JPH0616882A - Polypropylene resin composition - Google Patents

Abstract

PURPOSE:To improve the stiffness and clarity of a PP resin by compounding the resin with a specific metal salt of a phosphoric ester compd. and a phsporic ester compd. CONSTITUTION:100 pts.wt. PP resin having a melt flow rate (230 deg.C, 2.16kg load) of 0.1-100g/10min and a content of 10C or lower 1-olefins of 15wt.% or lower is compounded with 0.01-1.0 pt.wt. metal salt of a phosphoric ester compd. of formula I (wherein R1 and R2 are each independently a linear 1-4C alkylidene; R3 to R6 are each H or 1-8C alkyl; R7 is 3-18C alkyl; M is a mono-, di-. or trivalent metal atom; and n is 1-3) and 0.01-5.0 pts.wt. phosphoric ester compd. of formula II.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polypropylene resin composition. More specifically, it relates to a polypropylene resin composition capable of obtaining a molded product having remarkably improved rigidity and transparency.

[0002]

2. Description of the Related Art Polypropylene is used in various fields by taking advantage of its excellent moldability, mechanical properties, electrical properties and solvent resistance. However, it cannot be said that transparency is necessarily excellent, and therefore improvements have been made from various viewpoints. Among them, attempts by adding a transparency improving agent to polypropylene have been widely performed. Examples thereof include metal salts of carboxylic acids, metal salts of aromatic carboxylic acids, metal salts of aromatic phosphoric acids, and dibenzylidene sorbitol compounds. Among these transparency improving agents, carboxylic acid metal salts, aromatic carboxylic acid metal salts, and aromatic phosphoric acid metal salts can remarkably improve the rigidity, but the transparency improving effect is poor.

On the other hand, the dibenzylidene sorbitol type compound can remarkably improve both rigidity and transparency, and is added to most of commercially available transparent polypropylene moldings. However, this type of transparency improver has problems such as odor and stickiness on the surface of the molded product due to the compound itself or a decomposed product thereof, which causes a decrease in the commercial value of the molded product.

[0004]

The object of the present invention is rigidity,
A polypropylene resin composition having excellent transparency is provided.

[0005]

[Means for Solving the Problems] In view of the current situation as described above,
As a result of intensive investigations by the present inventors, the addition of a metal salt of a phosphoric acid ester compound and a phosphoric acid ester compound to a polypropylene resin can significantly improve the rigidity and transparency of the propylene resin. It has become possible to complete the present invention.

That is, the present invention is based on polypropylene resin 1
With respect to 00 parts by weight, a metal salt of a phosphoric acid ester compound represented by the following general formula (I) (hereinafter referred to as compound A)
And 0.01 to 5.0 parts by weight, and 0.01 to 5.0 parts by weight of a phosphoric acid ester compound represented by the following general formula (II) (hereinafter referred to as compound B). To a polypropylene resin composition.

[0007]

[Chemical 2] (Here, R1 and R2 are the same or different linear bonds, respectively, and are alkylidene groups having 1 to 4 carbon atoms, R3 to R6.
Is hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, R7 is an alkyl group having 3 to 18 carbon atoms, and M is 1 to 3
Valence metal atom, n shows an integer of 1-3) Hereinafter, the present invention will be described in detail.

The polypropylene resin used in the present invention has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 Kg of 0.1 to 100 g / 10.
A crystalline polymer is preferable at about min, and the effect of the present invention is remarkably exhibited in such a polymer. Also,
As the polypropylene resin, not only a homopolymer of propylene but also a random copolymer of propylene and one or more other olefins is used. Other olefins polymerized with propylene include ethylene and 1-
Butene, 1-pentene, 3-methyl-1-butene, 1-
Hexene, 4-methyl-1-pentene, 1-octene,
Examples thereof include 1-olefins having 10 or less carbon atoms such as 1-decene. Such a component to be copolymerized with propylene is usually used in an amount of 15% by weight or less, preferably 10% by weight or less in the random copolymer. Examples of polypropylene resins include homopolymers of propylene, random copolymers of propylene and one or more other olefins, and block copolymers of propylene and one or more other olefins. Are known. Since this block copolymer is generally opaque, even if this polymer is used in the present invention, the transparency, which is the gist of the present invention, is not significantly improved. However, since the rigidity is remarkably improved, the block copolymer is included in the polypropylene resin referred to in the present invention.

