JP3388070B2 - Propylene polymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene polymer composition, and more specifically, to obtain a molded product having a high crystallization rate, excellent rigidity, and excellent balance between rigidity and impact resistance. Propylene-based polymer composition.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene polymers such as propylene polymers and propylene block copolymers have excellent processability, chemical resistance, electrical properties, mechanical properties, etc. It is processed into products, hollow molded products, films, sheets, fibers, etc. and used for various purposes. However, depending on the application, the rigidity, heat resistance and transparency may not be sufficient.

It is known that in order to improve the rigidity, heat resistance rigidity and transparency of a molded product made of such a propylene-based polymer, fine crystals can be rapidly produced during the molding process. Therefore, conventionally, various crystal nucleating agents have been used to accelerate the crystallization rate of propylene-based polymers.

However, the conventional crystal nucleating agent is not always sufficient in improving the crystallization rate, and the mechanical properties such as rigidity and balance between rigidity and impact resistance of the resulting molded article are not always satisfactory. It was

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a molded product having a high crystallization rate, excellent rigidity, and excellent balance between rigidity and impact resistance. The object is to provide such a propylene-based polymer composition.

[0006]

SUMMARY OF THE INVENTION The propylene polymer composition according to the present invention comprises (A) a propylene polymer; 100 parts by weight; and (B) a crystal nucleating agent comprising a partial metal salt of rosin acid;
And 1 to 5 parts by weight, (C) fine powder talc; and 5-40 parts by weight, (D) an elastomer; or consisting of 0 to 80 parts by weight, or
Others (A) propylene-based polymer; and 100 parts by weight of the crystal nucleating agent consisting of (B) a rosin acid partial metal salts; 0.00
1 to 5 parts by weight, (C) fine powder talc; 0 to 100 parts by weight, and (D) elastomer; 5 to 40 parts by weight, or
Others (A) propylene-based polymer; and 100 parts by weight of the crystal nucleating agent consisting of (B) a rosin acid partial metal salts; 0.00
1 to 5 parts by weight, (C) fine powder talc; 5 to 40 parts by weight, and (D) elastomer; 5 to 40 parts by weight .

In the present invention, the propylene polymer (A) is preferably a propylene block copolymer satisfying the following (1) to (4). (1) 230 ° C. according to ASTM D1238, 2.
The melt flow rate measured under a load of 16 kg is in the range of 0.1 to 500 g / 10 min. (2) The crystalline polypropylene part is ASTM D123.
8, the melt flow rate measured under the conditions of 230 ° C. and 2.16 kg load is in the range of 1 to 500 g / 10 min, and the pentad isotacticity is 0.9.
(4) 23 ° C n-decane-soluble component containing 3 to 13% by weight of (3) 23 ° C n-decane-soluble component of 7 or more has an intrinsic viscosity measured in 135 ° C decalin. [eta]] is in the range of 4 to 12 dl / g, and the structural unit derived from ethylene is 30 to 60.
It is contained at a ratio of mol%.

In the present invention, the crystal nucleating agent (B) is at least one selected from rosin acid partial sodium salt, rosin acid partial potassium salt and rosin acid partial magnesium salt.
Desirably a partial metal salt of rosin acid.

The crystal nucleating agent (B) is preferably a partial metal salt of at least one rosin acid selected from natural rosin, modified rosin and purified products thereof, and the partial metal salt of rosin acid is , Dehydroabietic acid, dihydroabietic acid, dihydropimaric acid, and derivatives thereof, and more preferably, a partial metal salt of at least one rosin acid, the crystal nucleating agent (B) is represented by the following formula (Ia) rosin Particularly preferred is at least one partial metal salt of rosin acid selected from partial metal salts of acids and partial metal salts of rosin acids represented by the following formula (Ib).

[0010]

[Chemical 2]

(Where R¹, R²And R³Are each other
The same or different, a hydrogen atom, an alkyl group,
Indicates a cycloalkyl group or an aryl group). The formula
In (Ia) and (Ib), R¹Is isopropyl
R group, R ²And R³Desired to be a methyl group
Good

The propylene-based polymer composition of the present invention provides a molded product having a high crystallization rate, excellent rigidity, and a good balance between rigidity and impact resistance. Such a propylene polymer composition is suitably used as a raw material for a wide range of applications from household products to industrial products, for example, food containers, electric parts, electronic parts, automobile parts, machine mechanism parts and the like.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention will be specifically described below. The propylene-based polymer composition according to the present invention comprises (A) a propylene-based polymer and (B) a crystal nucleating agent comprising a partial metal salt of rosin acid.
It is formed of (C) fine powder talc and (D) elastomer.

