JPH0971710A - Polypropylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition improved in rigidity, heat resistance, etc., by mixing a propylene/ethylene block copolymer or the like, a specified basic polyvalent metal salt of a cyclic organophosphoric ester and a specified compound. SOLUTION: This polypropylene resin composition comprises 100 pts.wt. propylene/ethylene block copolymer composed of 95-70wt.% crystalline propylene polymer part and 5-30wt.% ethylene/propylene copolymer part and having properties such as an ethylene content of 3-22wt.% and a melt flow rate of 0.3-100g/10min, 0.01-5 pts.wt. at least one member selected from among alkali metal carboxylates, alkali metal β-diketonates and alkali metal β-ketoacetic ester salts and 0.01-5 pts.wt. at least one polyvalent metal salt of a cyclic organophosphoric ester, represented by formula I (wherein R1 is H or a 1-4C alkyl; R2 and R3 are each H or a 1-12 C alkyl; and M is a metal atom of group III or IV in the periodic table or the like) and 0.01-0.5 pts.wt. compound of formula II (wherein X is an anion; (n) is the valence of X; and (m) is 0-3).

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to rigidity, impact resistance,
The present invention relates to a polypropylene resin composition having excellent heat resistance, transparency and whitening resistance.

[0002]

2. Description of the Related Art Polypropylene is lightweight and excellent in rigidity, tensile strength, heat resistance, chemical resistance, electrical characteristics, transparency, workability, etc. It is widely used in various fields such as daily necessities, automobile parts and electric parts.

However, since propylene homopolymer has a low impact resistance, it was unsuitable for applications subject to strong impact. Such a propylene homopolymer having improved impact resistance is known as a so-called propylene-polymer composed of a crystalline propylene polymer and an ethylene-propylene copolymer.
Ethylene block copolymers are known. However, although such a propylene-ethylene block copolymer has significantly improved impact resistance, it has a problem that the transparency of the propylene homopolymer is impaired and the impacted part is whitened. .

So-called propylene random polymers prepared by copolymerizing propylene with a small amount of ethylene are known for the purpose of increasing transparency. These random polymers have excellent heat resistance which propylene homopolymers have. Properties and high rigidity are lost, and the degree of improvement in impact resistance at low temperatures is insufficient.

In order to improve the above-mentioned drawbacks, JP-A-54-24995, JP-A-61-264012, JP-A-61-271315, and JP-A-63-
No. 1,594,12, JP-A-63-168414, and JP-A-4-202409 disclose specific propylene-ethylene block copolymers.
All of these have rigidity, impact resistance, moldability, transparency,
The balance of whitening resistance is still insufficient. Also,
A method of carrying out the copolymerization in two steps in the production of a propylene-ethylene block copolymer is described in, for example, JP-A-54-1.
39693, JP-A-55-16048, JP-A-56-32516, JP-A-56-55416.
However, even with such a method, the balance of the physical properties of the block copolymer obtained is still not sufficient.

On the other hand, the polypropylene resin composition is still insufficient in heat resistance and transparency particularly when it is used in the fields of food containers, medical instruments, physics and chemistry experimental instruments and the like. As a method of improving heat resistance, a method of polymerizing propylene using a specific catalyst (for example, JP-A-61-161).
No. 209207, JP-A No. 62-104810, etc.) and a method of adding an organic phosphoric acid metal salt compound as a nucleating agent to polypropylene resin (for example, JP-A No. 62-209).
151, JP-A-62-243635, JP-A-63-37148, and JP-A-63-210152.
JP-A-63-243150, JP-A-63-243150
-284242, JP-A-2-49047,
Japanese Patent Laid-Open No. 2-102242, etc.) are known.

However, these methods did not achieve transparency and the heat resistance was not sufficient.

As a method of improving transparency, for example, a method of blending polypropylene with a poly (ethylene-butylene) polystyrene block copolymer (Japanese Patent Laid-Open No. 54-8).
8950); a method of blending a small amount of isotactic polypropylene with a specific hydrogenated block copolymer (JP-A-58-215446);
A method of adding an additive such as a carboxylic acid metal salt, an aromatic phosphoric acid metal salt, or a sorbitol-based compound is known. Of these, the addition of a sorbitol-based compound is most effective in improving transparency, but it has problems of insufficient heat resistance and poor odor generation and dissolution. Further, sorbitol-based compounds are expensive and therefore economically disadvantageous.

[0009]

Therefore, an object of the present invention is to provide a polypropylene resin composition having excellent rigidity, impact resistance, heat resistance, transparency and whitening resistance.

[0010]

As a result of intensive studies in view of the above problems, the inventors of the present invention have found that a specific propylene-ethylene block copolymer or composition has a specific alkali metal compound and a cyclic organophosphate ester. The present invention has been found out that a polypropylene resin composition having excellent properties in a well-balanced manner can be obtained by adding a basic polyvalent metal salt and a lithium aluminum composite hydroxide salt.

That is, the first aspect of the present invention is that (a) (A) a crystalline propylene polymer portion (95 to 70% by weight) and (B) an ethylene-propylene copolymer portion (5).
Propylene-ethylene block copolymer containing 30 to 30% by weight, wherein (i) ethylene content is 3 to 22% by weight.
And (ii) the melt flow rate is 0.3 to 100
g / 10 minutes, (iii) the content of cold xylene solubles is 2.5 to 20% by weight, and (iv) the ethylene content of the portion which is soluble in cold xylene and insoluble in acetone is 40 to 8
0% by weight, (v) the ratio of the intrinsic viscosity [η] CXIS of the part insoluble in cold xylene to the intrinsic viscosity [η] CXS of the part soluble in cold xylene, [η] CXIS / [η] CX
S is 0.4 to 2.0, and (vi) 118 ° C to 1
Propylene with a minute melting peak at 30 ° C
100 parts by weight of ethylene block copolymer, (b) at least one selected from the group consisting of alkali metal carboxylates, alkali metal β-diketonates and alkali metal β-ketoacetic acid ester salts 0.01 to 5
Parts by weight, (c) General formula (I) of the following [Chemical formula 5] (same as [Chemical formula 1]):

[0012]

Embedded image (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents
A metal atom of group III or group IV of the periodic table is shown,
X represents HO- when M represents a metal atom of Group III of the periodic table, and O = or (HO) ₂ -when M represents a metal atom of Group IV of the periodic table. Show. ) 0.01 to 5 parts by weight of at least one of the cyclic organic phosphoric acid ester basic polyvalent metal salt, and (d) the following general formula (I)
I):

[0013]

