JPH0214231A - Polypropylene composition - Google Patents

Abstract

PURPOSE:To obtain a polypropylene composition having excellent balance of physical properties and good appearance by compounding a specific polypropylene resin with a saturated polyester resin and a copolymer containing epoxy group. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a resin composition composed of (i) 1-99wt.% of a modified polypropylene grafted with an unsaturated carboxylic acid (derivative) or a polypropylene resin composed of the above modified polypropylene and a polypropylene and (ii) 99-1wt.% of a saturated polyester resin with (B) 0.1-300 pts.wt. of a polymer containing epoxy resin, (C) 0.1-300 pts.wt. of an ethylenic copolymer rubber, a modified ethylenic copolymer rubber, etc., and (C) 0-5 pts.wt. of a basic compound as a reaction accelerator. The amount of the component (ii) in the whole resin composition is <50wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a novel polypropylene composition that can be used as a molded article, sheet, film, etc. by injection molding, extrusion molding, etc.

More specifically, the present invention relates to a novel polypropylene composition with an excellent balance of physical properties and an excellent appearance, which is made by blending an epoxy group-containing copolymer with a polypropylene resin and a saturated polyester resin.

[Prior art] Polypropylene has excellent properties such as moldability, toughness, water resistance, gasoline resistance, and chemical resistance, and is low in specific gravity and inexpensive, so it is used in various molded products and films. , has been widely used as a sheet.

However, polypropylene has drawbacks or points that need improvement in terms of heat resistance, rigidity, impact resistance, scratch resistance, paintability, adhesion, printability, etc., and these are obstacles to the development of new practical applications. There is.

Among these, improvements in paintability, adhesion, printability, etc. are described in, for example, Japanese Patent Publication No. 58-47418 or Japanese Patent Application Laid-open No. 58-49736. A method of graft modification with an unsaturated carboxylic acid such as maleic acid or its anhydride has been devised.

However, even when such modified polypropylene is used, impact resistance, heat resistance, rigidity, and other physical properties are not essentially improved.

On the other hand, saturated polyester resin is widely used in the fields of automobile parts and electrical/electronic parts as an engineering resin with characteristics such as heat resistance, rigidity, surface impact resistance, scratch resistance, oil resistance, and electrical properties. However, further improvements are desired in terms of moldability, toughness, notch impact resistance, water resistance, chemical resistance, etc. Moreover, it has the essential disadvantage that it has a higher specific gravity and is more expensive than polyolefin.

[Problem to be solved by the invention]

From this point of view, if a polypropylene resin selected from modified polypropylene or a modified polypropylene/polypropylene composition is blended with a saturated polyester resin, a thermoplastic resin having the features of both a polypropylene resin and a saturated polyester resin can be obtained. The potential for a wide range of new applications is expected.

However, conventionally, polypropylene resins and saturated polyester resins have been considered to be a combination with extremely poor compatibility and dispersibility, and in fact, simply mixing them together has a significant balancing effect on the molten polymer, resulting in stable pulling of the extruded strand. It is almost impossible to remove it, and the molding workability is significantly reduced.

(2) Injection molded products exhibit extreme non-uniformity and have a poor appearance due to flow marks, so that only products that are practically unusable for applications such as automobile parts and electrical/electronic parts can be obtained.

■In addition, the mechanical properties of molded products made from a mixture of polypropylene resin and saturated polyester resin, especially impact resistance and tensile elongation, are usually lower than expected from the additivity of the physical properties of each individual resin. There were problems such as the fact that it often showed

According to the method exemplified in JP-A No. 61-60746,
Polypropylene and saturated polyester, which are originally incompatible,
By blending an epoxy group-containing copolymer with a polypropylene resin selected from modified polypropylene or a modified polypropylene/polypropylene composition and a saturated polyester resin, it is possible to make them compatible and disperse, improving moldability, rigidity, and heat resistance. It is possible to produce thermoplastic resin compositions that have a good balance of physical properties such as hardness, impact resistance, scratch resistance, paintability, oil resistance, chemical resistance, water resistance, etc., and have excellent uniformity and smoothness in appearance. It is possible.

However, there are applications in automobile parts, electrical/electronic parts, etc. that require even higher levels of heat resistance and impact resistance, especially impact resistance at low temperatures.

As a result of intensive studies aimed at further improving the heat resistance and impact resistance of the thermoplastic resin composition exemplified in JP-A-61-60746, the present invention was achieved.

[Means to solve the problem]

The present invention is a saturated polypropylene resin (C) selected from a modified polypropylene (A) obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof or a modified polypropylene (A)/polypropylene (B) composition. 0.1 to 300 parts by weight of epoxy group-containing copolymer (E) and ethylene copolymer rubber (F) to 100 parts by weight of a resin composition consisting of 99 to 1% by weight of polyester resin (D). , modified ethylene copolymer rubber (G) graft-copolymerized with unsaturated carboxylic acid or its derivative;
At least one rubber selected from modified ethylene copolymer rubber (H) obtained by graft copolymerizing an unsaturated carboxylic acid or its derivative and an unsaturated aromatic monomer 0.1~
It is characterized by containing 0 to 5 parts by weight of basic compound (I) as a reaction accelerator and 300 g of polyester resin (D) in the total resin composition, and less than 50% by weight of the saturated polyester resin (D) in the entire resin composition. The present invention relates to a polypropylene composition.

Furthermore, filler (J
), 1 to 99% by weight of a polypropylene resin (C) selected from modified polypropylene (A> or a modified polypropylene (A)/polypropylene (B) composition) obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof, and a saturated polyester. The present invention relates to a polypropylene composition characterized in that it is blended in an amount of 0.01 to 300 parts by weight to 100 parts by weight of a resin composition consisting of 99 to 1% by weight of resin (D).

Polypropylene resin (C) used in the present invention
is a resin selected from modified polypropylene (A) or modified polypropylene (A)/polypropylene (B) compositions.

Polypropylene will be explained in detail below, and the polypropylene referred to herein may be used as a raw material for modified polypropylene (A) or as polypropylene (B).

In the present invention, polypropylene refers to crystalline polypropylene, which is a block obtained by copolymerizing a propylene homopolymer with propylene in the first step and with an α-olefin such as ethylene and propylene or butene-1 in the second step. It includes copolymers or random copolymers made by copolymerizing propylene with α-olefins such as ethylene and butene-1.

Homopolymers, block or random copolymers of propylene can be obtained, for example, by reaction in the presence of a combined catalyst with titanium trichloride and an alkyl aluminum compound, commonly referred to as a Ziegler-Natsuta type catalyst.

Polymerization can be carried out over a temperature range of 0°C to 300°C. However, in the highly stereoregular polymerization of α-olefins such as propylene, it is usually preferable to carry out the polymerization at a temperature in the range of 0°C to 100°C, as a highly stereoregular polymer cannot be obtained at temperatures above 100°C. It is.

There is no particular restriction on the polymerization pressure, but a pressure of about 3 to 100 atm is desirable from the viewpoint of industrial and economical considerations.

The polymerization method can be carried out either continuously or batchwise.

Polymerization methods include slurry polymerization using an inert hydrocarbon solvent such as butane, pentane, hexane, heptane, and octane, solvent polymerization in which the resulting polymer is polymerized while dissolved in the inert hydrocarbon solvent, and solvent-free polymerization. Bulk polymerization in liquefied monomers and gas phase polymerization in gaseous monomers are possible.

It is also possible to add chain transfer agents such as hydrogen to adjust the molecular weight of the polymer.

The polypropylene used in the present invention has isospecificity (i
sospecific) can be produced using a Ziegler-Natsuta catalyst. The catalyst used preferably has high isospecificity.

A catalyst that can be suitably used is a composite solid compound of titanium trichloride or a magnesium compound and a titanium compound in which the transition metal catalyst component has a layered crystal structure, and the typical metal component is an organoaluminum compound. The catalyst can include a known electron donating compound as a third component.

Titanium trichloride produced by reducing titanium tetrachloride with various reducing agents can be used. As a reducing agent, metals such as aluminum and titanium,
Hydrogen, organometallic compounds, etc. are known. Typical titanium trichloride produced by metal reduction is:
A titanium trichloride composition (TIC13AA) containing chloride of aluminum activated by reducing titanium tetrachloride with metallic aluminum and then milling in equipment such as a ball mill or a vibratory mill. For the purpose of improving isospecificity, polymerization activity, and/or particle properties, a compound selected from ether, ketone, estenobe aluminum chloride, titanium tetrachloride, etc. may be coexisting during the grinding.

More preferred titanium trichloride for the purposes of the present invention is obtained by reducing titanium tetrachloride with an organoaluminum compound and subjecting the resulting titanium trichloride composition to a contact reaction with an ether compound and a halogen compound simultaneously or sequentially. Titanium trichloride. For ether compounds, the charge is R'
-0-R2 (R' and R2 are alkyl groups having 1 to 18 carbon atoms), especially di-n-butyl ether, di-
T-amyl ether is preferred, and the halogen compound is preferably selected from halogens, especially iodine, halogen compounds, especially iodine trichloride, titanium halides, especially titanium tetrachloride, halogenated hydrocarbons, especially carbon tetrachloride, 1,2-dichloroethane. Organoaluminum compounds are sold for one fee ＾IR
'nX, -n (R' is a hydrocarbon group having 1 to 18 carbon atoms,
X is a halogen selected from CI, Br, and I, and n is 3
Particularly preferred are diethylaluminum chloride and ethylaluminum sesquichloride.

Regarding the manufacturing method of these titanium trichlorides, please refer to JP-A No. 4
No. 7-34170, No. 53-33289, No. 53-5
No. 1285, No. 54-11986, No. 58-1429
No. 03, No. 60-28405, No. 60-228504
No. 61-218606 and the like.

When titanium trichloride having a layered crystal structure is used as a transition metal compound component, the typical metal compound component is AIR'mX3-m (R' is a hydrocarbon group having 1 to 18 carbon atoms, X is CI, Br , halogen selected from I, m
is preferably an organoaluminum compound represented by 3≧m>0). Particularly preferred organoaluminum compounds for the purposes of the present invention are those in which R4 is an ethyl or isobutyl group, m
is a compound in which 2.5≧m≧1.5. Specific examples include diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, and mixtures of these with triethylaluminum or ethylaluminum dichloride. 3≧m≧2 when using the third component described later
．． 5 or 1.5≧m>Q organoaluminum compounds can also be suitably used for the purpose of the present invention.

The ratio of organoaluminum compound to titanium trichloride is 1 to 1
000:1 molar ratio can be chosen from a wide range.

The catalyst consisting of titanium trichloride and organoaluminum may contain a known third component. As the third component, ε-caprolactam, methacrylate methinobe, ethyl benzoate,
Examples include ester compounds such as methyl toluate, triphenyl phosphite, tributyl phosphite, and phosphoric acid derivatives such as estenopehexamethylphosphoric triamide.

The amount of the third component to be used must be determined experimentally for each individual compound, as the acting power differs depending on the compound.
Generally, the amount is equal to or less than the molar amount relative to organoaluminum.

When a composite solid compound of a magnesium compound and a titanium compound is used as the transition metal solid catalyst component of the catalyst, the typical metal catalyst component is an organoaluminum compound, especially an organoaluminium compound, especially -removal AIR5pX3-p (R' is a carbonized compound having 1 to 18 carbon atoms). A compound represented by a hydrogen group, X is a halogen selected from Cl5Br and I, and p is 3≧p>2) is preferable. Specific examples include triethylaluminum, triisobutylaluminum, and mixtures of these with diethylaluminum chloride or diisobutylaluminum chloride.

Preferably, the catalyst further comprises an electron-donating compound, in particular an aromatic monocarboxylic acid ester and/or a silicon compound having a Si--OR' bond.

A silicon compound having a 5i-OR' bond (Rf'' is a hydrocarbon group having 1 to 20 carbon atoms) has a -removal R7aS
i(OR')4-a (R6 and R7 have 1 to 2 carbon atoms
0 hydrocarbon group, a represents a number of 0≦a≦3. ) is preferably used. Specific examples include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane. Silane, diphenyldimethoxysilane, diphenyljethoxysilane, butyltriethoxysilane, tetrabutoxysilane, vinyltributoxysilane,
Examples include diethyljethoxysilane.

