JPH02102242A - Crystalline propylene polymer composition and container produced therefrom - Google Patents

Abstract

PURPOSE:To obtain a crystalline polymer compsn. providing a molded article with excellent rigidity, resistance to thermal rigidity and transparency by compounding a specified crystalline propylene polymer with a phosphate compd. and a dibenzylidenesorbitol compd. CONSTITUTION:A polymer compsn. is obtd. by compounding 100 pts.wt. crystalline propylene polymer wherein the relation between the isotactic pentad fraction (P) and the melt flow rate(MFR) is 1.00>=P>=0.0151 ogMFR+0.955 with 0.01-1 pt.wt. phosphonate compd. of formula I or II (wherein R1 is a direct bonding, sulfur or a 1-4C alkylidene group; R2 and R3 are each H or a 1-8C alkyl; M is a mono- to tri-valent metal atom; n is 1-3). Said compsn. can be suitably used for such applications as food containers for a microwave oven where high rigidity and resistance to thermal rigidity are especially required, ordinary food containers, cosmetic containers, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a crystalline propylene polymer composition and a container using the composition. More specifically, the present invention relates to a crystalline propylene polymer composition from which a molded article with excellent rigidity, heat-resistant rigidity, and transparency can be obtained, and a container using the same.

(Prior Art) Generally, crystalline propylene polymer compositions have excellent processability and mechanical properties, so they are processed into injection molded products, blow molded products, films, sheets, fibers, etc. and used for various purposes. There is. However, although the crystalline propylene polymer composition has excellent mechanical properties, its use is limited due to poor transparency due to the high crystallinity of the crystalline propylene polymer composition. There is a problem. For this reason, various nucleating agents have conventionally been used for the purpose of improving the transparency of the crystalline propylene polymer composition. Dibenzylidene sorbitol compounds (hereinafter referred to as DBS) are widely used because they are relatively effective in improving transparency.

However, in recent years, as fields that require a high degree of transparency have increased, propylene and one type of α-olefin other than propylene, such as ethylene, phthene-1, pentene-1, hexene-1, and octene-1, etc. A propylene copolymer composition has been proposed using a random copolymer with the above and blending DBS into the copolymer (Japanese Patent Application Laid-open No. 209151/1983). However, although the transparency of this composition is significantly improved, a problem arises in that mechanical properties such as rigidity (flexural modulus) and heat-resistant rigidity (heat-resistant deformation resistance) are insufficient. In order to solve these problems, a composition has been proposed in which a combination of DBS and a 7-year-old sulfate compound is used to polymerize crystalline propylene (Japanese Patent Laid-Open Publication No. 209151/1982).

The above-mentioned JP-A-62-2091 is prepared by blending monoto-based compounds.
Although the composition disclosed in Publication No. 51 has a considerable effect of improving transparency, it cannot be used in applications that require a high degree of rigidity (flexural modulus) and heat-resistant rigidity (heat deformation resistance), such as containers. is still not completely satisfactory.

The present inventors have solved the above-mentioned problems regarding crystalline propylene polymer compositions containing various nucleating agents, that is, they have excellent transparency, stiffness (flexural modulus) and heat-resistant rigidity (heat-resistant deformation resistance). We conducted extensive research in order to obtain a crystalline propylene polymer composition that would yield excellent molded products. As a result, the crystalline propylene polymer having a specific isotactic pendant fraction was mixed with a phosphate compound (hereinafter referred to as compound A) represented by the following - removal allowance [1] or represented by the following general formula [II]. The present invention was completed based on this knowledge.

(However, in the formula, R0 is a direct bond, sulfur, or carbon number 1 to
R2 and R3 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms, M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3. ) (In the formula, R4 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3.) As is clear from the above description, The purpose of the present invention is to achieve a high degree of rigidity (high flexural modulus) and heat-resistant rigidity (high heat-resistant deformability).
Another object of the present invention is to provide a crystalline propylene polymer composition from which a molded article with excellent transparency can be obtained, and a container using the composition.

(Failure to solve the problem) The present invention has the following configuration.

The relationship between isotactic pendant fraction (P) and melt flow rate (MFR) is 1.00≧P≧0.015
A phosphate compound represented by the following general formula [1] (hereinafter referred to as compound A) or a phosphate compound represented by the following general formula (I [)] is added to 100 parts by weight of a crystalline propylene polymer having a 1ogMFR+0.955. A phosphate compound (hereinafter referred to as compound B) and DBS were each added to 0. A crystalline propylene polymer composition containing 1 to 1 part by weight of O.