Embedded image [Al ₂ Li (OH) ₆ ] _n X.mH ₂ O
0.01-0.5 weight of a compound represented by (II) (wherein, X is an inorganic or organic anion, n is a valence of the anion X, and m is a number of 0 to 3) Is a polypropylene resin composition containing parts. In a preferred embodiment,
You can list the following: (1) In (a), the polypropylene resin composition according to the above, wherein (B) the ethylene-propylene copolymer portion is contained in an amount of 10 to 25% by weight with respect to 90 to 75% by weight of the crystalline propylene polymer portion (A). Stuff. (2) In (a), the ethylene content is 7 to 20% by weight.
The polypropylene resin composition according to any one of the above. (3) The polypropylene resin composition as described in any of the above, which has an MFR of 0.4 to 80 g / 10 minutes in (a). (4) In (a), the amount of cold xylene solubles is 5 to 17.
The polypropylene resin composition according to any one of the above, which is 5% by weight. (5) The polypropylene resin composition according to any one of the above, wherein the ethylene content of the portion soluble in cold xylene and insoluble in acetone in (a) is 40 to 60% by weight. (6) The polypropylene resin composition according to any one of the above, wherein in [a], [η] CXIS / [η] CXS is 0.6 to 1.8. (7) The polypropylene resin composition as described in any one of the above, which has a minute melting peak at 124 to 129 ° C. in (a). (8) The polypropylene resin composition according to any one of the above, wherein the alkali metal carboxylate in (b) is an aliphatic monocarboxylate having 8 to 20 carbon atoms in lithium. (9) The polypropylene resin composition as described in any of the above, wherein in (c), M is aluminum. (10) In (d), X is selected from the group consisting of carbonic acid, sulfuric acid, nitric acid, chlorine oxyacids (eg perchloric acid) and phosphorus oxyacids (eg phosphoric acid, phosphorous acid, metaphosphoric acid). The polypropylene resin composition according to any one of the above, which is an anion of an acid.

The second aspect of the present invention is (a ') (A') crystalline propylene polymer 95 to 70% by weight and (B ') ethylene-propylene copolymer 5 to.
A composition containing 30% by weight, wherein (i) the ethylene content is 3 to 22% by weight, (ii) the melt flow rate is 0.3 to 100 g / 10 minutes, and (iii) cold xylene is acceptable. The dissolved amount is 2.5 to 20% by weight, and (i
v) The ethylene content of the portion soluble in cold xylene and insoluble in acetone is 40 to 80% by weight, and (v) the intrinsic viscosity [η] CXIS of the portion insoluble in cold xylene and soluble in cold xylene. Ratio of intrinsic viscosity [η] to CXS, [η]
100 parts by weight of a crystalline propylene polymer composition having a CXIS / [η] CXS of 0.4 to 2.0 and (vi) a minute melting peak at 118 ° C to 130 ° C, (b) an alkali At least one selected from the group consisting of metal carboxylates, alkali metal β-diketonates and alkali metal β-ketoacetic acid ester salts 0.01 to 5
Parts by weight, (c) General formula (I) of the following [Chemical formula 7] (same as [Chemical formula I]):

[0015]

[Chemical 7] (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents
A metal atom of group III or group IV of the periodic table is shown,
X represents HO- when M represents a metal atom of Group III of the periodic table, and O = or (HO) ₂ -when M represents a metal atom of Group IV of the periodic table. Show. 0.01 to 5 parts by weight of at least one of the cyclic organophosphate basic polyvalent metal salt represented by the formula (1), and (d) the following general formula (I)
I):

[0016]

[Al ₂ Li (OH) ₆ ] _n X.mH ₂ O (II) (wherein, X is an inorganic or organic anion, n is the valence of the anion X, and m is 0. Is a number of 3 to 3) and a polypropylene resin composition containing 0.01 to 0.5 part by weight of a compound represented by the formula. The following may be mentioned as preferred embodiments: (1) ′ In (a ′), 90% to 75% by weight of (A ′) crystalline propylene polymer (B ′) ethylene-propylene copolymer 10 to 25% by weight of the polypropylene resin composition described above. (2) 'The polypropylene resin composition according to any one of the above (a'), wherein the ethylene content is 7 to 20% by weight. (3) '(a'), MFR is 0.4 to 80 g / 1
The polypropylene resin composition according to any one of the above, which is 0 minutes. (4) '(a'), the amount of cold xylene solubles is 5 to 1
The polypropylene resin composition according to any one of the above, which is 7.5% by weight. (5) '(a'), The polypropylene resin composition according to any one of the above, wherein the ethylene content of the portion soluble in cold xylene and insoluble in acetone is 40 to 60% by weight. (6) '(a'), [η] CXIS / [η] CX
The polypropylene resin composition according to any one of the above, wherein S is 0.6 to 1.8. (7) '(a'), The polypropylene resin composition according to any one of the above, which has a minute melting peak at 124 to 129 ° C. (8) ′ In (b), the alkali metal carboxylate is
The polypropylene resin composition according to any one of the above, which is an aliphatic monocarboxylic acid salt of lithium having 8 to 20 carbon atoms. (9) ′ In the polypropylene resin composition as described in (c) above, M is aluminum. (10) ′ In (d), X is selected from the group consisting of carbonic acid, sulfuric acid, nitric acid, chlorine oxyacids (eg perchloric acid) and phosphorus oxyacids (eg phosphoric acid, phosphorous acid, metaphosphoric acid). The polypropylene resin composition according to any one of the above, which is an anion of an acid to be produced.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer (a) or the composition (a ′) by itself is
It has excellent mechanical properties, thermal properties and transparency to some extent, but when it is further blended with the above-mentioned alkali metal compound, cyclic organic phosphate ester basic polyvalent metal salt and lithium aluminum complex hydroxide salt, it is excellent. A resin composition having various properties can be obtained. In particular, the combined use of the alkali metal compound and the cyclic organic phosphoric acid ester basic polyvalent metal salt does not change the transparency almost even when added to the conventional impact-resistant polypropylene, but together with the lithium aluminum composite hydroxide salt. , (A) copolymer or (a ')
It has been found that when combined with the composition, a marked improvement in transparency is observed.

First, the polypropylene resin composition of the first invention will be described.

The propylene-ethylene block copolymer (a) comprises a crystalline propylene polymer portion (A) and an ethylene-propylene copolymer portion (B) based on 95-70% by weight of the (A) portion. B) 5 to 30% by weight, preferably 10 to 25% by weight of (B) relative to 90 to 75% by weight of (A).