The electron-donating compound is preferably used in an amount of 1 mol or less, particularly within a range of 0.05 to 1 mol, per 1 mol of the organoaluminum compound.

A composite solid compound of a magnesium compound and a titanium compound is titanium trichloride containing magnesium chloride obtained by reducing titanium tetrachloride with an organomagnesium compound, or a solid magnesium compound is brought into contact with a liquid phase titanium compound. So-called "supported catalysts" are used, which are produced by reacting. Solid magnesium compounds are electron-donating compounds, especially aromatic monocarboxylic acid esters, aromatic dicarboxylic acid diesters, ether compounds,
Preferably, it contains alcohols and/or phenols. The aromatic monocarboxylic acid ester can also be present in the catalytic reaction with the titanium compound.

The composite solid compound of the above-mentioned magnesium compound and titanium compound is described in many patent publications, but the catalyst suitable for the purpose of the present invention is disclosed in Japanese Patent Laid-Open No. 54-11.
No. 2988, No. 54-119586, No. 563040
No. 7, No. 57-59909, No. 57-59910,
No. 57-59911, No. 57-59912, No. 57
-59914, 57-59915, 57-59
No. 916, No. 54-112982, No. 55-1334
There are detailed descriptions in No. 08, No. 58-27704, etc.

When the polypropylene composition of the present invention is used for applications that particularly require heat resistance, rigidity, scratch resistance, etc., the polypropylene is a homopolymer of propylene, which is the first segment polymerized in the first step of the propylene homopolymer and block copolymer. The isotactic pentad fraction of the part insoluble in boiling hebutane is 0.970 or more, the content of the part soluble in boiling hebutane is 5.0% by weight or less, and the part soluble in xylene at 20°C It is preferable to use highly crystalline polypropylene having a content of 2.0% by weight or less.

The isotactic pentad fraction of the boiling hebutane insoluble part, the content of the boiling hebutane soluble part and 20
The content of xylene soluble polymer at °C is determined as follows.

After completely dissolving 5 g of polypropylene in 500 ml of boiling xylene, the temperature was lowered to 20° C. and left for 4 hours.

Thereafter, this is filtered to separate the xylene-insoluble portion at 20°C. The filtrate is concentrated to dryness to evaporate xylene, and further dried under reduced pressure at 60°C to obtain a polymer soluble in xylene at 20°C. The value obtained by dividing this dry weight by the weight of the prepared sample and expressing it as a percentage is the content of the xylene soluble portion at 20°C. The xylene insoluble portion at 20° C. is dried and then subjected to Soxhlet extraction with boiling n-hebutane for 8 hours. This extraction residue is called the boiling butane insoluble part, and the value obtained by subtracting this dry weight from the prepared sample weight 1 (5 g) divided by the prepared sample weight is the value expressed as a percentage of the boiling butane soluble part. content.

What is isotactic pentad fraction?A.

By Zambe l l i et al! , (acromo
6.925 (1973), that is, an isotactic chain of pentad units in a polypropylene molecular chain, in other words, five consecutive propylene monomer units. It is the fraction of propylene monomer units at the center of the men-bonded chain. However, regarding the attribution of NMR absorption peaks, Macrmol, which was subsequently published,
ecules 8.687 (1975).

Specifically, the eye-opening pentad fraction is measured as the area fraction of the mmmm peak among the total absorption peaks in the methyl carbon region of the 13C-NMR spectrum. By this method, the UK NATIONAL PHYSICAL LAB
ORATORY's NPL standard material CRM No. M19
-14Polypropylene PP/! 4W
The isotactic pentad fraction of D/2 was measured and found to be 0.944.

The highly crystalline polypropylene is disclosed in, for example, Japanese Patent Application Laid-Open No. 602840.
No. 5, No. 60-228504, No. 61-218606
It can be manufactured by the method exemplified in Japanese Patent No. 61287917.

When the polypropylene composition of the present invention is used for applications requiring i# impact resistance, the polypropylene consists of a portion of the homopolymer of propylene, which is the first segment polymerized in the first step, and a portion of the homopolymer of propylene, which is the first segment polymerized in the second step. It is preferable to use a propylene block copolymer obtained by copolymerizing ethylene as a segment with an α-olefin such as propylene or butene-1.

Propylene block copolymers can be produced by slurry polymerization and gas phase polymerization.

When used in applications that require particularly high impact resistance,
2nd segment) It is necessary to increase l, and it is suitably produced by gas phase polymerization.

High impact-resistant polypropylene produced by the gas phase polymerization method can be produced, for example, by the method exemplified in JP-A-61-287917.

In the propylene block copolymer, a portion of the propylene homopolymer polymerized in the first step may be a propylene homopolymer or a propylene and ethylene whose content in the polymer produced in this step is 6 mol% or less, or a carbon number of 4 to 6. It may also be a copolymer with α-olefin. A portion of the copolymer, which is the second segment polymerized in the second step, is either polymerized solely with ethylene, or ethylene and propylene in which the ethylene content in the polymer produced in the step is 10 mol% or more, or furthermore, 4 carbon atoms. Preferably, it is a copolymer with 6 to 6 α-olefins. The amount of the polymer produced in the second step is 10 to 70% by weight based on the total polymerization amount.

The amount of the second segment is suitably produced in the range of 10 to 30% by weight in the slurry polymerization method, and 10 to 70% by weight in the gas phase polymerization method.

A propylene block copolymer having a larger amount of second segments in the gas phase polymerization method is disclosed in Japanese Patent Application No. 62=256015.
It can be manufactured by the method exemplified in No. 1, and is suitably used for applications requiring ultra-high impact resistance.

The intrinsic viscosity of the second segment in tetralin solvent at 135°C needs to be changed depending on the productivity during manufacturing, the powder properties of the polymer, or the intrinsic viscosity of the first segment.
In slurry polymerization, the amount is approximately 3 to 8 J/g, and in gas phase polymerization, it is 1 to 5 J/g.

In the present invention, the modified polypropylene (A) can be obtained by regraft copolymerizing polypropylene using an unsaturated carboxylic acid or a derivative thereof as a graft monomer and coexisting with a radical initiator if necessary. .

Various known methods can be used to graft the graft monomer onto polypropylene.

For example, one method involves mixing polypropylene, a graft monomer, and a radical generator, and grafting the mixture by melt-kneading it in a melt-kneading device. After dissolving polypropylene in an organic solvent such as xylene, the radical generator is added under a nitrogen atmosphere and the mixture is stirred. There are methods to obtain grafted polypropylene by heating the polypropylene, cooling it after the reaction, washing and filtration, and drying.Other methods include irradiating polypropylene with ultraviolet rays or radiation in the presence of a graft monomer, or contacting it with oxygen or ozone. .

＼ Considering economic efficiency and the like, the method of graft copolymerization by melt-kneading in a melt-kneading apparatus is most preferably used.

15 to polypropylene in the presence of an unsaturated carboxylic acid or its derivative and, if necessary, a radical initiator.
Temperature of 0 to 300°C, preferably 190 to 280°C, 0
．． Melt kneading can be carried out using an extruder, Banbury mixer, kneader, etc. with a residence time of 3 to 10 minutes, preferably 0.5 to 5 minutes. Industrially, unreacted components (
It is advantageous to carry out continuous production while removing side reaction products such as unsaturated carboxylic acids or derivatives thereof, radical initiators, etc.), their oligomers, and decomposition products. Further, the reaction atmosphere may be in the air, but preferably in an inert gas such as nitrogen or carbon dioxide. In addition, in order to further remove trace amounts of unreacted components and side reaction products contained in the obtained modified polypropylene, heat treatment at a temperature of 60° C. or higher, solvent extraction, and evacuation while melting can be performed. .

In addition, for the modified polypropylene (A), antioxidants, heat stabilizers, light stabilizers, nucleating agents, lubricants, antistatic agents, inorganic or organic colorants, rust preventives, crosslinking agents, foaming agents, etc. Various additives such as additives, plasticizers, fluorescent agents, surface smoothing agents and surface gloss improvers can be added during the manufacturing process or in subsequent processing steps.

Examples of unsaturated carboxylic acids or derivatives thereof used in the modified polypropylene (A) include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo(2,2,2)octa-5
-ene-2,3-dicarboxylic acid, 4-methylcyclohex-4-ene-1,2 dicarboxylic acid, 1.2.3.4.
5.8.9.10-octahydronaphthalene-2,3-
Dicarboxylic acid, bicyclo(2,2,l) octa-7
-Unsaturated carboxylic acids such as nin-2.3.5.6-tetracarboxylic acid, 7-oxabicyclo(2,2,1)but-5-ene-2,3dicarboxylic acid, and unsaturated carboxylic acids Derivatives include acid anhydrides, estenobeamides, imides, and metal salts, such as maleic anhydride, itaconic anhydride, citraconic anhydride, hymic anhydride, maleic acid monoethyl estenope fumaric acid monomethyl ester , itaconic acid monomethyl ester, fumaric acid monomethyl ester, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N- Diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N,N
-diethylamide, fumaric acid-N-monobutylamide,
Examples include fumaric acid-N, N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, and potassium methacrylate.

Among these, it is most preferable to use maleic anhydride.

Although the modified polypropylene (A) can be produced in the absence of a radical initiator, it is usually preferably carried out in the presence of a radical initiator.

As the radical initiator, known ones can be used. For example, 2,2°-azobisisobutyronitrinope2.
Azo compounds such as 2'-azobis(2,4,4)-trimethylvaleronitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3.5
-) Limethylcyclohexanone oxide, 2.
2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
2,5-dimethylhexane-2,5-sibide lobaroxide, di-t-butyl peroxide, 1,3-bis(t-butylperoxyisopropyl)benzene, 2.
5-Dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylbutylperoxy)hexane-3, lauroyl peroxide, 3.3.5- ) IJ methylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl peroxyisobutyrate, t
-butyloxybivalate, t-butyl-oxy-2-
Ethylhexanoate, t-butylperoxy-3,5
, 5-) Limethylhexanoate, t-butyl peroxylaurate, t-f-)It peroxybenzoate, di t-butyl peroxyisophthalate, 2,5
-Dimethyl 2,5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, polystyrene peroxide, and various other organic peroxides.

In the method for producing the modified polypropylene (A>), the melt fluororate of the raw material polypropylene (crystalline propylene homopolymer, crystalline propylene-ethylene/α-olefin block copolymer, crystalline propylene-α-olefin random copolymer, etc.) is 0.05 to 60g/10
min, preferably 0.1 to 40 g/10 min, but the melt flow rate of the resulting modified polypropylene (A) is 0.1 to 100 g/10 min, preferably 0.5 to 50 g
/10 minutes is preferable. Also,
The number average molecular weight of the raw material polypropylene is 7.000~go
o, ooo, preferably 10,000 to 700,00
It is 0.

In the method for producing modified polypropylene (A) resin, the blending amount of each component is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight of the unsaturated carboxylic acid or its derivative, per 100 parts by weight of polypropylene. ~5
The amount of double parts and radical initiator is preferably 0 to 5 parts by weight, more preferably 0.001 to 2 parts by weight. Here, if the amount of unsaturated carboxylic acid or its derivative added is less than 0.01 part by weight, there is no significant modification effect;
If the amount exceeds 10 parts by weight, the modification effect reaches saturation and no further significant effect is exhibited, and a large amount remains in the polymer as unreacted substances, resulting in odor or deterioration of physical properties, which is not desirable for practical purposes. do not have. Furthermore, if the amount of the radical initiator added exceeds 5% by weight, it will not have any more significant effect on the graft reaction of unsaturated carboxylic acids or their derivatives, and the decomposition of polypropylene will increase, resulting in poor fluidity. (Melt flow rate) Changes are large, so it is not preferred in practice.

In the present invention, the polypropylene resin (C) selected from modified polypropylene (A) or a modified polypropylene (A)/polypropylene (B) composition has a melt flow rate Q of 1 to 100 g/10 min, particularly 0.5 to 40 g.
710 minutes is preferred.

The saturated polyester resin (D) in the present invention is composed of a dicarboxylic acid component in which at least 40 mol% of the dicarboxylic acid component is terephthalic acid, and a diol component. , aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as dodecanedicarboxylic acid, aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, either singly or in mixtures. As the diol component, aliphatic glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol and 1,4-cyclohexanediol may be used alone. or a mixture.

Among these saturated polyester resins (D), polybutylene terephthalate or polyethylene terephthalate can exhibit the effects of the present invention more desirably.