First, (A) a propylene polymer, (B)
The crystal nucleating agent, (C) fine powder talc and (D) elastomer will be described. (A) Propylene-based polymer The propylene-based polymer used in the present invention is a propylene homopolymer and a propylene block copolymer.

The propylene homopolymer, which is one of the preferred embodiments of the propylene-based polymer, is ASTM D12.
38, the melt flow rate (MFR) measured under the conditions of 230 ° C. and 2.16 kg load is 0.1 to 5
00g / 10 minutes, preferably 1 to 300 g / 10 minutes, particularly preferably 10 to 100 g / 10 minutes, and a density of 0.900 to 0.936 g / cm ³ , preferably 0.910. It is desirable to be in the range of 0.936 g / cm ³ , and the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.1 to 30 dl / g, preferably 0.3 to 10 dl / g, particularly Preferably 0.5-5d
It is desirable to be in the range of 1 / g, and the amount of the 23 ° C. decane-soluble component is 3.0% or less, preferably 2.5% or less, more preferably 2.0% or less, particularly preferably 1.5%. The following is desirable.

Such a propylene homopolymer is a ¹³ C
The value of pentad isotacticity (I ₅ ) determined by NMR method is 0.970 or more, preferably 0.980 or more, and more preferably 0.982 or more.

The crystallinity of the propylene homopolymer is preferably 60% or more, preferably 65% or more, more preferably 70% or more. The crystallinity is measured as follows. That is, the sample was molded into a square plate having a thickness of 1 mm by a pressure molding machine at 180 ° C. and immediately cooled with water, and the press sheet was used, and measured using a rotor flex RU300 measuring device manufactured by Rigaku Denki Co., Ltd. (Output 50 kV, 250 mA).
As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

Another embodiment of the propylene block copolymer which can be used in the present invention is 0 to 20 mol% of a structural unit derived from ethylene and / or an olefin having 4 to 10 carbon atoms, and propylene. A crystalline polypropylene part consisting of a structural unit having 2 to 2 carbon atoms
It is a block copolymer composed of a low crystalline copolymer part or an amorphous copolymer part containing two or more constituent units derived from 0 olefin.

The propylene block copolymer contains a constitutional unit derived from propylene in an amount of 50 to 98 mol%, preferably 60 to 97 mol%, and comprises ethylene and / or an olefin having 4 to 20 carbon atoms. It is desirable that the derived structural unit is contained in an amount of 50 to 2 mol%, preferably 40 to 3 mol%.

Specific examples of the olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene,
3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene,
5-ethyl-2-norbornene, tetracyclododecene, 2-
Examples thereof include ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. 4 to 2 carbon atoms
Two or more constituent units derived from 0 olefin or ethylene may be contained.

Such a propylene block copolymer has a temperature of 230 ° C. according to ASTM D1238, 2.
MFR measured under 16kg load is 0.1-50
0 g / 10 minutes, preferably 1 to 300 g / 10 minutes, particularly preferably 10 to 100 g / 10 minutes, and a density of 0.890 to 0.936 g / cm ³ , preferably 0.895 to It is desirable to be in the range of 0.936 g / cm ³ , and the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 0.1 to 30 dl / g, preferably 0.3 to 10 dl / g, particularly Preferably 0.5-8
Desirably, it is in the range of dl / g, and the amount of the decane-soluble component at 23 ° C. is 50% or less, preferably 30% or less, more preferably 20% or less, and particularly preferably 15% or less.

This propylene block copolymer has an MFR of the crystalline polypropylene part of 0.1 to 3000 g /
10 minutes, preferably 1 to 500 g / 10 min, more preferably preferably in the range of 10 to 100 g / 10 min, pentad isotacticity as determined by ¹³ C-NMR method of the crystalline polypropylene portion (I ₅ ) Is 0.970 or more, preferably 0.980 or more, and the crystallinity of the crystalline polypropylene part is 6 or more.
0% or more, preferably 65% or more, more preferably 68
% Or more is desirable.

The propylene block copolymer has 2
The intrinsic viscosity [η] measured in decalin at 135 ° C of 3 ° C n-decane soluble component (low crystalline copolymer part or amorphous copolymer part) is usually 1.0 to 20 dl / g. , Preferably in the range of 4 to 12 dl / g,
It is desirable that the structural unit derived from ethylene in the n-decane-soluble component at 30 ° C. is 30 to 60 mol%, preferably 35 to 45 mol%.