Examples of the crystalline propylene polymer (A) constituting the crystalline propylene polymer portion include a propylene homopolymer and a random copolymer of propylene and a small amount of ethylene. In this case, the propylene content is preferably set to 95% by weight or more. In addition, comonomer components other than ethylene, such as butene-1 and octene-1
Α-olefins and diene-based monomers, etc. may be further contained, but in this case, the propylene content is 95%.
It is preferable that the content be not less than weight%.

The ethylene-propylene copolymer (B) constituting the ethylene-propylene copolymer portion contains ethylene in an amount of preferably 65 to 90% by weight, more preferably 70 to 90% by weight.
It is contained in a proportion of 85% by weight. The copolymer may further contain, as a third component, an α-olefin other than ethylene such as butene-1, octene-1 and a diene-based monomer. In that case, the content of these third components is preferably 2% by weight or less.

(A) The ethylene content of the whole copolymer is 3 to 22% by weight, preferably 7 to 20% by weight, more preferably 12 to 18% by weight. When the ethylene content is lower than the above range, the impact strength is lowered, and when the ethylene content is higher than the above range, the transparency is deteriorated. The ethylene content can be measured by a known means such as an infrared absorptiometry (IR method).

The melt flow rate (MFR) of the copolymer (a) is 0.3 to 100 g / 10 minutes, preferably 0.4 to 80 g / 10 minutes, and more preferably 0.5 to 6 minutes.
0 g / 10 minutes. When the melt flow rate is lower than the above range, the moldability becomes poor, and when the melt flow rate is higher than the above range, the impact strength decreases. In addition, MFR is AST
It is measured according to MD1238.

The amount of the cold xylene-soluble component in the copolymer (a) is 2.5 to 20% by weight, preferably 5 to 17.5% by weight, more preferably 7.5 to 15% by weight. When the amount of cold xylene solubles is below the above range, impact resistance is lowered, and when above the above range, rigidity and heat resistance are lowered. In the present invention, the amount of cold xylene solubles was measured by the following method. That is, sample 2g
Is added to 200 ml of xylene and dissolved by heating at 140 ° C. This is left to cool to 23 ° C. and left for 15 hours, and then the dissolved portion and the precipitated portion are separated by filtration. After the solvent is removed from the dissolved portion (component soluble in cold xylene) by evaporation, the weight is weighed. The weight ratio (% by weight) of the above-mentioned dissolved components to the whole sample is defined as the cold xylene soluble content. However, if the sample contains an optional component such as a filler, remove it by an operation such as hot filtration in advance, and adjust the weight ratio of the cold xylene-dissolved component to the part excluding the component such as the filler from the sample. Ask.

In the copolymer (a), the ethylene content of the portion soluble in cold xylene and insoluble in acetone is 40.
-80% by weight, preferably 40-60% by weight, more preferably 40-50% by weight. When the ethylene content is lower than the above range, the transparency is significantly deteriorated and the rigidity is slightly lowered, and when the ethylene content is higher than the above range, the impact resistance is lowered. In the present invention, such ethylene content was measured by the following method. That is, 2 g of the sample is added to 200 ml of xylene and dissolved by heating at 140 ° C. This is left to cool to 23 ° C and left for 15 hours,
The dissolved portion and the deposited portion are separated by filtration. The dissolved portion (a component soluble in cold xylene) is collected, this solution is put into 10 times the amount of acetone, and after stirring, the precipitated portion is collected by filtration. The solvent is evaporated off from the precipitated portion, thus obtaining a portion soluble in cold xylene and insoluble in acetone. The ethylene content of this is measured by a known means such as an infrared absorptiometry (IR method).

In the copolymer (a), the intrinsic viscosity of a portion insoluble in cold xylene (referred to as [η] CXIS) and the intrinsic viscosity of a portion soluble in cold xylene (referred to as [η] CXS). Ratio), that is, [η] CXI
S / [η] CXS is 0.4 to 2.0, preferably 0.6
˜1.8, more preferably 0.8 to 1.6. When this ratio is below the above range, the transparency is deteriorated, and when it is above the above range, the impact resistance is deteriorated. In the present invention, [η] CXIS / [η] CXS was obtained by the following method. That is, 2 g of sample is 200 ml
Xylene, and dissolve by heating at 140 ° C. This is 2
After cooling to 3 ° C. and leaving for 15 hours, the dissolved portion and the precipitated portion are separated by filtration. The solvent of each of the dissolved portion (soluble in cold xylene) and the precipitated portion (insoluble in cold xylene) is removed by evaporation, and each portion is recovered separately. However, when the sample contains an arbitrary component such as a filler, the one removed by an operation such as hot filtration in advance is used. Intrinsic viscosity of each part, ie [η] CXS and [η] C
After measuring XIS in decalin at 135 ° C., the ratio of both, [η] CXIS / [η] CXS, is determined.

The copolymer (a) has a temperature of 118 ° C to 130 ° C.
And preferably has a fine melting peak at 124 to 129 ° C. If it has a fine melting peak in the temperature range below the above range, or if it has no fine melting peak at all, the transparency is poor, and if it has a fine melting peak in the temperature range above the above range, it is resistant. In addition to the impact resistance being lowered, the transparency may be deteriorated in some cases. In the present invention, the melting peak is
It measured using the differential scanning calorimeter (DSC). The measurement conditions of DSC are as follows. First, a sample pan containing 10 mg of a sample is heated in a DSC heating furnace to 230 ° C. and left for about 15 minutes to melt it. After that, 10 ° C /
The temperature is lowered to 50 ° C. at a cooling rate of minutes to crystallize. Finally, the temperature is raised to 200 ° C at a rate of 10 ° C / min and the melting pattern of the sample is recorded. From this melting pattern, the temperature of the fine melting peak is determined. Usually, a crystalline propylene homopolymer is at 160 to 180 ° C., and a so-called random copolymer obtained by copolymerizing propylene and a small amount of ethylene is 13
A major melting peak occurs at 5 to 155 ° C., but in the (a) block copolymer [or (a ′) composition], 11
The fine melting peak at 8 ° C. to 130 ° C. is generated by overlapping these main melting peaks, and the entire (a) block copolymer [or (a ′) composition] has only a fine peak. Not of. The size of the minute peak is usually about ⅕ or less of the main melting peak.

In the present invention, the same method was used in the following as the method for measuring each of the above characteristics.