(However, in the formula, R8 is a direct bond, sulfur, or has 1 to 1 carbon atoms.
& and R3 each represent hydrogen or the same or different alkyl group having 1 to 8 carbon atoms,
M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3. ) (In the formula, R4 represents hydrogen or an alkyl group having 1 to 8 carbon atoms, M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3.) Crystalline propylene used in the present invention Polymers include propylene crystalline homopolymer, propylene, ethylene,
Phtene-1, Pentene-1, Hexene-1, Octene-1
A crystalline random copolymer with one or more α-olefins selected from 1, wherein the relationship between isotactic pendant fraction (P) and melt flow rate (MFR) is 1.00. ≧P≧0.0151ogMFR+0.9
It is a crystalline propylene polymer that satisfies 55. In particular, a propylene crystalline homopolymer that satisfies the above-mentioned relationship between isotactic pendant fraction (P) and MFR is desirable.

Compound A used in the present invention includes 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, lithium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl) phosphate, sodium-2,2'
-ethylidene-bis(4-i-propyl-6-1-butylphenyl) phosphate, lithium-2,2'-methylene-bis(4-methyl-6-t-butylphenyl)
phosphate, lithium-2,2'-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate, calcium-bis-C2,2'-thiobis(4-methyl-6-t-butylphenyl) phosphate], calcium bis-(2,2'-thiobis(4-ethyl-
6-t-butylphenyl)7 phosphate], calcium-bis-(2,2'-thiobis-(4,6-di-t-
/tylphenyl)phosphate], magnesium-bis-(2,2'-thiobis(4,6-di-t-butylphenyl)phosphate), magnesium-bis(2,
2'-thiobis-(4-t-octylphenyl)7o7ate], sodium-2,2'-butylidene-bis(4,6-di-methylphenyl)phosphate, sodium-2,2'-butylidene -bis(4,6-Gt
-butylphenyl) 7 phosphate, sodium-2,
2'-t-octylmethylene-bis(4,6-di-methylphenyl)phosphate, sodium-2,2'-
t-Octylmethylene-bis(4,6-di-t-butylphenyl)phosphate, calcium-bis-(2,
2'-methylene-bis(4,6-di-t-butylphenyl) phosphate], magnesium-bis(2,2'
-methylene-bis-(4,6-di-t-butylphenyl)phosphate], barium-bis-C2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate], sodium-2 , 2'-methylene-bis(4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate, sodium (4 , 4'-dimethyl-6,6'-di-t-butyl-2,2'biphenyl) phosphate, calcium-
bis-C(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl)phosphate], sodium-2,2'-ethylidene-bis(4-8-butyl- 6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis(4,6-di-methylphenyl) 7m7ate, na)! Jum~2゜2'-methylene-bis(4,6-cyenitylphenyl) phosphate, potassium-2,2'-ethylidene-bis(4,
6-di-t-butylphenyl) phosphate, calcium-bis-(2,2'-ethylidene-bis(4,6-
di-t-butylphenyl) phosphate], magnesium-bis-C2,2'-ethylidene-bis(4,6-
di-t-butylphenyl) phosphate], barium-bis-C2,2'-ethylidene-bis(4,6-di-t-butylphenyl) phosphate], aluminate! J Su-(2゜2'-methylene-bis(4,6-
di-t-butylphenyl) phosphate] and aluminumtris-C2,2'-ethylidene-bis(4
, 6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof.

In particular, sodium-2,2'-methylene-bis(4,6-
Lamb-bis-(4-t-butylphenyl) phosphate, sodium-bis-(4-methylphenyl) phosphate, sodium-bis-(4-ethylphenyl)
phosphate, sodium bis-(4-i-propylphenyl) phosphate, sodium bis-(4
-t-octylphenyl)phosphate, potassium-
Bis-(4-t-'7'tylphenyl) phosphate, Calcium-bis-(4-t-butylphenyl) phosphate, Magnesium-bis-(4-t-butylphenyl) phosphate, Lithium-bis-( 4-1-
butylphenyl) phosphate aluminum bis-
Examples include (4-t-butylphenyl)phosphate and mixtures of two or more thereof. Particularly preferred is sodium-bis-(4-1-butylphenyl)phosphate.