In addition, these saturated polyester resins (D) are used as a solvent.
- Using chlorophenol, the intrinsic viscosity measured at 25°C is preferably in the range of 0.5 to 3.0 J/g,
Even if a saturated polyester resin (D) having an intrinsic viscosity outside this range is used, the desired mechanical strength cannot be expected.

The epoxy group-containing copolymer (E) in the present invention is a copolymer consisting of an unsaturated epoxy compound and an ethylenically unsaturated compound.

The composition ratio of the epoxy group-containing copolymer (E) is not particularly limited, but it is preferably copolymerized with an unsaturated epoxy compound in an amount of 0.1 to 50% by weight, preferably 1 to 30% by weight.

The unsaturated epoxy compound is a compound having an epoxy group and an unsaturated group copolymerizable with an ethylenically unsaturated compound in the molecule.

For example, unsaturated glycidyl ester acids and unsaturated glycidyl ethers represented by the general formula (LL(2)) are listed below.

(R is a hydrocarbon group having 2 to 18 carbon atoms and having an ethylenically unsaturated bond.) (R is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenically unsaturated bond, and X is -CH2- Specific examples include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

Ethylenically unsaturated compounds are olefins, having 2 or more carbon atoms.
Vinyl esters of 6 saturated carboxylic acids, carbon number 1-8
Examples include esters of saturated alcohol components and acrylic acid or methacrylic acid, maleic esters and methacrylic esters, yohyufumarates, vinyl halides, styrenes, nitriles, vinyl ethers, and acrylamides. .

Specific examples include ethylene, propylene, butene-11 vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, dimethinope fumarate vinyl chloride, vinylidene chloride, styrene, acrylonitrinobeisobutyl vinyl ether, and acrylamide. Ru.

Among these, ethylene is particularly preferred.

In order to further lower the glass transition temperature and improve the impact resistance properties at low temperatures, it is preferable to copolymerize ethylene as the second component and a third component such as vinyl acetate and/or methyl acrylate.

Epoxy group-containing copolymers can be made in various ways. Both a random copolymerization method in which the unsaturated epoxy compound is introduced into the main chain of the copolymer and a graft copolymerization method in which the unsaturated epoxy compound is introduced as the side chain of the copolymer can be adopted. Specifically, an unsaturated epoxy compound and an ethylenically unsaturated compound are heated at 500 to 4,000 atmospheres and 100 to 4,000 atmospheres in the presence of a radical generator.
A method of copolymerizing in the presence or absence of an appropriate solvent or chain transfer agent at 300°C, a method of mixing polypropylene with an unsaturated epoxy compound and a radical generator, and performing melt graft copolymerization in an extruder, or Examples include a method of copolymerizing an unsaturated epoxy compound and an ethylenically unsaturated compound in an inert medium such as water or an organic solvent in the presence of a radical generator.

In the present invention, an ethylene copolymer rubber (F), a modified ethylene copolymer rubber (G) obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof, an unsaturated carboxylic acid or a derivative thereof, and an unsaturated aromatic monomer The modified ethylene copolymer rubber (H) obtained by graft copolymerizing polymers is used for the purpose of improving impact resistance, particularly low-temperature needle IS resistance.

The modified ethylene copolymer rubber (G) is obtained by graft copolymerizing an ethylene copolymer rubber with an unsaturated carboxylic acid or a derivative thereof in the presence of a radical initiator if necessary.

Modified ethylene copolymer rubber (H) is produced by adding an unsaturated carboxylic acid or its derivative and an unsaturated aromatic monomer to the ethylene copolymer rubber, if necessary, and a radical initiator. Obtained by graft copolymerization. By graft copolymerization in the presence of an unsaturated aromatic monomer, the amount of unsaturated carboxylic acid or its derivative is increased, the amount of gel formed in the graft copolymer is small, and the moldability and Mooney viscosity during storage are improved. Modified ethylene copolymer rubber (H) with excellent storage stability without increase
is obtained.

Various known methods can be used to graft the graft monomer onto the ethylene copolymer rubber.

For example, ethylene copolymer rubber is mixed with a graft monomer and a radical initiator, and the mixture is melt-kneaded in a melt-kneading device to graft the ethylene copolymer rubber. After dissolving ethylene copolymer rubber in an organic solvent such as xylene, nitrogen Method for obtaining grafted ethylene copolymer rubber by adding a radical initiator under a snowy atmosphere, heating the reaction with stirring, cooling after the reaction, washing, filtration, and drying, and the presence of graft monomers in other ethylene copolymer rubbers. There are methods such as irradiation with ultraviolet rays or radiation at the bottom, or contact with acid or ozone.

In consideration of economical efficiency and the like, the most preferred method is to perform graft copolymerization by melt-kneading in a melt-kneading apparatus.

The ethylene copolymer rubber will be explained in detail below, but the ethylene copolymer rubber referred to here may be used as ethylene copolymer rubber (F), modified ethylene copolymer rubber (G) and ( In some cases, the raw material 11) is also used.

In the present invention, as the ethylene copolymer rubber, for example, ethylene-propylene copolymer rubber (hereinafter referred to as E P
! , abbreviated as l. ) Ethylene-propylene-non-functional diene copolymer rubber (hereinafter abbreviated as EPDM)
Ethylene-α-olefin copolymer rubber or ethylene-α-olefin-nonconjugated diene copolymer rubber, ethylene-vinyl acetate copolymer, ethylene-methyl (meth)acrylate copolymer, ethylene-α-olefin copolymer rubber represented by (meth)ethyl acrylate copolymer, ethylene-butyl (meth)acrylate copolymer, ethylene-(meth)acrylic acid or its partial metal salt copolymer, ethylene-(meth)acrylic acid-(meth)acrylic Acid ester copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate-
Various ethylene copolymer rubbers such as vinyl alcohol copolymer and ethylene-styrene copolymer can be used. Moreover, two or more types of these ethylene copolymer rubbers can also be used in combination. In addition, low-density polyethylene, which has good compatibility with these ethylene copolymer rubbers,
It is also possible to use it in combination with high density polyethylene.

Among these, ethylene-α-olefin copolymer rubber and ethylene-α-olefin-nonconjugated diene copolymer rubber are particularly preferred. Ethylene-α-olefin copolymer rubbers include ethylene and other α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. Polymers or terpolymer rubbers such as ethylene-propylene-1-butene copolymer rubber are included, and among them, ethylene-propylene copolymer rubber and ethylene-1-butene copolymer rubber are preferably used.

Further, an ethylene-α-olefin-nonconjugated diene copolymer rubber can also be used, but it is preferable that the nonconjugated diene content in the raw material rubber is 3% by weight or less. If the nonconjugated diene content exceeds 3% by weight, gelation occurs during kneading, which is not preferable.

The ethylene content in the ethylene-α-olefin copolymer rubber is 15 to 85% by weight, preferably 40 to 80% by weight. In other words, highly crystalline copolymers with an ethylene content of more than 85% by weight are difficult to process under normal rubber molding conditions;
Furthermore, if the ethylene content is less than 15% by weight, the glass transition temperature (Tg) will increase and the rubbery properties will be lost, which is not preferable.

The number average molecular weight of the ethylene-α-olefin copolymer rubber is preferably one that can be kneaded in an extruder, and is from 10.000 to 100.000. If the molecular weight is too small, it will be difficult to handle when fed to an extruder, and if the molecular weight is too large, fluidity will be low and processing will be difficult.

Furthermore, the molecular weight distribution of the ethylene-α-olefin copolymer rubber is not particularly limited, and any copolymer rubber having various molecular weight distributions such as monomodal type, bimodal type, etc. that are manufactured and commercially available can be used. Can be used.

The Q value (weight average molecular weight/number average molecular weight) of the molecular weight distribution is preferably in the range of 1 to 30, more preferably 2 to 20.

That is, the copolymer rubber is a copolymer rubber produced using a so-called Ziegler-Natsuta catalyst, which is a common production catalyst, and includes, for example, an organoaluminum compound and a hydrocarbon solvent-soluble 3 to 5 copolymer rubber as a catalyst. vanadium compounds and the like are used in combination. As the above aluminum compound, alkyl aluminum sesquichloride, trialkyl aluminum, dialkyl aluminum monochloride, or a mixture thereof is used, and as the vanadium compound, vanadium oxytrichloride, vanadium oxytrichloride,
Vanadium tetrachloride or VO(OR8)qX.

q (o<q≦3, R11 is a straight, branched, or cyclic hydrocarbon having 1 to 10 carbon atoms, and X is a halogen selected from CI, 3r, and I), or the like. I can do it.

In the present invention, the modified ethylene copolymer rubber (G) is prepared at 200 to 280°C, preferably in the coexistence of an unsaturated carboxylic acid or a derivative thereof and, if necessary, a radical initiator. 230-260℃
It varies depending on the temperature and type of radical initiator, but it is 0.2~
It can be obtained by melt-kneading using an extruder, Banbury mixer, kneader, etc. at a residence time of 10 minutes.

Modified ethylene copolymer rubber ()l) is prepared by preparing an ethylene copolymer rubber in the presence of an unsaturated carboxylic acid or its transparent conductor, an unsaturated aromatic monomer, and optionally a radical initiator. It can be obtained under the conditions mentioned above.

If too much oxygen is present during kneading, a gel-like substance may be formed or significant coloring may occur, so it is desirable to knead in the substantial absence of oxygen.

Furthermore, if the kneading temperature is lower than 200° C., the desired amount of unsaturated dicarboxylic anhydride cannot be obtained, and only a small effect on improving the amount of grafting reaction can be obtained. 28 again
Even if the temperature exceeds 0°C, the effect on improving the amount of grafting reaction is small (and in some cases, gel-like substances may be formed, coloring, etc. may occur), which is not preferable.

Although there are no particular limitations on the kneading machine for modification, it is generally preferable to use an extruder because continuous production is possible, and it uniformly mixes various raw materials supplied with one or two shafts. It is desirable to have a screw suitable for

An extruder is used to remove unreacted components (unsaturated carboxylic acids or derivatives thereof, unsaturated aromatic monomers, radical initiators, etc.), their oligomers, and side reaction products such as decomposition products from the reaction product. Methods such as suction using a vacuum pump from a vent line during or near the outlet, or purification by dissolving the reaction product in an appropriate solvent and precipitating it can also be used. Further, it is also possible to perform a heat treatment at a temperature of 60° C. or higher and to apply a vacuum while melting.

When supplying the three components to a kneading machine in the production of modified ethylene copolymer rubber (G), it is possible to supply each component separately, but it is possible to uniformly mix some or all of the components in advance. It can also be used. For example, a method may be adopted in which rubber is impregnated with a radical initiator, and during kneading, an unsaturated carboxylic acid or a derivative thereof is simultaneously fed and kneaded. Alternatively, a method of modifying the extruder by supplying a radical initiator and/or an unsaturated carboxylic acid or a derivative thereof from the middle of the extruder can also be used.

When feeding 4 portions to a kneader in the production of modified ethylene copolymer rubber (H), it is possible to feed each component separately, but some or all of the components may be mixed uniformly in advance. It can also be used as For example, a method may be adopted in which a rubber is impregnated with an unsaturated aromatic monomer together with a radical initiator, and at the time of cross-mixing, an unsaturated carboxylic acid or a derivative thereof is simultaneously fed and kneaded.

Alternatively, a method of modifying the extruder by supplying a radical initiator and/or an unsaturated carboxylic acid or a derivative thereof from the middle of the extruder can also be used.

In addition, modified ethylene copolymer rubber (G) and (II
), antioxidants, heat stabilizers, light stabilizers, nucleating agents, lubricants, antistatic agents, inorganic or organic colorants, rust preventives, crosslinking agents, foaming agents, lubricants, plasticizers, etc. agent, fluorescent agent,
Various additives such as surface smoothing agents and surface gloss improvers can be added during the manufacturing process or subsequent processing steps.

The unsaturated carboxylic acid or its derivative and the radical initiator used in the modified ethylene copolymer rubber (G) can be selected from compounds used in the production of the modified polypropylene (A).

In the method for producing the modified ethylene copolymer, rubber (G), the amount of unsaturated carboxylic acid or its derivative used is preferably 0.5 to 15 parts by weight based on 100 parts by weight of the raw material rubber.