Such a copolymer is produced, for example, by producing a crystalline propylene polymer portion in one or more steps of a conventional propylene polymerization method and then producing an ethylene-propylene copolymer portion in one or more steps. Can be obtained by At that time, the copolymer having the above-mentioned properties according to the present invention can be obtained by specifying the reaction conditions. For example, in the process of producing the crystalline propylene polymer portion, the reaction temperature is -80 to 150 ° C, preferably 40 to
MFR of 0.3 to 120 g / 10 min by a conventional method at 120 ° C. using hydrogen or other known molecular weight regulator.
The crystalline propylene polymer having
After synthesizing so as to be 95% by weight, propylene and ethylene were continuously supplied in the presence of propylene: ethylene (weight ratio) = 50: 50 to 10:90 to make 30 to 5% by weight of the total polymer. Copolymerize so that On this occasion,
Hydrogen or other known molecular weight regulators can be used to achieve the desired cold xylene insoluble content, soluble content and its intrinsic viscosity ratio.

The copolymer (a) may further contain polyethylene and the like in addition to the components (A) and (B) described above, as long as the object of the present invention is not impaired.

Next, as the alkali metal constituting the alkali metal carboxylate, the alkali metal β-diketonate or the alkali metal β-ketoacetic acid ester salt component (b) of the present invention, the alkali metal is lithium. , Sodium, potassium and the like.

Examples of the carboxylic acid constituting the alkali metal carboxylate include acetic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, Stearic acid, oleic acid, ricinoleic acid, 12-
Fats such as hydroxystearic acid, behenic acid, montanic acid, melissic acid, β-dodecylmercaptoacetic acid, β-dodecylmercaptopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl-N-lauroylaminopropionic acid Group monocarboxylic acids; malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid,
Aliphatic polycarboxylic acid such as butanetetracarboxylic acid;
Naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4
-Methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid,
Cyclohexenecarboxylic acid, 4-cyclohexene-1,
Alicyclic mono- or polycarboxylic acids such as 2-dicarboxylic acid; benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid, 4-tert-butylbenzoic acid, salicylic acid, phthalic acid,
Examples thereof include aromatic mono- or polycarboxylic acids such as trimellitic acid and pyromellitic acid.

Examples of the β-diketone compound constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, dibenzoylmethane and the like.

Examples of the β-ketoacetic acid ester constituting the alkali metal β-ketoacetic acid ester salt include, for example, ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoylacetate, lauryl benzoylacetate. And so on.

Further, the alkali metal carboxylate, alkali metal β-diketonate or alkali metal β-ketoacetic acid ester salt, which is the component (b), is the above-mentioned alkali metal and carboxylic acid, β-diketone compound or β-dye, respectively.
It is a salt with ketoacetate and can be produced by a conventionally known method. Further, among the respective alkali metal salt compounds of the component (b), an alkali metal aliphatic monocarboxylic acid salt, particularly a lithium aliphatic carboxylic acid salt is preferable, and particularly, an aliphatic monocarboxylic acid having 8 to 20 carbon atoms. Acid salts are preferred.

In the cyclic polyphosphate basic polyvalent metal salt represented by the general formula (I) of the above [Chemical formula 1] which is the component (c) of the present invention, the number of carbon atoms represented by R ¹ is 1 Examples of the alkyl group of 4 to 4 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl and the like, which has 1 carbon atom represented by R ² or R ^3.
Examples of the alkyl group of ~ 12 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Amyl, tertiary amyl, hexyl, heptyl, octyl,
Isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl,
Examples include dodecyl and third dodecyl.

Examples of the metal atom of group III or group IV of the periodic table represented by M include aluminum, gallium, germanium, tin, titanium and zirconium, and aluminum is particularly preferable.

Therefore, as the cyclic organic phosphoric acid ester basic polyvalent metal salt represented by the general formula (I) of the above [Chemical formula 1], for example, the following [Chemical formula 9] to [Chemical formula 14] are shown. And compounds (1) to (6).

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

[Chemical 12]

[0043]

Embedded image

[0044]

Embedded image

The cyclic organophosphate basic polyvalent metal salt is obtained, for example, by reacting an alkali metal salt of an acidic cyclic organophosphate ester with a polyvalent metal halide or an oxidized polyvalent metal halide, and thereafter, if necessary. It can be easily produced by a method of hydrolysis, a method of reacting an acidic cyclic organic phosphoric acid ester with a polyvalent metal alkoxide, and then hydrolyzing as necessary.

As a concrete example of the production of the cyclic organic phosphoric acid ester basic polyvalent metal salt, there is disclosed in JP-A-5-15.
It is disclosed in Japanese Patent No. 6078.

The component (d) of the present invention is a lithium aluminum composite hydroxide salt represented by the general formula (II) of [Chemical Formula 2]. Such compounds are known per se and are described, for example, in JP-A-5-179052.

In the general formula of [Chemical Formula 2], when X is an inorganic anion, for example, carbonic acid, sulfuric acid, chlorine oxyacid (eg, perchloric acid), phosphorus oxyacid (eg, phosphoric acid, phosphorous acid). , Metaphosphoric acid) and the like, and these can be used alone or in combination of two or more kinds. When X is an organic anion, for example, from acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, p-oxybenzoic acid, salicylic acid, picric acid, etc. The obtained anions are mentioned, and these can be used alone or in combination of two or more kinds. Preferred X is an inorganic anion, particularly carbonic acid, sulfuric acid, nitric acid, oxyacids of chlorine (eg, perchlorine number) and oxyacids of phosphorus (eg, phosphoric acid, phosphorous acid, metaphosphoric acid).
Selected from the group consisting of:

As the component (d), one type of salt may be used alone, or two or more types may be used in combination.

In the first polypropylene resin composition, 100 parts by weight of the propylene-ethylene block copolymer as the component (a) is used as the component (b) of the alkali metal carboxylate or alkali metal β-diketonate. And 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, and at least one selected from the group consisting of alkali metal β-ketoacetic acid esters and the general formula (I) of [Chemical Formula 1] of component (c). ) 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight, of at least one of the cyclic organic phosphoric acid ester basic polyvalent metal salts represented by the formula (1).

If the amount of each of the above-mentioned components (b) and (c) is less than 0.01 parts by weight, transparency and heat resistance are deteriorated, while if it exceeds 5 parts by weight, there is no substantial effect and it is uneconomical. Further, the component (b) and the component (c) used in the present invention
The components are less prone to be eluted from the inside during use of the polypropylene resin composition, and are also excellent in low elution property.

Further, the lithium aluminum complex hydroxide salt represented by the general formula (II) of the [formula 2] of the component (d) is based on 100 parts by weight of the propylene-ethylene block copolymer of the component (a). 0.01 to 0.5 parts by weight, preferably 0.02 to 0.2 parts by weight.
When the amount of the component (d) is less than 0.01 parts by weight, the transparency is lowered, while when it exceeds 0.5 parts by weight, the cost is high and the effect of the present invention is not improved.

