which a polyphenylene ether added for heat resistance imparting a polypropylene component as a matrix forms a dispersed phase, and although having these problems, a marked improvement in heat resistance is achieved as compared with a single polypropylene resin. It is one of the attractive industrial materials.

For this reason, polypropylene-polyphenylene ether-based polymer alloys having improved heat resistance have a potential for delamination, but substantially improved heat resistance has been proposed, and therefore various improvements have been proposed. Above all, since the rigidity of the obtained resin composition is lowered due to the influence of the admixture used, a high crystalline polypropylene tends to be used in recent years as the polypropylene constituting the matrix. However, the polypropylene-polyphenylene ether-based polymer alloy using this high-crystal polypropylene has a practical drawback such as a decrease in toughness (especially a decrease in elongation) after heat history and poor durability as a heat-resistant material. Is the current situation.

[0010]

In view of such a situation, the present inventors have made a composition containing polypropylene and polyphenylene ether have a high level of compatibility, heat resistance, rigidity and thermal history. In order to impart the toughness (especially elongation) of the polymer, a result of extensive studies on a hydrogenated block copolymer that can be an admixture and a polypropylene resin that can be a matrix material. As a result, a hydrogenated block copolymer having a specific structure is a polypropylene. And a polyphenylene ether which act as an excellent admixture of a composition, have little dispersed phase orientation at the time of injection molding, and bring about a thermoplastic resin composition with improved delamination. By controlling two types of polypropylene resins having different properties within a specific range, The present invention has been completed by finding that the composition containing pyrene and polyphenylene ether improves the heat resistance, rigidity and toughness (especially elongation) after heat history to provide a thermoplastic resin composition having excellent durability as a heat resistant material. Came to.

That is, in the present invention, the proportion of the crystal phase of the homo-polypropylene portion of (a) the polypropylene resin is 96% or more, which is determined by (a-1) free induction decay (FID) by pulse NMR. , A high crystalline polypropylene having a melting point of 163 ° C. or higher, and (a-2) the proportion of the crystalline phase of the homo-polypropylene portion obtained from free induction decay (FID) by pulse NMR is 93 to less than 96%, Polypropylene resin having two different properties, polypropylene resin consisting of medium crystalline polypropylene having a temperature of less than 155 to 163 ° C. High crystalline polypropylene resin / medium crystalline polypropylene resin = 95 / 5 to 10/90 (weight ratio) included 30 to 90% by weight (b) Polyphenylene resin 70 to 10% by weight The amount of 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound (c) is 65 to 75% based on 100 parts by weight of the components (a) and (b). A block copolymer comprising a polymer block B containing at least one conjugated diene compound as a main component and a polymer block A containing at least one vinyl aromatic compound as a main component is 65% to less than 80%. The present invention provides a thermoplastic resin composition comprising 5 to 30 parts by weight of a hydrogenated selective hydrogenated block copolymer.

The polypropylene resin used as the component (a) in the present invention is a crystalline propylene homopolymer, and a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and And / or a crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer moiety obtained by copolymerizing at least one other α-olefin (eg, butene-1, hexene-1 etc.). Further, it may be a mixture of these crystalline propylene homopolymers and crystalline propylene-ethylene block copolymers.

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

Further, 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 the third component in order to enhance the isotacticity and the polymerization activity of the polypropylene obtained. . 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 is obtained by the above-mentioned method, but it has different properties if the resulting thermoplastic resin composition is subjected to heat history as a heat resistant material and durability is required. It is essential to use a polypropylene-based resin in which two types of polypropylene-based resins are mixed in a specific range.

That is, in the present invention, (a-1) homo-determined from free induction decay (FID) by pulse NMR.
The proportion of the crystalline phase in the polypropylene portion is 96% or more and the melting point is 163 ° C. or more, and the high crystalline polypropylene resin and (a-2) the homo-polypropylene portion obtained by free induction decay (FID) by pulse NMR. The proportion of crystalline phase is 93 to less than 96% and the melting point is 155 to 1
A polypropylene resin in which a medium crystal polypropylene resin having a temperature of less than 63 ° C. is blended in a specific range is more often used [hereinafter, (a-1) is a high crystal polypropylene, (a
-2) is abbreviated as medium crystalline polypropylene, and these blends are abbreviated as polypropylene resins. ].

