JPH1025377A - Polypropylene resin composition - Google Patents

Abstract

(57) [Problem] To provide a polypropylene-based resin composition containing talc and a crystal nucleating agent, sufficiently exhibit the function of an added crystal nucleating agent, and improve the flexural modulus and heat resistance of the composition. SOLUTION: (A) 40 to 99 parts by weight of a polypropylene resin, (B) 1 to 60 parts by weight of talc, and (A) + (B) = 100
A resin composition comprising (C) 0.01 to 3 parts by weight of a phosphate crystal nucleating agent represented by the following formula (I) or (II) and (D) 0.01 to 1 part by weight of ethylenediaminetetraacetic acid, relative to parts by weight. Embedded image (R ¹ is a direct bond, S atom or C _1-9 alkylene or alkylidene group; R ² and R ³ are H atom or C
_{1 to 8} alkyl groups; M is a metal atom having 1 to 3 valences; n is a valence of M) (R ⁴ is a H atom or a C _1-8 alkyl group;
Trivalent metal atom; n 'is the valence of M')

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polypropylene resin composition, and more particularly, to a polypropylene resin composition useful for industrial materials, general goods, and the like.

[0002]

SUMMARY OF THE INVENTION Polypropylene resins are widely used for industrial materials such as automobiles and home appliances, and for general goods such as various containers and daily necessities. It is common practice to add talc as a means for improving its elastic modulus and heat resistance. On the other hand, as a means for improving the elastic modulus, there is a method of adding a crystal nucleating agent. Therefore, both are used together (Japanese Patent Publication No. 59-174)
No. 1).

[0003] However, talc easily adsorbs a nucleating agent, and the adsorbed nucleating agent cannot exert its function sufficiently. Therefore, a nucleating agent must be added more than necessary. However, in some cases, if a large amount of a crystal nucleating agent is added, the impact resistance of the resin may be reduced.

An object of the present invention is to provide a polypropylene resin composition containing talc and a crystal nucleating agent, in which the function of the added crystal nucleating agent is sufficiently exhibited, and the elastic modulus and heat resistance of the composition are effectively improved. Aim.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on a polypropylene resin composition containing talc, and as a result, when a specific nucleating agent and ethylenediaminetetraacetic acid are combined and compounded, The present inventors have found that adsorption of a crystal nucleating agent by talc can be suppressed, and thus a resin composition having a high flexural modulus and excellent impact resistance and heat resistance can be obtained.

That is, the present invention relates to (A) 40 to 99 parts by weight of a polypropylene resin, (B) 1 to 60 parts by weight of talc, and (A) and (B) a total of 100 parts by weight.
(C) The following formula (I):

[0007]

Embedded image (In the formula, R ¹ represents a direct bond, is sulfur atom or an alkylene or alkylidene group having 1 to 9 carbon atoms; R ²
And R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; M is a metal atom having 1 to 3 valences; n is a valence of M) or (II):

[0008]

Embedded image (In the above formula, R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; M ′ is a 1 to 3 valent metal atom; n ′
Is a valence of M '), and 0.01 to 3 parts by weight of a phosphate crystal nucleating agent represented by the formula (D) and 0.01 to 1 part by weight of ethylenediaminetetraacetic acid (D).