The amount of the radical initiator to be used depends on the type of radical initiator and crosstalk conditions, but is usually 0.005 to 1.0 parts by weight, preferably 0.01 to 0.00 parts by weight, per 100 parts by weight of raw rubber.
It can be used in a range of 5 parts by weight.

If the amount used is less than 0.005 parts by weight, the desired amount of unsaturated carboxylic acid or derivative thereof cannot be obtained, and if it is used in excess of 1.0 parts by weight, a gel-like substance will be formed, which is undesirable.

The modified ethylene copolymer rubber (G) thus obtained has an added amount of unsaturated carboxylic acid or a derivative thereof of 0.
1 to 5% by weight, Mooney viscosity (MLl, 4121
C) is preferably 5 to 120.

The unsaturated carboxylic acid or its derivative and the radical initiator used in the modified ethylene copolymer rubber (H) can be selected from compounds used in the production of the modified polypropylene (A).

Furthermore, as the unsaturated aromatic monomer used in the modified ethylene copolymer rubber (It), styrene is most preferable, but ○-methylstyrene, p-methylstyrene, m
-Methylstyrene, α-methylstyrene, vinyltoluene, divinylbenzene, etc. can also be used, and it is also possible to use a mixture of these.

In the method for producing the modified ethylene copolymer rubber (H), the amount of unsaturated aromatic monomer used is preferably 0.2 to 20 parts by weight based on 100 parts by weight of the raw material rubber, and the amount of unsaturated aromatic monomer used is preferably 0.2 to 20 parts by weight, and or its derivative is preferably used in an amount of 0.
．． 5 to 15 parts by weight, and the weight ratio of unsaturated aromatic monomer/unsaturated carboxylic acid or its derivative is 0.1 to 15 parts by weight.
Preferably it is 3.0.

The weight ratio of the unsaturated aromatic monomer is more preferably 0.
5 to 2.0.

If the amount of unsaturated aromatic monomer used is less than 0.1 weight ratio with respect to unsaturated carboxylic acid or its derivative, no effect on preventing gel formation and improving the amount of grafting reaction will be observed; Even if the weight ratio exceeds 0, no more favorable effects can be expected.

The amount of the radical initiator to be used depends on the type of radical initiator and crosstalk conditions, but is usually 0.005 to 1.0 parts by weight, preferably 0.01 to 0.0 parts by weight, per 100 parts by weight of raw rubber.
It can be used in a range of 5 parts by weight.

If the amount used is less than 0,005 parts by weight, the desired amount of unsaturated carboxylic acid or derivative thereof cannot be obtained, and the unsaturated carboxylic acid or derivative thereof can be added in combination with an unsaturated aromatic monomer, which is a feature of the present invention. The effect of increasing the amount of addition becomes smaller. Moreover, if it is used in an amount exceeding 1.0 parts by weight, it is not preferable because a gel-like substance may be formed.

The modified ethylene copolymer rubber (H) thus obtained has an added amount of unsaturated carboxylic acid or a derivative thereof of 0.
The amount of unsaturated aromatic monomer added is preferably 0.1 to 5% by weight, and the Mooney viscosity (ML
,. 4121°C) is preferably 5 to 120.

In one embodiment of the present invention, polypropylene and ethylene copolymer rubber can be co-modified by simultaneously adding an unsaturated carboxylic acid or a derivative thereof.

That is, when producing modified polypropylene (A) and modified ethylene copolymer rubber (G), each of the modified polypropylene (A) or modified ethylene copolymer rubber (G) used individually Using a similar manufacturing method, co-modification can be achieved by graft copolymerizing raw material polypropylene and raw material ethylene copolymer rubber in the presence of an unsaturated carboxylic acid or its derivative and, if necessary, a radical initiator. be.

When the raw material polypropylene and the raw material ethylene copolymer rubber are made to coexist, if both raw materials are pellets, powder, or pulverized materials, they can be fed separately to a co-modification device such as an extruder or from the same feeder. There are two methods, such as a method where the raw materials are mixed together in the equipment, a method where the raw materials are uniformly premixed using a simple mixer such as a tumbler-Henschel mixer, and when any of the raw materials is a large solid such as a bale, it is possible to Various known methods can be used, such as melt-kneading and homogenizing using a batch-type melt-kneading apparatus such as Banbury, etc., and forming pellets or pulverized products so that they can be easily fed to a co-denaturation apparatus.

Processes other than coexisting raw material polypropylene and raw material ethylene copolymer rubber are modified polypropylene (
Co-modification can be carried out in the same manner as the modification step used in A) or the modification step used in modified ethylene copolymer rubber (G).

In the co-modification, the blending ratio of the raw material polypropylene and the raw material ethylene copolymer rubber can be selected as appropriate; It is preferable to decide based on assumptions.

In co-modification, the unsaturated carboxylic acid or its derivative is preferably added in an amount of 0.0 parts by weight based on a total of 100 parts by weight of the raw material polypropylene and the raw material ethylene copolymer rubber.
It is 1 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, and if necessary, a radical initiator can be used preferably in an amount of 0 to 5 parts by weight, more preferably 0,001 to 2 parts by weight.

In order to dynamically co-modify and disperse raw material polypropylene and raw material ethylene copolymer rubber, it is preferable to use a high-kneading melt-kneading device such as a high-kneading twin-screw extruder.

When producing the polypropylene composition of the present invention, the modified polypropylene (A) and the modified ethylene copolymer rubber (G) or (It) are graft-copolymerized with an unsaturated carboxylic acid or a derivative thereof and an epoxy group-containing copolymer. A basic compound (1) is added to promote the reaction between the epoxy group in the epoxy group (F) and the unreacted terminal carboxylic acid of the saturated polyester resin (D) and the epoxy group in the epoxy group-containing copolymer (E). It is possible to coexist. By coexisting the basic compound (I), the reaction time can be shortened, and the time required for production can be shortened.

Examples of the basic compound (1) include benzyldimethylamine, 2.4.6-tris(dimethylaminoethyl)
Amine-based organic compounds such as phenol are preferably used.

When producing the polypropylene composition, these basic compounds themselves may be mixed together, or in order to improve dispersion, they may be added to a part of the resin component or a resin compatible with the polypropylene composition in advance. Mixing may be carried out using a masterbatch dispersed at a high concentration.

In the present invention, in order to obtain a polypropylene composition,
A filler (J) can be mixed and used for the purpose of strengthening, imparting functions, or increasing the amount (cost reduction).

Fillers (J) include glass IIJi fibers, carbon fibers, polyamide fibers, metal fibers such as aluminum and stainless steel, and fibers such as metal whiskers, silica, alumina, calcium carbonate, talc, mica clay, kaolin, carbon black, TiO□, 2nO and 5
An inorganic filler such as b203 can be used.

Any filler can be used for reinforcement. Fillers such as carbon fibers, metal fibers, and carbon black can lower the surface resistivity and volume resistivity and impart electrical conductivity to the polypropylene composition of the present invention. Fillers that are cheaper than resins can be used as fillers to reduce costs.

The filler (J) increases the rigidity of the polypropylene composition of the present invention,
When the purpose is to improve heat resistance, it is particularly preferable to use inorganic fillers such as glass fiber, potassium titanate whiskers, talc, mica, and calcium carbonate.

The polypropylene composition of the present invention further includes a flame retardant or a flame retardant aid, a lubricant, a nucleating agent, a plasticizer, a dye, a pigment,
One of the preferred embodiments is to use it as a composite material to which an antistatic agent, an antioxidant, a weather resistance imparting agent, etc. are added.

In the polypropylene composition according to the present invention, the polypropylene resin (C) as the first component is 1 to 99% by weight.
, preferably 15 to 98% by weight.

If the polypropylene resin (C) is less than 1% by weight, moldability, toughness, water resistance, chemical resistance, etc. are not sufficient.

When using a modified polypropylene (A)/polypropylene (B) composition as the polypropylene resin (C), the modified polypropylene (A) is contained in the composition in an amount of 5% by weight.
It is necessary to include the above. If it is less than 5% by weight, there will be problems with the compatibility and dispersibility of the final resin composition, and sufficient toughness and impact resistance will not be obtained, and improvements in paintability, adhesion, printability, etc. will not be sufficient. .

In the total resin composition of the polypropylene composition of the present invention, the saturated polyester resin (D) is less than 50% by weight, preferably 45 to 2% by weight, more preferably 40 to 2% by weight.
Contains 5% by weight. Saturated polyester resin (D) has the effect of improving heat resistance, rigidity, impact resistance, etc., but if it exceeds 50% by weight, favorable properties such as moldability, toughness, water resistance, chemical resistance, etc. cannot be obtained. . There is also the disadvantage that the specific gravity is large and the price is also high.

In the present invention, the epoxy group-containing copolymer (E) is composed of a polypropylene resin (C) and a saturated polyester resin (0
) 0.1 to 3 parts by weight per 100 parts by weight of the resin composition
00 parts by weight, preferably 1 to 200 parts by weight, more preferably 2 to 150 parts by weight. If the amount is less than 0.1 part by weight, there will be problems with the compatibility and dispersibility of the resin composition, the toughness and impact resistance will be insufficient, and the extrusion stability will also be poor. 100
If the weight is ff1R or more, it is useful as a thermoplastic elastomer, but if it exceeds 300 parts by weight, the toughness, heat resistance, etc. are significantly reduced, and favorable results cannot be obtained.

Ethylene copolymer rubber (F), modified ethylene copolymer rubber (G), used for the purpose of improving impact resistance, particularly low-temperature impact resistance, in the polypropylene composition of the present invention,
The amount of at least one rubber selected from modified ethylene copolymer rubber (H) is 0.1 to 300 parts by weight per 100 parts by weight of the resin composition consisting of polypropylene resin (C) and saturated polyester resin (D). 1 part, preferably 1 to 200 parts by weight. If it is less than 0.1 part by weight, there is no effect of improving impact resistance, and if it is more than 100 parts by weight, it is useful as a thermoplastic elastomer, but if it exceeds 300 parts by weight, the toughness, heat resistance, etc. are significantly decreased, and favorable results are not obtained. I can't do it.

In the polypropylene composition, each of these three types of rubber can be used independently for the purpose of improving impact resistance.

Modified ethylene copolymer rubbers (G) and (H) have a greater effect of improving impact resistance than ethylene copolymer rubber (F), but a high molecular weight polymer is produced by reaction and fluidity is reduced. Therefore, in order to improve impact resistance and maintain fluidity to some extent, it can also be used in combination with ethylene copolymer rubber (F).

The basic compound (1) used as a reaction accelerator in the polypropylene composition of the present invention is 0 to 5 parts by weight based on 100 parts by weight of the resin composition consisting of the polypropylene resin (C) and the saturated polyester resin (D). Preferably 0
．． 01-2 parts by weight. If the kneading strength during kneading is sufficient and the residence time in the kneader is sufficient for the reaction, it is not necessary to mix it. If more than 5 parts by weight is added, the effect of accelerating the reaction is great, but problems with the appearance and odor of the molded product due to bleeding etc. occur, making it impossible to obtain desirable results.

In the polypropylene composition of the present invention, the filler (J) used for the purpose of reinforcing, imparting functions, increasing the amount (cost reduction), etc. is a resin composition 100 consisting of a polypropylene resin (C) and a saturated polyester resin (D). 011 to 300 parts by weight, preferably 1 to 200 parts by weight
Add weight. If it is less than 0.01 parts by weight, no filling effect will be obtained, and if it exceeds 300 parts by weight, the toughness and impact resistance will decrease, the original properties of the resin will be lost, and the resin will become brittle, making it impossible to obtain favorable results.

There are no particular limitations on the method for producing the polypropylene composition of the present invention, and any conventional known method can be used.

Methods of mixing in a solution state and evaporating the solvent or precipitating it in a non-solvent are also effective, but from an industrial standpoint,
In practice, a method of kneading in a molten state is used. For melt-kneading, commonly used kneading devices such as Banbury Mixer 1 extruder, rolls, various kneaders, etc. can be used.

When kneading, it is preferable to uniformly mix each resin component in the form of powder or pellets in advance using a device such as a tumbler or Henschel mixer, but if necessary, mixing can be omitted and each resin component is mixed separately in the kneading device. Separate metering methods can also be used.