The proportion of the crystal phase of the homo-polypropylene portion in the present invention is determined by the well-known pulse NMR method by utilizing the different motility of the crystalline portion and the amorphous portion, and the magnetization after 90-degree pulse based on spin-spin relaxation. It can be obtained from the free induction damping (FID) which is a change. Specifically, solid-state polypropylene is converted to pulsed NMR (Bruker).
PC-120) manufactured by K.K. at a temperature of 40 ° C., a proton resonance frequency of 20 MHZ, a pulse time of 4 μsec, and an integration of 3 times. R ₁₂ = {1 when the peaks of SA1 and SA2 are attributed to the crystalline phase and the amorphous phase by the Gaussian curve and the amorphous phase by the Lorenz curve, respectively.
00 × (SA1-SA2) × F} ÷ {(SA1-SA
The ratio of the crystal phase can be calculated from (2) × F + SA2}. Here, R ₁₂ is the ratio of the crystal phase of the measured homo-polypropylene portion, and F is a correction coefficient obtained from the strength ratio when using the standard sample salad oil and polymethylmethacrylate.

The composition containing polypropylene having a crystal phase ratio of less than 93% gives a thermoplastic resin composition having excellent toughness (elongation) after heat history, but tends to have low rigidity and heat resistance. . Further, a thermoplastic resin composition containing polypropylene having a crystal phase ratio of 96% or more has high rigidity and good heat resistance, but the toughness (elongation) after thermal history tends to be small.

The melting point of the homo-polypropylene portion in the present invention is 20 ° C./m with a differential scanning calorimeter (DSC: Perkin Elmer DSC-2 type).
It is a value of melting point measured at in and a temperature decreasing rate of 20 ° C./min. More specifically, first, about 5 mg of the sample is divided into 2
After keeping at 0 ° C for 2 minutes, the temperature was raised to 230 ° C at 20 ° C / min and kept at 230 ° C for 2 minutes.
The temperature of the top peak of the endothermic peak that appears when the temperature is lowered to 20 ° C. for min, further held at 20 ° C. for 2 minutes, and then raised at a heating rate of 20 ° C./min can be obtained as the melting point.

In the composition containing polypropylene having a melting point of less than 155 ° C., the resulting thermoplastic resin composition has excellent toughness (elongation) after thermal history, but rigidity and heat resistance tend to be low. Further, a composition containing polypropylene having a melting point of 163 ° C. or higher gives a thermoplastic resin composition having excellent rigidity and heat resistance after heat history, but the toughness (elongation) after heat history tends to be small.

The polypropylene-based resin used in the present invention contains, in addition to the above-mentioned polypropylene-based resin, the polyolefin-based resin and α, β-unsaturated carboxylic acid or its derivative in the absence of a radical generator. Known modification (0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative is grafted or added) obtained by reacting in a molten state or a solution state at a temperature of 30 to 350 ° C. It may be a polypropylene resin, or may be a mixture of the above-mentioned polypropylene resin and the modified polypropylene resin in an arbitrary ratio.

Next, the component (b), polyphenylene ether (hereinafter simply referred to as PPE) used in the present invention, is an essential component for imparting heat resistance and flame retardancy to the thermoplastic resin composition of the present invention. Yes, the PPE has the following binding units:

Embedded image

(Where R1, R2, R3, and R4
Are hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or at least two carbon atoms each being a halogen atom. It is selected from the group consisting of halohydrocarbonoxy groups separating an oxygen atom, and may be the same or different from each other. And a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of 0.15 to 0.70, more preferably 0.20 to 0.60. And / or a copolymer.

Specific examples of this PPE include poly (2,6-dimethyl-1,4-phenylene ether), 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, and further 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl). Also included are polyphenylene ether copolymers such as copolymers with phenol and 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether),
A copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-diphenylphenol)
6-dimethyl-1,4-phenylene ether) is preferred.