Preferred embodiments of the present invention are described below. (A) For a total of 100 parts by weight of (A) and (B),
(C) The above resin composition containing 0.02 to 1 part by weight of a crystal nucleating agent. (B) For a total of 100 parts by weight of (A) and (B),
(D) Any one of the above resin compositions containing 0.05 to 0.5 parts by weight of ethylenediaminetetraacetic acid. (C) Any one of the above resin compositions containing (B) 30 to 5 parts by weight with respect to (A) 70 to 95 parts by weight. (D) The (C) crystal nucleating agent is a phosphate compound represented by the above formula (I), R ¹ is an alkylene or alkylidene group having 1 to 4 carbon atoms, R ² is a hydrogen atom, and R Any of the preceding resin compositions wherein ³ is a t-butyl group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The polypropylene resin (A) used in the present invention is not particularly limited, and any known polypropylene resin can be used. Examples of the polypropylene resin include homopolypropylene, copolymers of propylene and α-olefins (including block copolymers and random copolymers), and the like. Preferably, impact-resistant propylene copolymer (ICP) For example, a propylene-ethylene block copolymer can be mentioned. In the case of a copolymer, the amount of the copolymer component with propylene is adjusted so that the elastic modulus does not decrease significantly.
Desirable is 50% by weight or less. The method for producing the polypropylene resin is not particularly limited. The melt flow rate (MFR) of the polypropylene-based resin is preferably higher than 0.01, more preferably higher than 0.1 in order not to lower the moldability. Further, in order not to lower the impact resistance and ductility, it is preferably less than 1000, more preferably less than 300. The MFR is ASTM
Measured at 230 ° C. under a load of 2160 g according to D1238.

As the component (A) polypropylene resin, a part of the above polypropylene resin (preferably 50% by weight or less of the polypropylene resin) may be a rubbery polymer such as ethylene-propylene rubber (EPR), Ethylene-butylene rubber (EBR), styrene-ethylene-
It can be replaced by butylene-styrene rubber (SEBS) or the like.

The talc (B) used in the present invention is:
The particle size and the like are not particularly limited. Also, talc is
Surface treatment may be performed.

When performing a surface treatment, an organic silane or titanium coupling agent, various surfactants, silicone oil, various silane compounds, metal soap, higher alcohol, polymerizable monomer, polyolefin, unsaturated carboxylic acid modified Polyolefin or the like can be used.
In particular, various silane compounds, such as a silane coupling agent and silicone oil, which have a high effect of suppressing the aggregation of talc and improving the dispersion in the composition, are preferable.

[0014] (B) 1 to 60 parts by weight of talc is blended with 40 to 99 parts by weight of the polypropylene resin. Preferably, (A) 70 to 95 parts by weight and (B) 5 to 30 parts by weight. If the amount of talc is too small, the flexural modulus and heat resistance of the polypropylene resin cannot be improved, and if it is too large, the impact resistance decreases.

The (C) crystal nucleating agent used in the present invention is a phosphate compound represented by the above formula (I) or (II).

In the above formula (I) or (II), the alkyl group having 1 to 8 carbon atoms may be linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl, sec. -Butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, te
rt-hexyl group, heptyl group, octyl group, tert-octyl group and the like. The alkylene group having 1 to 9 carbon atoms may be linear or branched, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group,
Pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene and the like. Examples of the alkylidene group having 1 to 9 carbon atoms include a methylene group,
Ethylidene group, propylidene group, isopropylidene group,
Butylidene group, isobutylidene group, sec-butylidene group,
and a t-octylmethylene group. Preferably, it is selected from a methylene group, an ethylidene group, a propylidene group and a butylidene group. Examples of the trivalent metal M or M ′ include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, boron, aluminum, gallium, indium, thallium, copper, Zinc and the like.