Next, the polypropylene resin composition of the second invention will be described.

The composition containing (a ') (A') crystalline propylene polymer and (B ') ethylene-propylene copolymer contains (A') and (B ') as (A') 95- 7
0 to 30% by weight of (B '), preferably 90 to 75% by weight of (A') and 10 to 25 of (B ')
Included as a percentage by weight.

As the crystalline propylene polymer (A '), the crystalline propylene polymer (A) used in the above-mentioned (a) propylene-ethylene block copolymer can be similarly used. That is, in addition to the propylene homopolymer, a random copolymer containing ethylene or another α-olefin or a diene monomer can be used. The propylene content is preferably 95% by weight or more.

The ethylene-propylene copolymer (B ') contains ethylene in an amount of preferably 65 to 90% by weight, more preferably 75 to 85% by weight. The copolymer may further contain, as a third component, an α-olefin other than ethylene such as butene-1, octene-1 and a diene-based monomer. In that case, the content of these third components is preferably 2% by weight or less.

The composition (a ') comprises the above-mentioned component (A').
In addition to (B ') and (B'), the above-described (a) propylene-ethylene block copolymer may be included.

The ethylene content in the composition (a ') is
It is 3 to 22% by weight, preferably 7 to 20% by weight, more preferably 12 to 18% by weight. When the ethylene content is below the above range, the impact strength is lowered, and when it is above the above range, the transparency is deteriorated.

The melt flow rate (MFR) in the composition (a ') is 0.3 to 100 g / 10 minutes, preferably 0.4 to 80 g / 10 minutes, more preferably 0.5 to 6 minutes.
It is 0 g / 10 minutes. When the melt flow rate is below the above range, moldability becomes poor, and when it is above the above range, the impact strength decreases.

The amount of cold xylene solubles in the composition (a ') is 2.5 to 20% by weight, preferably 5 to 17.5% by weight, more preferably 7.5 to 15% by weight. When the amount of cold xylene solubles is below the above range, impact resistance is lowered, and when above the above range, rigidity and heat resistance are lowered.

In the composition (a '), the ethylene content in the portion soluble in cold xylene and insoluble in acetone was 40.
-80% by weight, preferably 40-60% by weight, more preferably 40-50% by weight. When the ethylene content is lower than the above range, the transparency is significantly deteriorated and the rigidity is slightly lowered, and when the ethylene content is higher than the above range, the impact resistance is lowered.

In the composition (a '), the ratio of the intrinsic viscosity ([η] CXIS) of the portion insoluble in cold xylene to the intrinsic viscosity ([η] CXS) of the portion soluble in cold xylene, that is, [Η] CXIS / [η] CXS is 0.4 to 2.
0, preferably 0.6 to 1.8, more preferably 0.8
~ 1.6. When this ratio is below the above range, the transparency is deteriorated, and when it is above the above range, the impact resistance is deteriorated.

The composition (a ') has a temperature of 118 ° C to 130 ° C.
And preferably has a fine melting peak at 124 to 129 ° C. If it has a fine melting peak in the temperature range below the above range, or if it has no fine melting peak at all, the transparency is poor, and if it has a fine melting peak in the temperature range above the above range, it is resistant. In addition to the impact resistance being lowered, the transparency may be deteriorated in some cases.

The composition of (a ') is, for example,
′) Crystalline propylene polymer and (B ′) ethylene-
It can be produced by separately producing a propylene copolymer, then blending both (further optional components) in a predetermined ratio, and melt-kneading. As the crystalline propylene polymer (A ′) and the ethylene-propylene polymer (B ′), those produced by a conventional method can be used. The apparatus and conditions used during melt-kneading are known to those skilled in the art.

Such specific (A ') and (B
The combination of ′) is, for example, as (A ′), 0.3 to 1 produced by a conventional method or obtained as a commercial product.
0.001 to 100 g / 1 produced by using a crystalline propylene polymer having an MFR of 20 g / 10 minutes and copolymerizing propylene and ethylene as (B ′)
By selecting an ethylene-propylene copolymer having an MFR of 0 minutes, an ethylene content of 65-90% by weight and a fine melting peak at 118 ° C-130 ° C.
A composition having the above properties can be obtained. Such (B ') is known per se, and is disclosed in, for example, JP-A-62 / 62.
It can be manufactured according to the method disclosed in Japanese Patent Publication No. 295906.

In the second polypropylene resin composition, the components (b) and (c) are the same as the components (b) and (c) used in the first polypropylene resin composition. it can.

In the second polypropylene resin composition, 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight of component (b) and (c) are added to 100 parts by weight of component (a '). 0.01 to 5 parts by weight, preferably 0.
Add 0 to 3 to 3 parts by weight. When the amount of the component (b) and the component (c) is less than 0.01 parts by weight, the transparency and the rigidity are lowered. On the other hand, the cost is more than 5 parts by weight,
The effect of the present invention is not improved.

Further, in the second polypropylene resin composition, the component (d) can be the same as the component (d) used in the first polypropylene resin composition.

In the second polypropylene resin composition, the component (d) is 0.01 to 0.5 part by weight, preferably 0.02 to 0.2, per 100 parts by weight of the component (a ').
Mix parts by weight. If the amount of the component (d) is less than 0.01 parts by weight, the transparency will decrease. On the other hand, if the amount exceeds 0.5 parts by weight, the cost is increased and the effect of the present invention is not improved.