DBS used in the present invention (hereinafter referred to as compound C)
Examples include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p
-Ethylbenzylitine sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol,
1,3-p-ethylbenzylidene-2,4-benzylitine sorbitol, 1,3-p-methylbenzylidene-2
・4-p-ethylbenzylidene sorbitol, 1.3-
p-ethylbenzylidene-2.4-p-methylbenzylidene sorbitol, 1.3゜2.4-di(p-methylbenzylidene) sorbitol, ■.3,2.4-di(p-
ethylbenzylidene) sorbitol, 1,3,2,4-
Di(p-n-propylbenzylidene)sorbitol, 1
・3゜2,4-di(p-i-propylbenzylidene) sorbitol, 1,3,2,4-di(p-n-butylbenzylidene) sorbitol, ■・3,2,4-di(p-s
-butylbenzylidene) sorbitol, 1, 3, 2, 4
-di(pt-butylbenzylidene)sorbitol, 1
・3,2・4-di(2'.

4'-dimethylbenzylidene) sorbitol, 1,3゜2,4-di(p-methoxybenzylidene) sorbitol, 1,3,2,4-di(p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2- 4-p-chlorobenzylidene sorbitol, ■・3-p-chlorobenzylidene-2.4-benzylidene sorbitol, 1.3
-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1.
3-p-methylbenzylidene-2,4-pi chlorobenzylidene sorbitol 1,3-p=ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-cy(p-chlorobenzylidene) sorbitol and mixtures of two or more of these, particularly 1.3゜2.4-dibenzylidene sorbitol, 1.
3゜2,4-di(p-methylbenzylidene) sorbitol, 1,3,2,4-di(p-ethylebenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4
-p-methylbenzylidene sorbitol, 1, 3, 2,
4-di(p-chlorobenzylidene) sorbitol and mixtures of two or more thereof are preferred. These compounds A
Alternatively, the blending ratio of Compound B and Compound C is 0.00 parts by weight, respectively, based on 100 parts by weight of the crystalline propylene polymer.
01 to 1 part by weight, preferably 0.01 to 0.5 part by weight. If the amount is less than 0.01 part by weight, the stiffness, heat resistance stiffness,
Desired effects such as transparency are not sufficiently exhibited, and although it is possible to use more than 1 part by weight, no further improvement in effects can be expected, which is not only impractical but also uneconomical.

The composition of the present invention contains various additives that are normally added to crystalline propylene polymers, such as phenolic, thioether, and phosphorus antioxidants, light stabilizers, clarifying agents, and nucleating agents. , lubricants, antistatic agents, antifogging agents, antiblocking agents, anti-drop agents, pigments, heavy metal deactivators (copper inhibitors), radical generators such as peroxides, dispersants such as metal soaps, or Neutralizing agents and inorganic fillers (e.g. talc, mica, clay, wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide,
surface treatment agents such as magnesium hydroxide, barium sulfate, calcium silicate, glass fiber, carbon fiber, etc.) or coupling agents (such as silane, titanate, boron, aluminate, zircoaluminate, etc.). Treated inorganic or organic fillers (
(e.g. wood flour, pulp, waste paper, synthetic resin, natural fibers, etc.)
can be used in combination within the range that does not impair the purpose of the present invention. The composition of the present invention is prepared by adding predetermined amounts of Compound A or Compound B and Compound C and the various additives mentioned above that are usually added to crystalline propylene polymer to a crystalline propylene polymer using a conventional mixing device such as a Hensel mixer ( (product name), Super Mixer, ribbon blender, Banbury mixer, etc., and mix with a normal single-screw extruder, twin-screw extruder, plastic bender, roll, etc. at a melt mixing temperature of 160°C to 300°C, preferably 180°C. It can be obtained by melt-mixing pelletizing at a temperature of 250°C to 250°C.

The obtained composition is used to produce a desired molded article by various molding methods such as injection molding, extrusion molding, and blow molding.

In addition, there are no particular restrictions on the shape of the containers and food containers obtained using the composition of the present invention, and they may be of any shape such as a box, a cylinder, or a triangular prism, and there are no particular restrictions on the dimensions.
For example, length 50m~800g1c, width 50+m~1000
+n, height 20m TIL ~ 500mm, wall thickness 0.5 edition w
Any size between ~2.5 w can be adopted.

By using the composition of the present invention, molded products with extremely excellent rigidity, heat-resistant rigidity, and transparency can be obtained, so that products in various molding fields can be used, especially food containers for microwave ovens that require a high degree of rigidity and heat-resistant rigidity. It can be suitably used in applications such as ordinary food containers and cosmetic containers.

(Function) In the present invention, it is generally known that the phosphate compound represented by Compound A or Compound B mainly contributes to improving rigidity, and the DBS represented by Compound C mainly contributes to improving transparency. It is being However, compound A
Alternatively, by blending Compound B and Compound C with a crystalline propylene polymer that satisfies the specific relationship between isotactic pendant fraction (P) and MFR according to the present invention, a conventionally known nucleating agent can be used. A surprising synergistic effect, which could not have been predicted from the combination of the two, is exhibited, resulting in a composition that provides a molded article with a high degree of rigidity, heat-resistant rigidity, and outstanding transparency.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The evaluation method used in Examples and Comparative Examples was as follows.