Examples of the method for polymerizing the polypropylene resin include slurry polymerization, bulk polymerization, gas phase polymerization and the like, and the effect of the present invention is sufficiently exerted even if the resin is polymerized by any of these methods. It In general, a Ziegler-based catalyst such as a titanium trichloride reduction-type catalyst or a magnesium-supported catalyst is generally used for the polymerization, but even if a polymer is polymerized by any of these catalyst systems, the effect of the present invention is obtained. There is no problem. The metal salt of a phosphoric acid ester compound (hereinafter referred to as compound A) used in the present invention is a compound represented by the following general formula (I), and is a phosphoric acid ester compound (hereinafter referred to as compound B). Is a compound represented by the following general formula (II).

[0010]

[Chemical 3] (Here, R1 and R2 are the same or different linear bonds, respectively, and are alkylidene groups having 1 to 4 carbon atoms, R3 to R6.
Is hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, R7 is an alkyl group having 3 to 18 carbon atoms, and M is 1 to 3
Valent metal atom, n represents an integer of 1 to 3) Compounds A and B
Both R1 and R2 are C1-4 alkylidene groups,
Specifically, it is a methylene group, an ethylidene group, a propylidene group, or a butylidene group. The alkylidene groups of the compound A and the compound B do not need to be the same, but the compound A,
B is preferably a methylene group. R3 to R6 are hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, but may be a branched alkyl group as well as a linear alkyl group. Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group and an octyl group.
As the branched alkyl group, i-propyl group, 1
-Methylpropyl group, t-butyl group, 2-methylbutyl group, 1-ethylpropyl group, 2,3-dimethylbutyl group, 2-ethylhexyl group and the like can be mentioned. R
The substituents of 3 to R6 do not have to be the same kind of groups as the respective substituents in the compounds A and B and the substituents in the two compounds. However, both compounds A and B have R3 to R
As the substituent of 6, a t-butyl group is preferable. Compound B
R7 in the formula is an alkyl group having 3 to 18 carbon atoms, and specific examples thereof include propyl group, butyl group, amyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, heptadecyl group, octadecyl group and the like. In addition to linear alkyl groups, branched alkyl groups such as i-propyl group, t-butyl group, 2-ethylhexyl group, 4-propylheptyl group, 2-butyl, 3-propyloctyl group can be exemplified. . Among such alkyl groups, an octyl group is particularly preferable. M in the compound A is a metal atom having a valence of 1 to 3, specifically, Li, Na, K, Mg, Ca and B.
Although a, Fe, Mn, Zn, Cu, Al, etc. can be mentioned, Na is particularly preferable. The value of n in the compound A is the same number as the valence of the metal atom M, and is 1, for example, for Na or K, 2 for Mg, Ca, Zn, and 3 for Al.

Specific examples of the compound A include sodium-
2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4,6-di-t-butylphenyl)
Phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate
G, calcium-bis- [2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphine
], Magnesium-bis- [2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphine
], Aluminum-tris- [2,2'-methylene-
Bis- (4,6-di-t-butylphenyl) phosphate], sodium-2,2'-propylidene-bis-
(4,6-di-t-butylphenyl) phosphate,
Sodium-2,2'-methylene-bis- (4-i-propyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-di-phenylphosphate, sodium-2, 2'-methylene-bis- (4
-Ethyl-6-butylphenyl) phosphate, calcium-bis- [2,2'-methylene-bis- (4-methyl-6-t-butylphenyl) phosphate], sodium-2,2'- Butylidene-bis- (4,6-di-methylphenyl) phosphate, aluminum-tris- [2,2'-methylene-bis- (4-propyl-)
6-Ethylphenyl) phosphate] and the like. Among these, sodium- (2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate is particularly preferable.

