JPH08295762A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin compsn. which contains a polyamide and a polyolefin well compatibilized with each other and is excellent in mechanical, thermal, surface, and environmental characteristics. CONSTITUTION: The compsn. comprises 0.1-99wt.% polyamide, 0.1-99wt.% polyolefin, and 0.01-99wt.% terminal-modified polypropylene having terminal groups represented by the formula (wherein R<a> is H or methyl; R<b> is a 2-10C alkenyl group having a terminal double bond; and n is a mean number in the range of 0.1-500).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing a polyamide and a polyolefin, and more particularly to a thermoplastic resin composition containing a polyamide and a polyolefin in which respective components are well compatibilized. The present invention particularly relates to the above-mentioned resin composition which is useful in applications such as automobile interior and exterior parts, electrical components, home appliances, sports equipment, furniture, office supplies and the like.

[0002]

2. Description of the Related Art Polyamide resin is a resin excellent in heat resistance, mechanical strength, insulation and the like. on the other hand,
Polyolefin has the characteristics of low specific gravity and excellent impact resistance, and good environmental characteristics such as moldability, water resistance, and chemical resistance. Therefore, attempts have been made to blend a polyamide and a polyolefin to produce a resin composition having the advantages of both. However, since the polyamide and the polyolefin have poor compatibility with each other, there is a problem that impact resistance, mechanical strength, and the like are deteriorated in a thermoplastic resin composition containing the both.

In an attempt to improve the compatibility of polyamide and polyolefin, the polyamide is blended with a polyolefin obtained by adding an unsaturated carboxylic acid or a derivative thereof, in particular, an unsaturated dicarboxylic acid anhydride such as maleic anhydride (MAH), and melted. A method of kneading is known. According to this method, the compatibility and dispersibility of both are improved, and therefore, a composition having excellent impact resistance and preventing deterioration due to water absorption is obtained. However, in this method, when the dicarboxylic acid anhydride is added to the polyolefin, alteration or deterioration may occur due to crosslinking of the polyolefin, and a specific portion of the polyolefin cannot be modified. Since associations and the like occur, the physical properties are not sufficiently improved by compatibilization. In addition, the unreacted acid remaining after the modification of the polyolefin reacts with the polyamide to color it,
There was also the problem of impairing the appearance.

Therefore, the applicant of the present invention has already proposed a method of melt-kneading polyamide and polyolefin with a polymerizable compound having at least one glycidyloxy group in the molecule and a polymerization initiator (Japanese Patent Laid-Open No. 5-39330), and aroma. A composition (Japanese Patent Laid-Open No. 4-164960) in which a modified olefin elastomer grafted with a group-type glycidyl compound is blended with polyamide was found.

The present invention provides mechanical properties such as impact resistance, tensile strength, and peel resistance, thermal properties such as heat resistance, and surface properties such as appearance, in which polyamide and polyolefin are well compatibilized, and It is an object to provide a thermoplastic resin composition having excellent environmental characteristics such as water resistance and chemical resistance.

[0006]

Means for Solving the Problems As a result of extensive studies on the compatibilization of a polyamide and a polyolefin, the present inventors have found that as a compatibilizer, a specific structure containing an alkenyl group having a double bond at the end is used as a compatibilizer. The inventors have found that the use of the polypropylene provided makes it possible to obtain a resin composition having good compatibility with both of them and without causing coloring, and having the excellent properties described above.

That is, the present invention relates to (A) polyamide 0.
1 to 99 wt%, (B) polyolefin 0.1 to 99 wt%, and (C) at the end have the following formula (I):

[0008]

Embedded image (In the above formula, R ^a represents a hydrogen atom or a methyl group; R
^b represents an alkenyl group having a double bond at the terminal and having 2 to 10 carbon atoms; n is an average value and is in the range of 0.1 to 500).
It is a thermoplastic resin composition containing 01 to 99% by weight.

