JPH02251548A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition resistant to whitening on impact and having excellent impact resistance, rigidity, etc., by compounding a specific propylene random copolymer with a specific organic phosphorus compound. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a propylene random copolymer containing 1 to 10wt.% of alpha-olefin unit other than propylene and having a melt index of 0.2 to 60g/10min, a boiling n-hexane insoluble content of 60 to 97wt.% and a triad random fraction of >=7unit% with (B) 0.001 to 0.5 pts.wt. of at least one kind of component selected from the organic phosphorus compound of formula I (R<1> is H or 1 to 18C alkyl; R<2> is 1 to 18C alkyl, group of formula II or formula III; M<1> is Na, K, Mg, Ca or Al; a is valence of M<1>) and the organic phosphorus compound of formula IV (Z is 1 to 3C alkylene; R<3> to R<6> are H or 1 to 6C alkyl; M<2> is same as M<1>; b is valence of M<2>).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel propylene polymer composition. More specifically, the present invention discloses a propylene random copolymer which does not cause whitening upon impact, has excellent impact resistance and rigidity, and is suitable for injection molding materials, soft extrusion molding materials, cold-resistant film materials, etc. This invention relates to a propylene polymer composition in which a specific organic phosphorus compound is blended into the polymer.

[Conventional technology] Polypropylene resin generally has heat resistance, chemical resistance, rigidity,
Due to its good moldability, it is widely used as a material for film molding, sheet molding, blow molding, injection molding, etc.

By the way, when the polypropylene resin is a homopolymer, it does not necessarily have sufficient impact resistance, so there is a problem in that it is subject to limitations in use.

Therefore, block polypropylene and random copolymers of propylene and α-olefins such as ethylene have been used as polypropylene resins with good impact resistance.

However, the former type of block polypropylene has the disadvantage that it tends to whiten upon impact, impairing its surface appearance and lowering its commercial value.On the other hand, the latter type of random copolymerization of propylene and α-olefin In coalescence, increasing the content of the α-olefin unit lowers crystallinity and improves impact resistance, but has the disadvantage that rigidity decreases too much and the applications are inevitably limited. .

[Problems to be Solved by the Invention] Under these circumstances, the present invention aims to provide a propylene polymer composition that does not cause whitening upon impact and has excellent impact resistance and rigidity. It was done for a purpose.

[Means for Solving the Problem] As a result of intensive research to develop a propylene polymer composition having the above-mentioned preferable properties, the present inventor has identified a specific propylene random copolymer as a nucleating agent. It was discovered that the objective could be achieved by blending an organic phosphorus compound having the structure in a predetermined ratio, and based on this knowledge, the present invention was completed.

That is, the present invention provides (A) a content of α-olefin units other than propylene of 1 to 10% by weight, a melt index of 0.2 to 60y/10min, and an amount of boiling 11n-hexane insoluble matter of 60 to 97% by weight. % and triad random fraction of 7 unit % or more, (B)-maximum % formula % () (R1 in the formula is a hydrogen atom or a carbon atom having 1 to 18 carbon atoms) Ca or Aj!, a is the valence of Ml), and -maximum % formula % () (2 in the formula is an alkylene group having 1 to 3 carbon atoms, R3R4,
R% and R6 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and they may be the same or different, Ml is Na, Mg, C
Provided is a propylene polymer composition comprising 0.001 to 0.5 parts by weight of at least one organic phosphorus compound selected from the following: (a or AI, b is the valence of Ml) It is something to do.

The present invention will be explained in detail below.

In the composition of the present invention, the propylene random copolymer used as component (A) has a content of α-olefin units other than 10-byrene of 1 to 10% by weight, preferably 2% by weight.
It is necessary that the content be in the range of ~8% by weight. When this content is less than 1% by weight, impact resistance is poor, and when it exceeds 10% by weight, rigidity, heat resistance, hardness, etc. tend to decrease.

In addition, examples of α-olefins copolymerized with propylene include ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1,
Examples include linear monoolefins such as decene-1, branched monoolefins such as 4-methylpentene-1,4-methylhexene-1,4,4-dimethylpentene-1, and dienes such as butadiene. Among these, ethylene and butene-1 are preferred. Further, these α-olefins may be used alone or in combination of two or more.

The melt index of the propylene random copolymer (
MI) is 0.2 to 60 g/10 min, preferably 0.5 to
It is necessary to be within the range of 50y/10 minutes. This M
If l is less than 0.2 y/10 min, the composition will have poor moldability and will not have sufficient rigidity, heat resistance, or hardness;
If the time exceeds 10 minutes, the impact resistance of the composition tends to decrease.