Specific examples of the compound B include 2,2'-methylene-bis- (4,6-di-t-butylphenyl) octyl phosphate and 2,2'-ethylidene-bis-.
(4,6-di-t-butylphenyl) octyl phosphate, 2,2'-propylidene-bis- (4,6-di-t-butylphenyl) amyl phosphate, 2,
2'-methylene-bis- (4,6-di-t-butylphenyl) 2-ethylhexyl phosphate, 2,2'-
Methylene-bis- (4,6-di-i-propylphenyl) propyl phosphate, 2,2'-butylidene-
Bis- (4-methyl-6-butylphenyl) dodecylphosphate, 2,2'-methylene-bis- (4-propyl-6-ethylphenyl) octadecylphosphate
2,2'-methylene-bis- (4,6-di-methylphenyl) octyl phosphate, 2,2'-methylene-di-phenyl octyl phosphate, 2,2'-
Examples thereof include ethylidene-bis- (4-i-propyl-6-butylphenyl) decyl phosphate. Among these, 2,2'-methylene-bis- (4,6-
Di-t-butylphenyl) octyl phosphate is preferred.

Compound A to be added to polypropylene resin
The amounts of Compound B and Compound B are 0.01 to 1.0 parts by weight and 0.01 to 5.0 parts by weight, respectively, preferably 0.03 to 0.
3 parts by weight and 0.03 to 1.5 parts by weight. Even in such an addition range, the rigidity can be remarkably improved by adding only the compound A, but a molded article having excellent transparency cannot be obtained. Addition of only compound B cannot improve the physical properties such as rigidity and transparency at any added amount. Even when the compounds A and B are used in combination, if the addition amount is less than the above range, the effect of improving transparency and rigidity is poor, and if the amount exceeds the above range, the rigidity can be improved, but the transparency is high. No improvement in sex can be expected. The mechanism by which the transparency of the resin is improved when the compounds A and B are added to the polypropylene resin is not clear, but it is considered that these interact with each other and act as a nucleating agent for improving the transparency. Compound B is added in the amount of Compound A
Is preferably equal to or more than. Although the compounds A and B may be added to the resin as they are, both compounds A and B may be dissolved in a solvent in advance and dried and recrystallized by an appropriate means such as vacuum drying. A better effect can be expected when it is added to the resin.

In the composition of the present invention, various additives commonly used for polyolefins include antioxidants, neutralizing agents, ultraviolet absorbers, hindered amine light stabilizers, lubricants, and antiblocking agents. , An antistatic agent, a nucleating agent, a dispersant, a peroxide, a pigment and the like can be added.

To prepare the composition of the present invention, 0.01 to 1.0 parts by weight of compound A and 0.01 to 5 parts by weight of compound B are added to 100 parts by weight of polypropylene resin.
0 parts by weight, and commonly used stabilizers such as pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate],
Tris (2,4-di-t-butylphenyl) phosphite, calcium stearate 0.05,
0.1 and 0.1 parts by weight are added, and these compositions are loaded.
A suitable kneader such as an extruder, a plastomill, or an extruder may be used to heat and knead at a melting point of the polypropylene resin or higher. The resin composition thus obtained is injection molded, extruded,
It is used as a polymer molding material that is applied to ordinary molding methods such as compression molding. It is also possible to obtain a desired molded product by a method of preparing a highly filled resin of the composition used in the present invention in advance and adding these at the time of molding or re-granulation, that is, by adding in a master-batch. Is.

[0016]

The present invention will now be described with reference to the following examples, which are not intended to limit the present invention.

Examples 1 to 3 Sodium which is a metal salt of a phosphoric acid ester compound
(2,2'-Methylene-bis- (4,6-di-t-butylphenyl) phosphate (Compound A) and 2,2'-methylene-bis- (4, which is a phosphoric acid ester compound.
6-di-t-butylphenyl) octyl phosphate (Compound B) was dissolved in methanol at the weight ratio shown in Table 1 and dried under reduced pressure to obtain a powdery sample. . Pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] 0.05 part by weight, tris (2,4-di-t-butylphenyl) phosphite 0.1 part by weight,
Ethylene with 0.1 part by weight of calcium stearate
25m added to propylene random copolymer (ethylene content 3.5% by weight, MFR 7.9g / 10min)
Granulation was performed at 240 ° C. using an mφ single screw extruder.