Preferred embodiments include the following: In the above formula (I), R ^b is a vinyl group, an allyl group,
3-butenyl group, 4-pentenyl group, 5-hexenyl group and
The above thermoplastic resin composition selected from 2-methyl-4-pentenyl group. In the above formula (I), the thermoplastic resin composition according to any one of the above, wherein n is in the range of 0.5 to 100. (C) The terminal-modified polypropylene is present in the presence of a catalyst composed of a vanadium compound and an organoaluminum compound,
The thermoplastic resin composition according to any one of the above, which is obtained by living polymerization of propylene. The amount of each component is (A) 1 to 95% by weight, (B) 1 to 9
5% by weight and (C) 0.1 to 95% by weight of the thermoplastic resin composition as described above. A method for producing a thermoplastic resin composition according to any one of the above, wherein each component is melt-kneaded at 200 to 350 ° C.

Next, the present invention will be described. First, as the (A) polyamide, for example, a polyamide obtained by a reaction of a diamine and a dicarboxylic acid; a polyamide derived from an aminocarboxylic acid; a polyamide derived from a lactam; and a copolyamide composed of these components,
Alternatively, a mixture of these polyamides can be used. As the diamine, any of aliphatic, alicyclic or aromatic diamines can be used, for example, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethyl. Hexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine and the like can be mentioned. As the dicarboxylic acid, any of aliphatic, alicyclic or aromatic dicarboxylic acids can be used, and examples thereof include adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid. Examples of the aminocarboxylic acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples of the lactam include ε-caprolactam and ω-dodecaractam. Specific examples of polyamides include nylon 6, nylon 66, and nylon 61.
0, nylon 9, nylon 6/66, nylon 66/610,
Examples include nylon 6/11, nylon 6/12, nylon 12, nylon 46, and amorphous nylon. Among these, nylon 6 and nylon 66 are preferable in terms of good rigidity and heat resistance.

Although the molecular weight is not particularly limited, a polyamide having a relative viscosity η _r (measured in 98% sulfuric acid according to JIS K6810) of 0.5 or more is usually used, and among them, a polyamide having a mechanical strength of 2.0 or more is mechanical strength. Is preferable because it is excellent.

The (B) polyolefin used in the present invention is not particularly limited, and known polyolefins can be used. For example, a homopolymer of α-olefin (including ethylene); a copolymer of two or more types of α-olefin (including any copolymer such as random, block, and graft, and may be a mixture thereof); Alternatively, an olefin elastomer may be used. Examples of α-olefins include ethylene, propylene, 1-butene, 1-hexene, 3-
Methyl-1-butene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene and the like can be mentioned.

Ethylene homopolymers include low density polyethylene (LDPE) and high density polyethylene (HDP).
E) and linear low density polyethylene (LLDPE) can be used. The polypropylene is not limited to a propylene homopolymer, and includes a block copolymer or a random copolymer of propylene and ethylene. In the case of a copolymer, it is an ethylene-propylene copolymer having an ethylene content of 20% by weight or less, and such polypropylene usually has a melt flow rate (MFR, JIS K7210) in the range of 0.1 to 200 g / 10 min. Load 2.16 kg, 230 ° C
Measurement). The above-mentioned polyethylene or polypropylene may contain up to about 40% by weight of an olefin elastomer.

Here, the olefin elastomer means
Ethylene and one or more α-other than ethylene
It means a copolymer rubber with an olefin (for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, etc.). Typically, ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer rubber (EB
R), ethylene-propylene-diene copolymer rubber (E
PDM) and the like. As the diene in the ethylene-propylene-diene copolymer rubber (EPDM), for example, a non-conjugated diene such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene or a conjugated diene such as butadiene or isoprene is used. can do. Also, these EPR, EBR and EP
The DM may contain other repeating units, for example, repeating units derived from other α-olefins such as 4-methyl-1-pentene up to a proportion of 10 mol% or less.

