JPH09296084A - Propylene polymer composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene polymer compsn. having a high rate of crystallization and improved in rigidity, rigidity under heating conditions, transparency, gloss, surface hardness, etc., by blending a propylene polymer obtd. using a metallocene catalyst with a nucleating agent. SOLUTION: A propylene polymer obtd. using a metallocene catalyst is blended with a nucleating agent. Examples of the propylene polymer include a propylene homopolymer, block copolymers obtd. using propylene as the main monomer, and random copolymers obtd. using propylene as the main monomer. Usable examples of the metallocene catalyst include catalysts comprising a metallocene compd. contg. a transition metal such as Ti, Zr or Hf and an organoaluminumoxy compd. Examples of the nucleating agent include organophosphorus nucleating agents, sorbitol nucleating agents, arom. carboxylic acid nucleating agents, high-melting polymer nucleating agents, inorg. nucleating agents, and rosin nucleating agents, which may be used either alone or in combination, and the amt. of which to be used is 0.001 to 5 pts.wt. per 100 pts.wt. propylene polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition and a molded product of a polyolefin, particularly a propylene-based polymer, obtained by polymerization using a metallocene-based catalyst containing a transition metal such as zirconium, hafnium or titanium, and more particularly to crystallization. The present invention relates to a composition having a high speed, improved rigidity, heat resistance rigidity, transparency, gloss, surface hardness, and the like, and a molded article obtained from this composition.

[0002]

2. Description of the Related Art Polyolefins, particularly propylene-based polymers, obtained by polymerization using metallocene catalysts containing transition metals such as zirconium, hafnium and titanium are
Since the catalyst is a single site, it has unique properties, and depending on each metallocene-based catalyst, it is possible to obtain a polyolefin having a target property, particularly a propylene-based polymer, such as a propylene-based polymer having a relatively narrow composition distribution or molecular weight distribution.

Polyolefins, particularly propylene polymers, obtained by using such metallocene catalysts are processed into injection molded products, hollow molded products, films, sheets, fibers and the like, depending on their properties, and used for various purposes. .
However, depending on the application, the rigidity, heat resistance rigidity, transparency, gloss, surface hardness, etc. may not be sufficient.

[0004]

An object of the present invention is to provide a polyolefin composition, especially a propylene-based polymer composition, which has a high crystallization rate and is excellent in rigidity, heat resistance rigidity, transparency, gloss, surface hardness, and the like, and The object is to provide a molded body obtained.

[0005]

The present invention provides the following polyolefin, especially propylene-based polymer compositions, and molded articles obtained from these compositions. (1) A propylene polymer composition comprising a propylene polymer (A) obtained by using a metallocene catalyst and a nucleating agent (B). (2) The propylene-based polymer composition according to the above (1), wherein the amount of the nucleating agent (B) is 0.001 to 5 parts by weight based on 100 parts by weight of the propylene-based polymer (A). (3) A molded product comprising the composition according to (1) or (2) above.

The polyolefin used in the present invention, especially the propylene polymer (A), has a metallocene catalyst which is a single site catalyst, and has 3 or more carbon atoms, particularly propylene as a main monomer, and other α-olefin as required. Alternatively, it is an α-olefin obtained by polymerizing a polyunsaturated olefin such as diene or triene, particularly a homopolymer of propylene or a copolymer having propylene as a main monomer. The structural unit derived from propylene in the propylene-based polymer (A) is 50 to 100 mol%, preferably 80 to 100 mol%, and the structural unit derived from other copolymerizable monomers is 0 to 50 mol%, preferably It is preferably 0 to 20 mol%. The property of the propylene-based polymer (A) is not particularly limited, and any of resin-like, wax-like, liquid-like etc. can be used.

As the above α-olefin, ethylene,
1-butene, 1-pentene, 3-methyl-1-butene,
Examples include 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene. As the polyunsaturated olefin,
1,3-butadiene, 1,3-pentadiene, 1,4-
Pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene, 6
-Methyl-1,6-octadiene, 7-methyl-1,6
-Octadiene, 6-ethyl-1,6-octadiene,
6-propyl-1,6-octadiene, 6-butyl-
1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-
1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-
Dienes having 4 to 20 carbon atoms such as 1,6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. Examples include compounds.

Specific examples of the propylene polymer (A) include propylene homopolymers, propylene / ethylene copolymers, propylene / butene copolymers, propylene / butene / ethylene copolymers, propylene / hexene copolymers. Examples thereof include a polymer, a propylene / 3-methyl-1-butene copolymer and a propylene-4-methyl-1-pentene copolymer. In the case of a copolymer, it may be a random copolymer or a block copolymer. The propylene-based polymer (A) may be used alone or in combination of two or more.

The propylene homopolymer used as the propylene polymer (A) in the present invention has a density of 0.88 to 0.92 g / cm ³ and an intrinsic viscosity [η] of 0.5 to 10 dl / g. , The crystallinity (by X-ray) is 40 to 80%, and the molecular weight distribution (Mw / Mn) is 1.
The thing of 5-20 is illustrated.

The block copolymer containing propylene as the main monomer used as the propylene-based polymer (A) in the present invention has a comonomer content of 0.5.
˜20 mol%, density 0.86 to 0.91 g / cm ³ ,
Intrinsic viscosity [η] is 0.5 to 10 dl / g, crystallinity (X
30-70%, molecular weight distribution (Mw / Mn)
Is 1.5 to 20.

The random copolymer mainly composed of propylene used as the propylene polymer (A) in the present invention has a comonomer content of 0.5.
˜20 mol%, density 0.86 to 0.91 g / cm ³ ,
Intrinsic viscosity [η] is 0.5 to 10 dl / g, crystallinity (X
30-70%, molecular weight distribution (Mw / Mn)
Is 1.5 to 20.

The propylene-based elastomer containing propylene as a main monomer used as the propylene-based polymer (A) in the present invention has a comonomer content of 10 to 50 mol% and a density of 0.85 to 0.90 g / c.
m ³ , intrinsic viscosity [η] of 0.5 to 10 dl / g, crystallinity (by X-ray) of 0 to 60%, molecular weight distribution (Mw / M
The thing whose n) is 1.5-20 is illustrated.