Among the propylene block copolymers mentioned above, propylene block copolymers satisfying the following (1) to (4) are particularly preferable. (1) MFR is 0.1 to 500 g / 10 minutes, preferably 1
The crystalline polypropylene part (2) in the range of up to 300 g / 10 min has an MFR of 1 to 500.
g / 10 min, preferably 10 to 100 g / 10 min, and the pentad isotacticity (I ₅ ) is 0.
97 or more, preferably 0.98 or more (3) 23 ° C n-decane soluble component is contained in a proportion of 3 to 13% by weight, preferably 4 to 10% by weight (4) 23 ° C n-decane is acceptable The soluble component has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 4 to 12 dl / g, preferably 5 to 8 dl / g, and a structural unit derived from ethylene of 30 to 60 mol%. Preferably 35
It is contained at a rate of 45%.

Here, the 23 ° C. n-decane-soluble component was dissolved by dipping 5 g of the sample in 200 cc of boiling n-decane for 5 hours and then cooling to room temperature, and the precipitated solid phase was filtered with a G4 glass filter. It is a value calculated back from the solid-phase weight measured after drying after filtration with.

The composition of the propylene-based polymer can be determined by measuring it by a conventional method such as infrared spectroscopy or NMR. The pentad isotacticity (I ₅ ) is measured by the method proposed by A. Zambelli et al. In Macromolecules 6 , 925 (1973), that is, the ¹³ C-NMR method (nuclear magnetic resonance method). It is an isotactic fraction in a pentad unit in a polypropylene molecular chain, and is a fraction of a propylene monomer unit in which five propylene units are isotactically bonded in succession.

Assignment of peaks in the above-mentioned NMR measurement is carried out based on the description in Macromolecules 8 , 687 (1975). ¹³ C-NMR is a Fourier transform NMR [5
00MHz (at the time of hydrogen nucleus measurement)] device, frequency 1
By performing integrated measurement at 20,000 times at 25 MHz, it is possible to improve the signal detection limit to 0.001 and perform measurement.

The above-mentioned propylene homopolymer and propylene block copolymer are the 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene and 3-methyl-1-butene.
It contains a homopolymer or copolymer such as hexene, 3,5,5-trimethyl-1-hexene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane as a prepolymer formed by prepolymerization, for example. Preferably, when such a homopolymer or copolymer is contained, the crystallization rate is high.

The above-mentioned propylene homopolymer and propylene block copolymer can be produced by various methods, for example, using a stereoregular catalyst. Specifically, it can be produced using a catalyst formed from a solid titanium catalyst component, an organometallic compound catalyst component, and optionally an electron donor.

Specific examples of the solid titanium catalyst component include titanium trichloride or a titanium trichloride composition supported on a carrier having a specific surface area of 100 m ² / g or more, or magnesium, A solid titanium catalyst component having halogen, an electron donor (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether) and titanium as essential components, which are supported on a carrier having a specific surface area of 100 m ² / g or more. Is mentioned. Of these, the latter solid titanium catalyst component is particularly preferable.

The organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halides, alkylaluminum sesquihalides, and alkylaluminum dihalides. The organoaluminum compound can be appropriately selected according to the type of titanium catalyst component used.

As the electron donor, an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom or the like can be used, and an ester compound and an ether compound having the above-mentioned atoms are preferable. Is mentioned.

Such a catalyst may be further activated by a method such as co-pulverization, or the above olefin may be prepolymerized. (B) Crystal Nucleating Agent The crystal nucleating agent (B) is composed of a rosin acid partial metal salt.

In the present specification, the rosin acid partial metal salt is a reaction product of rosin acid and a metal compound, and includes a mixture of the rosin acid metal salt and unreacted rosin acid and unreacted rosin acid. It means both metal salts of rosin acid not containing.

Examples of the metal compound which reacts with rosin acid to form a metal salt include compounds having a metal element such as sodium, potassium and magnesium and forming a salt with the above rosin acid. Examples thereof include chlorides, nitrates, acetates, sulfates, carbonates, oxides, and hydroxides of the above metals.

As rosin acid, natural rosin such as gum rosin, tall oil rosin and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α,
Examples include various modified rosins such as rosin modified with β-ethylenically unsaturated carboxylic acid; purified products of the natural rosin and purified products of the modified rosin.

Natural rosin includes resin acids such as pimaric acid, sandaracopimaric acid, parastophosphoric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid and tetrahydroabietic acid. , Usually multiple species are included.