Preferred polyolefins are homopolymers of ethylene or propylene, copolymers of ethylene and propylene, copolymers of ethylene or propylene with other α-olefins, and olefin elastomers.

Next, the (C) terminal-modified polypropylene is
A polypropylene having a terminal structure represented by the above formula (I). Such a terminal-modified polypropylene was found by the present applicant and is described in JP-A No. 5-194631. Here, polypropylene is not limited to propylene homopolymer, but propylene and other α-olefins (for example, ethylene, 1-butene,
1-hexene, 4-methyl-1-pentene, etc.) and one or more block copolymers or random copolymers or copolymer rubbers. The polypropylene having the terminal structure represented by the formula (I) is a composition of terminal-modified polypropylene having various degrees of polymerization of terminal groups,
n is the average value. n is 0.1 to 500, preferably 0.
5 to 100. In the formula (I), R ^b is, for example, vinyl group, allyl group, isopropenyl group, 3-
Butenyl group, 4-pentenyl group, 1-methyl-3-butenyl group, 2-methyl-3-butenyl group, 5-hexenyl group, 1-methyl-4-pentenyl group, 2-methyl-4-pentenyl group, 3 -Methyl-4-pentenyl group, 6-heptenyl group, 1-methyl-5-
Hexenyl group, 2-methyl-5-hexenyl group, 3-methyl-5
-Hexenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group and the like. Preferred R ^b is a vinyl group,
It is selected from allyl, 3-butenyl, 4-pentenyl, 5-hexenyl and 1-methyl-4-pentenyl.

The polypropylene having the above-mentioned terminal structure (I) can be produced as follows. That is, the following equation (II):

[0018]

Embedded image (In the above formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, provided that at least one of R ^{1 to} R ³ is a hydrogen atom. A living polypropylene obtained by living polymerization of propylene in the presence of a catalyst consisting of a vanadium compound represented by the formula ( ¹⁾ , and R ^{1 to} R ³ must not be all hydrogen atoms. Is expressed by the following formula (III):

[0019]

[Chemical 4] (In the above formula, R ^a and R ^b have the same meanings as described above).

Now, specific examples of the vanadium compound represented by the above formula (II) will be described. (1) When R ² is a hydrogen atom and both R ¹ and R ³ are hydrocarbon groups. Examples of the combination of R ¹ / R ³ include CH ₃ / CH ₃ , CH ₃ / C ₂ H ₅ , C ₂ H ₅ / C ₂
H ₅ , CH ₃ / C ₆ H ₅ , C ₂ H ₅ / C ₆ H ₅ , C ₆ H
₅ / C ₆ H ₅ , CH ₃ / C ₆ H ₅ CH ₂ , C ₆ H ₅ CH
_{2 / C 6 H 5 CH 2} , C 2 H 5 / C 6 H 5 CH 2, C 6
_{H 5 / C 6 H 5 CH} 2 and the like. (2) When R ² is a hydrocarbon group, one of R ¹ and R ³ is a hydrogen atom and the other is a hydrocarbon group. R ²
Examples of the combination of / R ¹ (or R ³ ) include CH
₃ / CH ₃ , C ₂ H ₅ / CH ₃ , CH ₃ / C ₂ H ₅ , C
₂ H ₅ / C ₂ H ₅ , C ₆ H ₅ / CH ₃ , CH ₃ / C ₆ H
_{5, C 6 H 5 / C} 2 H 5, C 2 H 5 / C 6 H 5, C 6 H
_{5 / C 6 H 5, C} 6 H 5 CH 2 / CH 3, CH 3 / C 6
_{H 5 CH 2, C 6 H} 5 CH 2 / C 6 H 5 CH 2, C 6 H
_{5 CH 2 / C 2 H 5} , C 2 H 5 / C 6 H 5 CH 2, C 6
_{H 5 CH 2 / C 6 H} 5, C 6 H 5 / C 6 H 5 CH 2 and the like. (3) When R ² is a hydrogen atom, one of R ¹ and R ³ is a hydrogen atom and the other is a hydrocarbon group. Examples of R ¹ or R ³ include CH ₃ , C ₂ H ₅ , C
₆ H ₅ , C ₆ H ₅ CH _{2 and the} like can be mentioned.