Preferred examples of the phosphate crystal nucleating agent represented by the above formula (I) include, for example, sodium-2,2'-
Methylene-bis- (4,6-di-tert-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4,6-
Di-tert-butylphenyl) phosphate, lithium-2,
2'-methylene-bis- (4,6-di-tert-butylphenyl)
Phosphate, lithium-2,2'-ethylidene-bis- (4,6
-Di-tert-butylphenyl) phosphate, sodium
-2,2'-Ethylidene-bis- (4-isopropyl-6-tert-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4-methyl-6-tert-butylphenyl) phosphate, lithium -2,2'-Methylene-bis- (4-ethyl-6-t
ert-butylphenyl) phosphate, calcium-bis- [2,2'-thiobis- (4-methyl-6-tert-butylphenyl) phosphate], calcium-bis- [2,2'-thiobis- (4-ethyl -6-tert-butylphenyl) phosphate], calcium-bis- [2,2'-thiobis- (4,6-di-t
ert-butylphenyl) phosphate], magnesium-
Bis- [2,2′-thiobis- (4,6-di-tert-butylphenyl) phosphate], magnesium-bis- [2,2′-thiobis- (4-tert-octylphenyl) phosphate],
Sodium-2,2'-butylidene-bis- (4,6-dimethylphenyl) phosphate, sodium-2,2'-butylidene-
Bis- (4,6-di-tert-butylphenyl) phosphate,
Sodium-2,2'-tert-octylmethylene-bis- (4,6
-Dimethylphenyl) phosphate, sodium-2,2'-
tert-octylmethylene-bis- (4,6-di-tert-butylphenyl) phosphate, calcium-bis- [2,2'-
Methylene-bis- (4,6-di-tert-butylphenyl) phosphate], magnesium-bis- [2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate], barium- Bis- [2,2'-methylene-bis- (4,6-di-ter
t-butylphenyl) phosphate], sodium-2,2'-
Methylene-bis- (4-methyl-6-tert-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis- (4-
Ethyl-6-tert-butylphenyl) phosphate, sodium (4,4'-dimethyl-6,6'-di-tert-butyl-2,2'-biphenyl) phosphate, calcium-bis-[(4,4 '-Dimethyl-6,6'-di-tert-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis- (4-sec-
Butyl-6-tert-butylphenyl) phosphate, sodium-2,2'-methylene-bis- (4,6-dimethylphenyl)
Phosphate, sodium-2,2'-methylene-bis- (4,6
-Diethylphenyl) phosphate, potassium-2,2'-ethylidene-bis- (4,6-di-tert-butylphenyl) phosphate, calcium-bis- [2,2'-ethylidene-bis- (4,6- Di-tert-butylphenyl) phosphate], magnesium-bis- [2,2'-ethylidene-bis- (4,6-di
-tert-butylphenyl) phosphate], barium-bis- [2,2′-ethylidene-bis- (4,6-di-tert-butylphenyl) phosphate], aluminum-tris- [2,
2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate], aluminum-tris- [2,2'-ethylidene-bis- (4,6-di-tert-butylphenyl) phosphate] And the like. Of these, especially sodium
2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate is preferred.

Preferred examples of the phosphate crystal nucleating agent represented by the above formula (II) include sodium-bis- (4-tert-butylphenyl) phosphate, sodium-bis- (4-methylphenyl) phosphate, sodium -Bis- (4-ethylphenyl) phosphate, sodium-bis- (4-isopropylphenyl) phosphate, sodium-bis- (4-tert-octylphenyl) phosphate, lithium-bis- (4-tert-butylphenyl) phosphate , Potassium-bis- (4-tert-butylphenyl) phosphate, calcium-bis- [bis (4-t
ert-butylphenyl) phosphate], magnesium-
Bis- [bis (4-tert-butylphenyl) phosphate], aluminum-tris- [bis (4-tert-butylphenyl) phosphate] and the like.

As the crystal nucleating agent (C), the above-mentioned phosphate compounds can be used alone or in combination of two or more.

(C) The crystal nucleating agent is 0.01 part by weight or more, preferably 0.1 part by weight, based on 100 parts by weight of the total of (A) and (B).
It is added in an amount of 02 parts by weight or more and 3 parts by weight or less, preferably 1 part by weight or less. (C) If the amount of the crystal nucleating agent is too small, the effect as the crystal nucleating agent cannot be obtained, and a high elastic modulus cannot be obtained. On the other hand, if the amount is too large, the impact resistance decreases.