The method for producing PPE is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. It can be easily prepared by oxidative polymerization of 2,6-xylenol, for example.
No. 875, No. 3257357 and No. 3257358, JP-B-52-17880 and JP-A-50-51197 and 63.
It can be easily produced by the method described in JP-A-152628.

In addition to the above PPE, the PPE used in the present invention contains the PPE and a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof in the absence of a radical generator. A known modification (the styrene-based monomer and / or the α, β-unsaturated carboxylic acid or its derivative is obtained by reacting in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C.). (01 to 10 wt% graft or addition) PPE, or a mixture of the above PPE and the modified PPE in any proportion.

And, in addition, 9,10-dihydro-9-
Oxa-10-phosphaphenanthrene was added to PPE10.
The phosphorus compound-treated PPE, which was added by 0.2 to 5 parts by weight with respect to 0 parts by weight and melt-kneaded, also had excellent P
It can be used as PE. In addition to the above PPE, the PPE used in the present invention is PPE100
Polystyrene or high-impact polystyrene added in an amount of 400 parts by weight with respect to parts by weight can also be suitably used.

Next, the selected hydrogenated product of vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as "selective hydrogenated block copolymer") which can be used as the component (c) in the present invention is conjugated. A polymer block B mainly composed of at least one conjugated diene compound having a 1,2-vinyl bond content or a 3,4-vinyl bond content of 65 to 75% in the diene compound and at least one vinyl aromatic compound Is a hydrogenated block copolymer consisting of a polymer block A of 65 to less than 80%, for example, AB, ABA, BAA-
It is a selective hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as B-A, (A-B-) _4- Si, and A-B-A-B-A. This (c)
Selection of components The hydrogenated block copolymer is 20 to 95% by weight, preferably 45 to 80% by weight, more preferably 50 to 70% by weight of the vinyl aromatic compound bonded to the block copolymer before hydrogenation. % Included.

Further, referring to the block structure,
The polymer block B containing a conjugated diene compound as a main component is a homopolymer block of a conjugated diene compound, or a copolymer of a conjugated diene compound and a vinyl aromatic compound containing more than 50% by weight and preferably 70% by weight or more of the conjugated diene compound. The polymer block A having a structure of a polymer block and further containing a vinyl aromatic compound as a main component is preferably a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound exceeding 50% by weight. It has a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound contained in an amount of 70% by weight or more.

Further, the polymer block B mainly containing these conjugated diene compounds and the polymer block A mainly containing these vinyl aromatic compounds are the vinyl aromatic compound or the conjugated diene in the molecular chain of each polymer block. The distribution of the compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped or any combination thereof, and the polymer having the conjugated diene compound as a main component When each of the block B and the polymer block A mainly containing the vinyl aromatic compound is two or more, the polymer blocks may have the same structure or different structures.

Examples of the conjugated diene compound constituting the block copolymer include butadiene, isoprene,
One type or two or more types are selected from 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable. In the polymer block mainly composed of the conjugated diene compound, the microstructure (bonding form of the conjugated diene compound) in the block can be arbitrarily selected. For example, in the polymer block mainly composed of butadiene, 1,2-vinyl is used. The bond is 65-75%. Further, in the polymer block mainly containing isoprene, 3,4-
Vinyl bonds are 65-75%. The bonding form of these conjugated diene compounds can usually be known by an infrared spectrophotometer, NMR, or the like.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, vinyltoluene,
One or more of p-tert-butylstyrene and diphenylethylene can be selected, and styrene is preferable. The number average molecular weight of the block copolymer having the above structure is 5,000 to 1,000,0.
00, preferably 10,000 to 800,000, more preferably 30,000 to 500,000, and molecular weight distribution [weight average molecular weight (Mw) and number average molecular weight (Mn measured by gel permeation chromatography). The ratio]) is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

The block copolymer having such a structure is obtained by selective hydrogenation by selectively hydrogenating the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the above block copolymer. A block copolymer (selective hydrogenation product of vinyl aromatic compound-conjugated diene compound block copolymer) can be used as the component (c) of the present invention. The hydrogenation rate of such aliphatic double bond is 65 to 8
It is less than 0%. In order to selectively carry out the hydrogenation rate as described above, in the hydrogenation reaction of the aliphatic double bond of the block copolymer, the hydrogen consumption is controlled to be within the predicted hydrogenation rate of 65 to less than 80%. Can be easily obtained. And this hydrogenation rate can usually be known by an infrared spectrophotometer, NMR, or the like.