Examples of the unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, and citraconic acid. , Acrylic acid, methacrylic acid and the like.

Among the above rosin acids, disproportionated rosin,
It is preferably at least one rosin acid selected from hydrogenated rosin and dehydrogenated rosin, and at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid, dihydropimaric acid and derivatives thereof. More preferable.

Examples of the partial metal salt of rosin acid include the partial sodium salt of rosin acid, the partial potassium salt of rosin acid and the partial magnesium salt of rosin acid.

In the present invention, the following formula (I
It is particularly preferable to use the compound [compound (Ia)] represented by a) or the compound [compound (Ib)] represented by the following formula (Ib).

[0042]

[Chemical 3]

In the formulas (Ia) and (Ib), R ¹ and R
² and R ³ may be the same or different from each other,
It is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,
Examples include tert-butyl, pentyl, heptyl, octyl, and other alkyl groups having 1 to 8 carbon atoms, and these groups may have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, or a halogen. .

Specific examples of the cycloalkyl group include cycloalkyl groups having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and cycloheptyl. These groups include hydroxyl group, carboxyl group, alkoxy group and halogen. It may have a substituent.

Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group. These groups include a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group and a halogen group. May have.

Among such compounds (Ia) and (Ib), compounds in which R ¹ , R ² and R ³ are the same or different alkyl groups are preferable, and R ¹ is an i-propyl group. , R ² and R ³ are more preferably methyl groups. The partial metal salt of such a compound is particularly excellent in the effect of improving the crystallization rate of the crystalline resin.

Specific examples of the compound (Ia) include dehydroabietic acid, and specific examples of the compound represented by the compound (Ib) include dihydroabietic acid.

Among such compounds (Ia) and (Ib), dehydroabietic acid represented by the formula (Ia) is, for example, disproportionation or dehydration of natural rosin such as gum rosin, tall oil rosin and wood rosin. Obtained by nitration and subsequent purification.

Examples of the metal salt of the compound (Ia) include compounds represented by the following formula (IIa) [compound (IIa)], and examples of the metal salt of the compound (Ib) include the following formula (IIb). The compound [compound (IIb)] represented by is mentioned.

[0051]

[Chemical 4]

In the formulas (IIa) and (IIb), R ¹ and R ²
And R ³ are the same as those in the formulas (Ia) and (Ib). M is a monovalent metal ion such as lithium, sodium, potassium, rubidium and cesium; and divalent metal such as beryllium, magnesium, calcium, strontium, barium and zinc. Metal ions; trivalent metal ions such as aluminum. Of these, monovalent or divalent metal ions are preferable, and sodium ions, potassium ions, and magnesium ions are more preferable.

N is the same integer as the valence of the metal ion M, and is an integer of 1 to 3. A compound (IIa) and a compound (IIb), wherein R ¹ , R ² and R ³ are the same or different alkyl groups,
Alternatively, a compound in which M is a monovalent or divalent metal ion is preferable, a compound in which R ¹ is an i-propyl group, R ² and R ³ are methyl groups, or a compound in which M is a sodium ion, a potassium ion or A compound which is a magnesium ion is more preferable, a compound in which R ¹ is an i-propyl group, R ² and R ³ are methyl groups, and M is a sodium ion, a potassium ion or a magnesium ion is particularly preferable. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of the compound (IIa) include lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, zinc dehydroabietic acid, and dehydro. Examples thereof include metal salts of dehydroabietic acid such as aluminum abietic acid, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferably used.

Specific examples of the compound (IIb) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, zinc dihydroabietic acid, and dihydro. Examples thereof include metal salts of dihydroabietic acid such as aluminum abietic acid, and sodium dihydroabietic acid, potassium dihydroabietic acid, and magnesium dihydroabietic acid are preferably used.

The rosin acid partial metal salt as described above can be produced by reacting the rosin acid with the metal compound by a conventionally known method. (C) Fine powder talc As the fine powder talc, a conventionally known one used as a modifier such as polyolefin can be used.

In the present invention, as the fine powder talc, fine powder talc having an average particle size in the range of 0.5 to 20 μm and a ratio of aspect ratio to aspect ratio of 2 or more, preferably 10 or more. Is preferred.

The fine powder talc preferably contains 5% by weight or less of particles having a particle diameter of 5 μm or more. (D) Elastomer Examples of elastomers include olefin-based elastomers and styrene-based thermoplastic elastomers.

The olefin elastomer is an elastomer obtained by copolymerizing at least two olefins selected from α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene and 1-pentene, or Examples thereof include an elastomer obtained by copolymerizing these with a diene.