If the basic compound for promoting the reaction is a powder or a masterbatch, any of the above methods can be used, but if it is a liquid, it is preferable to mix it in advance with a tumbler or Henschel mixer.
It is also possible to use a method in which the kneading device is equipped with a metering pump and the liquid is added through piping.

The kneaded resin composition is molded by various molding methods such as injection molding, extrusion molding, etc., but the present invention also allows for melt processing by tri-blending during injection molding or extrusion molding without going through the kneading process in advance. It also includes a method of directly kneading into a molded product to obtain a molded product.

In the present invention, there is no particular restriction on the order of cross-wires; modified polypropylene (A), polypropylene (B), saturated polyester (D), epoxy group-containing copolymer (E), ethylene copolymer rubber (F), modified ethylene Copolymer rubber (G
) and modified ethylene copolymer rubber (H), a basic compound (1), and a filler (J) may be bulk kneaded. Polypropylene (B) is kneaded in advance to produce a polypropylene resin (C), which is then mixed with a saturated polyester resin (D), an epoxy group-containing copolymer (E), an ethylene copolymer rubber (F), At least one rubber selected from modified ethylene copolymer rubber (G) and modified ethylene copolymer rubber (H), a basic compound (I), and a filler (J) are blended and kneaded. Furthermore, the polypropylene resin (C) and the saturated polyester resin (D) are kneaded in advance, and then the epoxy group-containing copolymer (ε) and the ethylene copolymer rubber (
F), at least one rubber selected from modified ethylene copolymer rubber (G) and modified ethylene copolymer rubber (It), a basic compound (1) and a filler (J) are blended. It may be kneaded or other kneading orders may be used.

However, modified polypropylene (A) and epoxy group-containing copolymer (E), epoxy group-containing copolymer (E) and modified ethylene copolymer rubber (G) and/or (11), or saturated polyester resin (D ) and the epoxy group-containing copolymer (E), gelation may occur during kneading depending on the quantitative ratio of the two components. It is necessary to select an appropriate proportion and knead in advance.

In order to simplify the kneading process, the process of producing modified polypropylene (A) or modified ethylene copolymer rubber (G) or (H) in advance is included in the kneading process of the modified polypropylene resin composition of the present invention. It is also possible to incorporate it.

That is, in the first step, raw material polypropylene (A) or raw material ethylene-based copolymer rubber is modified, and in the second step, the remaining component, modified polypropylene (A) or modified ethylene-based copolymer rubber, is added while the modified product is in a molten state. It can be produced by adding copolymer rubber (G) or (H), polypropylene (B), saturated polyester resin (D), epoxy group-containing copolymer (E), and basic compound (1).

In order to further simplify the kneading process, the process of producing modified polypropylene (A) and modified ethylene copolymer rubber (G) may be incorporated into the kneading process of the polypropylene composition of the present invention. It is possible.

That is, in the first step, raw material polypropylene and raw material ethylene copolymer rubber are co-modified, and in the second step, polypropylene (B), saturated polyester resin (D), and epoxy group-containing copolymer rubber are added to the co-modified product in a molten state. It can be produced by adding the polymer (E) and the basic compound (G).

In order to more effectively produce the polypropylene composition of the present invention, it is preferable to use a high kneading twin screw extruder having a long L/D and having two or more feeders. That is, from the time when raw materials for modification are inputted from the first feedlot until the other components other than the modified polypropylene (A) or the modified ethylene copolymer (G) or (H) are supplied to the next feedlot. A composition can be efficiently produced by sufficiently modifying the mixture, adding other components as appropriate from the second feeder onwards, and kneading them. In the case of co-modification, raw materials for co-modification are input from the first feeder and modified polypropylene (A
) and other components other than the modified ethylene copolymer (G) are sufficiently co-modified before being added, and other components are added as appropriate from the second feeder onwards and kneaded, thereby making it efficient. A composition can be manufactured.

In order to develop good impact resistance, a method is used in which a part of the epoxy group-containing copolymer (FE) is kneaded in advance with the saturated polyester resin (D), and then the remaining components are blended and kneaded. In order to more effectively strengthen J) and exhibit good rigidity and heat resistance, the filler (J) is kneaded in advance with one component of the resin constituting the polypropylene composition of the present invention with good dispersion, Next, the remaining components are blended and kneaded, the filler (J) is introduced into the extruder midway through the extruder after the composition has been melt-kneaded, and the reaction accelerating effect of the basic compound (1) is evaluated. In order to efficiently express the basic compound (1), a masterbatch is prepared in which the basic compound (1) is dispersed in advance at a high concentration in one of the resin components constituting the polypropylene composition of the present invention or in a resin compatible with the polypropylene composition. In order to preferably express the physical properties of the polypropylene composition of the present invention, various kneading methods can be used, such as a method in which the polypropylene composition is then mixed with other components and kneaded.

〔Example〕

The present invention will be explained below with reference to examples, but these are merely illustrative and the present invention is not limited to these examples unless it departs from the gist.

Next, methods for measuring physical property values in Examples are shown below.

(1) Specific gravity According to the method specified in JIS K6758.

(2) Melt flow rate according to the method specified in JIS K675g. The measurement temperature is 230℃ and the load is 2.16 unless otherwise specified.
Measure in kg.

(3) Tensile test According to the method specified in ASTM 0638. The thickness of the test piece is 3.2 mm, and the tensile yield point strength and tensile elongation are evaluated. The measurement temperature is 23°C unless otherwise specified.

(4) Bending test According to the method specified in JIS K7203. The thickness of the test piece is 3.2 mm, and the bending elastic modulus and bending strength are evaluated under the conditions of a span length of 50 mm and a loading rate of 1.5 mm/min. The measurement temperature is 23°C unless otherwise specified. If the temperature is other than that, the measurement is performed after adjusting the condition for 30 minutes in a constant temperature bath at a predetermined temperature.

(5) Izot impact strength According to the method specified in JIS 711O. The thickness of the test piece is 3.2 mm, and the notched impact strength is evaluated. The measurement temperature is 23°C unless otherwise specified.

If the temperature is other than that, the measurement is performed after adjusting the condition for 2 hours in a constant temperature bath at a predetermined temperature.

(6) Surface impact strength High Rate I manufactured by Rheometrics (USA)
Using mpact Te5ter (RIT-8000 model), a 3 mm thick flat plate testing machine piece was fixed with a 2 inch circular holder, and a 578 inch (spherical tip 5716 inch radius) impact probe was used, and the impact probe was moved at a speed of 3 m and 7 seconds. The surface impact strength is evaluated by applying the test piece to a test piece, detecting the deformation and stress of the test piece, drawing a curve as shown in Figure 1, and calculating the area integral value.

The energy value required for the material to yield is evaluated as the yield point energy, and the energy value required for the material to break as the total energy, and both units are expressed in joules (J).

Condition adjustment is performed using a constant temperature bath attached to the device.

The test piece is placed in a constant temperature bath that has been adjusted to a predetermined temperature in advance, and is left to stand for 2 hours before performing the above test. This predetermined temperature is taken as the measurement temperature.

(7) Heating deformation temperature according to the method specified in JIS K7207. Fiber stress is measured at 4.6 kg/crl.

(8) According to the method specified in Rockwell hardness JIS K7207. The thickness of the test piece is 3.2 mm, the steel ball uses R, and the evaluation value is expressed on the R scale.

(9) Amount of maleic anhydride added The amount of maleic anhydride added to the modified polypropylene (A) is:
After purification by dissolving a small amount of the sample in heated xylene and precipitating it with anhydrous acetone, it was made into a xylene solution again, and phenolphthalein was used as an indicator under heating (1
(10 to 120°C) by titration with a Na leaf methanol solution.

The amount of maleic anhydride added to modified ethylene copolymer rubbers (G) and (H) can be determined by dissolving a small amount of the sample in toluene,
After purification by precipitation with anhydrous acetone, it was made into a toluene solution again, and determined by titration with an ethanol solution under heating (85°C) using phenolphthalein as an indicator.

Further, the amount of styrene added was determined using the intensity of the absorption peak corresponding to the substituted benzene ring appearing in the infrared absorption spectrum measured using the purified product.

(10) Mooney viscosity according to the method specified in JIS K6300. The measurement temperature is 121°C.

(11) Number average molecular weight Kervermeation chromatography Measured by graphography (GPC), I went there on this matter.

GPC: Waters 150C type column:
5hodex 3QMA manufactured by Showa Denko ■ Sampling amount: 300μm (polymer concentration 0.2wt%) Flow rate: 1 mj! /m+n Temperature=135°C Solvent Nitrichlorobenzene A calibration curve for calculating the number average molecular weight was prepared by a conventional method using standard polystyrene manufactured by Toyo Soda ■. In addition, data processing is done using Toyo Soda's data processor CP.
-8 model ■ was used.

(12) Methyl (-Ct13) and methylene (-CH
It was determined by the calibration curve method using the absorbance of the characteristic absorption of 2-).

The above test pieces for evaluating physical properties were produced under the following injection molding conditions unless otherwise specified. The composition is dried in a hot air dryer for 12 minutes.
After drying at 0°C for 2 hours, Toshiba Machine @ 15150 E −
Injection molding was performed using a V-type injection molding machine at a molding temperature of 240°C, a mold cooling temperature of 70°C, an injection time of 15 seconds, and a cooling time of 30 seconds.

The following compositions were manufactured under the following conditions unless otherwise specified. After weighing the predetermined amount of each component and pre-mixing them uniformly using a Henschel mixer, the extrusion rate was 30 kg/hour using a continuous twin-screw kneader (Japan Steel Works, Ltd. T-Sumi X 44 SS 30BW-2V model), and the resin temperature was The test was carried out at 240°C, at a screw rotation speed of 350 revolutions/minute, and under vent suction. The screw was constructed by arranging a three-thread type rotor and a kneading disk in two kneading zones, each in the zone next to the first feeder and the second feeder.

Examples 1-5, Comparative Examples 1-2 (Table 1-1,-2) Modified polypropylene (A) was produced by the following method.

Melt flow rate is 1.3 (g/10 min, 135°C,
Intrinsic viscosity in tetralin solvent is 2.45 (a/g),
The content of the cold xylene soluble part at 20°C is 2.9% by weight, the content of the boiling hebutane soluble part is 6.7% by weight, and the isotactic pentad fraction of the boiling hebutane insoluble part is 0. 9
The raw material propylene homopolymer No. 55, which was produced by the slurry polymerization method as exemplified in JP-A-6028405, was modified in the following manner. 1.0ffi maleic anhydride per 100 parts by weight of raw material propylene homopolymer
ffiil, 1,3-bis(
A propylene homopolymer with 8% by weight of tertiary-butylperoxyisopropyl)benzene (manufactured by Sansei Kako ■; Sanperox ■-TYI・3) supported on a propylene homopolymer was prepared with 0.
6 parts by weight and stabilizer Irganox ■1010
(Manufactured by Ciba Geigy) 0.1 part by weight was homogenized using a Henschel mixer. After mixing, TEX manufactured by Nippon Steel Corporation was mixed.
445S-30BW-2V type twin screw extruder, temperature 22
Maleic anhydride-modified polypropylene (A) melt-kneaded at 0°C, average residence time 1.5 minutes, maleic anhydride addition amount 0.08% by weight, melt flow rate 36 axis 710 minutes)
was manufactured. Below, the modified polypropylene (A)! ,
It is abbreviated as 1-PP-1.

As the saturated polyester resin (D), polybutylene terephthalate (Toughpet PBT N manufactured by Mitsubishi Rayon Q@)
1000) was used. Hereinafter, this raw material polybutylene terephthalate will be abbreviated as PBT-1.

An epoxy group-containing copolymer (E) was produced by the following method. JP-A-47-23490 and JP-A-48-11
According to the method exemplified in Publication No. 888, the melt flow rate was 7 (g/10 minutes) by high-pressure radical polymerization.
(190°C, load 2.16 kg) Ethylene-vinyl acetate-glycidyl methacrylate weight 1 ratio, 85-5-1
0 (wt%) of the terpolymer was produced. Hereinafter, the acid epoxy group-containing copolymer will be abbreviated as E-VA-GMA-1.

Number average molecular weight as ethylene copolymer rubber (F): 60
．． 000, ethylene-propylene copolymer rubber pellets having an ethylene content of 78% by weight were used. Hereinafter, the acid ethylene-propylene copolymer rubber will be abbreviated as EP 1.1-1.