The polyolefin used in the present invention, particularly the propylene polymer (A), can be produced by a metallocene catalyst in any of multi-stage, batch, semi-batch and continuous polymerization reactions. It can be produced by a method such as a gas phase polymerization method in a state where substantially no liquid medium exists, a bulk polymerization method using an olefin itself as a liquid medium, and a slurry polymerization method using a hydrocarbon-based liquid medium inert to polymerization. preferable. Further, the metallocene catalyst may be used by supporting at least one of the components in the catalyst on an inorganic carrier such as SiO ₂ , Al ₂ O ₃ , MgO or TiO ₂ , if necessary. Further, these polymerizations may be carried out after preliminarily polymerizing with a propylene monomer.

The polymerization pressure is from normal pressure to 50 kg / cm ² (gauge pressure), and the polymerization temperature is from room temperature to 150 ° C. In the case of a multi-stage system, in the first polymerization step, in the presence of a metallocene catalyst, propylene is homopolymerized or propylene is copolymerized with ethylene and / or an olefin having 4 to 10 carbon atoms to crystallize. Of a crystalline polymer (crystalline polypropylene part), and in the second polymerization step, copolymerization of two or more kinds of monomers selected from ethylene and an olefin having 3 to 20 carbon atoms is carried out to obtain a low crystalline copolymerization weight. It is preferable to produce a polymer (low crystalline copolymer part) or an amorphous copolymer (amorphous copolymer part).

As the metallocene catalyst as a single-site catalyst used for the production of polyolefin, especially propylene polymer (A), known metallocene catalysts which have been conventionally used can be used without limitation, for example, titanium, zirconium and hafnium. Examples of the catalyst include a metallocene compound (a) having a transition metal such as the above and an organoaluminum oxy compound (b), and a catalyst including the metallocene compound (a) and an ionized ionic compound (c).

Specific examples of the metallocene compound (a) include transition metal compounds represented by the following general formula (1). ML _x (1)

In the general formula (1), M is a transition metal atom selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, and x is the valence of the transition metal.

In the general formula (1), L is a ligand that coordinates with a transition metal, and at least one of these ligands L
Is a ligand having a cyclopentadienyl skeleton, and this ligand having a cyclopentadienyl skeleton may have a substituent. As the ligand having a cyclopentadienyl skeleton, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, Alkyl- or cycloalkyl-substituted cyclopentadienyl groups such as methylhexylcyclopentadienyl group and methylbenzylcyclopentadienyl group, further indenyl groups, 4,5,6,7
-Tetrahydroindenyl group, fluorenyl group and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

The compound represented by the general formula (1) is a ligand L
When it has two or more groups having a cyclopentadienyl skeleton, the two groups having two cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, and substituted alkylenes such as isopropylidene and diphenylmethylene. It is desirable that they are bound via a substituted silylene group such as a group, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group.

As L other than the ligand having a cyclopentadienyl skeleton, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (--SO
₃ R ¹ ), a halogen atom or a hydrogen atom (wherein R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or a halogen atom or an aryl group substituted with an alkyl group), and the like. To be

The metallocene compound (a) represented by the general formula (1) is more specifically represented by the following general formula (2) when the valence of the transition metal is 4, for example. R ² _k R ³ _l R ⁴ _m R ⁵ _n M (2)

In the general formula (2), M is a transition metal similar to the general formula (1), R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ is the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the general formula (1). k is an integer of 1 or more, and k + 1 + m + n = 4.

In the present invention, a transition metal compound represented by the following general formula (3) can be used as the metallocene compound (a).

Embedded image

In the general formula (3), M represents a transition metal atom of Group IVB of the periodic table, specifically titanium, zirconium or hafnium.

In the general formula (3), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a silicon-containing group. , An oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, specifically, a halogen atom such as fluorine, chlorine, bromine, iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl,
Nonyl, dodecyl, eicosyl, norbornyl, adamantyl and other alkyl groups, vinyl, propenyl, cyclohexenyl and other alkenyl groups, benzyl, phenylethyl, phenylpropyl and other arylalkyl groups, phenyl, tolyl, dimethylphenyl, trimethylphenyl, Ethylphenyl, propylphenyl, biphenyl,
A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as naphthyl, methylnaphthyl, anthracenyl, phenanthryl; a halogenated hydrocarbon group in which the above hydrocarbon group is substituted with a halogen atom; a monohydrocarbon substitution such as methylsilyl or phenylsilyl. Dihydrocarbon-substituted silyl such as silyl, dimethylsilyl, diphenylsilyl, trimethylsilyl,
Triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl,
Silicon-containing groups such as trihydrocarbon-substituted silyls such as trinaphthylsilyl, silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether, silicon-substituted alkyl groups such as trimethylsilylmethyl, silicon-substituted aryl groups such as trimethylsilylphenyl, and hydroxy-containing groups; Oxygen-containing groups such as alkoxy groups such as methoxy, ethoxy, propoxy and butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, arylalkoxy groups such as phenylmethoxy and phenylethoxy; the oxygen of the oxygen-containing groups is sulfur. A sulfur-containing group such as a substituent substituted with an amino group; an alkyl group such as an amino group, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino Groups, nitrogen-containing groups such as arylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino and alkylarylamino groups; phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino Is.

In the general formula (3), R¹Is a hydrocarbon group
Is preferred, especially methyl, ethyl, propyl
Is preferably a hydrocarbon group having 1 to 3 carbon atoms. Ma
R ^TwoIs preferably a hydrogen atom or a hydrocarbon group, especially water.
Number of carbon atoms of elementary atom or methyl, ethyl or propyl
It is preferably a hydrocarbon group of 1 to 3.

In the general formula (3), R ³ , R ⁴ , R ⁵ and R ⁶
Are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms are shown, and two groups including R ³ among R ³ , R ⁴ , R ⁵ and R ⁶ are preferably alkyl groups. , R ³ and R ⁵ , or R ³ and R ⁶ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom, a silicon-containing group or the like. Examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ² above.

In the general formula (3), among the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , groups other than the alkyl group are preferably hydrogen atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and t.
chain alkyl groups and cyclic alkyl groups such as ert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, tolylmethyl, etc. It may include a double bond and a triple bond.