As the diene, 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6
Chain non-conjugated dienes such as -methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-
Vinyl norbornene, 5-ethylidene-2-norbornene, 5
Cyclic non-conjugated dienes such as -methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2 Examples include diene compounds such as -ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

Specific examples of such olefinic elastomers include ethylene / propylene copolymer elastomers, ethylene / 1-butene copolymer elastomers,
Ethylene / propylene / 1-butene copolymer elastomer, ethylene / propylene / non-conjugated diene copolymer elastomer, ethylene / 1-butene-non-conjugated diene copolymer elastomer, ethylene / propylene / 1-butene-non-conjugated diene copolymer An amorphous elastic copolymer having an olefin as a main component such as a polymer elastomer can be mentioned.

MF of the above olefin elastomer measured at 230 ° C. under a load of 2.16 kg
R is 0.01 to 50 g / 10 minutes, preferably 0.01 to
It is desirable to be in the range of 10 g / 10 minutes, and more preferably 0.01 to 5 g / 10 minutes.

The iodine value (unsaturation) of the olefin elastomer is preferably 16 or less. Examples of the styrene-based thermoplastic elastomer include a block copolymer of a styrene-based compound and a conjugated diene compound.

Examples of the styrene compound include styrene, α-methylstyrene, p-methylstyrene, alkylstyrene such as pt-butylstyrene, p-methoxystyrene, vinylnaphthalene and the like. Of these, styrene is preferable.

As the conjugated diene compound, butadiene,
Isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-
Examples include diethyl-1,3-octadiene. Of these, butadiene and isoprene are preferable.

These compounds may be used in combination of two or more kinds. In the styrene-based thermoplastic elastomer, the weight ratio of the unit derived from the styrene compound to the unit derived from the conjugated diene compound is 10/90 to 6
5/35 is preferable, and 20/80 to 50/5
It is more preferably 0.

The molecular structure of the styrene thermoplastic elastomer may be linear, branched, radial, or a combination thereof. Specific examples of such styrene-based thermoplastic elastomers include styrene / butadiene diblock copolymers, styrene / butadiene / styrene triblock copolymers, styrene / isoprene diblock copolymers, styrene / isoprene /
Styrene triblock copolymer, hydrogenated styrene / butadiene diblock copolymer, hydrogenated styrene / butadiene / styrene triblock copolymer, hydrogenated styrene / isoprene diblock copolymer, styrene / A hydrogenated product of an isoprene / styrene triblock copolymer can be mentioned.

The styrene thermoplastic elastomer used in the present invention preferably has an MFR measured at 230 ° C. under a load of 2.16 kg of 1 to 100 g / 10 minutes. Among these elastomers, hydrogenated products of styrene / butadiene diblock copolymers, hydrogenated products of styrene / butadiene / styrene triblock copolymers, hydrogenated products of styrene / isoprene diblock copolymers, styrene / butadiene Hydrogenated products of isoprene / styrene triblock copolymers are particularly preferred.

Propylene Polymer Composition The propylene polymer composition according to the present invention comprises a crystal nucleating agent consisting of 100 parts by weight of (A) propylene polymer and (B) partial metal salt of rosin acid; 001 to 5 parts by weight, preferably 0.05 to 5 parts by weight, and (C) fine powder talc; 0
To 100 parts by weight, preferably 5 to 40 parts by weight, (D)
Elastomer; 0 to 80 parts by weight, preferably 5 to 40 parts by weight.

In the present invention, at least two rosin acid partial metal salts may be used as the crystal nucleating agent (B). The at least two rosin acid partial metal salts may include at least two rosin acid metal salts having the same rosin acid and different metals, and at least two rosin acid metal salts having different rosin acids and the same metal can be used. Two kinds may be contained, and at least two kinds of rosin acid metal salts having different rosin acids and different metals may be contained. It is preferable that the rosin acid metal salt is contained in the at least two kinds of rosin acid partial metal salts in a total amount of 5 to 100% by weight, preferably 10 to 100% by weight.

The amount ratio of the rosin metal salt in the at least two rosin acid partial metal salts is arbitrary, but one kind of rosin metal salt in the at least two rosin acid partial metal salts can be used. Of rosin acid metal salt is more than 0 mol%, preferably 5 to 95 mol%, and one or more other rosin acid metal salt is 1 mol%.
It is desirable to combine them in an amount of less than 00 mol%, preferably 95 to 5 mol%.