■) Rigidity: Using the obtained pellets, a test piece with a length of 100n, a width of 10xrn, and a wall thickness of 4mrn was made by injection molding, and the flexural modulus was measured using the test piece (JIS
K 7203).

■) Heat resistance rigidity: length 130m using the obtained pellets
A test piece with a width of 13 mm and a wall thickness of 6.5 mm was made by injection molding, and the heat distortion temperature was measured using the test piece (JIS
Compliant with K 7203; 4.6#f/crl load)
I rated it highly.

■) Transparency: Length 50m5 using the obtained pellets
A test piece with a width of 25 mm and a wall thickness of 1 mm, and a box-shaped container with a length of 100 mm, a width of 100 mm, a height of 40 m, and a wall thickness of 1 mm were made by injection molding, and the same test pieces were cut from the test piece and the container. Measure haze using a test piece of the same dimensions (ASTMD-1
003-61).

Examples 1 to 8, Comparative Examples 1 to 10 Sodium-based compound A was added to 100 parts by weight of a powdered crystalline propylene homopolymer having each MFR and each isotactic pendant fraction shown in Table 1 below. 2
, 2'-methylene-bis(4,6-di-t-butylphenyl) phosphate, compound B as sodium-bis-(4-1-butylphenyl) phosphate, compound C as 1.3,2.4- Dibenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene)sorbitol or 1,3-p-chlorobenzylidene-
Predetermined amounts of 2,4-p-methylbenzylidene sorbitol and other additives were placed in a Hensel mixer (trade name), mixed, and then melt-kneaded and pelletized at 200°C in a single-screw extruder with a diameter of 40+++ m. . As Comparative Examples 1 to 10, 100 parts by weight of a powdered crystalline propylene homopolymer having each MFR and each isotactic pendant fraction shown in Table 1 below was added with the additives listed in Table 1 below. Predetermined amounts of each were blended to obtain pellets according to Examples 1 to 8.

Test pieces used for rigidity, heat resistance rigidity, and transparency tests were prepared by injection molding the obtained pellets at a resin temperature of 250°C.

Using the obtained test piece, stiffness, heat-resistant stiffness, and transparency were evaluated according to the test method described above. These results are shown in Table 1.

Examples 9 to 16, Comparative Examples 11 to 20 Sodium-based compound A was added to 100 parts by weight of a powdered crystalline propylene homopolymer having each MFR and each isotactic pendant fraction shown in Table 2 below. 2
, 2'-methylene-bis(4,6-di-t-butylphenyl) phosphate, compound B as sodium-bis-(4-t-butylphenyl) phosphate, compound C,! : L-1 (1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene) sorbitol or 1,3-p-chlorobenzylidene-2,4-p-methyl Predetermined amounts of benzylidene sorbitol and other additives were placed in a Hensel mixer (trade name), mixed, and then melt-kneaded and pelletized at 200°C in a single-screw extruder with a diameter of 40 Vx. Comparative Examples 11 to 20 Each MF shown in Table 2 below as
R and 100 parts by weight of powdered crystalline propylene homopolymer having various isotactic pendant fractions were blended with predetermined amounts of each of the additives listed in Table 2 below, and the mixture was prepared according to Examples 9 to 16. Obtained pellets.

Test pieces used for rigidity, heat resistance rigidity, and transparency tests were prepared by injection molding the obtained pellets at a resin temperature of 250°C.

Using the obtained test piece, υ stiffness, heat-resistant stiffness, and transparency were evaluated according to the test method described above. These results are shown in Table 2.

Examples 17 to 24, Comparative Examples 21 to 29 Sodium-based compound A was added to 100 parts by weight of a powdered crystalline propylene homopolymer having each MFR and each isotactic pendant fraction shown in Table 3 below. 2
, 2'-methylene-bis(4,6-di-t-butylphenyl) phosphate, compound B as sodium-bis-(4-t-butylphenyl) phosphate, compound C as 1.3,2.4- Dibenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene)sorbitol or 1,3-p-chlorobensyritene-
2,4-p-Methylbenzylidene sorbitol and other additives were placed in predetermined amounts in a Hensel mixer (trade name), mixed, and then mixed in a single-screw extruder with a diameter of 40.
The mixture was melt-kneaded and pelletized at 00°C. Also, comparative example 21
To 100 parts by weight of a powdered crystalline propylene homopolymer having each MFR and each isotactic pendant fraction shown in Table 3 below as ~29, predetermined amounts of each of the additives listed in Table 3 below were added. The mixture was blended to obtain pellets according to Examples 17-24.