In each of the above-mentioned polypropylene resin compositions of the present invention, in addition to the above-mentioned components, other resins such as polyethylene can be blended within the range not impairing the object of the present invention. Also, depending on the application, a filler,
Antioxidants (phenolic, thioether, phosphorus, etc.), light stabilizers, clarifiers, nucleating agents (organic carboxylic acids such as benzoic acid or metal salts thereof), lubricants, antistatic agents,
Anti-fog agent, anti-blocking agent, pigment, heavy metal deactivator, radical generator (peroxide, etc.), dispersant, neutralizing agent, heat stabilizer, light stabilizer, ultraviolet absorber, flame retardant, plasticizer , Various kinds of additives such as a release agent can be added.
As the filler, as the inorganic filler, for example, a granular, powdery or flaky filler, a fibrous filler and the like can be used.
Granular, powdery or scaly fillers include, for example, silica, alumina, talc, mica, kaolin, clay, wollastonite, zeolite, silica-alumina,
Calcium carbonate, aluminum hydroxide, titanium dioxide,
Zinc oxide, magnesium oxide, zirconium oxide, zinc sulfide, barium sulfate, calcium sulfate, calcium phosphate, magnesium phosphate, aluminum silicate, silicon nitride, glass, hydrotalcite (Mg _4.5 Al ₂
(OH) ₁₃ CO, 3.5H ₂ O, etc.) and the like. As the fibrous filler, for example, glass fiber,
Potassium titanate fiber, carbon fiber, carbon black,
Examples include graphite, mica ceramics fiber, metal fiber, and the like. The surface of the inorganic filler is silane-based,
It may be treated with a titanate-based, boron-based, aluminate-based, or zircoaluminate-based coupling agent.
Examples of the organic filler include wood flour, pulp, synthetic fiber,
Examples include natural fibers. Further, as the dispersant or the neutralizer, the metal salts of organic carboxylic acids and hydrotalcite compounds described in JP-A-5-9390 can be used. As the metal in the metal salt of an organic carboxylic acid,
Periodic Table Group I (eg Li, Na, K, etc.), Group II
Group metal atoms (eg Mg, Ca, Sr, Ba, Zn
Etc.) Further, as the organic carboxylic acid,
Aliphatic saturated carboxylic acids (acetic acid, propionic acid, decanoic acid, lauric acid, myristic acid, etc.), aliphatic unsaturated carboxylic acids (eg, oleic acid, etc.), alicyclic carboxylic acids (eg, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid) Etc.), aromatic carboxylic acids (eg benzoic acid,
Salicylic acid, etc.) and the like. Examples of the hydrotalcite compound include Mg _4.5 Al ₂ (OH) ₁₃ C
Examples include O · 3.5H ₂ O.

The method for producing the polypropylene resin composition of the present invention is not particularly limited. For example, the above-mentioned respective components are mixed using a Henschel mixer, a super mixer, a ribbon blender, etc., and a single screw extruder, a twin screw extruder, a Banbury mixer, a Brabender, a roll, etc. are used to obtain 170 to 300 ° C. It can be manufactured by melt-kneading in the temperature range of.

[0072]

EXAMPLES Production Example 1 (Production of polymerization catalyst) In a 1-liter reaction vessel having a reflux condenser, under a nitrogen gas atmosphere, chip-shaped metallic magnesium (purity: 99.
5%, average particle size 1.6 mm) 8.3 g and n-hexane 250 ml were added and stirred at 68 ° C. for 1 hour, then metallic magnesium was taken out and dried at 65 ° C. under reduced pressure to obtain pre-activated metallic magnesium. Obtained.

Next, 140 ml of n-butyl ether and 0.5 ml of a solution of n-butyl magnesium chloride in n-butyl ether (1.75 mol / liter) were added to this metallic magnesium, and the mixture was stirred to form a suspension. The suspension was kept at 55 ° C. Further, a solution of 38.5 ml of n-butyl chloride dissolved in 50 ml of n-butyl ether was added dropwise over 50 minutes. Then, while stirring, the reaction was carried out at 70 ° C for 4 hours, and then the reaction solution was heated to 25 ° C.
Held.

Next, HC (OC ₂ H ₅ ) was added to this reaction solution.
₃ 55.7 ml was added dropwise over 1 hour, and after completion of the addition, 60 ° C
The reaction is performed for 15 minutes, and the obtained reaction product solid is n-
It was washed 6 times with 300 ml of hexane each. Then, it was dried under reduced pressure at room temperature for 1 hour to obtain 31.6 g of a magnesium-containing solid containing 19% by weight of magnesium and 28.9% by weight of chlorine.

Into a 300 ml reaction vessel equipped with a reflux condenser, a stirrer and a dropping funnel, 6.3 g of the magnesium-containing solid obtained above and 50 ml of n-heptane were charged under a nitrogen gas atmosphere and stirred to suspend them. As a liquid, a mixture of 20 ml (0.02 mmol) of 2,2,2-trichloroethanol and 11 ml of n-heptane was added dropwise to this suspension in a dropping funnel over 30 minutes while continuing stirring at room temperature. The mixture was stirred at 80 ° C for 1 hour. The suspension was filtered, and the obtained solid was washed 4 times with 100 ml each of n-hexane at room temperature and twice with 100 ml each of toluene to obtain a solid component (solid component A).

To the solid component A thus obtained, 40 ml of toluene was added, and titanium tetrachloride was further added at a ratio of titanium tetrachloride / toluene (volume ratio) of 3/2, and the temperature was raised to 90 ° C. Warmed. Next, a mixture of 2 ml of di-n-butyl phthalate and 5 ml of toluene was added dropwise to this mixture over 5 minutes while stirring, and then the mixture was stirred at 120 ° C. for 2 hours. The solid substance was obtained by filtering this mixed liquid at 90 degreeC. This solid substance was heated to 90 ° C. with 100 m of toluene each.
1 × twice. Furthermore, the same amounts of titanium tetrachloride and toluene as before were added, and the mixture was stirred at 120 ° C. for 2 hours. The solid substance was obtained by filtering this mixed liquid at 110 degreeC. This solid substance was added to room temperature n-hexane 100 ml each.
It was washed 7 times. Thus, 5.5 g of the polymerization catalyst was obtained.

Example 1 Synthesis of propylene-ethylene block copolymer

(1) Preparation for Polymerization 27.7 mg of the polymerization catalyst obtained in Production Example 1, n-heptane 1
4 ml of a solution containing 0.3 mol of triethylaluminum in 1 liter and 3 ml of a solution containing 0.08 mol of diphenyldimethoxysilane in 1 liter of n-heptane were mixed and held for 5 minutes. It was put into a fully dried 5 liter autoclave.

(2) Production of Propylene Homopolymer Part After 13.0 liters of hydrogen and 3 liters of liquid propylene were press-fitted into this autoclave, the internal temperature of the autoclave was raised to 70 ° C. and polymerization was carried out for 1 hour. To obtain a crystalline propylene polymer. After the polymerization was completed, unreacted propylene and hydrogen were purged, and the pressure inside the autoclave was adjusted to 0.2 kg / cm ² · G.

(3) Production of ethylene-propylene copolymer part Next, 4 liters of hydrogen gas was introduced into the system. continue,
The internal temperature of the autoclave was raised to 75 ° C., and a mixed gas of propylene and ethylene (propylene: ethylene (weight ratio) = 28: 72) was added to a monomer partial pressure of 6 kg / cm ² ·.
While maintaining at G, the polymerization reaction was carried out for about 2.5 hours until the ethylene-propylene copolymer fraction became 20% by weight. After completion of the polymerization, unreacted gas was purged to obtain a white powdery propylene-ethylene block copolymer.