The hydrogenated block copolymer of the above-mentioned component (c) may be obtained by any production method as long as it has the above-mentioned structure.
Examples of known production methods include, for example, JP-A-47-1
1486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255.
JP-A-56-10542, JP-A-56-10542
No. 62847, JP-A-56-100840,
British Patent No. 1130770 and US Patent No. 3
281383 and 3639517, and the methods described in British Patent No. 1020720 and U.S. Pat. Nos. 3,333,024 and 4,501,857.

In such a selectively hydrogenated block copolymer, the conjugated diene compound has a 1,2-vinyl bond or a 3,4-vinyl bond of less than 65% and a hydrogenation ratio of 65.
When it is less than 0.1%, the compatibility between the polypropylene resin and the polyphenylene ether is not improved, the orientation during injection molding is remarkable, and the layer peeling is not preferable.

Further, in the selectively hydrogenated block copolymer, the 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound exceeds 75%, and the hydrogenation rate thereof exceeds 80%. Also, there is no remarkable improvement effect on the compatibility (layer separation) between the polypropylene resin and the polyphenylene ether, and the impact strength tends to be low.
Further, even if such a selectively hydrogenated block copolymer has 65-75% of 1,2-vinyl bonds or 3,4-vinyl bonds of the conjugated diene compound, the hydrogenation rate is 6
If it is less than 5%, the compatibility between the polypropylene resin and the polyphenylene ether is not improved, the orientation during injection molding is remarkable, and layer peeling occurs undesirably. Similarly, such a selectively hydrogenated block copolymer is conjugated. The 1,2-vinyl bond or 3,4-vinyl bond of the diene compound is 65
Even if the hydrogenation ratio is up to 75%, no significant improvement effect on the compatibility (layer separation) between the polypropylene resin and the polyphenylene ether is observed even if the hydrogenation rate exceeds 80%, and the impact strength tends to decrease. is there.

The selective hydrogenated block copolymer of the component (c) used in the present invention has an amount of bound styrene of 20 to 95% by weight as described above.
Not only one kind, but also two or more kinds of selectively hydrogenated block copolymers having different amounts of bound styrene can be used together.
The selective hydrogenated block copolymer of the component (c) used in the present invention is, in addition to the above-mentioned selective hydrogenated block copolymer, the selective hydrogenated block copolymer and the α, β-unsaturated carboxylic acid. Or its derivative in the presence of a radical generator,
In the absence, the molten state, the solution state, the slurry state 80 ~
It may be a modified hydrogenated block copolymer obtained by reacting at a temperature of 350 ° C. (modified with 0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative). Further, it may be a mixture of the above-mentioned selected hydrogenated block copolymer and the modified selected hydrogenated block copolymer in an arbitrary ratio.

The thermoplastic resin composition of the present invention comprises the above-mentioned components (a) to (c) as basic components.
In order to use the high crystalline polypropylene and the medium crystalline polypropylene, in which the polypropylene resin as the component (a) is used, the ratio of the high crystalline polypropylene / medium crystalline polypropylene is 95/5 to 10/90 (weight ratio), preferably 90 /. 10-70 / 30, more preferably 90 /
Used in a ratio of 10-50 / 50. In such a ratio, when the high-crystal polypropylene exceeds 95%, the thermoplastic resin composition obtained has excellent heat resistance and rigidity, but the toughness (elongation) after heat history (80 ° C. × 48 hours) becomes small. There is a tendency. Further, when the content of the medium crystalline polypropylene is more than 90%, the toughness (elongation) of the obtained composition after the heat history (80 ° C. × 48 hours) is not significantly reduced, but the heat resistance and the rigidity tend to be low. Show.