Using the obtained pellets, at a molding temperature of 230°C,
00 size, width 100mm, height 40+i, wall thickness 1ml! A box-shaped container was molded by injection molding, and the transparency of the container was evaluated using predetermined dimensions used in the transparency test. These results are shown in Table 3.

The compounds and additives according to the present invention shown in Tables 1 to 3 are as follows.

Compound A; Sodium-2,2'-methylene-bis(
4,6-di-t-butylphenyl) phosphate compound B; sodium-bis-(4-t-butylphenyl) phosphate compound C [1); 1,3,2,4-dibenzylidene sorbitol compound C [, II); 1,3,2,4-di(p-methylbenzylidene) sorbitol compound C [■]; 1,3-p-chlorobenzylidene-
2,4-p-methylbenzylidene sorbitol nucleating agent; pt-butylbenzoate aluminum phenolic antioxidant; tetrakis[methyl-3-(3'
, 5'-di-t-butyl-4'-hydroxyphenyl)
Propionate comethane phosphorus antioxidant; tris(2,4-di-t-butylphenyl)phosphite Ca-S t: Calcium stearate Examples and comparisons listed in Table 1 are crystalline propylene This is the case where crystalline propylene homopolymers having each MFR and each isotactic pendant fraction listed in Table 1 were used as the polymer. As can be seen from Table 1, in the embodiment, the relationship between the isotactic pendant fraction (P) and MFR, which is within the scope of the present invention, is 1.00≧P≧
Compound A or Compound B and Compound C are blended with a crystalline propylene polymer satisfying 0.0151 ogMFR+ 0.955. (P) and M
Comparing a crystalline propylene polymer whose relationship with FR does not satisfy the above formula with Compound A or Compound B and Compound C, Examples 1 to 8 have low rigidity, heat resistance rigidity, and transparency. It turns out that it is excellent. Also, isotactic pendant fraction (P) and MFR
Comparative Examples 4 to 9 and Examples 1 to 9, in which Compound A, Compound B, Compound C, or other nucleating agent were individually blended with a crystalline propylene polymer whose relationship with satisfies the above formula.
8, Comparative Examples 4 to 9 still do not have sufficient improvement effects in any of the rigidity, heat-resistant rigidity, and transparency. Furthermore, comparing Comparative Example 10 in which Compound C was used in combination with an aromatic carboxylic acid compound, which is a conventionally known nucleating agent, and Examples 1 to 8, Comparative Example 10 had an improvement effect on stiffness, heat-resistant stiffness, and transparency. is still not sufficient. From the above, it can be seen that Examples 1 to 8, which are the compositions of the present invention, have a high degree of rigidity, heat-resistant rigidity, and transparency. This indicates that the isotactic pendant fraction (P) of the crystalline propylene polymerization used in the present invention and the MF
It can be said that this is a unique synergistic effect that is observed only when Compound A or Compound B and Compound C are blended with a crystalline propylene polymer having a specific relationship with R.

Table 2 shows the case where a crystalline propylene homopolymer having a lower MFR than the crystalline propylene polymer used in Table 1 was used, and the same effects as described above were confirmed for these as well.

Table 3 shows the results of molding box-shaped containers and evaluating their transparency, and it can be seen that all containers using the composition of the present invention have excellent transparency.

(Effect of the invention)

Claims (3)

[Claims] (1) The relationship between isotactic pendant fraction (P) and melt flow rate (MFR) is 1.00≧P≧0.
A phosphate compound represented by the following general formula [I] (hereinafter referred to as compound A) or a phosphate compound represented by the following general formula [II] is added to 100 parts by weight of a crystalline propylene polymer having a 0151ogMFR+0.955. compound (hereinafter referred to as compound B) and dibenzylidene sorbitol compound, respectively, at 0.01 to 1
A crystalline propylene polymer composition containing parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, R_1 in the formula is a direct bond, sulfur, or 1 carbon number.
-4 alkylidene groups, R_2 and R_3 each represent hydrogen or the same or different alkyl groups having 1 to 8 carbon atoms, M represents a monovalent to trivalent metal atom, and n represents an integer of 1 to 3. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (However, in the formula, R_4 is hydrogen or an alkyl group having 1 to 8 carbon atoms, M is a monovalent to trivalent metal atom, and n is 1 to 3 ) (2) A container using the composition according to claim 1. (3) A food container using the composition according to claim 1.