Among these, particularly, a compound represented by the following formula (IV), that is, V (acetylacetonato) ₃ ; a compound represented by the following formula (V), that is, V (2-methyl-
1,3-butanedionate) ₃ ; a compound represented by the following formula (VI), that is, V (1,3-butanedionate) ₃ is preferable.

[0022]

Embedded image

[0023]

[Chemical 6]

[0024]

[Chemical 7] Next, the organoaluminum compound used as the catalyst described above has a general formula:

[0025]

Embedded image R _m AlY _3-m (wherein R is an alkyl group or an aryl group,
Y is a halogen atom or a hydrogen atom, and m is 1 ≦ m <
Any number satisfying 3) can be used. A preferred organoaluminum compound has 1 to 1 carbon atoms.
It is an organoaluminum compound having 18, preferably 2 to 6 carbon atoms, or a mixture or complex compound thereof, and examples thereof include dialkylaluminum monohalide, monoalkylaluminum dihalide, and alkylaluminum sesquihalide. Examples of the dialkyl aluminum monohalide include dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride and the like; examples of the monoalkyl aluminum dihalide include methyl aluminum dichloride, ethyl aluminum dichloride, Methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride and the like can be mentioned; as alkylaluminum sesquihalide,
Examples include ethylaluminum sesquichloride.

The ratio of the vanadium compound to the organoaluminum compound in the catalyst is preferably 1 to 1,000 moles of the organoaluminum compound per mole of the vanadium compound.

Living polymerization of propylene includes, in addition to homopolymerization of propylene, ethylene, 1-butene,
It is also possible to polymerize in the coexistence of α-olefins such as 1-hexene and 4-methyl-1-pentene.

The polymerization reaction is inert to the polymerization reaction,
And it is preferable to carry out in a solvent which is liquid at the time of polymerization. Examples of such a solvent include saturated aliphatic hydrocarbons such as propane, butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons such as cyclopropane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene. Is mentioned.

The amount of the polymerization catalyst used during the polymerization of propylene is 1 × 10 ^{−4 to} 0.1 mol, preferably 5 × 10 ^{−4 to} 5 × of vanadium compound per 1 mol of propylene (and other α-olefin). In 10 ^-2 mol, the organoaluminum compound is 1 x 10 ^{-4 to} 0.5 mol, preferably 1 x 10 ^{-3 to} 0.1 mol. The organoaluminum compound is preferably used in an amount of 4 to 100 mol per mol of the vanadium compound.

Living polymerization is usually from -100 ° C to 100 ° C.
It is carried out at 0 ° C for 0.5 to 50 hours.

The molecular weight and yield of the living polypropylene obtained can be adjusted by changing the reaction temperature and the reaction time. By setting the polymerization temperature to a low temperature, particularly -30 ° C or lower, a polymer having a molecular weight distribution close to monodispersion can be obtained. At −50 ° C. or lower, a living polymer having Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.05 to 1.40 can be obtained.

A reaction accelerator can be used during the polymerization reaction. As the reaction accelerator, anisole, water, oxygen,
Examples thereof include alcohols (methanol, ethanol, isopropanol, etc.) and esters (ethyl benzoate, ethyl acetate, etc.). The amount of the accelerator used is usually 0.1 to 2 mol per mol of the vanadium compound.

As described above, living polypropylene having a number average molecular weight of about 800 to 400,000 and being nearly monodisperse can be produced.