Further, in the general formula (3), two kinds of groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than the aromatic ring. .

In the general formula (3), X ¹ and X ² are each independently a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or The sulfur-containing group is shown, and specific examples thereof include the same halogen atom as R ¹ and R ² , a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group and the like. it can.

Examples of the sulfur-containing group include the same groups as those for R ¹ and R ² , and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Phonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate,
Sulfonate groups such as pentafluorobenzene sulfonate, methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate and other sulfinate groups, etc. Can be illustrated.

In the general formula (3), Y is 2 having 1 to 20 carbon atoms.
Divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-,
_{-SO -, - SO 2 -,} - NR 7 -, - P (R 7) -, - P
^{(O) (R 7) -} , - BR 7 - or AlR ⁷ - [however, R ⁷
Represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and specifically, methylene, dimethylmethylene, 1, 2
-Alkylene groups such as ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-dichlorohexylene, diphenylmethylene, diphenyl-1, 1 to 20 carbon atoms such as arylalkylene groups such as 2-ethylene
Divalent hydrocarbon group; halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) Silylene, di (i
-Propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, and other alkylsilylenes, alkylarylsilylenes, arylsilylene groups, tetramethyl-1 A divalent silicon-containing group such as an alkyldisilene such as 1,2-disilirene, or tetraphenyl-1,2-disilirene, an alkylaryldisilirene, or an aryldisilirene group;
2 in which silicon in the valent silicon-containing group is replaced with germanium
A divalent germanium-containing group; a divalent tin-containing group substituent obtained by substituting tin for silicon in the above divalent silicon-containing group, and R ⁷ is the same halogen atom and carbon number as those of R ¹ and R ^2. Examples thereof include a hydrocarbon group having 1 to 20 and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable,
Of these, alkylsilylene, alkylarylsilylene, and arylsilylene are particularly preferred.

In the general formula (3), the combination of R ^{1 to} R ⁶ is such that R ¹ is a hydrocarbon group, R ³ is an aryl group having 6 to 16 carbon atoms, R ² , R ⁴ , R ⁵ and R ⁶ Is also preferably a hydrogen atom. In this case, X ¹ and X ² are halogen atoms,
It is preferably a hydrocarbon group having 1 to 20 carbon atoms.

R above¹The hydrocarbon group of is methyl,
Ethyl, propyl, butyl hydrocarbon groups having 1 to 4 carbon atoms
It is preferred that Also above R^Three6 to 16 carbon atoms
Examples of the aryl group include phenyl, α-naphthyl, β-
Naphthyl, anthracenyl, phenanthryl, pireni
Le, acenaphthyl, phenalenyl (perinaphthenyl),
For example, aceanthrylenyl. Pheny out of these
Ru and naphthyl are preferred. These aryls
The group is the above R ¹Halogen atom similar to, C1-20
Hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms
Etc. may be substituted.

Specific metallocene compounds (a) in the combination of R ^{1 to} R ⁶ include rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride and rac-dimethylsilylene-bis (2).
-Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis ( 2-methyl-4- (1-anthracenyl)-
1-indenyl) zirconium dichloride and the like.

In the present invention, the metallocene compound (a) may be used alone or in combination of two or more. The above metallocene compound (a) may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

Further, the metallocene compound (a) as described above
Can also be used in contact with a particulate carrier compound. Examples of the carrier compound include SiO ₂ , Al ₂ O ₃ , and M.
An inorganic carrier compound such as gO, a resin such as polyethylene, polypropylene, and a styrene-divinylbenzene copolymer can be used. These carrier compounds may be used alone or in combination of two or more.

In the present invention, the organoaluminum oxy compound (b) used together with the metallocene compound (a) is a conventionally known aluminoxane, specifically, represented by the following general formula (4) or (5). It is an aluminum compound.

Embedded image (In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably 5 to 5 It is an integer of 40.)

Here, this aluminoxane is represented by the formula (OA
1 (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OA1 (R ² )) [wherein R ¹ and R ² are the same hydrocarbon groups as R. And R ¹ and R ² represent different groups].

The organoaluminum oxy compound (b) used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. The organoaluminum oxy compound (b) may be used alone, or
Two or more can be used in combination.

In the present invention, examples of the ionizable ionic compound (c) used together with the metallocene compound (a) include Lewis acids, ionic compounds, borane compounds and carborane compounds. Examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group, or fluorine.), And the like. Trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p- Trily) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.

Examples of the ionic compounds include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, triarylphosphonium salts, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, Examples thereof include N-dimethylanilinium tetrakis (pentafluorophenyl) borate and ferrocenium tetra (pentafluorophenyl) borate.

Examples of the borane compound include decaborane (14) and bis [tri (n-butyl) ammonium] nonaborate. The ionized ionic compound (c) may be used alone or in combination of two or more.

As described above, the present invention can be applied to polyolefin. Among them, the propylene-based polymer is a preferred embodiment of the present invention and will be described below.

<< Nucleating Agent (B) >> In the present invention, by blending the nucleating agent (B), the crystal grains can be made finer and the crystallization rate can be improved to enable high-speed molding.
A propylene-based polymer composition excellent in rigidity, heat resistance rigidity, transparency, gloss, surface hardness, etc. can be obtained. As the nucleating agent (B), a nucleating agent such as an organic phosphate nucleating agent, a sorbitol nucleating agent, an aromatic carboxylic acid nucleating agent, a high melting point polymer nucleating agent, an inorganic nucleating agent or a rosin acid nucleating agent is used. They may be used alone or in combination of two or more.

In the propylene-based polymer composition of the present invention, the nucleating agent (B) is 100% of the propylene-based polymer (A).
0.001 to 5 parts by weight, preferably 0.0
1 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight is desirable. By blending the nucleating agent (B) in the above amount in the propylene-based polymer (A), the crystal grains are fine and the crystallization rate is improved, high-speed molding is possible, and rigidity, heat resistance, transparency, The gloss and surface hardness are improved, and other excellent properties originally possessed by the propylene-based polymer (A) are not impaired.