The combination of at least two rosin acid partial metal salts is preferably a combination of rosin acid partial potassium salt and rosin acid partial sodium salt or rosin acid partial magnesium salt. Further, potassium rosinate is 20 mol% or more, preferably 40 to 95 mol%, more preferably 45 to 80 mol%, and rosin acid based on the total amount of rosin acid metal salts in the two types of rosin acid partial metal salts. Sodium salt or magnesium rosin acid salt is less than 80 mol%, preferably 60 to 5 mol%, more preferably 55 to 55 mol%.
It is desirable to combine them in a proportion of 20 mol%.

Such a rosin acid partial metal salt containing at least two metals is superior in dispersibility in a propylene polymer as compared with a rosin acid partial metal salt containing only one kind of metal.

In the present invention, a compatibilizing agent such as higher fatty acid metal salt, rosing lysene phosphorus ester, antistatic agent, polyolefin wax and hydrogenated petroleum resin may be added. Such a compatibilizer is a propylene-based polymer 10
It is usually used in an amount of 0.01 to 5 parts by weight with respect to 0 parts by weight. When the compatibilizer is added, the crystal nucleating agent (B) can be dispersed in the propylene polymer (A) in a short kneading time.

The propylene-based polymer composition having such a composition has excellent properties inherent to the propylene-based polymer and has a high crystallization rate. Such a propylene-based polymer composition has excellent rigidity and can produce a molded product having an excellent balance between rigidity and impact resistance.

As a method for preparing the propylene-based polymer composition, any conventionally known method can be arbitrarily adopted. For example, the propylene-based polymer (A), the crystal nucleating agent (B) and, if necessary, a fine powder. A method of melt-kneading talc (C) and / or elastomer (D) using an extruder, a kneader or the like is used.

Further, the propylene polymer composition of the present invention comprises a crosslinking agent, a heat resistance stabilizer, a weather resistance stabilizer, a hydrochloric acid absorbent, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant and a release agent. Various compounding agents such as agents, inorganic fillers, pigment dispersants, pigments, dyes, natural oils, synthetic oils and waxes may be contained within the range not impairing the object of the present invention.

The propylene polymer composition of the present invention has a wide range of uses from household products to industrial products, for example, food containers, electric parts (used in vacuum cleaners, washing machines, etc.), electronic parts, automobile parts ( It is preferably used as a material for bumpers, interior materials, exterior materials, etc., mechanical mechanism parts, etc.

As the molding method, injection molding, extrusion molding,
Examples include stretch molding, blow molding, and mold stamping molding. From the propylene-based polymer composition of the present invention, from the molding method as described above, particularly a molded article having excellent transparency, a molded article having an excellent balance between transparency and rigidity, particularly a molded article having excellent rigidity, etc. Is obtained.

[0080]

Since the propylene polymer composition according to the present invention is formed from the propylene polymer, the crystal nucleating agent, the fine powder talc and / or the elastomer, the crystallization rate is high and The molded product has excellent rigidity,
Moreover, it has an excellent balance between rigidity and impact resistance.

[0081]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

The performance evaluation of the rosin acid partial metal salt and the propylene polymer composition was carried out by the following method. Crystallization rate The obtained pellets were cooled from the molten state at a constant rate (10 ° C / min) by a differential scanning calorimeter (DSC), and the crystallization exothermic peak temperature [crystallization temperature (Tc)] was measured. The crystallization rate was evaluated. The higher the effect of increasing the crystallization temperature (Tc), the faster the crystallization rate.

Flexural Modulus (FM) A test piece having a length of 126 mm, a width of 12.6 mm and a thickness of 3.2 mm was injection-molded, and in accordance with ASTM D638, 2
The flexural modulus at 3 ° C. was measured. A material having a large flexural modulus has high rigidity.

Izod impact strength (IZ) A test piece having a length of 31.5 mm, a width of 12.6 mm and a thickness of 6.4 mm was injection-molded to form a notch having a notch tip R of 0.25 mm and a depth of 1.2 mm. After putting in, ASTM D2
According to 56, the Izod impact strength at 23 ° C. was measured.

[0085]

Example 1 Propylene block polymer (temperature 230
MFR measured at ℃ and load of 2.16 kg: 19 g / 10
Min) 100 parts by weight of Irganox 1010 ^™ (manufactured by Ciba Geigy) and 0.1 parts by weight of calcium stearate, and 0.6 parts by weight of a crystal nucleating agent A shown below, and a small amount. Powder talc (average particle size;
2.0 μm) was added in an amount of 10 parts by weight, and the mixture was melt-blended with a 20 mm uniaxial extruder at a resin temperature of 220 ° C. and pelletized.