Further, the propylene random copolymer has a boiling n-hexane insoluble content of 60 to 97% by weight, preferably 70 to 9% by weight.
It is necessary that the content be in the range of 5% by weight. This boiling n-
If the hexane-insoluble content is less than 60% by weight, the crystallinity will be too low and the rigidity of the composition will be poor, and if it exceeds 97% by weight, the impact resistance of the composition will tend to decrease.

Further, the propylene random copolymer needs to have a triad random fraction of 7 unit % or more, preferably 10 unit % or more. If the triad random fraction is less than 7 unit %, the composition does not have sufficient impact resistance.The triad random fraction herein is the one obtained by the 1'C-NMR method,
Macromolecules
)” Volume 15, No. 4. Of each triat fraction listed in 1150 pages (1982), PPE
, PEP, EPE, the sum of four types of EEP, and the formula triad random fraction (unit %) = f pp
It can be expressed as t+f ptp +f tpflies+f EEIP. Note that the above formula shows an example of a copolymer of propylene and ethylene.

There are no particular restrictions on the method for producing the propylene random copolymer, and it can be produced by conventionally known methods. For example, slurry polymerization, solution polymerization, gas phase polymerization, etc. The polymerization temperature is usually 100°C, which can be easily produced by copolymerizing propylene and other α-olefins by a liquid phase polymerization method using an olefin monomer as a medium.
The following is preferably selected in the range of 30 to 90°C, and
The pressure varies depending on the polymerization conditions such as the type of catalyst, the characteristics of the reactor, and the polymerization method, but it is usually 1 to 50 A#/cm"・G.
selected within the range.

In the composition of the present invention, as the nucleating agent of component (B),
Organic phosphorus compounds represented by the general formula % formula % (1) (R1, R2, Ml and a in the formula have the same meanings as above), -maximum % formula % () (Z, R3 in the formula , R4, RS, RS, M2 and b
41 (having the same meaning as above) is used.

R' in the above-maximum (I) is a hydrogen atom or a carbon number of 1
-18 alkyl group, and examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5ec-butyl group, t- Butyl group, n-amyl group, t
- amyl group, hexyl group, heptyl group, n-octyl group, 2-ethylhexyl group, t-octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

In addition, R2 has 1 to 18 carbon atoms as exemplified above)
or M'l/+1, where Ml is Na, K, Mg, Ca
or AI, a is the valence of these M's.

Specific examples of the organic phosphorus compound represented by (1) above include the following compounds.

, R2°-Na 0-C4H while - R3, R4, RS and R at maximum (II)
6 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, 5ec- Butyl group, t-butyl group, n
-amyl group, t-amyl group, hexyl group, etc. The above 111j3, R4, R5 and R' may be the same or different, and 2 is an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylidene group, a propylene group, or an isopropylene group. group, M2 is Na, Mg, Ca or AI, and b is the valence of these M2.

Specific examples of the organic phosphorus compound represented by -maximum (II) include the following compounds.

In the composition of the present invention, one type of organic phosphorus compound represented by the above general formula (I) may be used as the component (B), or two or more types may be used in combination. One type of organic phosphorus compound represented by II) may be used, or two or more types may be used in combination, and further,
One or more organic phosphorus compounds represented by the general formula (1) and one or more organic phosphorus compounds represented by the general formula (■) may be used in combination.

The organic phosphorus compound of the component (B) is o, oo, etc. based on 100 parts by weight of the propylene random copolymer of the component (A).
It is necessary to mix it in a proportion of i to 0.5 parts by weight, preferably 0.003 to 0.3 parts by weight. This amount is o, o
If the amount is less than 0.00 parts by weight, the effect of the present invention will not be fully exhibited, and if it exceeds 0.5 parts by weight, no improvement in the effect will be observed considering the amount.

If desired, the composition of the present invention may contain various additives conventionally used in propylene resin compositions, such as antioxidants, light stabilizers, lubricants, etc., as long as they do not impair the purpose of the present invention.
Antistatic agents, antifogging agents, other nucleating agents, antiblocking agents, residual chlorine scavengers, clarifying agents, metal deactivators, coloring agents, and the like can be added.