<< Organophosphoric Acid Nucleating Agent (B) >> As the organic phosphoric acid nucleating agent (B), compounds represented by the following general formula (6) can be exemplified.

Embedded image

Where R¹Is oxygen, sulfur or carbon number
1 to 10 hydrocarbon groups, R^Two, R ^ThreeIs hydrogen or charcoal
A hydrocarbon group having a prime number of 1 to 10,^Two, R^ThreeIs the same kind
Or heterogeneous,^TwoEach other, R^ThreeEach other or R
^TwoAnd R^ThreeMay be combined to form a ring, and M is 1 to 3
Is a valent metal atom, and n is an integer of 1 to 3. )

Specific examples of the compound represented by the general formula (6) 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, lithium-2,2 ' -Echiliden-
Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-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 [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate] , Calcium-bis [2,2'-thiobis (4-ethyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) Phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate Fate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-
(Di-t-butylphenyl) 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 [2,2'-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 Fate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-di -t-butyl-2,2'-biphenyl) phosphate], sodium-2,
2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4,6-
Di-methylphenyl) phosphate, sodium-2,2'-
Methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2'- Ethylidene-bis (4,6-di-t-butylphenyl) phosphonate], magnesium-bis [2,2'-ethylidene-bis (4,6-di)
-t-Butylphenyl) phosphate], barium-bis
[2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfell) phosphate ] And aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and a mixture of two or more thereof. Especially sodium-
2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

Examples of preferable organic phosphoric acid type nucleating agent (B) include compounds represented by the following general formula (7).

Embedded image (In the formula, R ¹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a 1 to 3 valent metal atom, and n is an integer of 1 to 3.)

Specific examples of the compound represented by the general formula (7) include sodium-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-butylphenyl) phosphate, calcium-bis (4 -t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t
Examples thereof include -butylphenyl) phosphate and a mixture of two or more thereof. Especially sodium
-Bis (4-t-butylphenyl) phosphate is preferred.

<< Sorbitol Nucleating Agent (B) >> As a preferable sorbitol nucleating agent (B), a compound represented by the following general formula (8) can be exemplified.

Embedded image (In the formula, each R ¹ is the same or different and is hydrogen, halogen such as chlorine, or a hydrocarbon group having 1 to 10 carbon atoms. M and n are each an integer of 0 to 5.)

Specific examples of the compound represented by the general formula (8) include 1,3,2,4-dibenzylidene sorbitol,
1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1, 3-p-Ethylbenzylidene-2,4-benzylidene 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,
1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,3,
2,4-di (pi-propylbenzylidene) sorbitol, 1,3,
2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,
4-di (ps-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, 1,3-p-
Chlorbenzylidene-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 -p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof And the like, particularly 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p
-Methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) 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.

As a preferable sorbitol-based nucleating agent (B), compounds represented by the following general formula (9) can be exemplified.

[Chemical 6] (In the formula, each R ¹ is the same or different and is an alkyl group having 1 or 2 carbon atoms.)

<< Aromatic Carboxylic Acid Nucleating Agent (B) >> A preferable aromatic carboxylic acid nucleating agent (B) is aluminum hydroxydipara t-represented by the following general formula (10).
Butyl benzoate etc. can be illustrated.

Embedded image

Other examples of the nucleating agent (B) include high melting point polymers, other aromatic carboxylic acid metal salts and aliphatic carboxylic acid metal salts, and inorganic compounds.
Examples of the high melting point polymer include polyvinyl cyclohexane, polyvinyl cycloalkane such as polyvinyl cyclopentane, poly 3-methylpentene-1, poly 3-methylbutene-1, and polyalkenylsilane. As the metal salt, aluminum benzoate, p-
Examples thereof include t-butylbenzoic acid aluminum salt, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate. Further, as the inorganic compound, silica, diatomaceous earth, alumina, titanium oxide,
Magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate,
Examples thereof include barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder and molybdenum sulfide. In addition, brominated biphenyl ether, cyclic triethylene glycol terephthalate and the like can also be used.

<< Rosin Acid Nucleating Agent (B) >> In the present invention, a well-known rosin nucleating agent can be used. Examples of the rosin acid-based nucleating agent (B) include rosin acid partial metal salts, for example, rosin acid partial sodium salt, rosin acid partial potassium salt, and rosin acid partial magnesium salt.

The rosin acid-based nucleating agent (B) is preferably at least one partial metal salt of rosin acid selected from natural rosin, modified rosin and purified products thereof, and the partial metal salt of rosin acid is dehydroabietic acid, More preferably, it is at least one partial metal salt of rosin acid selected from dihydroabietic acid, dihydropimaric acid and derivatives thereof, and the partial metal salt of rosin acid represented by the following general formula (11a) and the above general formula At least 1 selected from the partial metal salts of rosin acid represented by (11b)
Particularly preferred are rosin acid partial metal salts of the species. In the following general formulas (11a) and (11b), R ¹
Is an isopropyl group, and R ² and R ³ are preferably methyl groups.

[0060]

Embedded image (In the formula, R ¹ , R ² and R ³ may be the same or different, and represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.)

In the present specification, the rosin acid partial metal salt is a reaction product of a 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 metal chlorides, nitrates, acetates, sulfates, carbonates, oxides and hydroxides.

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 β-ethylenically unsaturated carboxylic acid modified rosins; purified products of the natural rosin and purified products of the modified rosin.

Natural rosins include 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 preferred.

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 compound represented by the general formula (11a) [compound (11a)] or the compound represented by the general formula (11b) [compound (1
1b)] is particularly preferred. General formula (11
a) and general formula (11b), R ¹ , R ² and R
³ may be the same or different from each other, and represent a hydrogen atom,
It is 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 and i-
Butyl, tert-butyl, pentyl, heptyl, octyl, and other alkyl groups having 1 to 8 carbon atoms are mentioned, and these groups have substituents such as hydroxyl group, carboxyl group, alkoxy group, and halogen. Good.

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 phenyl group, tolyl group, and naphthyl group. These groups include substituents such as hydroxyl group, carboxyl group, alkoxy group and halogen. May have.