Using the pellets thus obtained, an injection molding machine (IS-55 manufactured by Toshiba Machine Co., Ltd.) was used for injection molding under the conditions of a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C. to prepare a test piece for physical property test. . Using this test piece, various physical properties were measured by the above-mentioned test methods. The results are shown in Table 1.

Crystal nucleating agent A: Partial metal salt of rosin acid represented by the following formula (III) (potassium salt content 30%) Crystal nucleating agent B: Partial metal salt of rosin acid represented by the following formula (III) ( Potassium salt content 15%, sodium salt content 15%) [Note that the above salt content means (metal equivalent) / (carboxyl group equivalent) (%)]

[0088]

[Chemical 5]

[0089]

Example 2 Pellets were produced in the same manner as in Example 1 except that the crystal nucleating agent B was used in place of the crystal nucleating agent A. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 1.

[0090]

Comparative Example 1 Pellets were produced in the same manner as in Example 1 except that the crystal nucleating agent A was not used in Example 1. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 1.

[0091]

Reference Example 1 Pellets were produced in the same manner as in Example 1 except that the crystal nucleating agent A was used in place of the crystal nucleating agent A in Gelol MD ^™ (manufactured by Shin Nippon Rika Co., Ltd.).
Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 1.
Shown in.

[0092]

Reference Example 2 Pellets were produced in the same manner as in Example 1 except that the crystal nucleating agent NA11 (manufactured by Asahi Denka Co., Ltd.) was used in place of the crystal nucleating agent A. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 1.

[0093]

[Table 1]

[0094]

Example 3 Propylene block polymer (temperature 230
MFR measured at ℃ and load of 2.16 kg: 19 g / 10
Minutes) 100 parts by weight of Irganox 1010 ^™ (manufactured by Ciba Geigy) and 0.1 parts by weight of calcium stearate, and 0.6 parts by weight of a crystal nucleating agent A shown below, and ethylene. -Propylene copolymer elastomer (propylene content; 19.5 mol%, MFR measured at a temperature of 230 ° C and a load of 2.16 kg: 0.
74 g / 10 min) was added in an amount of 20 parts by weight, and the mixture was melt-blended with a 20 mm uniaxial extruder at a resin temperature of 220 ° C. and pelletized.

Using the pellets thus obtained, in the same manner as in Example 1, test pieces for physical property tests were prepared and various physical properties were measured. The results are shown in Table 2.

[0096]

Example 4 Pellets were produced in the same manner as in Example 3 except that the crystal nucleating agent B was used in place of the crystal nucleating agent A. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 2.

[0097]

Comparative Example 2 Pellets were produced in the same manner as in Example 3 except that the crystal nucleating agent A was not used in Example 3. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 2.

[0098]

Reference Example 3 Pellets were produced in the same manner as in Example 3 except that the crystal nucleating agent A was used in place of the crystal nucleating agent A in Gelol MD ^™ (manufactured by Shin Nihon Rika Co., Ltd.).
Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 2.
Shown in.

[0099]

Reference Example 4 Pellets were produced in the same manner as in Example 3 except that the crystal nucleating agent NA11 (manufactured by Asahi Denka Co., Ltd.) was used in place of the crystal nucleating agent A. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 2.

[0100]

[Table 2]

[0101]

Example 5 Propylene block polymer (temperature 230
MFR measured at ℃ and load of 2.16 kg: 19 g / 10
Minutes) 100 parts by weight of Irganox 1010 ^™ (manufactured by Ciba Geigy) and 0.1 parts by weight of calcium stearate, and 0.6 parts by weight of a crystal nucleating agent A shown below, a fine powder. Talc (average particle size; 2.0μ
m) and ethylene-propylene copolymer elastomer (propylene content; 19.5 mol%, temperature 230 ° C., load 2.16 kg, MFR: 0.7).
4 g / 10 min) was added by 20 parts by weight, and the mixture was melt-blended with a 20 mm uniaxial extruder at a resin temperature of 220 ° C. and pelletized.

Using the pellets thus obtained, in the same manner as in Example 1, test pieces for physical property tests were prepared and various physical properties were measured. The results are shown in Table 3.

[0103]

Example 6 Pellets were produced in the same manner as in Example 5 except that the crystal nucleating agent B was used in place of the crystal nucleating agent A. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 3.

[0104]

Comparative Example 3 Pellets were produced in the same manner as in Example 5 except that the crystal nucleating agent A was not used in Example 5. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 3.