(4) Analysis of the Block Copolymer Obtained The propylene-ethylene block copolymer thus obtained was determined from the change in weight at each reaction step to show that 80% by weight of the propylene homopolymer block and ethylene-propylene random block were used. It was a block copolymer consisting of 20% by weight of the copolymer block. As a result of ¹³ C-NMR measurement, it was found that the ethylene content in the ethylene-propylene random copolymer was 80% by weight. Furthermore, MFR of this copolymer, ethylene content of the whole copolymer, DSC,
The amount of cold xylene solubles, the intrinsic viscosity ratio between the cold xylene insoluble part and the soluble part, and the ethylene content of the cold xylene soluble acetone insoluble part were measured. The results are shown in Table 1.

(5) Production of Polypropylene Resin Composition 100 parts by weight of the propylene-ethylene block copolymer obtained above was mixed with an alkali metal salt of component (b) and (c).
Mixture of cyclic organophosphate ester basic polyvalent metal salt as component "NA-21" (manufactured by Asahi Denka Co., Ltd., hereinafter NA-
21) and 0.05 part by weight of a lithium aluminum complex hydroxide salt.
Add 6-di-t-butyl-4-methylphenol to 0.18
Parts by weight of distearyl thiodipropionate to 0.08
0.04 parts by weight of tetrakis {methylene- (3,5-di-t-butyl-4-hydroxyhydrocinnamate)} methane, respectively, are added, and the temperature is set to 210 ° C. in a twin-screw extruder. The mixture was melt-kneaded and extruded at a rotation speed of 200 rpm to prepare pellets. 23 of these pellets
A test piece was prepared by injection molding at 0 ° C., and the flexural modulus and DuPont impact strength were measured. In addition, haze measurement was also performed. The results are shown in Table 2.

The flexural modulus is JIS K7203-
In 1982, DuPont impact strength (-20 ° C, 1 mm) was measured according to JIS K7211-1976.

The haze (measurement of transparency) was 60 × 60 obtained by injection molding at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C.
JIS K7105-198 using a test piece of × 1 mm
1 was measured.

Example 2 The hydrogen supply amount in step (2) of Example 1 was 15.0 liters, the hydrogen supply amount in step (3) was 3.6 liters, and the copolymerization time was 4.1 hours. A propylene-ethylene block copolymer was produced in the same manner as in Example 1 except for the above.

The propylene-ethylene block copolymer thus obtained was obtained by using the propylene homopolymer block 7
It was a block copolymer composed of 0% by weight and 30% by weight of an ethylene-propylene random copolymer block. As a result of ¹³ C-NMR measurement, it was found that the ethylene content in the ethylene-propylene random copolymer was 80% by weight. Furthermore, the MF of this copolymer
Table 1 shows R, ethylene content, DSC, amount of cold xylene solubles, intrinsic viscosity ratio between cold xylene insoluble part and soluble part, and ethylene content of cold xylene soluble acetone insoluble part.

Next, a resin composition was prepared in the same manner as in Example 1 except that the above copolymer was used and the amount of the lithium-aluminum composite hydroxide salt was 0.10 parts by weight based on 100 parts by weight of the copolymer. Was manufactured, and physical properties and haze were measured under the same conditions as in Example 1. Table 2 shows the results.

Comparative Example 1 The hydrogen supply amount in the step (2) of Example 1 was 17.6 liters, the hydrogen supply amount in the step (3) was 3.9 liters, and the copolymer time was 5.9 hours. A propylene-ethylene block copolymer was produced in the same manner as in Example 1 except for the above.

The propylene-ethylene block copolymer thus obtained was obtained by using the propylene homopolymer block 60.
It was a block copolymer consisting of 40% by weight of ethylene-propylene random copolymer block.
As a result of ¹³ C-NMR measurement, it was found that the ethylene content in the ethylene-propylene random copolymer was 80% by weight. Further, Table 1 shows MFR, ethylene content, DSC, amount of cold xylene-soluble matter, intrinsic viscosity ratio between cold xylene-insoluble part and soluble part, and ethylene content of cold xylene-soluble acetone insoluble part of this copolymer.

Then, a polypropylene resin composition was produced in the same manner as in Example 1 except that the above copolymer was used.
The physical properties and haze were measured under the same conditions as in Example 1. Table 2 shows the results.

Comparative Example 2 The hydrogen supply amount in the step (2) of Example 1 was 10.0 liters, the hydrogen supply amount in the step (3) was 5.3 liters, and the copolymerization time was 2.0 hours. A propylene-ethylene block copolymer was produced in the same manner as in Example 1 except for the above.

The propylene-ethylene block copolymer thus obtained is a propylene homopolymer block 80.
It was a block copolymer composed of 20% by weight of ethylene-propylene random copolymer block.
As a result of ¹³ C-NMR measurement, it was found that the ethylene content in the ethylene-propylene random copolymer was 80% by weight. Further, Table 1 shows MFR, ethylene content, DSC, amount of cold xylene-soluble matter, intrinsic viscosity ratio between cold xylene-insoluble part and soluble part, and ethylene content of cold xylene-soluble acetone insoluble part of this copolymer.

Then, a polypropylene resin composition was produced in the same manner as in Example 2 except that the above copolymer was used.
The physical properties and haze were measured under the same conditions as in Example 1. Table 2 shows the results.

Comparative Example 3 A resin composition was produced in the same manner as in Example 1 except that the lithium aluminum composite hydroxide salt was not used and 0.06 parts by weight of calcium stearate was added instead.
The physical properties and haze were measured under the same conditions as in Example 1. Table 2 shows the results.

Example 3 Production of Crystalline Propylene Polymer Composition In the same manner as in step (1) of Example 1, an autoclave was charged with an n-heptane solution containing a polymerization catalyst, triethylaluminum and diphenyldimethoxysilane.
After adding a mixture consisting of a heptane solution, 300 g of dried calcium chloride was further added thereto, and the mixture was stirred for 30 minutes.

Hydrogen gas and a mixed gas of propylene and ethylene were supplied to this under the same conditions as in step (3) of Example 1 to produce an ethylene-propylene copolymer. After completion of the polymerization, unreacted gas was purged, and the product was washed with water to remove calcium chloride to obtain an ethylene-propylene random copolymer. The ethylene content of this copolymer is 7
It was 9.9% by weight.