(D) Ethylenediaminetetraacetic acid (hereinafter sometimes abbreviated as EDTA) used in the present invention comprises:
0.01 parts by weight or more, preferably 0.05 parts by weight or more, and 1 part by weight or less, preferably 0.5 part by weight or less, based on 100 parts by weight of the total of (A) and (B). (D) If the amount of ethylenediaminetetraacetic acid is too small, the adsorption of the nucleating agent by talc cannot be suppressed, so that the elastic modulus does not increase, and if it is too large, the impact resistance decreases.

The method for producing the resin composition of the present invention is not particularly limited. For example, the above components are dry-blended and then melt-kneaded. Alternatively, the components are melt-blended. As the device, for example, a known device such as a single-screw or twin-screw extruder, a Banbury mixer, a Brabender, a roll, a Henschel mixer, a ribbon blender, and a super mixer can be used. The order of blending the components is not particularly limited, and the components may be mixed at once, or the components may be added in an arbitrary order.

In addition to the above components, the resin composition of the present invention may further contain various conventional additives such as antioxidants, antistatic agents, heat stabilizers, light stabilizers, flame retardants, plasticizers, A molding agent, a foaming agent, a pigment, a dye, and the like can be blended.

[0024]

In the present invention, a phosphate crystal nucleating agent having a specific structure and a small amount of EDTA are combined with a resin composition obtained by mixing talc with a polypropylene resin. Then, the adsorption of the crystal nucleating agent to talc, which has been a problem in the past, is suppressed, so that the function of the added crystal nucleating agent can be sufficiently exhibited, and the elastic modulus and heat resistance of the composition can be effectively improved. I could improve. This is presumed to be because the affinity between the crystal nucleating agent and EDTA was good, so that the crystal nucleating agent was less likely to be adsorbed by talc and could be sufficiently dispersed in the polypropylene resin.

[0025]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following Examples and Comparative Examples, the melt kneading was performed using a twin-screw kneader (TEX30 type, manufactured by Japan Steel Works, φ30 mm,
L / D = 42), kneading temperature 200 ° C., rotation speed 300 rp
m.

Various physical properties were measured as follows. (i) Flexural modulus: measured according to ASTM D790. (ii) Izod impact strength: according to ASTM D256
At 23 ° C., the notched Izod impact strength was measured. (iii) Rockwell hardness (R hardness): ASTM D78
5 was measured. (iv) Heat distortion temperature: Measured according to ASTM D648. (v) Melt flow rate (MFR): ASTM D12
According to No. 38, it was measured at 230 ° C. under a load of 2160 g.

Example 1 The following components were dry-blended at the ratios shown in Table 1, melt-kneaded, and pelletized. (A) PP1: Homopolypropylene (manufactured by Tonen Chemical Co., Ltd.
(HJ240, MFR = 40 g / 10 min) (B) Talc: not surface-treated (LMS100, manufactured by Fuji Talc Co., Ltd.) (C) Crystal nucleating agent: sodium-2,2'-methylene-bis- (4 , 6
-Di-tert-butylphenyl) phosphate (ADK STAB NA-11, manufactured by Asahi Denka Co., Ltd.) (D) EDTA: ethylenediaminetetraacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) A test piece was injection-molded, and physical properties were measured using this. Table 1 shows the results.

Comparative Example 1 Pellets were produced in the same manner as in Example 1 except that EDTA was not blended, and a test piece was prepared therefrom and subjected to a physical property test. Table 1 shows the results.

Example 2 Pellets were produced in the same manner as in Example 1 except that PP2 (homopolypropylene, manufactured by Tonen Chemical Co., Ltd., HJ220, MFR = 20 g / 10 min) was used instead of PP1.
From this, a test piece was prepared and subjected to a physical property test. Table 1 shows the results.

Comparative Example 2 Pellets were produced in the same manner as in Example 2 except that EDTA was not blended, and a test piece was prepared therefrom and subjected to a physical property test. Table 1 shows the results.