[0105]

Reference Example 5 Pellets were produced in the same manner as in Example 5 except that the crystal nucleating agent A was replaced by the crystal nucleating agent Gelol MD ^™ (manufactured by Shin Nippon Rika Co., Ltd.).
Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 3.
Shown in.

[0106]

Reference Example 6 Pellets were produced in the same manner as in Example 5, except that the crystal nucleating agent NA11 (manufactured by Asahi Denka Co., Ltd.) was used in place of the crystal nucleating agent A. Using the obtained pellets, various test pieces were prepared in the same manner as in Example 1 and various physical properties were measured. The results are shown in Table 3.

[0107]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI (C08L 23/10 53:02) (72) Inventor Toru Kasai Ishi 6-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hiroyuki Hori 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hiroshi Matsumoto Tsurumi-ku, Osaka City, Osaka Prefecture 1-9, Tsurumi Arakawa Chemical Industry Co., Ltd. (72) Inventor Masao Maeda 1-9, Tsurumi 1-chome, Tsurumi Ward, Osaka City, Osaka Prefecture Arakawa Chemical Industry Co., Ltd. (72) Inventor Natsuhara Eisuke 1-9, Tsurumi, Tsurumi-ku, Osaka-shi, Osaka (56) References JP-A-7-331081 (JP, A) JP-A-8-277366 (JP, A) Kaihei 9-71728 (JP , A) Patent 3320584 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (9)

(57) [Claims] 1. A crystal nucleating agent comprising (A) a propylene polymer; 100 parts by weight, and (B) a rosin acid partial metal salt;
1 to 5 parts by weight, (C) fine powder talc; 5 to 40 parts by weight, and (D) elastomer; 0 to 80 parts by weight, a propylene polymer composition. 2. A crystal nucleating agent comprising (A) a propylene polymer; 100 parts by weight, and (B) a rosin acid partial metal salt;
1 to 5 parts by weight, (C) fine powder talc; 0 to 100 parts by weight, and (D) elastomer; 5 to 40 parts by weight, a propylene polymer composition. 3. A crystal nucleating agent comprising (A) a propylene-based polymer; 100 parts by weight, and (B) a rosin acid partial metal salt;
A propylene-based polymer composition comprising 1 to 5 parts by weight, (C) fine powder talc; 5 to 40 parts by weight, and (D) an elastomer; 5 to 40 parts by weight. 4. The propylene-based polymer has the following (1) to
The propylene-based polymer composition according to any one of claims 1 to 3, which is a propylene block copolymer satisfying (4); (1) 230 ° C according to ASTM D1238;
The melt flow rate measured under a load of 16 kg is in the range of 0.1 to 500 g / 10 min. (2) The crystalline polypropylene part is ASTM D123.
8, the melt flow rate measured under the conditions of 230 ° C. and 2.16 kg load is in the range of 1 to 500 g / 10 min, and the pentad isotacticity is 0.9.
(4) 23 ° C n-decane-soluble component containing 3 to 13% by weight of (3) 23 ° C n-decane-soluble component of 7 or more has an intrinsic viscosity measured in 135 ° C decalin. [eta]] is in the range of 4 to 12 dl / g, and the structural unit derived from ethylene is 30 to 60.
It is contained at a ratio of mol%. Wherein said rosin acid partial metal salts is, rosin acid partial sodium salts, according to claim 1-4 is at least one rosin acid partial metallic salt selected from rosin acid moiety potassium salt and rosin acid partial magnesium salt The propylene-based polymer composition according to any one of claims. 6. The partial metal salt of rosin acid is natural rosin,
Modified rosin and propylene-based polymer composition according to any one of claims 1 to 5, at least one partial metal salt of rosin acid selected from those purified product. Wherein said rosin acid partial metal salts, dehydroabietic acid, dihydroabietic acid, claim 1-5 is at least one partial metal salt of rosin acid selected from Jihidoropimaru acid and derivatives thereof The propylene-based polymer composition described in 1. 8. The rosin acid partial metal salt has the following formula (I
a) propylene according to any one of claims 1 to 5, at least one rosin acid partial metallic salt selected from a partial metallic salt of rosin acid represented by partial metal salt, and the following formula of rosin acid (Ib) -Based polymer composition; (In the formula, R ¹ , R ² and R ^{3, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group). 9. In the formulas (Ia) and (Ib),
The propylene-based polymer composition according to claim 8 , wherein R ¹ is an isopropyl group, and R ² and R ³ are methyl groups.