The granulated resin was molded into a sheet having a thickness of 1 mm by a press molding machine heated to 230 ° C.

Using this sheet, the head (JIS K-6
714) and rigidity (JIS K-7106) were measured and evaluated. The results are shown in Table 1.

Examples 4 to 8 Compounds A and B were dissolved in methanol at the weight ratios shown in Table 2 and dried under reduced pressure to obtain powder-like samples.
Evaluation was carried out in the same manner as in Example 1 except that ethylene-propylene random copolymer (ethylene content 4.3% by weight, MFR 6.5 g / 10 min) was added. The results are shown in Table 2.

Comparative Example 1 Evaluation was carried out in the same manner as in Example 1 except that Compound A and Compound B were not added. The results are shown in Table 1.

Comparative Example 2 Evaluation was carried out in the same manner as in Example 1 except that only compound A was added in the weight parts shown in Table 1. The results are shown in Table 1.

Comparative Example 3 Evaluation was carried out in the same manner as in Example 1 except that only the compound B was added in the weight parts shown in Table 1. The results are shown in Table 1.

Comparative Example 4 Evaluation was carried out in the same manner as in Example 4 except that Compound A and Compound B were not added. The results are shown in Table 2.

Comparative Examples 5 to 6 Evaluations were made in the same manner as in Example 4 except that only Compound A was added in the weight parts shown in Table 2. The results are shown in Table 1.

Comparative Examples 7 to 8 As Example 4 except that compounds A and B were dissolved in methanol at the weight ratios shown in Table 2 and the powdery sample obtained by drying under reduced pressure was added. It evaluated by the same method. The results are shown in Table 2.

[0027]

[Table 1]

[0028]

[Table 2] As shown in Comparative Example 2 in Table 1, when only Compound A is added, the rigidity is remarkably improved but the transparency is remarkably improved as compared with Comparative Example 1 in which Compounds A and B are not added. Absent. Further, as in Comparative Example 3, addition of only the compound B does not improve rigidity and transparency. However, when the compound A and the compound B are added at various compounding ratios as in Examples 1 to 3, the rigidity and the transparency are remarkably improved by the interaction of these compounds.

From Table 2, as shown in Example 4, Compound A
It can be seen that the rigidity and transparency of the molded product are improved as compared with Comparative Example 5 when Compound B is used in combination therewith even if the addition amount of is small. Further, as shown in Examples 4 to 8, compound A,
If the addition amount of B is within a specific range, the rigidity and transparency of the molded product will be significantly improved. When the addition amount of the compounds A and B is less than or exceeds the specific range as in Comparative Examples 7 to 8, it is not possible to obtain a molded product having excellent transparency.

[0030]

The polypropylene resin composition of the present invention can remarkably improve the rigidity and transparency of the molded product. Therefore, transparent and rigid products such as injection molded products such as caps and clothing cases, blow products represented by bottles, and extruded products such as binders and video cassette cases are required. Suitable for manufacturing.

[Table 3]

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[Procedure amendment]

[Submission date] May 14, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[ Claims ]

[Chemical 1] (Here, R1 and R2 are the same or different linear bonds, respectively, and are alkylidene groups having 1 to 4 carbon atoms, R3 to R6.
Is hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, R7 is an alkyl group having 3 to 18 carbon atoms, and M is 1 to 3
Valent metal atom, n represents an integer of 1 to 3)

Claims (1)

[Claims] 1. A metal salt of a phosphoric acid ester compound represented by the following general formula (I) in an amount of 0.01 to 1.0 part by weight based on 100 parts by weight of a polypropylene resin, and the following general formula (II): The phosphoric acid ester compound represented by
A polypropylene resin composition characterized by containing up to 5.0 parts by weight. [Chemical 1] (Here, R1 and R2 are the same or different linear bonds, respectively, and are alkylidene groups having 1 to 4 carbon atoms, R3 to R6.
Is hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, R7 is an alkyl group having 3 to 18 carbon atoms, and M is 1 to 3
Valent metal atom, n represents an integer of 1 to 3)