Comparative Example 3 Pellets were produced in the same manner as in Comparative Example 2 except that the amount of the crystal nucleating agent was changed to the ratio shown in Table 1, and a test piece was prepared therefrom and subjected to a physical property test. Table 1 shows the results. Comparative Example 4 Instead of talc, a surface-treated talc (prepared by treating with 1 part by weight of a silazane-modified polysiloxane per 100 parts by weight of talc used in Example 1) and using ED
Pellets were produced in the same manner as in Example 2 except that TA was not used, and a test piece was prepared therefrom and subjected to a physical property test. Table 1 shows the results.

Comparative Example 5 Pellets were produced in the same manner as in Example 2 except that no crystal nucleating agent was used, and a test piece was prepared therefrom and subjected to a physical property test. Table 1 shows the results.

[0033]

[Table 1] Example 3 Example 1 was repeated except that ICP (impact propylene copolymer) (propylene-ethylene block copolymer, manufactured by Tonen Chemical Co., Ltd., BJ730K, MFR = 30 g / 10 min) was used instead of PP1. Produce pellets in the same manner as 1
From this, a test piece was prepared and subjected to a physical property test. Table 2 shows the results.

Comparative Example 6 Pellets were produced in the same manner as in Example 3 except that EDTA was not blended, and a test piece was prepared therefrom and subjected to a physical property test. Table 2 shows the results.

Example 4 Pellets were produced in the same manner as in Example 2 except that part of the polypropylene resin was replaced with EPR (EP961SP, manufactured by Nippon Synthetic Rubber Co., Ltd., MFR = 0.8 g / 10 min). From this, a test piece was prepared and subjected to a physical property test. Table 2 shows the results.

Comparative Example 7 Pellets were produced in the same manner as in Example 4 except that EDTA was not blended, and a test piece was prepared therefrom and subjected to a physical property test. Table 2 shows the results.

[0037]

[Table 2]

From Tables 1 and 2, it can be seen that even with the same amount of crystal nucleating agent, those containing EDTA can obtain higher flexural modulus than those without EDTA (Examples 1 and 2). Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 6, Example 4 and Comparative Example 7). Further, in Examples 1 and 2, impact resistance, Rockwell hardness, and heat distortion temperature are also high.

Further, in Comparative Example 3 in which three times the amount of a crystal nucleating agent was blended in order to obtain the same bending elastic modulus as in Example 2 without blending EDTA, the impact resistance was still low.

In Comparative Example 4 using talc surface-treated with silazane-modified polysiloxane, the flexural modulus was improved as compared with Comparative Example 2 (using talc without surface treatment), but EDTA was used. Therefore, both the flexural modulus and the impact resistance are inferior to those of Example 2. When only EDTA was added and no crystal nucleating agent was added (Comparative Example 5), the flexural modulus was very low and the impact resistance was low as compared with Example 2. Therefore, nucleating agent and ED
It can be seen that physical properties are not improved unless combined with TA.

[0041]

According to the present invention, in a polypropylene-based resin composition containing talc and a nucleating agent, the amount of a nucleating agent adsorbed on talc can be reduced. In addition, the effect of improving the flexural modulus and heat resistance of the composition and the effect of preventing a decrease in impact resistance can be achieved.

Claims (1)

[Claims] (1) 40 to 99 parts by weight of a polypropylene resin, (B) 1 to 60 parts by weight of talc, and (A) and (B) a total of 100 parts by weight, I): embedded image (In the formula, R ¹ represents a direct bond, is sulfur atom or an alkylene or alkylidene group having 1 to 9 carbon atoms; R ²
And R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; M is a metal atom having 1 to 3 valences; n is a valence of M) or (II): Formula 2 (In the above formula, R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; M ′ is a 1 to 3 valent metal atom; n ′
Is a valence of M '), and 0.01 to 3 parts by weight of a phosphate crystal nucleating agent represented by the formula (D) and 0.01 to 1 part by weight of ethylenediaminetetraacetic acid.