Next, in order to introduce a terminal structure, living polypropylene is reacted with the compound represented by the above formula (III). As the compound (III), for example, vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate and the like can be preferably used. The reaction between living polypropylene and compound (III) is the reaction of compound (III) in the reaction system in which living polypropylene is present.
Is preferred for the reaction. The reaction is usually −
It is carried out at a temperature of 100 ° C to 150 ° C for 5 minutes to 50 hours. By increasing the reaction temperature or increasing the reaction time,
It is possible to increase the rate of modification of the polypropylene terminal with the compound (III) unit. Living polypropylene 1
The compound (III) is usually used in an amount of 1 to 1,000 mol per mol.

The reaction product of living polypropylene and compound (III) is then contacted with a proton donor. Examples of the proton donor include alcohols such as methanol and ethanol; phenols; mineral acids such as hydrochloric acid and sulfuric acid. Alcohols, phenols and mineral acids may be used simultaneously. The proton donor is usually used in large excess. Contact with a proton donor is usually -100.
It is performed at 1 to 10 hours at 100 to 100 ° C.

The terminal-modified polypropylene obtained as described above has a number average molecular weight (Mn) of about 800 to 500,000.
And a very narrow molecular weight distribution (Mw / Mn = 1.05 to 1.
40). Moreover, at the end, on average 0.1-50
It has 0, preferably 0.5 to 100 of the terminal structures.

The above-mentioned component (C) may include polypropylene which is not end-modified.

The terminal-modified polypropylene thus produced has a syndiotactic dyad fraction of
One feature is that it is 0.6 or more.

The thermoplastic resin composition of the present invention contains the above components in the following proportions. That is, (A) 0.1
~ 99 wt%, (B) 0.1-99 wt% and (C)
0.01 to 99% by weight, preferably (A) 1 to 9
5% by weight, (B) 1 to 95% by weight and (C) 0.1
It is 95% by weight.

In the thermoplastic resin composition of the present invention, in addition to the above-mentioned components, conventional additives such as fillers and reinforcing materials (glass fiber, carbon fiber, carbon black, silica,
(Titanium oxide etc.), heat stabilizer, light stabilizer, oxidative deterioration inhibitor, flame retardant, plasticizer, antistatic agent, nucleating agent, foaming agent, weathering agent, lubricant, release agent, fluidity improver, etc. It may have been done.

Further, the thermoplastic resin composition of the present invention comprises
A commercially available engineering plastics impact modifier may be contained up to about 50% by weight. Examples of such an impact resistance improver include Staphyloid (manufactured by Takeda Pharmaceutical Co., Ltd.).

The method for producing the thermoplastic resin composition of the present invention is not particularly limited, but a melt kneading method is preferable. Examples of the melt kneading method include a uniaxial or biaxial continuous extruder, a Banbury mixer, a kneading roll, a Brabender,
Any known method such as a batch type kneader such as a kneader can be used. The kneading temperature is preferably 200 to 350.
C., and the kneading time is usually 0.5 to 15 minutes. At the time of melt-kneading, the kneading order of the respective components is not particularly limited, and the respective components may be melt-kneaded at the same time or may be sequentially added in an arbitrary order. It can also be manufactured by a solution method.

[0043]

In the resin composition of the present invention, the respective components are satisfactorily compatibilized, exhibiting excellent properties such as high impact resistance and high MFR. The reason for this is not clear, but it is presumed that this is because the polyamide and the polyolefin are compatibilized via the terminal-modified polypropylene having a specific terminal structure (alkenyl group-containing structure having a double bond at the terminal). That is, it is considered that when melt-kneading, the modified portion of the terminal-modified polyolefin acts at the interface of the polyamide, while the polypropylene portion of the terminal-modified polypropylene is compatible with the polyolefin, so that the respective components become compatible. In particular, the modified polypropylene used as a compatibilizer in the conventional method has a modifier (MAH, epoxy functional group, etc.) introduced in a branched form on the main chain of polypropylene, whereas the present invention It is considered that, since the alkenyl group-containing structure having a double bond at the end is introduced only at the end of the molecular chain and the structure is a true block, an excellent effect can be obtained. Also in the method disclosed in Japanese Patent Laid-Open No. 5-39330, the polymerizable compound is bonded in a branched form on the polyolefin main chain.