The compounding amount of the polypropylene resin as the component (a) of the present invention is 30 to 90% by weight, preferably 45 to 65% by weight, and the high crystalline polypropylene and the medium crystalline polypropylene are within the above specified range. Even when it contains, the total amount is 30 to 90% by weight, preferably 45 to 65% by weight. When the blending amount is less than 30% by weight, the thermoplastic resin composition obtained is excellent in heat resistance, but inferior in moldability and solvent resistance, which is not preferable. When it exceeds 90% by weight, the moldability and solvent resistance are good, but the heat resistance is poor and the material cannot be used as a heat resistant material.

The content of the polyphenylene ether as the component (b) is 70 to 10% by weight, preferably 60 to 30% by weight.
It is. When the blending amount exceeds 70% by weight, the heat resistance of the thermoplastic resin composition obtained is extremely excellent, but the moldability and solvent resistance are poor, which is not preferable. Also,
If it is less than 10% by weight, the moldability and solvent resistance are excellent, but the heat resistance is poor and it cannot be used as a heat resistant material.

Selection of component (c) The blending amount of the hydrogenated block copolymer is usually 5 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b). If the blending amount is less than 5 parts by weight, the effect as an admixture is not observed and it is not preferable. On the other hand, if the amount is more than 30 parts by weight, the effects of the components (a) and (b), such as heat resistance, solvent resistance, rigidity and mechanical strength, are significantly lowered, which is not preferable.

In the present invention, in addition to the above-mentioned components, other optional components such as a styrene-butadiene block copolymer having a bound styrene content of 10 to 90% may be added, if necessary, within a range that does not impair the characteristics and effects of the present invention. Polymer, bound styrene content 1
0-90% of styrene-isoprene block copolymers and hydrogenated block copolymers obtained by hydrogenating 80% or more of aliphatic double bonds resulting from conjugated diene compounds of these block copolymers, antioxidants, Metal deactivators, flame retardants (organic phosphate compounds, inorganic phosphorus compounds,
Aromatic halogen flame retardants, silicone flame retardants, etc.),
Fluorine-based polymers, plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide,
Weather (light) resistance improver, nucleating agent for polyolefin, slip agent, inorganic or organic filler or reinforcing material (glass fiber,
Carbon fiber, polyacrylonitrile fiber, whiskers, mica, talc, carbon black, titanium oxide,
Calcium carbonate, potassium titanate, wollastonite,
Conductive metal fibers, conductive carbon black, etc.), various coloring agents, release agents, etc. may be added.

The thermoplastic resin composition of the present invention is a method in which the components (b) and (c) are melt-kneaded in advance by using the above-mentioned components, and the mixture is melt-kneaded together with the component (a). Part of the (c) component is (a) component or (b) in advance.
Method of pre-kneading with the components and melt-kneading these pre-kneaded materials together again, from the first feed port of the extruder (b)
It can be produced by various methods such as a method of supplying the component and the component (c), and then supplying the component (a) into the composition in a molten state from the intermediate port of the extruder and melt-kneading. Examples of these methods include a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, and a heat-melt kneading method using a Banbury mixer.
Of these, the melt-kneading method using a twin-screw extruder is most preferable. The melt-kneading temperature at this time is not particularly limited, but can be arbitrarily selected from the range of usually 200 to 350 ° C.

The thermoplastic resin composition of the present invention thus obtained can be molded into various molded articles by various conventionally known methods such as injection molding, extrusion molding and blow molding. These various parts include, for example, automobile parts.Specifically, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc. Suitable for interior parts such as instrument panel, console box, trim etc. Further, it can be suitably used as an interior / exterior component of electric equipment, specifically, various computer and its peripheral equipment, other office automation equipment, televisions, videos, cabinets such as disc players, and parts such as refrigerators. Suitable for

[0045]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. <Reference Example 1: Preparation of high crystalline polypropylene of component (a-1)> PP-1: homo-polypropylene Ratio of crystalline phase of homo-polypropylene portion = 97.1% Melting point = 168 ° C, MFR = 10.7 PP -2: Homo-polypropylene Proportion of crystal phase of homo-polypropylene portion = 96.7% Melting point = 167 ° C, MFR = 6.8 PP-3: Homo-polypropylene Proportion of crystal phase of homo-polypropylene portion = 96.2 % Melting point = 165 ° C., MFR = 13.4 Polypropylene MFR (melt flow rate) is AS
According to TM D1238, 230 ℃, 2.16kg
The load was measured.