The above raw materials are mixed with EPM-1 and E-VA-GMA-1 at a constant ratio and M-PP-1 and PBT-1 at various ratios as shown in Table 1-1, and the predetermined crosstalk is achieved. A composition was manufactured under the specified conditions, a test piece was prepared under the predetermined injection molding conditions, and the physical properties were evaluated using a predetermined evaluation method.

The proportions are expressed as % by weight of the composition (
The same applies to the following Examples and Comparative Examples) The physical property evaluation results are shown in Table 1-2.

Further, an example of surface impact strength measurement at 23° C. of Example 3 is shown in FIG. Izot impact strength is commonly used as a method for evaluating 1JR impact strength, but there are often cases where even if the Izot impact strength is low, the surface impact strength is high. Although polybutylene terephthalate has a lower notched isot impact strength at -30°C than a propylene ethylene/propylene block copolymer, its surface impact strength is significantly higher. A low-temperature falling ball test is used for practical evaluation of automobile parts, and this practical evaluation and the laboratory evaluation method for surface impact strength correspond well.

In this flf evaluation, the higher the yield point energy and the larger the total energy shown in FIG. 1, the better.

These are calculated from the measurement chart. Furthermore, the state of fracture of the test piece at the fracture point is important in relation to practical evaluation.

The state of destruction cannot be read from the measurement chart,
Judgment is made by observing the fracture state of the test piece after fracture. A fracture state in which a sharp crack occurs or the test specimen is divided into several fractured pieces is called brittle fracture. A state in which the specimen is fractured along the shape of the impact probe is called ductile fracture.

As for the fracture state, ductile fracture is preferable.
It can be seen that the isot impact strength and surface impact strength of Examples 1 to 5 of the present invention are significantly improved compared to Comparative Examples 1 to 2 in which no 1° ethylene-propylene copolymer rubber is blended.

Examples 6 to 9 (Table 2 -1, -2) Using the same raw materials as those used in Examples 1 to 5, Table 2 to
+ as shown in 1: PBT-1 and E-VA-GMA-
1 at a constant ratio, M-PP-1 and EF'! Compositions were prepared in the same manner as in Examples 1 to 5 by blending J-1 in various proportions, and their physical properties were evaluated. Table 2 shows the results of physical property evaluation =
Shown in 2.

The larger the proportion of ethylene-propylene copolymer rubber EPM-1 blended, the better the isot impact strength and surface impact strength. Conversely, the heat distortion temperature becomes lower and the heat resistance decreases.

Examples 10 to 12, Comparative Example 3 (Table 3-1, -2) Using the same raw materials as those used in Examples 1 to 5, Table 3-1
As shown! , 4-PP-1 and PBT-1 at a certain ratio, and ridge! To1 and E-VA-G! , l^-1 were mixed in various proportions, compositions were produced in the same manner as in Examples 1 to 5, and the physical properties were evaluated. The results of physical property evaluation are shown in Table 3. Epoxy group-containing copolymer E-VA-G! , IA-
Examples 10 to 1 of the present invention compared to Comparative Example 3 in which 1
It can be seen that No. 12 has significantly improved Izo/T impact strength and surface 1# impact strength.

Example 13 (Table 4 -1, -2) The same raw materials as those used in Examples 1 to 5 were used, and benzyldimethylamine (manufactured by Order Kagaku @ Sumicure ■80) 4th
They were blended in the proportions shown in Table 1, and compositions were produced in the same manner as in Examples 1 to 5, and their physical properties were evaluated. The results of physical property evaluation are shown in Table 4-2.

Example 3 of the present invention in which the basic compound (1) was not blended also showed good physical properties, but in this example in which the basic compound (1) was blended, the level of Izot impact strength and surface 1# impact strength was further improved. will improve.

Example 14 (Table 5 -1, -2> Modified polypropylene (A) was produced by the following method. At 135°C, the intrinsic viscosity in tetralin solvent was 2.42.
(a7/g>, melt flow rate is 1.6 (g/1
0 minutes), the content of the soluble part in xylene cooled at 20°C is 0.6% by weight, the content of the soluble part in boiling hebutane is 2.9% by weight, the isotactic pentad content of the part insoluble in boiling hebutane In Examples 1 to 5, the raw material highly crystalline propylene homopolymer produced by the slurry polymerization method exemplified in JP-A No. 60-228504 having a ratio of 0.980 was used. J
Polypropylene modified with maleic anhydride was modified in the same manner as -PP-1 to obtain maleic anhydride-modified highly crystalline polypropylene having an added amount of maleic anhydride of 0.08% by weight and a melt flow rate of 36 axial and 710 min). Hereinafter, the modified highly crystalline polypropylene will be referred to as M-P P
-2 for short.

As modified polypropylene! , l -P P -2 was used, but the same raw materials as in Examples 1 to 5 were used, and Table 5 -
A composition was prepared in the same manner as in Examples 1 to 5, and the physical properties were evaluated. Table 5 shows the results of physical property evaluation.
Shown in 2.

Ordinary modified polypropylene! Example 3 of the present invention using J-PP-1 also shows good physical properties, but by using modified highly crystalline polypropylene M-PP-2, the flexural modulus and heat distortion temperature increase, and the rigidity It can be seen that favorable results can be obtained in terms of heat resistance and heat resistance.

Example 15 (Table 6-1, -2) As ethylene copolymer rubber (F), number average molecular weight 5
5.000 and a pulverized ethylene-propylene copolymer rubber having an ethylene content of 47% by weight was used. Hereinafter, the ethylene-propylene copolymer rubber will be abbreviated as εPM-2.

Using the same raw materials as in Example 14 except for using EPM-2 as the ethylene-propylene copolymer rubber,
A composition was prepared in the same manner as in Examples 1 to 5, and the physical properties were evaluated. Table 6 shows the results of physical property evaluation.
Shown in 2.

Example 14 of the present invention in which EPMl was used as the ethylene-propylene copolymer rubber also showed good physical properties, but EPM-
When using No. 2, favorable results can be obtained in low-temperature isot impact strength and low-temperature surface impact strength.

Examples 16 to 17 (Table 7-1, -2) Polyethylene terephthalate (Petra 130 manufactured by Allied Chemical Co., Ltd.) was used as the saturated polyester resin (D). Hereinafter, this raw material polyethylene terephthalate will be abbreviated as PET-1.

As Yuwa polyester resin, PET-1 alone or P
Example 15 except for using the ET-1/PBT-1 mixed system
Using the same raw materials as above, blending in the proportions shown in Table 7-1,
A composition was produced in the same manner as in Example 15, except that the resin temperature was changed to 270°C, and test pieces were prepared by injection molding in the same manner as in Example 15, except that the molding temperature was changed to 270°C, and the physical properties were evaluated. The results of physical property evaluation are shown in Table 7-2.

Example 15 of the present invention using PBT-1 alone also shows good physical properties, but PET-1 alone or PET-1/PB
When the T-1 mixed system is used, the heat distortion temperature increases and favorable results can be obtained in terms of heat resistance.

Examples 18 to 19 (Table 8-1,-2) Epoxy group-containing copolymers (E) were produced by the following method. Using methyl acrylate as a comonomer instead of vinyl acetate, high-pressure radical polymerization was performed as shown in Examples 1 to 5, and the melt flow rate was 21 (g/10 min) (190°C, load 2.
16 kg) Ethylene-methyl acrylate-glycidyl methacrylate weight ratio, 64-14-22 (wt%
A terpolymer with a high content of glycidyl methacrylate 7 was prepared. Hereinafter, the epoxy group-containing copolymer will be described as E.! J
It is abbreviated as A-GMA-1.

E・M A -G M as an epoxy group-containing copolymer
Using the same raw materials as in Example 15 except for using A-1,
They were blended in the proportions shown in Table 8-1, and compositions were produced in the same manner as in Examples 1 to 5, and their physical properties were evaluated. The results of physical property evaluation are shown in Table 8-2.

Similar to Example 15, it shows good physical properties.

Examples 20 to 22 (Tables 9-1 and -2) As the filler (J), short glass fibers of Microglass ■ Chopped Toast Trunk 'R Mi5O3X-TP10532 manufactured by Nippon Glass Shii@J were used. Hereinafter, the short glass fiber will be abbreviated as GF-1.

Examples 18-19 except using GF-1 as filler
Using the same raw materials as above, mix the ingredients other than GF1 in the proportions shown in Table 9-1, feed the ingredients other than GF-1 in the first feeder and melt-knead them in advance, and mix the remaining ingredients from the second feeder. A composition was prepared by feeding one component of GF-1. The physical properties were evaluated in the same manner as in Examples 1 to 5. The results of physical property evaluation are shown in Table 9-2.

When GF-1 is used as a filler, compared to Example 18 of the present invention when GF-1 is not used, the isot impact strength and surface impact strength are slightly lower, but the flexural modulus and heat distortion temperature are significantly increased, and the rigidity is Favorable results can be obtained in terms of heat resistance and heat resistance.

Examples 23 to 25 (Table 10 -1, -2) Examples 1 to 5 except that the raw material propylene homopolymer of M-PP-1 (hereinafter abbreviated as PP-1) was used as polypropylene (B). Using the same raw materials as in Table 10-1, PBT-1, E-VA-G! , IA-1 and EP Tol in fixed proportions, and various proportions of MS-PP-1 and PP-1 were blended to produce compositions in the same manner as in Examples 1 to 5, and the physical properties were evaluated. .

The results of physical property evaluation are shown in Table 10-2. It can be seen that, compared to Comparative Example 1 in which ethylene propylene copolymer rubber (F) EPM-1 was not blended, Examples 23 to 25 of the present invention were significantly improved in Izod 1JR impact strength and surface impact strength.

Examples 26 to 30 (Table 11 -1, -2) Modified ethylene copolymer rubber (G) was produced by the following method. To 100 parts by weight of an ethylene-propylene copolymer rubber pellet with a number average molecular weight of 1t60.000 and an ethylene content of 78%, 2.0 parts by weight of maleic anhydride and 1,3-bis(tert. -Butylperoxyisopropyl) Henzen (manufactured by Sansoku Kako ■; Sanverox ■-TY13) supported on propylene homopolymer in an amount of 8% by weight was mixed in a Henschel mixer at a ratio of 1.0% by weight, and then Steelworks made by TEX
Melt-kneaded in a 445S-30BL-2V type twin-screw extruder under a nitrogen atmosphere at a kneading temperature of 250°C and an extrusion rate of 18 kg/hour to obtain a mixture of 0.7% by weight of maleic anhydride and 1'2.
A modified ethylene-propylene copolymer rubber having a Mooney viscosity at 1°C (ML+.4121°C) of 72 was produced. Hereinafter, the modified ethylene-propylene copolymer rubber will be abbreviated as Nido εP-1.

Using the same raw materials as in Examples 1 to 5 except for M-EPM-1, as shown in Table 11, M-BP! ,! -1 and E-
Make VA/GMAl a constant ratio of 4! Compositions were prepared in the same manner as in Examples 1 to 5 by blending J-PP-1 and POT-1 in various proportions, and their physical properties were evaluated. The physical property evaluation results are shown in Table 11-2.

It can be seen that, compared to Comparative Examples 1 to 2 in which no modified ethylene-propylene copolymer rubber was blended, Examples 26 to 30 of the present invention had significantly improved isot impact strength and surface impact strength.

Compared to Examples 1 to 5 using EPM-1, the rigidity, isot impact strength and surface impact strength are excellent, but the melt flow rate is low and the fluidity is poor.

Examples 31 to 34 (Table 12 -1, -2) Example 26 to
M-PP-1 and M-εP! , 4-1 were blended in various proportions, compositions were produced in the same manner as in Examples 1 to 5, and the physical properties were evaluated. Table 12 shows the results of physical property evaluation.
Shown in 2.

Modified ethylene-propylene copolymer rubber M-EP
The larger the proportion of M-1 blended, the better the isot impact strength and surface impact strength. Conversely, the heat distortion temperature becomes lower and the heat resistance decreases.

Examples 35 to 37, Comparative Example 4 (Table 13 -1, -2)
Using the same raw materials as those used in Examples 26 to 30, the first
3 As shown in Table-1, M-EPM-1 and E-VA-GMA-
Compositions were prepared in the same manner as in Examples 1 to 5, and their physical properties were evaluated. The results of physical property evaluation are the first
3 Shown in Table-2. Epoxy group-containing copolymer ε/C A-G
It can be seen that the Izotl impact strength and surface impact strength of Examples 35 to 37 of the present invention were significantly improved compared to Comparative Example 4 in which MA-1 was not blended.