Moreover, in the present invention, since an acid is not used as a compatibilizing component, deterioration of the appearance of the resin composition due to coloring does not occur unlike the conventional method. Furthermore, by producing polypropylene using a living polymerization method, the molecular weight can be controlled, and the amount of the introduced terminal functional group can be freely changed. In addition, since the resin composition can be obtained by kneading the respective components at once, it is industrially easy to carry out, the cost associated with the kneading is low, and the practicability is extremely high.

[0045]

The present invention will be described in more detail with reference to the following examples. The following substances were used in the examples and comparative examples. (A) Polyamide Ny-6: Nylon 6 (manufactured by Unitika Ltd., A1030BR
L) Ny-66: Nylon 66 (manufactured by ICI Corporation,
Maranille A125) AmNy: Amorphous Nylon (EX, EX)
3038) (B) Polyolefin PP: polypropylene, (Tonen Chemical Co., Ltd., Y20
1), Melt flow rate (MFR) (230 ℃, 2.16kg
1.5 g / 10 minutes EPR: ethylene-propylene copolymer rubber (manufactured by Japan Synthetic Rubber Co., Ltd., EP912P), MFR (230 ° C, 2.
7.5 g / 10 minutes (measured with a load of 16 kg) (C) End-modified polypropylene syn-PP-VMA: Syndiotactic polypropylene end-modified with vinyl methacrylate ( ^Ra :
^{_{CH 3, R b: -CH =}} CH 2), was prepared as follows: into a 1 liter stainless steel autoclave was sufficiently substituted with (1) propylene living polymerization nitrogen gas, putting n- heptane 600 ml, Cooled to -60 ° C. 200 ml of liquefied propylene was added at this temperature. Then 150 mmol of Al (C ₂ H ₅ ) ₂ Cl
n-heptane solution and 30 mmol of V (2-methyl-1,3-
A toluene solution of (butanedionate) ₃ was added, and polymerization was started with stirring. Polymerization of propylene was carried out at -60 ° C for 5 hours. (2) Reaction with vinyl methacrylate (VMA) Vinyl methacrylate (VMA) 100 m in the above reaction system
1 at -60 ° C, and the temperature in the system was 0 ° C over 1 hour.
Then, the mixture was stirred at the same temperature and reacted with VMA. After 5 hours, the reaction solution was poured into 3 liters of ethanol to precipitate a polymer. The obtained polymer was again dissolved in n-heptane and centrifuged to obtain a supernatant. The supernatant was poured into 3 liters of methanol to precipitate the polymer again. The obtained polymer was washed with methanol 5 times and then dried under reduced pressure at room temperature. 53 g of polymer was obtained.

The molecular weight and molecular weight distribution of the obtained polymer were determined using GPC (gel permeation chromatography) model 150 (manufactured by Waters). Using o-dichlorobenzene as the solvent, the measurement temperature was 135 ° C., and the solvent flow rate was 1.0 ml / min. As the column, GMH6HT (trade name, manufactured by Tosoh Corporation) was used. For the measurement, a standard curve of polystyrene was obtained using a standard sample of monodisperse polystyrene manufactured by Tosoh Corporation, and a standard curve of polypropylene was prepared from this by a universal method. The GPC efflux curve of the resulting polymer was unimodal. Mn of this polymer was 4.9 × 10 ⁴ , and Mw / Mn was 1.22, which was a value close to monodispersion. (3) Structural determination of polymer IR: Model IR-810 (trade name) manufactured by JASCO Corporation
It measured by the liquid film method (KBr board) using the infrared spectrophotometer. 1740 cm ^-1 to the absorption based on the stretching vibration of carbonyl, and 1640 cm ^-1 is absorption based on C = C stretching vibration was observed.