<Reference Example 2: Preparation of medium crystalline polypropylene of component (a-2)> PP-4: homo-polypropylene Ratio of crystalline phase of homo-polypropylene portion = 94.0% Melting point = 160 ° C, MFR = 10 .1 PP-5: Homo-polypropylene Ratio of crystalline phase of homo-polypropylene portion = 95.2% Melting point = 161 ° C, MFR = 6.4 PP-6: Homo-polypropylene Ratio of crystalline phase of homo-polypropylene portion = 93.3% Melting point = 159 ° C., MFR = 0.3 Polypropylene MFR (melt flow rate) is AS
According to TM D1238, 230 ℃, 2.16kg
The load was measured.

Reference Example 3: Preparation of PPE as component (b)> Polyphenylene ether having a reduced viscosity of 0.54 obtained by oxidative polymerization of b-1: 2,6-xylenol b-2: 2,6-xylenol Polyphenylene ether having a reduced viscosity of 0.31 obtained by oxidative polymerization of

<Reference Example 4: Both of the hydrogenated blocks of the component (c)
Preparation of Polymer> c-1: Polystyrene-Hydrogenated polybutadiene-Polystyrene structure, bound styrene amount 65%,
Number average molecular weight 108,000, molecular weight distribution 1.08, polybutadiene before hydrogenation has a 1,2-vinyl bond content of 7
5%, hydrogenation rate of polybutadiene part is 78%, selective hydrogenated block copolymer c-2: polystyrene-having a structure of hydrogenated polybutadiene-polystyrene, bound styrene amount of 50%,
Number average molecular weight 83,000, molecular weight distribution 1.05, 1,2-vinyl bond amount of polybutadiene before hydrogenation is 71
%, Hydrogenation rate of polybutadiene part is 77%, selective hydrogenated block copolymer

C-3: Polystyrene-having a structure of hydrogenated polybutadiene, bound styrene content 42%, number average molecular weight 71,000, molecular weight distribution 1.05, 1,2-vinyl polybutadiene before hydrogenation The amount of binding is 67
%, The hydrogenation rate of the polybutadiene part is 77%, and the selective hydrogenated block copolymer has a structure of polystyrene-hydrogenated polybutadiene c-4: bound styrene amount 60%, number average molecular weight 6
Selective hydrogenated block copolymer having a molecular weight distribution of 4,000, a molecular weight distribution of 1.05, the amount of 1,2-vinyl bonds of polybutadiene before hydrogenation of 74%, and the hydrogenation rate of the polybutadiene portion of 68%.

C-5: Polystyrene-having a structure of hydrogenated polybutadiene-polystyrene, bound styrene amount 61%, number average molecular weight 58,000, molecular weight distribution 1.04, polybutadiene 1,2 before hydrogenation -The vinyl bond content is 63%, and the hydrogenation rate of the polybutadiene part is 7
5% selectively hydrogenated block copolymer c-6: polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene amount 62%,
The number average molecular weight is 88,000, the molecular weight distribution is 1.09, and the 1,2-vinyl bond amount of the polybutadiene before hydrogenation is 61.
%, Hydrogenation rate of polybutadiene part is 99.9%, hydrogenated block copolymer

<Examples 1 to 6 and Comparative Examples 1 to 3> Highly crystalline polypropylene, medium crystalline polypropylene, polyphenylene ether and an admixture were blended in the composition shown in Table 1 and 2
Twin-screw extruder with a vent port set to 60 to 280 ° C (ZSK-25; WERNER & PFLEIDERER
(Manufactured by Germany, Germany) and melt-kneaded to obtain pellets.