In such compound (11a) and compound (11b), R ¹ , R ² and R ³ are respectively
Compounds having the same or different alkyl groups are preferred,
A compound in which R ¹ is an i-propyl group and R ² and R ³ are methyl groups is more preferable. The partial metal salt of such a compound is particularly excellent in improving the crystallization speed of the crystalline resin.

Specific examples of the compound (11a) include dehydroabietic acid and the like, and specific examples of the compound represented by the compound (11b) include dihydroabietic acid and the like.

Among such compounds (11a) and (11b), dehydroabietic acid represented by the formula (11a) 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.

As the metal salt of the compound (11a),
A compound represented by the following general formula (12a) [compound (12
a)], and examples of the metal salt of the compound (11b) include compounds represented by the following general formula (12b) [compound (12b)].

Embedded image

In the general formulas (12a) and (12b), R
¹ , R ² and R ³ are each represented by the general formula (11a) or (1
Similar to 1b). M is a monovalent metal ion, specifically, a monovalent metal ion such as lithium, sodium, potassium, rubidium, and cesium; a divalent metal ion such as beryllium, magnesium, calcium, strontium, barium, and zinc. Metal ions: Trivalent metal ions such as aluminum can be used. 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.

Compound (12a) and compound (12b)
Among them, compounds in which R ¹ , R ² and R ³ are the same or different alkyl groups respectively, or compounds in which M is a monovalent or divalent metal ion are preferred, and R ¹ is an i-propyl group. , R ² and R ³ are methyl groups, or M is a sodium ion, potassium ion or magnesium ion, R ¹ is an i-propyl group, and R ² and R ³ are methyl groups. And a compound in which M is sodium ion, potassium ion or magnesium ion is particularly preferable. Such a compound is particularly excellent in the effect of improving the crystallization rate.

Specific examples of the compound (12a) 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 (12b) include lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, zinc dihydroabietic acid, 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.

In the present invention, at least two rosin acid partial metal salts may be used as the 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. In at least two kinds of rosin acid partial metal salts, the total amount of rosin acid metal salts is 5 to 100% by weight,
It is preferable that the content is 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 ratio is based on the total amount of the rosin acid metal salts in the at least two rosin acid partial metal salts. 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 such that the proportion is less than 00 mol%, preferably 95 to 5 mol%.

As a combination of at least two rosin acid partial metal salts, a combination of a rosin acid partial potassium salt and a rosin acid partial sodium salt or a rosin acid partial magnesium salt is preferable. 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 20 mol%
It is desirable to combine them so that the ratio becomes.

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

The propylene-based polymer composition of the present invention includes the propylene-based polymer (A) and the nucleating agent (B).
In addition to the above essential components, if necessary, a phenolic stabilizer (C), a phosphorus stabilizer (D), a sulfur stabilizer (E), a hindered amine stabilizer (F), an antistatic agent ( Other additives such as G) and a lubricant (H) may also be added. Hereinafter, other additives used in the present invention will be sequentially described.

<< Phenolic Stabilizer (C) >> As the phenolic stabilizer (C), a phenolic stabilizer conventionally used as a stabilizer can be used without particular limitation. The following compounds are used as specific examples of the phenolic stabilizer (C).

2,6-di-t-butyl-4-methylphenol, 2,
6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4 -n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2
-Isopropyl-4-methyl-6-t-butylphenol, 2-t-
Butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, dl-α-tocopherol, t- Butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-thiobis
(3-methyl-6-t-butylphenol), 2,2-thiobis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-
Di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2 '-Butylidene bis (2-t-butyl-4-methylphenol), 2-t-butyl-6- (3
-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-
Pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,1,3-tris (2-methyl-4-hydroxy-5)
-t-butylphenyl) butane, triethylene glycol-
Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate],
2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4- Hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, Tris
(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t- Butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5 -Triazine,
Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-t-butylphenol) terephthalate,
1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2
-{β- (3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [ 4- (2- (3,5-di-t-butyl-
4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester and the like.

Among these, β- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionic acid stearyl ester, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-
Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-hydroxybenzyl) benzene, dl-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris [(3,5-di-t-butyl-4
-Hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl]- 2,4,8,10-Tetraoxaspiro [5,5] undecane is preferred.

As the phenolic stabilizer (C), a commercially available product may be used. For example, Irganox 1010
(Irganox1010, Ciba-Geigy, trademark), Irganox 1076 (Irganox1076, Ciba-Geigy, trademark),
Irganox 1330 (Irganox 1330, Ciba Geigy, trademark), Irganox 3114 (Irganox 3114, Ciba Geigy, trademark), Irganox 3125 (Irgano
x3125, Ciba Geigy, trademark, BHT (Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (Cyanox1790,
Cyanamid, trademark, Sumilizer GA-80 (Su
milizer GA-80, Sumitomo Chemical Co., Ltd., Vitamin E
(Eisai Co., Ltd.) and the like.

These phenolic stabilizers (C) can be used alone or in combination. The amount of the phenolic stabilizer (C) blended is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, and more preferably 0.0, based on 100 parts by weight of the propylene polymer (A).
It is desirable that the amount is 5 to 0.5 parts by weight.

When the content of the phenolic stabilizer (C) is within the above range with respect to 100 parts by weight of the propylene polymer (A), the effect of improving stability such as heat resistance and aging resistance is improved. And the cost of the stabilizer is kept low,
The properties of the propylene-based polymer (A), such as tensile strength, do not deteriorate.

<< Phosphorus Stabilizer (D) >> As the phosphorus stabilizer (D), phosphorus stabilizers conventionally used as stabilizers can be used without any particular limitation.
The following compounds are used as specific examples of the phosphorus-based stabilizer (D).

Trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris
(Butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2
- methyl -5-t-butyl-4-hydroxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4, 4'-butylidene bis (3-methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-butyl-
4-hydroxyphenyl) phosphite, tris (mono / di mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl
-6-t-Butylphenol)], 1,6-hexanediol diphosphite, phenyl, 4,4'-isopropylidenediphenol, pentaerythritol diphosphite, Tris
[4,4'-isopropylidene bis (2-t-butylphenol)]
Phosphite, phenyl diisodecyl phosphite,
Di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl)
Phosphite, 4,4'-isopropylidene bis (2-t-butylphenol) di (nonylphenyl) phosphite, 9,10-
Di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,4-di-t-butyl-6-methylphenyl) -ethylphosphite, 2-[{ 2,4,8,10-Tetrakis (1,1-dimethylethyl) dibenzo (D, F) (1,3,2)-
Dioxaphosphine-6-yl} oxy] -N, N-bis [2-
[{2,4,8,10-Tetrakis (1,1-dimethylethyl) dibenzo
(D, F) (1,3,2) -Dioxaphosphephin-6-yl} oxy]
Ethyl] ethanamine and the like.

Further, bis (dialkylphenyl) pentaerythritol diphosphite ester is represented by the following general formula (1
The spiro type represented by 3) to the cage type represented by the general formula (14) are also used. Usually, mixtures of both isomers are most often used for economic reasons arising from the process for producing such phosphite esters.

[0095]

Embedded image

Here, R ¹ , R ² and R ³ are each hydrogen or an alkyl group having 1 to 9 carbon atoms, particularly a branched alkyl group, preferably a tert-butyl group. The substitution position is most preferably 2,4,6 position. Suitable phosphite esters are bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and the like, and phosphonite having a structure in which carbon and phosphorus are directly bonded, for example, tetrakis (2,4-di-t Examples also include compounds such as -butylphenyl) -4,4'-biphenylenediphosphonite.

As the phosphorus-based stabilizer (D), a commercially available product may be used. For example, Irgafos 168 (Irgafos) may be used.
168, Ciba Geigy, trademark, Irgafos 12 (Irg
afos12, Ciba Geigy, trademark), Irgafos 38
(Irgafos 38, Ciba Geigy, trademark), Mark 329
K (Mark 329K, Asahi Denka Co., Ltd., trademark), Mark PEP
36 (Mark PEP36, Asahi Denka Co., Ltd., trademark), Mark PE
P-8 (Mark PEP-8, Asahi Denka Co., Ltd., Trademark), Sand
stab P-EPQ (Clariant, trademark), Weston 618 (Weston 618, GE, trademark), Weston 619G (Weston 619G, GE, trademark), Weston-624 (Weston-624, GE, trademark), etc. can give.

These phosphorus stabilizers (D) can be used alone or in combination. Phosphorus stabilizer (D)
The compounding amount of 0.005 to 2 parts by weight, preferably 0.0 to 100 parts by weight of the propylene-based polymer (A).
The amount is preferably 1 to 1 part by weight, more preferably 0.05 to 0.5 part by weight.

When the content of the phosphorus-based stabilizer (D) is within the above range with respect to 100 parts by weight of the propylene-based polymer (A), the effects of improving stability such as heat resistance and aging resistance are improved. The cost of the stabilizer is kept low, and the properties of the propylene-based polymer (A), such as tensile strength, are not deteriorated.

<< Sulfur Stabilizer (E) >> As the sulfur stabilizer (E), sulfur stabilizers conventionally used as stabilizers can be used without particular limitation. The following compounds are used as specific examples of the sulfur stabilizer (E).

Dialkylthiodipropionates such as dilauryl-, dimyristyl-, distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, stearyl- (eg glycerin, trimethylolethane, trimethylol). Propane, pentaerythritol, trishydroxyethyl isocyanurate) ester such as pentaerythritol tetralauryl thiopropionate. More specifically, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate and the like can be mentioned.

As the sulfur-based stabilizer (E), commercially available products can be used. For example, DSTP (Yoshitomi) (trade name, Yoshitomi Co., Ltd.), DLTP (Yoshitomi) (Yoshitomi Co., Ltd.)
Company, trademark), DLTOIB (Yoshitomi Corporation, trademark), D
MTP (Yoshitomi) (trademark of Yoshitomi Co., Ltd.), Seen
ox 412S (trademark of Shiraishi Calcium Co., Ltd.), C
yanox 1212 (trademark of Cyanamid Co., Ltd.) and the like.

These sulfur stabilizers (E) can be used alone or in combination. The amount of the sulfur-based stabilizer (E) blended is the above-mentioned propylene-based polymer (A) 1
0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.
It is desirable to use 5 parts by weight.

When the content of the sulfur-based stabilizer (E) is within the above range with respect to 100 parts by weight of the propylene-based polymer (A), the effects of improving stability such as heat resistance and aging resistance are improved. The cost of the stabilizer is kept low, and the properties of the propylene-based polymer (A), such as tensile strength, are not deteriorated.

<< Hindered Amine Stabilizer (F) >> The hindered amine stabilizer (F) has a structure in which all hydrogens bonded to carbons at the 2nd and 6th positions of conventionally known piperidine are substituted with methyl groups. The compound having is used without particular limitation, and specifically, the following compounds are used. (1) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate Tetramethylpiperidine polycondensate, (3) poly [[6- (1,1,3,3-tetramethylbutyl)
Imino-1,3,5-triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,
6,6-Tetramethyl-4-piperidyl) imino]], (4) Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-
Butane tetracarboxylate, (5) 2,2,6,6-tetramethyl-4-piperidinyl benzoate, (6) bis- (1,
2,6,6-pentamethyl-4-piperidinyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate,
(7) Bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, (8) 1,1 '-(1,2-ethanediyl) bis (3,3,5, 5-tetramethylpiperazinone), (9) (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (10)
(Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate,
(11) Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) Undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (12) mixed {1,2,
2,6,6-Pentamethyl-4-piperidyl / β, β, β ', β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (13) N, N'-bis (3-aminopropyl) ethylenediamine-2-4-bis [N-butylN- (1,2,2,6 , 6-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, (14) poly [[6-N-morpholyl-1,3,5-triazine-2-4- Diyl] [(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], (15) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) Condensation product of hexamethylenediamine and 1,2-dibromoethane, (16) [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2- (2,2,6 , 6-Tetramethyl-
4-piperidyl) imino] propionamide and the like.

Among them, the above (1), (2), (3),
The compounds (4), (8), (10), (11), (14) and (15) are preferably used. These hindered amine stabilizers (F) are used alone or in combination.