¹ H-NMR: JSX GSX-40 manufactured by JEOL Ltd.
0 (trade name), using a Fourier transform type NMR spectrometer, the measurement was carried out under the conditions of 400 MHz, 30 ° C. and a pulse interval of 15 seconds. The sample was prepared by dissolving it in deuterated chloroform. Peak due to the proton of polypropylene (δ =
In addition to 0.7-1.7 ppm), vinyl end groups (-CH = CH
₂ ) peak due to -C H = (δ = 7.1 ppm) and peak due to = C H ₂ (δ = 4.6 and 4.9 ppm)
) Was recognized.

Further, the proton signal of the polypropylene portion (δ = 0.7 to 1.7 ppm) and the above signal (δ = 7.
From the area ratio of 1 ppm), it was found that the obtained polymer had 8.1 VMA units introduced at the ends of polypropylene (n = 8.1). (4) Measurement of dyad fraction Next, in order to measure the syndiotactic dyad fraction of the obtained polypropylene, after separately performing living polymerization of propylene by the same operation as above, the reaction solution was-
Polymerization was stopped by pouring it into an ethanol-hydrochloric acid solution (500 ml) cooled to 78 ° C.
It was washed 5 times with 0 ml of ethanol and dried at room temperature to obtain polypropylene.

The obtained polypropylene was analyzed by ¹³ C-NMR. 50M using a XL-200 type (trade name) with a PFT pulse Fourier transform device manufactured by Varian
It was measured under the conditions of Hz, 120 ° C., pulse width 8.2 μs π / 3, pulse interval 4 seconds, and number of integration times 5,000. The sample was prepared by dissolving it in a mixed solvent of trichlorobenzene and benzene (2: 1).

The stereoregularity of polypropylene calculated from the multiplex intensity ratio of methyl carbon in the spectrum is shown below.

[0051]

TABLE 1 triad fraction dyad fraction ^{a) [rr] [rm]} [mm] [r] 0.629 0.314 0.057 0.786 a) calculated from the triad fraction syn-PP-VMA: syndiotactic polypropylene terminal-modified vinyl methacrylate (R ^a :
^{_{CH 3, R b: -CH =}} CH 2). The syn-PP-
It was produced according to the production method of VMA, but with a reaction time of 30 minutes. The polymer obtained was 7.8 g, M
n = 3.1 × 10 ³ and Mw / Mn = 1.19. ¹ H-N
From the MR analysis result, it was found that n = 6.9.

Syn-PP-AMA: Syndiotactic polypropylene end-modified with allyl methacrylate (R ^a : CH ₃ , R ^b : -CH ₂ -CH = CH ₂ ).
According to the above-mentioned method for producing syn-PP-VMA, allyl methacrylate (AMA) was used instead of vinyl methacrylate (VMA), and the reaction time was 2 hours. The polymer obtained was 22 g, Mn = 1.8 × 10
⁴ , Mw / Mn = 1.21. ^{From the 1} H-NMR analysis results, peaks having the following chemical shift values were observed in addition to the peak (δ = 0.7 to 1.7 ppm) attributable to the proton of polypropylene. From these results, the obtained polymer has the following (i) and
It is presumed that the unit of (ii) is a combined mixture.

[0053]

[Chemical 9]

[0054]

[Table 2] In addition, the proton signal of the polypropylene part (δ = 0.
7 to 1.7 ppm) and the area ratio of the above signals d and f, the polymer obtained shows that 40 mol% of the unit (i) is present at the end of 1 mol of polypropylene.
And the above unit (ii) is estimated to be a mixture in which 60 mol% of each unit is bound. Also, n = 8.1. This mixture was used as synPP-AMA.

The following substances were used in Comparative Examples instead of the component (C). PP-MAH: Graft copolymer of maleic anhydride and polypropylene, maleic anhydride content 0.25 mol%, weight average molecular weight 133,000. The weight average molecular weight is GP
It was measured by the C method and was calculated as a polypropylene conversion value. BF: Bond First (Sumitomo Chemical Co., Ltd.) IG
ETABOND, Grade E, Glycidyl Methacrylate (G
(MA) and ethylene copolymer, GMA content 12% by weight, MFR 3 g / 10 min.