20% by weight of the ethylene-propylene copolymer thus obtained and propylene homopolymer (manufactured by Tonen Kagaku KK, grade name: Tonen Polypro J240F) 80
And wt% were melt-kneaded at 230 ° C. in an extruder to obtain a crystalline propylene polymer composition. For this, as in Example 1, MFR, ethylene content, DSC,
The amount of cold xylene solubles, the intrinsic viscosity ratio between the cold xylene insoluble part and the soluble part, and the ethylene content of the cold xylene soluble acetone insoluble part were measured. The results are shown in Table 1.

Production of Resin Composition Next, 0.3 parts of NA-21 was added to 100 parts by weight of the above composition.
Parts by weight and lithium aluminum complex hydroxide salt
A polypropylene resin composition was produced in the same manner as in Example 1 except that 20 parts by weight was blended. About this, physical property measurement and haze measurement were performed on the same conditions as Example 1. Table 2 shows the results.

Comparative Example 4 Production of Crystalline Propylene Polymer Composition Instead of the ethylene-propylene copolymer of Example 3, ethylene-propylene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd., grade name: EP07P) was used. A crystalline propylene polymer composition was obtained in the same manner as in Example 3. This composition was measured for MFR, ethylene content, DSC, amount of cold xylene solubles, intrinsic viscosity ratio of cold xylene insoluble part to soluble part, and ethylene content of cold xylene soluble acetone insoluble part. The results are shown in Table 1.

Production of Resin Composition Next, NA-21 was added to 0.3 part by weight to 100 parts by weight of this composition.
Parts by weight and lithium aluminum complex hydroxide salt
A polypropylene resin composition was produced in the same manner as in Example 1 except that 20 parts by weight was blended. About this, physical property measurement and haze measurement were performed on the same conditions as Example 1. Table 2 shows the results.

Comparative Example 5 Only the same propylene-ethylene block copolymer as used in Example 1 was used. The respective characteristics are shown in Table 1.

A resin composition was produced in the same manner as in Example 1 except that NA-21 and lithium aluminum complex hydroxide salt were not added, and the physical properties and haze were measured under the same conditions as in Example 1. It was Table 2 shows the results.

Comparative Example 6 Only the same propylene-ethylene block copolymer as used in Example 2 was used. The respective characteristics are shown in Table 1.

A resin composition was produced in the same manner as in Example 2 except that NA-21 and lithium aluminum complex hydroxide salt were not added, and the physical properties and haze were measured under the same conditions as in Example 1. It was Table 2 shows the results.

Comparative Example 7 Only the same crystalline propylene polymer composition as used in Example 3 was used. The respective characteristics are shown in Table 1.

A resin composition was produced in the same manner as in Example 3 except that NA-21 and lithium aluminum complex hydroxide salt were not added, and the physical properties and haze were measured under the same conditions as in Example 1. It was Table 2 shows the results.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

The polypropylene resin composition of the present invention has
Since it has excellent rigidity, impact resistance, heat resistance, transparency and whitening resistance, it can be advantageously used for molded articles requiring these characteristics. In particular, it is useful in products widely obtained by injection molding, extrusion molding, blow molding and the like, including food containers, medical instruments, physics and chemistry experimental instruments, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08K 5/527 C08K 5/527

Claims (2)

[Claims] 1. A propylene-ethylene block copolymer comprising (a) (A) a crystalline propylene polymer portion of 95 to 70% by weight and (B) an ethylene-propylene copolymer portion of 5 to 30% by weight. , (I) ethylene content of 3 to 22% by weight, (ii) melt flow rate of 0.3 to 100 g / 10 min, (iii) cold xylene solubles of 2.5 to 20% by weight. And (iv) the ethylene content of the portion soluble in cold xylene and insoluble in acetone is 40 to 80% by weight, and (v) the intrinsic viscosity [η] CXIS of the portion insoluble in cold xylene and cold xylene. Ratio of the part soluble in water to the intrinsic viscosity [η] CXS, [η] CXIS
/ [Η] CXS is 0.4 to 2.0, and (vi)
100 parts by weight of a propylene-ethylene block copolymer having a minute melting peak at 118 to 130 ° C., (b) consisting of an alkali metal carboxylate, an alkali metal β-diketonate and an alkali metal β-keto acetic acid ester salt. At least one selected from the group 0.01-5
Parts by weight, (c) the following general formula (I) of [Chemical Formula 1]: (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents
A metal atom of group III or group IV of the periodic table is shown,
X represents HO- when M represents a metal atom of Group III of the periodic table, and O = or (HO) ₂ -when M represents a metal atom of Group IV of the periodic table. Show. 0.01 to 5 parts by weight of at least one basic polyvalent metal salt of a cyclic organic phosphoric acid ester represented by the formula (4), and (d) the following general formula (II) of [Chemical Formula 2]: [Chemical Formula 2] [Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (II) (In the formula, X is an inorganic or organic anion, n is a valence of the anion X, and m is a number of 0 to 3.) A polypropylene resin composition containing 0.01 to 0.5 part by weight of a compound represented by: 2. A composition comprising (a ') (A') a crystalline propylene polymer of 95 to 70% by weight and (B ') an ethylene-propylene copolymer of 5 to 30% by weight,
(I) The ethylene content is 3 to 22% by weight, and (i
i) the melt flow rate is 0.3 to 100 g / 10 minutes, (iii) the amount of cold xylene solubles is 2.5 to 20% by weight, (iv) soluble in cold xylene and insoluble in acetone. The ethylene content of the part is 40 to 80% by weight, and (v) the intrinsic viscosity [η] C of the part insoluble in cold xylene.
XIS and the intrinsic viscosity [η] C of the soluble part in cold xylene
Ratio with XS, [η] CXIS / [η] CXS is 0.4 to
2.0 and (vi) 100 parts by weight of a crystalline propylene polymer composition having a minute melting peak at 118 ° C to 130 ° C, (b) an alkali metal carboxylate, an alkali metal β-diketonate and At least one selected from the group consisting of alkali metal β-ketoacetic acid ester salts 0.01 to 5
Parts by weight, (c) General formula (I) of the following [Chemical Formula 3] (same as [Chemical Formula 1]): (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents
A metal atom of group III or group IV of the periodic table is shown,
X represents HO- when M represents a metal atom of Group III of the periodic table, and O = or (HO) ₂ -when M represents a metal atom of Group IV of the periodic table. Show. 0.01 to 5 parts by weight of at least one of the cyclic organophosphate basic polyvalent metal salt represented by the formula (4), and (d) the following general formula (I)
I): [Al ₂ Li (OH) ₆ ] _n X.mH ₂ O (II) (wherein, X is an inorganic or organic anion, and n is the valence of the anion X, A polypropylene resin composition containing 0.01 to 0.5 part by weight of a compound represented by the formula (m is a number from 0 to 3).