Example 38 (Table 14 -1, -2) The same raw materials as those used in Examples 26 to 30 were used, and benzyldimethylamine (manufactured by Sumitomo Chemical Co., Ltd.) was added as a basic compound (G) as a reaction accelerator. Sumicure (BD) was blended in the proportions shown in Table 14-1, and compositions were prepared in the same manner as in Examples 1 to 5, and their physical properties were evaluated. The results of physical property evaluation are shown in Table 14-2.

Example 28 of the present invention in which the basic compound (G) was not blended also showed good physical properties, but in this example in which the basic compound (G) was blended, the levels of Izot impact strength and surface impact strength were further improved. do.

Practical Example 39 (Table 15-1, -2) The same raw materials as in Examples 26 to 30 were used except that M-PP-2 was used as the modified polypropylene, and the materials were blended in the proportions shown in Table 15-1. Compositions were produced in the same manner as in Examples 1 to 5, and their physical properties were evaluated. Table 15-2 shows the results of physical property evaluation.
Shown below.

Example 28 of the present invention using ordinary modified polypropylene M-PP-1 also shows good physical properties, but by using modified highly crystalline polypropylene M-PP-2, the flexural modulus and heat distortion temperature increase. However, it can be seen that favorable results can be obtained in terms of rigidity and heat resistance.

Example 40 (Table 16 -1, -2) A modified ethylene copolymer rubber (G) was produced by the following method. Number average molecular weight 55.000, ethylene content 47
% by weight of pulverized ethylene-propylene copolymer rubber was modified by the Ω method in the same manner as M-EPMJ-1 in Examples 26 to 30, and 10.5% by weight of maleic anhydride was added.
121t: Mooney viscosity (ML, +, 121°C) is 65
A modified ethylene-propylene copolymer rubber was obtained. Below, the modified ethylene propylene copolymer rubber is M-EPM-
It is abbreviated as 2.

M-EP as modified ethylene-propylene copolymer rubber
Using the same raw materials as in Example 39 except for using M-2,
They were blended in the proportions shown in Table 16-1, and compositions were produced in the same manner as in Examples 1 to 5, and their physical properties were evaluated.

The results of physical property evaluation are shown in Table 16-2.

M-EP as modified ethylene-propylene copolymer rubber
Example 39 of the present invention using M-1 also shows good physical properties, but M-B P! It can be seen that when J-2 is used, favorable results can be obtained in low-temperature isot impact strength and low-temperature surface impact strength.

Examples 41 to 42 (Table 17-1, -2) PIET-1 alone or PET-1/ as saturated polyester resin
A composition was produced in the same manner as in Example 40, except for using the PBT-1 mixed system, using the same raw materials as in Example 40, blending them in the proportions shown in Table 17-1, and setting the resin temperature to 270 ° C. A test piece was prepared by injection molding in the same manner as in Example 40, except that the molding temperature was 270°C, and the physical properties were evaluated. The results of physical property evaluation are shown in Table 17-2.

Example 40 of the present invention using PBT-1 alone also shows good physical properties, but PET-1 alone or PET-1/PB
When the T-1 mixed system is used, the heat distortion temperature increases and favorable results can be obtained in terms of heat resistance.

Examples 43 to 44 (Table 18-1,-2) E.! as an epoxy group-containing copolymer The same raw materials as in Example 40 were used except for the use of JA-GMA-1, and the compositions were blended in the proportions shown in Table 18, and compositions were produced in the same manner as in Examples 1 to 5 and their physical properties were evaluated. The results of physical property evaluation are shown in Table 18-2.

Similar to Example 40, it shows good physical properties.

Examples 45 to 47 (Table 19-1, -2) The same raw materials as Examples 43 to 44 were used except for using GF-1 as a filler, and components other than GF1 were added in the proportions shown in Table 19-1. A composition was prepared by blending the following ingredients, feeding the components other than GF-1 in the first feeder and melt-kneading them in advance, and feeding the remaining component GF-1 from the second feeder. Physical property evaluation was performed in the same manner as in Examples 1-5. The results of physical property evaluation are shown in Table 19-2.

When GF-1 is used as a filler, the isot impact strength and surface impact strength are slightly lower than in Example 43 of the present invention when GF-1 is not used, but the flexural modulus and heat distortion temperature are significantly increased, and the rigidity is Favorable results can be obtained in terms of heat resistance and heat resistance.

Examples 48-50 (Table 20-1, -2) Examples 26-50 except that PP-1 was used as polypropylene (B)
Using the same raw materials as No. 30, PB was prepared as shown in Table 20-1.
T-1, E・shi A-G! JA-1 and M-EPM-1
The compositions were prepared in the same manner as in Examples 1 to 5 by blending M-PP-1 and PP-1 at a constant ratio and varying the ratio of M-PP-1 to PP-1, and their physical properties were evaluated.

The results of physical property evaluation are shown in Table 20-2. Modified ethylene
Propylene copolymer rubber (G)! Examples 48 to 50 of the present invention compared to Comparative Example 1 in which J-EPM-1 was not blended.
It can be seen that the isot impact strength and surface impact strength are significantly improved.

Example 51 (Table 21-1, -2) M-PP-1 and M-EPM-1 in Example 28
Instead of using these co-modified products, compositions were manufactured using these co-modified products. 1.5 parts by weight of maleic anhydride for 100 parts by weight of a mixture of polypropylene powder as a raw material for M-PP-1 and pellets of ethylene-propylene copolymer rubber as a raw material for M-EPM-1 in a ratio of 55/15. As a radical initiator, 1,3-bis(t-butylperoxyisopropyl)benzene (manufactured by Sansei Kako ■; Samberox ■-TYI・3) was added to propylene homopolymer 7 and 8.
0.6 parts by weight of the weight percent supported and 0.6 parts by weight of Irganox ■ 1010 (manufactured by Ciba Geigy) as a stabilizer.
．． After uniformly mixing 1 part by weight with a Henschel mixer,
Made in Japan w4@TEX 445S-308111-2V
Type twin screw extruder, temperature 220℃, average residence time 1.5
Melt kneaded in minutes, maleic anhydride addition amount 0.16% by weight
, anhydrous polymer with a melt flow rate of 12 (g/10 min)
A twin acid co-modified polypropylene (A)/ethylene-propylene copolymer rubber (G) was produced.

Below are the co-modified products! J-(PP-1/BP!J-1)
It is abbreviated as.

As shown in Table 21, a composition was prepared in the same manner as in Example 28, except that a co-modified product of M-(PP-1/EPM-1) was used, and the physical properties were evaluated. Table 21 shows the results of physical property evaluation.
Shown in 2.

Even when co-modified product M-(PP-1/EP!J-1) is used, each individually modified product M-PP-1, M
Similar to Example 28 using -PPM-1, the isot impact strength and surface impact strength are good.

Example 52 (Table 22-1, -2)) Raw material polypropylene powder of J-PP-2 and E
Maleic anhydride co-modification was carried out in the same manner as in Example 51, except that PPI3 pellets were mixed at a ratio of 30/15, and the maleic anhydride addition fi was 0.23% by weight and the melt flow rate was 8 (axis: 710 min). polypropylene (A)/ethylene-propylene copolymer rubber (G)
was manufactured. Below, the co-modified product is M-(PP-2/EP
It is abbreviated as M-1).

Table 22-
A composition was prepared in the same manner as in Examples 1 to 5, and the physical properties were evaluated. Table 21 shows the results of physical property evaluation.
Shown in 2. It can be seen that compared to Comparative Examples 1 and 2 in which no modified ethylene-propylene copolymer rubber was blended, Example 52 of the present invention had significantly improved isot impact strength and low temperature surface impact strength.

Furthermore, compared to Examples 30 and 39, the heat distortion temperature and Rockwell hardness are higher, and features are seen in heat resistance and scratch resistance.

Examples 53 to 57 (Table 23-1, -2) Modified ethylene copolymer rubber (H) was produced by the following method. 2.0 parts by weight of maleic anhydride, 2.0 parts by weight of styrene and a radical initiator for 100 parts by weight of an ethylene-propylene copolymer rubber pellet with a number average molecular weight of 160.000 and an ethylene content of 78% by weight. as 1,3-
Bis(t-butylperoxyisopropyl)benzene (
8% by weight of propylene homopolymer supported on Sanperox ■-TY13 (manufactured by Sansoku Kako@) was mixed in a Henschel mixer at a ratio of 1.0% by weight, and then TEX 445S-308111 manufactured by Japan Steel Works ■ was mixed in a Henschel mixer. Melt-kneading was carried out in a -2V type twin-screw extruder under a nitrogen atmosphere at a kneading temperature of 250°C and an extrusion rate of 18 kg/hour.The amount of maleic anhydride added was 1.5% by weight, and the amount of styrene added was 0.8% by weight and 9%. , 12
A modified ethylene-propylene copolymer rubber having a Mooney viscosity (ML, ., 121°C) of 70 at 1°C was produced. Below, the modified ethylene-propylene copolymer rubber is MS-EP
It is abbreviated as M-1.

MS-EP! , using the same raw materials as in Examples 1 to 5 except for l-1, as shown in Table 23-1: l:Ms-EPM-1 and Pi-VA-G! , x+-P with IA-1 as a constant ratio
Compositions were prepared in the same manner as in Examples 1 to 5 by varying the proportions of P-1 and PBT-1, and their physical properties were evaluated. The physical property evaluation results are shown in Table 23-2.

Examples 53 to 5 of the present invention compared to Comparative Examples 1 to 2 in which the modified ethylene-propylene copolymer rubber (lI) was not blended at all.
It can be seen that No. 7 has significantly improved isot impact strength and surface impact strength.

Examples 58-61 (Table 24-1,-2) Example 53
Using the same raw materials as those used in ~57, make l:PBT-1 and E-VA-GMA-1 at a constant ratio as shown in Table 24-1. With J-PP-1! Compositions were prepared in the same manner as in Examples 1 to 5 by blending JS-Ko M-1 in various proportions, and their physical properties were evaluated. The results of physical property evaluation are shown in Table 24-2.

Modified ethylene-propylene copolymer rubber MS-EPM-
The larger the proportion of 1 is blended, the better the isot impact strength and surface impact strength. Conversely, the heat distortion temperature becomes lower and the heat resistance decreases.

Examples 62 to 64, Comparative Example 5 (Table 25-1,-2)
Using the same raw materials as those used in the examples, MS-EPM-1 and IE-VA-GMA-1 ( 7
) The compositions were prepared in the same manner as in Examples 1 to 5 by blending them in various proportions, and their physical properties were evaluated. The results of the physical property evaluation are shown in the 25th
It is shown in Table-2. On epoxy group-containing copolymer V A −
It can be seen that the Izot impact strength and surface impact strength of Examples 62 to 64 of the present invention were significantly improved compared to Comparative Example 5 in which G i,l A-1 was not blended.

Example 65 (Table 26 -1, -2) Using the same raw materials as those used in Examples 53 to 57, benzyldimethylamine (manufactured by Kanto Kagaku Sumicure (BD) was blended in the proportions shown in Table 26-1, and compositions were prepared in the same manner as in Examples 1 to 5, and their physical properties were evaluated. The results of physical property evaluation are shown in Table 26-2.

Example 55 of the present invention in which the basic compound (1) was not blended also showed good physical properties, but in this example in which the basic compound (1) was blended, the levels of impact strength and surface impact strength were further improved. will improve.

Example 66 (Table 27-1, -2) The same raw materials as Examples 53 to 57 were used except that M-PP-2 was used as the modified polypropylene, and the materials were blended in the proportions shown in Table 26-1. Compositions were produced in the same manner as Examples 1 to 5, and their physical properties were evaluated. Table 27-2 shows the results of physical property evaluation.
Shown below.

Example 55 of the present invention using ordinary modified polypropylene M-PP-1 also shows good physical properties, but by using modified highly crystalline polypropylene PP-2, the flexural modulus and heat distortion temperature increase. It can be seen that favorable results can be obtained in terms of stiffness and heat resistance.