The hindered amine stabilizer (F) is blended in an amount of 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, and more preferably 0.1 part by weight per 100 parts by weight of the propylene polymer (A). It is desirable that the amount is 05 to 0.5 parts by weight.

When the content of the hindered amine-based stabilizer (F) is within the above range with respect to 100 parts by weight of the propylene-based polymer (A), the effects of improving stability such as heat resistance and aging resistance are improved. The cost of the stabilizer is kept low, and the properties of the propylene-based polymer (A), such as tensile strength, are not deteriorated.

<< Antistatic Agent (G) >> As the antistatic agent (G) used in the present invention, those conventionally used as an antistatic agent or an antistatic agent are not particularly limited. It can be used, and examples thereof include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.

Examples of the anionic surfactants used as the antistatic agent (G) include fatty acid or rosin acid soap, carboxylic acid salts such as N-acyl carboxylic acid salts, ether carboxylic acid salts and fatty acid amine salts; sulfosuccinic acid. Sulfates such as acid salts, ester sulfonates and N-acyl sulfonates; sulfated oils, sulfate ester salts, sulfate alkyl salts, sulfate alkyl polyoxyethylene salts, sulfate ether salts, sulfate amide salts and other sulfate esters Salts: alkyl phosphate salts, alkyl phosphate polyoxyethylene salts, phosphoric acid ether salts, phosphoric acid ester salts such as phosphoric acid amide salts, and the like.

The cationic surfactant used as the antistatic agent (G) includes amine salts such as alkylamine salts; alkyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, dialkyldimethyl. Quaternary ammonium salts such as ammonium chloride, tetraalkylammonium salt, N, N-di (polyoxyethylene) dialkylammonium salt, and N-alkylalkanamidoammonium salt; 1-hydroxyethyl-2-alkyl-2-imidazoline , 1-
Hydroxyethyl-1-alkyl-2-alkyl-2-
Alkyl imidazoline derivatives such as imidazoline; imidazolinium salts, pyridinium salts, isoquinolinium salts and the like.

Examples of the nonionic surfactant used as the antistatic agent (G) include ether types such as alkyl polyoxyethylene ether and p-alkylphenyl polyoxyethylene ether; fatty acid sorbitan polyoxyethylene ether and fatty acid. Ether ester forms such as sorbitol polyoxyethylene ether and fatty acid glycerin polyoxyethylene ether; ester forms such as fatty acid polyoxyethylene ester, monoglyceride, diglyceride, sorbitan ester, sucrose ester, dihydric alcohol ester and borate ester; dialcohol Alkylamine, dialcohol alkylamine ester, fatty acid alkanolamide, N, N-di (polyoxyethylene) alkaneamide, alkanolamine ester,
Nitrogen-containing forms such as N, N-di (polyoxyethylene) alkaneamine, amine oxide, and alkylpolyethyleneimine can be mentioned.

Examples of the amphoteric surfactant used as the antistatic agent (G) include amino acid forms such as monoaminocarboxylic acid and polyaminocarboxylic acid; N-alkylaminopropionate, N, N-di (carboxyethyl). ) N-alkyl-β-alanine forms such as alkylamine salts; N-alkylbetaines, N-alkylamidobetaines, N-alkylsulfobetaines, N, N-di (polyoxyethylene) alkylbetaines, imidazolinium betaines, etc. Betaine form of 1-carboxymethyl-1-hydroxy-
Examples thereof include alkylimidazoline derivatives such as 1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.

As the above-mentioned surfactant, nonionic surfactants and amphoteric surfactants are preferable, and among them, ester forms such as monoglyceride, diglyceride, boric acid ester, dialcohol alkylamine, dialcohol alkylamine ester, amide and the like are included. Nitrogen type nonionic surfactants; betaine type amphoteric surfactants are preferred.

As the antistatic agent (G), it is possible to use a commercially available product, for example, electrostripper TS5.
(Kao Corporation, trademark, glycerin monostearate), Electrostripper EA (Kao Corporation, trademark, lauryl diethanolamine), Denon 331P
(Trade name, stearyldiethanolamine monostearate, manufactured by Marubishi Yuka Co., Ltd.), Electrostriper EA
-7 (trademark, manufactured by Kao Corporation, polyoxyethylene laurylamine capryl ester), Resist PE-13
9 (Daiichi Kogyo Seiyaku Co., Ltd., trademark, stearic acid mono &
Diglyceride borate ester), chemistat 4700
(Trademark, alkyl dimethyl betaine manufactured by Sanyo Kasei Co., Ltd.) and the like.

These antistatic agents (G) can be used alone or in combination. The blending amount of the antistatic agent (G) is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the propylene-based polymer (A).

When the compounding amount of the antistatic agent (G) is within the above range with respect to 100 parts by weight of the propylene polymer (A), the surface specific resistance can be reduced to prevent the trouble due to electrification. A composition having excellent electrical characteristics can be obtained, and the properties of the propylene-based polymer (A), such as tensile strength, are not deteriorated.

<< Lubricant (H) >> As the lubricant (H) used in the present invention, those conventionally used as lubricants for resins can be used without particular limitation. The following compounds are used as specific examples of the lubricant (H).

Natural plant waxes such as candelilla wax, carnauba wax, rice wax, wax, jojoba oil; natural animal waxes such as beeswax, lanolin, whale wax; natural mineral waxes such as montan wax, ozokerite and ceresin. Natural petroleum waxes such as paraffin wax, microcrystalline wax and petrolactam; Synthetic hydrocarbons such as Tropsch wax and polyethylene wax; Synthetic modified waxes such as montan wax derivatives, paraffin wax derivatives and microcrystalline wax derivatives; hydrogenated castor oil, Synthetic hydrogenated wax such as hydrogenated castor oil derivative, hydrogenated rapeseed oil and hydrogenated soybean oil; Synthetic metal soap such as Ca stearate, Ba stearate, Zn stearate and Li stearate;
Synthetic higher-grade fatty acids such as stearic acid and 12-hydroxystearic acid; synthetic fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, ethylenebisstearic acid amide, and EBS; butyl stearate, long-chain fatty acid ester, etc. Synthetic fatty acid ester; synthetic higher alcohols such as cetanol and stearyl alcohol.