The pellets were supplied to a screw in-line type injection molding machine set at 240 to 280 ° C.,
A test piece for tensile test, a test piece for flexural modulus measurement test, a test piece for Izod impact test and a test piece for heat distortion temperature measurement were injection-molded under a mold temperature of 60 ° C. At this time, the gate portion of the test piece for tensile test in the hot state immediately after molding, which was taken out by opening the molding die, was sandwiched with pliers, bent and ruptured, and the presence or absence of layer delamination was confirmed from this fracture surface.

Then, using these test pieces, a tensile strength test (ASTM D-638: 23 ° C.) was conducted to measure the tensile strength and elongation at break, and further flexural modulus (ASTM D-790: 23 ° C.), Izod (notched) impact strength (ASTM D-256: 2
3 ° C) and heat distortion temperature (ASTM D-648) were measured. In addition, a part of these test pieces is assumed to have a predicted heat history, and is subjected to a heat history environment (80 ° C. × 48 hours) using a gear oven, and similarly subjected to a tensile strength test (ASTM D-638). : 23 ° C.) to measure tensile strength and elongation at break, and further flexural modulus (ASTM D-790: 23 ° C.), Izod (notched) impact strength (ASTM D-256: 2).
3 ° C) and heat distortion temperature (ASTM D-648: 1
8.6 kg / cm ² load) was measured. The obtained results are also shown in Table 1.

[0054]

[Table 1]

From these results, in the thermoplastic resin composition containing the selectively hydrogenated block copolymer having the specific structure of the present invention, delamination was not observed even in the gate portion where a large orientation is expected during molding. However, when a hydrogenated block copolymer other than the present invention was used, the orientation of this gate portion was remarkable, and it was split like a bamboo in a bending fracture test with pliers.
Further, the thermoplastic resin composition of the present invention, by containing the high-crystalline polypropylene and the medium-crystalline polypropylene specified in the present invention in a specific range, the heat resistance, the rigidity is good, the heat resistance after heat history, the rigidity The balance of physical properties of toughness and toughness is maintained at a high level, and a large synergistic effect can be seen by using high crystalline polypropylene and medium crystalline polypropylene together.

[0056]

Since the thermoplastic resin composition of the present invention is composed of a polypropylene resin, polyphenylene ether and a specific hydrogenated block copolymer, the compatibility is greatly improved and a layer associated with orientation during molding is obtained. Peeling is improved, and the polypropylene-based resin is composed of a high-crystalline polypropylene-based resin and a medium-crystalline polypropylene-based resin that exhibit a specific structure, and these are configured in a specific range. A thermoplastic resin composition having improved heat resistance, rigidity, and toughness after heat history, which has been difficult with a thermoplastic resin composition containing polyphenylene ether, and a thermoplastic resin composition having excellent durability as a heat resistant material.

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 71/12 LQP C08L 71/12 LQP

Claims (1)

[Claims] 1. In a thermoplastic resin composition, (a) a polypropylene resin has a homo-polypropylene portion having a crystal phase ratio of 96% or more as determined by (a-1) free induction decay (FID) by pulse NMR. And the proportion of the crystalline phase of the homo-polypropylene portion calculated from free induction decay (FID) by (a-2) pulse NMR having a melting point of 163 ° C. or higher is 93 to less than 96%. A high-crystalline polypropylene resin / medium-crystalline polypropylene, a polypropylene-based resin having two different properties: a polypropylene-based resin having a melting point of less than 155 to 163 ° C. and a medium-crystalline polypropylene. Resin: 95/5 to 10/90 (weight ratio) is included. Polypropylene resin 30 to 90% by weight (b) Polyphe Renether 70 to 10% by weight Based on 100 parts by weight of the components (a) and (b), the amount of 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound (c) is 65 to 75. % Of a block copolymer consisting of a polymer block B containing at least one conjugated diene compound as the main component and a polymer block A containing at least one vinyl aromatic compound as the main component. A thermoplastic resin composition comprising 5 to 30 parts by weight of a selectively hydrogenated block copolymer obtained by hydrogenation of less than.