Example 67 (Table 28-1, 2) A modified ethylene copolymer rubber (H) was produced by the following method. Number average molecule 155.000, ethylene content 47
λl5-EP in Examples 53 to 57 using pulverized ethylene-propylene copolymer rubber of % by weight! ,! -1
A modified ethylene-propylene copolymer rubber having a maleic anhydride addition amount of 1.2% by weight, a styrene addition amount of 0.7% by weight, and a Mooney viscosity at 121°C (ML+.4121°C) of 40 was modified in the same manner as above. Obtained. The following is a politically modified ethylene propylene copolymer rubber. IS-EP! J-2
It is abbreviated as.

MS as modified ethylene-propylene copolymer rubber
-BP! , 1-2 were used, the same raw materials as in Example 66 were used, and the compositions were prepared in the same manner as in Examples 1 to 5 by blending them in the proportions shown in Table 28-1, and the physical properties were evaluated.

The physical property evaluation results are shown in Table 28-2.

As a modified ethylene-propylene copolymer rubber! , 4
Example 66 of the present invention using S-E P M-1 also shows good physical properties, but when using M S-E PN2-2, favorable results are obtained in low-temperature Izot vIr impact strength and low-temperature surface impact strength.

Examples 68 to 69 (Table 29-1, -2) As saturated polynisder resin, I'ET-1 alone or PET-1/
A composition was produced in the same manner as in Example 67, except for using the PBT-1 mixed system, using the same raw materials as in Example 67, blending them in the proportions shown in Table 29-1, and setting the resin temperature to 270 ° C. A test piece was prepared by injection molding in the same manner as in Example 67, except that the molding temperature was 270°C, and the physical properties were evaluated. The results of physical property evaluation are shown in Table 29-2.

Example 67 of the present invention using PBT-1 alone shows good physical properties, but PET-1 alone or PET-1/PB
When the T-1 mixed system is used, the heat distortion temperature increases and favorable results can be obtained in terms of heat resistance.

Examples 70 to 71 (Table 30-1, -2) E-MA-G! as an epoxy group-containing copolymer! The same raw materials as in Example 67 were used except for using IA-1, and the compositions were blended in the proportions shown in Table 30-1. Compositions were produced in the same manner as in Examples 1 to 5, and their physical properties were evaluated. The results of physical property evaluation are shown in Table 30-2.

It shows good physical properties like Example 67.

Examples 72 to 74 (Table 31-1, -2) The same raw materials as Examples 70 to 71 were used except that GF-1 was used as the filler, and other than GF-1 was used in the proportions shown in Table 31-1. A composition was produced by blending the components, melt-kneading them in advance by feeding the components other than GF-1 in the first feeder, and feeding the remaining component GF-1 from the second feeder. Physical property evaluation was performed in the same manner as in Examples 1-5. The results of physical property evaluation are shown in Table 31-2.

When GF-1 is used as a filler, the isot impact strength and surface impact strength are slightly lower than in Example 70 of the present invention when GF-1 is not used, but the flexural modulus and heat distortion temperature are significantly increased, and the rigidity is In terms of heat resistance and heat resistance, favorable results can be obtained.

Examples 75 to 77 (Table 32-1, -2) Examples 53 to 77 except that PP-1 was used as polypropylene (B)
Using the same raw materials as 57, as shown in Table 10-1':P
BT-1, ε・VA-GMA-1 Yobi! , IS-E
P! , 4-1 at a constant ratio, M-PP-1 and P
Compositions were prepared in the same manner as in Examples 1 to 5 by blending P-1 in various proportions, and their physical properties were evaluated.

The results of physical property evaluation are shown in Table 32-2. Modified ethylene
Propylene copolymer rubber (H)! Examples 75 to 7 of the present invention compared to Comparative Example 1 in which JS-EPM-1 was not blended.
It can be seen that No. 7 has significantly improved isot impact strength and surface impact strength.

Example 78 (Table 33-1, -2) Polypropylene (B) with a low rate of 7.5 (g
/10 minutes), 135°C, intrinsic viscosity in tetralin solvent of 2.18 (a/g), the first polymerized in the first step
The proportion of the homopolymer part of propylene to be segmented (hereinafter referred to as P part) is 84% by weight, and the proportion of the ethylene and propylene copolymer (hereinafter referred to as EP part), which is the second segment polymerized in the second step, is 84% by weight. The molecular structure of the P part is 135°C, the intrinsic viscosity in tetralin solvent is 1.60 (a/g), and the content of the cold xylene soluble part at 20°C is 1.6% by weight. , the content of the boiling hebutane soluble part is 4.6% by weight, the isotactic pentad fraction of the boiling hebutane insoluble part is 0.975, and the EP
The molecular structure of the part is 135°C, the intrinsic viscosity in tetralin solvent is 5.2 (J/g), and the ethylene/
The proportion of propylene is 37/63% by weight, JP-A-6
Raw material highly crystalline propylene block copolymer (hereinafter referred to as PP) polymerized by the slurry polymerization method illustrated in No. 0-228504
-3 for short. ) was used.

A maleic anhydride co-modified polypropylene (A)/ethylene-propylene copolymer rubber (G) was produced by the following method. Anhydrous maleic acid was added to 100 parts by weight of a mixture of pulverized polypropylene powder as a raw material for M-PP-2 and ethylene-propylene copolymer rubber as a raw material for M-EPM-2 in a ratio of 40.6/17.4. 0.5 parts by weight of acid and 8% by weight of 1,3-bis(t-butylperoxyisopropyl)benzene (manufactured by Sansei Kako ■: Sanperox ■-TYI・3) as a radical initiator were supported on a propylene homopolymer. 0.5 parts by weight and stabilizer Irganox 1010 (Ciba Geigy'I
M) After uniformly mixing 0.1 part by weight with a Henschel mixer, Japanese w4@ TEX 44SS-30BW-2
V-type twin-screw extruder unit, temperature 220°C, average residence time 1.
Melt kneaded for 5 minutes to obtain maleic anhydride co-modified polypropylene (A)/ethylene-propylene copolymer rubber (G) with 10.09% by weight of maleic anhydride addition and a melt flow rate of 9.5 (g710 min). Manufactured. Hereinafter, the co-modified product will be abbreviated as M-(PP-2/BP!, 1-2).

Furthermore, PBT-1 was used as the saturated polyester resin (D), and E-MA-GMA- was used as the epoxy group-containing copolymer (E).
1 and blended in the proportions shown in Table 33-1, Example 1
A composition was produced in the same manner as in 5 to 5, and its physical properties were evaluated.

The results of physical property evaluation are shown in Table 33-2. By using a propylene block copolymer as polypropylene (B), fluidity is greatly improved, and favorable results can be obtained in terms of both fluidity and physical properties.

Examples 79-80 (Table 34-1, -2) M-PP-2
The raw material polypropylene powder and the raw material ethylene-propylene copolymer rubber pellets of 48P and 55
Maleic anhydride co-modification was carried out in the same manner as in Example 52, except that the mixture was carried out at a ratio of 10.23.
A maleic anhydride co-modified polypropylene (A)/ethylene-propylene copolymer rubber (G) having a melt flow rate of 10 axes/10 minutes) was produced. Hereinafter, the co-modified product will be abbreviated as M-(PP-2/EP!J-1)-2.

In the above, number average molecules instead of pellets of raw material ethylene-propylene copolymer rubber! 150.000, ethylene-butene-1 copolymer rubber pellets with an ethylene content of 82% by weight were co-modified in exactly the same manner, and the amount of maleic anhydride added was 0.19% by weight, and the melt flow rate was 1.
A maleic anhydride co-modified polypropylene (A)/ethylene-butene-1 copolymer rubber (G) was produced. Below are the co-modified products! ,! -(PP-2/E
It is abbreviated as BM-1).

Furthermore, PBT-1 was used as the saturated polyester resin (D), and E-MA-GMA- was used as the epoxy group-containing copolymer (E).
1 and blended in the proportions shown in Table 34-1, Example 1
A composition was produced in the same manner as in 5 to 5, and its physical properties were evaluated.

The results of physical property evaluation are shown in Table 34-2. Both Examples 79 and 80 exhibit good physical properties. Example 80, which used ethylene-butene-1 copolymer rubber, had a higher Rockwell hardness than Example 79, which used ethylene-propylene copolymer rubber, and was characterized by its scratch resistance.

〔Effect of the invention〕

The polypropylene composition according to the present invention not only has good molding processability, but also has much better physical properties of molded articles than molded articles made from the individual component polymers themselves. It has a remarkable effect.

The novel composition provided by the present invention can be easily processed into molded products, film sheets, etc. by molding methods normally used for thermoplastic resins, such as injection molding and extrusion molding. To provide a product with an extremely good balance of rigidity, heat resistance, impact resistance, scratch resistance, paintability, oil resistance, chemical resistance, water resistance, etc., and excellent uniformity and smoothness in appearance. It is suitably used in applications requiring exceptionally high levels of heat resistance and impact resistance, especially low-temperature impact resistance.

[Brief explanation of the drawing]

FIG. 1 shows an example of a measurement chart for evaluating surface impact strength. The horizontal axis is the amount of deformation of the test piece, and the vertical axis is the stress for a certain amount of deformation. The measurement chart is obtained by continuously detecting both values and plotting them continuously on an X-Y plotter. The yield point energy is determined by integrating the area of the displacement and stress from the rising part of the detected stress to the point at which the material yields, and the total energy is calculated by integrating the area of the displacement and stress from the rising part of the detected stress until the material breaks. seek. The fracture state of the material is determined by looking at a fracture test piece of the actual material, whether it is ductile fracture (D) or brittle fracture (B).

Claims (10)

[Claims] (1) 1 to 99% by weight of a polypropylene resin (C) selected from a modified polypropylene (A) obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof or a modified polypropylene (A)/polypropylene (B) composition and a saturated polyester 0.1 to 300 parts by weight of the epoxy group-containing copolymer (E), ethylene copolymer rubber (F), and 100 parts by weight of the resin composition consisting of 99 to 1% by weight of the resin (D). Modified ethylene copolymer rubber (G) obtained by graft copolymerization of saturated carboxylic acid or its derivative, modified ethylene copolymer rubber obtained by graft copolymerization of unsaturated carboxylic acid or its derivative and unsaturated aromatic monomer (G)
H) At least one type of rubber selected from 0.1 to 300
Part by weight, and basic compound (I) 0 as a reaction accelerator
A polypropylene composition, characterized in that the saturated polyester resin (D) in the entire resin composition is less than 50% by weight. (2) In the polypropylene composition according to claim 1,
The filler (J) is a modified polypropylene (A) obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof, or a polypropylene resin (C) selected from a modified polypropylene (A)/polypropylene (B) composition, 1 to 99% by weight % and saturated polyester resin (D) 99 to 1% by weight, 0.01 to 3 parts by weight
A polypropylene composition characterized in that it contains 00 parts by weight. (3) The polypropylene composition according to claim 1 or 2, wherein in the modified polypropylene (A), the unsaturated carboxylic acid or its derivative is maleic anhydride. (4) The polypropylene composition according to claim 1 or 2, wherein the saturated polyester resin (D) is polyethylene terephthalate and/or polybutylene terephthalate. (5) Claim 1, wherein the epoxy group-containing copolymer (E) is a copolymer consisting of an unsaturated epoxy compound and ethylene, or a copolymer consisting of an unsaturated epoxy compound, ethylene, and an ethylenically unsaturated compound other than ethylene. Or the polypropylene composition according to 2. (6) The polypropylene composition according to claim 1 or 2, wherein in the modified ethylene copolymer rubber (G), the unsaturated carboxylic acid or its derivative is maleic anhydride. (7) The polypropylene composition according to claim 1 or 2, wherein in the modified ethylene copolymer rubber (H), the unsaturated carboxylic acid or its derivative is maleic anhydride, and the unsaturated aromatic monomer is styrene. . (8) Ethylene copolymer rubber (F), modified ethylene copolymer rubber (G), or modified ethylene copolymer rubber (
In H), the ethylene copolymer rubber is ethylene-α
-Olefin copolymer rubber and/or ethylene-α
-Olefin-nonconjugated diene copolymer rubber, the polypropylene composition according to claim 1 or 2. (9) The polypropylene composition according to claim 1 or 2, wherein the basic compound (I) is an amine-based organic compound. (10) The polypropylene composition according to claim 2, wherein the filler (J) is an inorganic filler such as glass fiber, potassium titanate whiskers, talc, mica, or calcium carbonate.