Preferable examples of the antioxidant include phenol-based and phosphorus-based antioxidants, and it is particularly preferable to use these in combination.As the phenolic antioxidant, for example, 2
, 6-di-t-butyl-4-methylphenol, tris(3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate (manufactured by Ciba Geigy, Irgano
x3114), 2,2°-methylenebis(4-ethyl-
6-t-butylphenol), n-octadecyl-3-
(3′,5°-di-t-butyl-4′-hydroxyphenyl)propionate (manufactured by Ciba Geigy, Irga
nox1076), 4,4°-thiobis(3-methyl-
6-t-butylphenol), tetrakis[methylene-
3-(3°,5′-di-t-butyl-4°-hydroxyphenyl)propionate]methane (manufactured by Ciba Geigy, Irganoxlolo), 4,4′-butylidenebis(3-methyl-6-t-butylphenol), 2.
2°-methylenebis(4-methyl-6-t-butylphenol), N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide) (manufactured by Ciba Geigy, I rganox1098 ), triethylene glycol-bis[3-(3'-t-butyl-5
[-Methyl-4-hydroxyphenyl)propionate], a mixture of bis(ethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate) calcium and PE wax (weight ratio 1:1), etc. . Examples of phosphorus-based antioxidants include distearyl pentaerythritol diphosphite, tetrakis(2,4-di-butylphenyl)-4,4°-biphenylene diphosphite (manufactured by Sandoz, 5andostab).

P-EPQ) ,) lisnonylphenyl phosphite,
Examples include tris(2,4-di-t-butylphenyl) phosphite. Examples of light stabilizers include salicylates, benzophenones, triazoles, alinide oxalates, and hindered amines, and examples of lubricants include stearamide, balmitic acid amide, oleic acid amide, and erucic acid amide. Examples include.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

In addition, each physical property and copolymer boiling point 1! The amount of n-hexane insoluble matter was determined according to the method shown below.

(1) Rigidity Based on JIS K-7203, bending strength ('g/
Cl2) and flexural modulus (Ay/cm'') were determined to evaluate the rigidity.

(2) Izotsu impact strength (Ay-cm/ci+) JI
Izot impact strength at 23°C and 0°C was determined according to SK-7110.

(3) Compliant with whitening JISK-7211, height 50-100mm,
The degree of whitening was determined at a temperature of 23°C.

O: No whitening ×: Large whitening (4) Boiling n-hexane insoluble amount of copolymer (-1%)
The pulverized copolymer pellet was extracted with n-hexane for 6 hours using a Soxhlet extractor, and the amount of insoluble matter was determined.

In addition, the following organic phosphorus compounds were used.

NA-10 Sodium bis(4-t-butylphenyl) diphosphate NA-1t: Sodium methylene bis(2,4-di-t-butylphenol) acid phosphate (Example 1
~12, Comparative Examples 1 to 10) 100 parts by weight of the ethylene-propylene random copolymer of the type shown in Table 1 was blended with an organic phosphorus compound (nucleating agent) of the type and amount shown in Table 1. A resin composition was prepared by uniformly kneading the mixture at 230°C, and its physical properties were evaluated. The results are shown in Table 1.

(Comparative Example 11) The same operation as in Example 1 was performed under the conditions shown in Table 1 using an ethylene-propylene block copolymer instead of the ethylene-propylene random copolymer. The results are shown in Table 1.

[Effects of the Invention] The propylene polymer composition of the present invention is a propylene random copolymer blended with a specific organic phosphorus compound as a nucleating agent, and does not cause whitening upon impact. It has excellent impact resistance and rigidity, and is suitably used, for example, as an injection molding material, a soft extrusion molding material, a cold-resistant film material, etc.

Patent applicant: Idemitsu Petrochemical Co., Ltd.

Claims (1)

[Claims] (1) (A) Content of α-olefin units other than propylene is 1 to 10% by weight, melt index is 0.2 to 0.2
60g/10 minutes, boiling n-hexane insoluble amount 60-9
7% by weight and triad random fraction of 7 units%
For 100 parts by weight of the above propylene random copolymer, (B) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R^1 in the formula is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ^2 is an alkyl group having 1 to 18 carbon atoms, ▲ formula,
There are chemical formulas, tables, etc. ▼R^1 or M^1_1_/_
a, M^1 is Na, K, Mg, Ca or Al, a is M^
There are organic phosphorus compounds represented by the general formula ▲ numerical formula, chemical formula, table, etc. ▼ (in the formula, Z is an alkylene group having 1 to 3 carbon atoms, R^3, R
^4, R^5 and R^6 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and they may be the same or different from each other, and M^2 is Na ,
Propylene containing 0.001 to 0.5 parts by weight of at least one organic phosphorus compound selected from K, Mg, Ca or Al (b is the valence of M^2) Polymer composition.