The tests carried out in the examples and comparative examples were measured as follows. 1) Melt flow rate (MFR): JIS K7210
In accordance with, measured at 275 ℃, 2.16 kg load. 2) Tensile rigidity: Measured according to JIS K7113. 3) Breaking strength (elongation at break): Measured according to JIS K7113. 4) Izod impact strength: Measured with a notch at 23 ° C. according to JIS K7110. 5) Surface peeling rate: 100 squares of 1 mm ² square were put in a No. 2 dumbbell in a grid pattern, and the degree of peeling was observed using cellotape (manufactured by Nichiban Co., Ltd.). The number of peeled pieces per 100 pieces was calculated in%.

Examples 1 to 7 The components shown in Table 3 were kneaded using a Labo Plastomill under a nitrogen blanket at 280 ° C. and 80 rpm for 5 minutes,
It was crushed by a crusher. After drying the obtained product in a drying oven, a test piece is prepared by injection molding and MF
R, tensile rigidity, elongation at break, Izod impact strength, and surface peeling rate were measured, and the presence or absence of coloring was observed. The results are shown in Table 3.

[0058]

[Table 3] Comparative Example 1 Only 80 parts by weight of (A) polyamide and 20 parts by weight of (B) polyolefin were compounded, and the component (C) was not compounded. A composition was produced in the same manner as in Example 1, then injection-molded, and each evaluation was performed. The results are shown in Table 4.

Comparative Example 2 A composition was prepared in the same manner as in Comparative Example 1 except that 0.4 part by weight of PP-MAH was further compounded and the polyolefin was 19.6 parts by weight, and then injection-molded. Each evaluation was performed. The results are shown in Table 4.

Comparative Example 3 15 parts by weight of BF and 80 parts by weight of polyamide (A) and 5 parts by weight of polyolefin (B) were blended. A composition was produced in the same manner as in Example 1, then injection-molded, and each evaluation was performed. The results are shown in Table 4.

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[Table 4]

Comparing Example 4 and Comparative Examples 1 and 2 in which the composition ratios of the components (A) and (B) are close to each other, in Comparative Example 1 in which the compatibilizer component (C) was not added, the compatibility was found. Since it is bad, the tensile rigidity and the elongation at break are low, and the Izod impact strength is remarkably low. Further, the surface peeling rate is also very high. Further, in Comparative Example 2 in which polypropylene modified with MAH was used in place of the compatibilizing agent component (C), the flowability (MFR) was slightly poor, and the Izod impact strength was also low, resulting in coloration and surface. The peeling rate is also increasing.

In Comparative Example 3 using Bondfast which is an impact resistance agent, the Izod impact strength was relatively high, but the flowability (MFR) was very poor, and the tensile rigidity and the elongation at break were low, and the surface Peeling is also seen.

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INDUSTRIAL APPLICABILITY In the composition of the present invention, the respective components are well compatibilized, and therefore mechanical properties such as impact resistance, tensile rigidity and peeling resistance, thermal properties such as heat resistance, appearance, etc. It has excellent surface characteristics and environmental characteristics such as water resistance and chemical resistance. Therefore, as various engineering plastics, especially interior and exterior parts of automobiles, electrical components, home appliances,
It is suitable for use in applications such as industrial material parts, sports equipment, furniture, office supplies, and packaging materials.

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Claims (1)

[Claims] 1. (A) 0.1 to 99% by weight of polyamide,
(B) 0.1 to 99% by weight of polyolefin, and (C) at the end have the following formula (I): (In the above formula, R ^a represents a hydrogen atom or a methyl group; R
^b represents an alkenyl group having a double bond at the terminal and having 2 to 10 carbon atoms; n is an average value and is in the range of 0.1 to 500).
A thermoplastic resin composition containing 01 to 99% by weight.