As the lubricant (H), a commercially available product may be used. For example, Armoslip CP (Lion Co., Ltd.)
Trademark, Neutron 2 (trademark of Nippon Seika Co., Ltd.), Alflo P-10 (trademark of NOF CORPORATION), Armowax EBS (Lion Armor Co., Ltd.)
Manufactured, trademark) and the like.

These lubricants (H) can be used alone or in combination. The blending amount of the lubricant (H) is 0.0 with respect to 100 parts by weight of the propylene-based polymer (A).
It is desirable that the amount is 05 to 2 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight.

When the blending amount of the lubricant (H) is within the above range relative to 100 parts by weight of the propylene polymer (A), the propylene polymer composition of the present invention is melted by heating and molded. The fluidity is improved, the adhesion to the molding machine and the mold is suppressed, and the mold release of the molded body is improved,
Furthermore, when formed into a film, slip properties such as mouth opening are improved, and the properties of the propylene-based polymer (A), such as tensile strength, are not deteriorated. Further, since the metal salt (H) of higher fatty acid such as Ca stearate has an effect as a lubricant and a rust preventive, a propylene-based polymer composition containing such a metal salt (H) of higher fatty acid is separated. It has excellent moldability and is effective in preventing rust in molding machines.

Further, in the present invention, a compatibilizing agent such as higher fatty acid metal salt, rosing lysene phosphorus ester, polyolefin wax, hydrogenated petroleum resin and the like may be added. Such a compatibilizer is usually used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the propylene-based polymer. When the compatibilizer is added, the nucleating agent (B) can be dispersed in the propylene-based polymer (A) in a short kneading time.

Further, the propylene-based polymer composition of the present invention may be blended with a rubber component for improving impact strength, and may be blended with a weather resistance stabilizer, an antiblocking agent, an antifogging agent, a dye, a pigment and the like. It is possible and the compounding ratio is an appropriate amount.

Further, in the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, and hydroxide are added to the propylene polymer composition within the range not impairing the object of the present invention. Magnesium, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum Fillers such as powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber may be blended.

As a method for preparing the propylene-based polymer composition, any conventionally known method can be adopted, for example, a propylene-based polymer (A), a nucleating agent (B), and optionally other additives. A method of melt-kneading is used by using an extruder, a kneader or the like.

The propylene-based polymer composition of the present invention comprises
Fields where polypropylene has been used in the past, such as a wide range of applications from household products to industrial products, such as food containers, electric parts (used in vacuum cleaners, washing machines, etc.), electronic parts, automobile parts (bumpers, interior materials) , Exterior materials, etc.), machine mechanical parts, etc., but is not particularly limited, but is particularly used for extruded sheets, unstretched films, stretched films, filaments, extrusion molded products, injection molded products, blow molded products, etc. It is preferably used for.

The molded product of the present invention is a molded product obtained by molding the propylene polymer composition of the present invention. The molding method is not particularly limited, and known molding methods such as extrusion molding, injection molding, blow molding, extrusion blow molding, injection blow molding, inflation molding, and mold stamping molding can be adopted, and an extrusion molded body depending on the molding method, Injection molded body,
Blow molding, extrusion blow molding, injection blow molding,
An inflation molded product, a mold stamping molded product, etc. can be obtained. As a molding method, an extrusion molding method or an injection molding method is preferable.

The shape and product type of the extruded product which is the molded product of the present invention are not particularly limited, and specific examples thereof include a sheet, a film, a pipe, a hose, an electric wire coating, a filament, and the like. It is particularly preferably used as

When an extrusion molded article such as a sheet or a film (unstretched film) is produced by extrusion molding the propylene-based polymer composition of the present invention, a known extrusion device can be used. For example, it can be produced by extruding the molten propylene-based polymer composition from a T-die using a single screw extruder, a kneading extruder, a ram extruder, a gear extruder or the like. As the molding conditions, known conditions can be adopted. Such an extruded sheet or film (unstretched film) has a high crystallization rate, rigidity,
It has excellent heat resistance, transparency, luster and surface hardness.

The stretched film can be produced by a known stretching device using a sheet or film made of the propylene polymer composition of the present invention. For example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method and the like can be mentioned. The stretch ratio of the stretched film is preferably 20 to 70 times in the case of a biaxially stretched film, and is usually 2 to 10 times in the case of a uniaxially stretched film. Further, the thickness of the stretched film is usually preferably 5 to 200 μm.
Such a stretched film has a high crystallization rate, rigidity,
It has excellent heat resistance, transparency, luster and surface hardness.

A blown film can also be produced from the propylene polymer composition of the present invention.

The sheet, unstretched film and stretched film made of the propylene-based polymer composition of the present invention have a high crystallization rate, excellent rigidity, heat resistance rigidity, transparency, gloss and surface hardness, and a propylene-based polymer ( Since the heat resistance, aging resistance, moisture resistance, and gas barrier property that A) originally have have not deteriorated, packaging films and chemical tablets,
It can be preferably used for a press through pack used for packaging capsules and the like.

The filament comprising the propylene-based polymer composition of the present invention can be produced, for example, by extruding a molten propylene-based polymer composition through a spinneret. The filament thus obtained may be further stretched. The extent of this stretching is
It may be carried out to such an extent that the propylene-based polymer (A) is effectively provided with at least uniaxial molecular orientation, and the draw ratio is usually preferably 5 to 10 times. Such a filament has a high crystallization speed, rigidity, heat resistance rigidity,
Excellent transparency, gloss and surface hardness.

The injection-molded article comprising the propylene-based polymer composition of the present invention can be manufactured by a known injection-molding apparatus. As the molding conditions, known conditions can be adopted. The injection-molded product, which is the molded product of the present invention, has a high crystallization rate, is excellent in rigidity, heat resistance rigidity, transparency, luster, surface hardness, and the like, and has the heat resistance originally possessed by the propylene polymer (A). Aging resistance, impact resistance, chemical resistance,
Since the abrasion resistance has not deteriorated, it can be widely used for trim materials for automobile interiors, exterior materials for automobiles, housings for home electric appliances, containers and the like.

The blow-molded article made of the propylene-based polymer composition of the present invention can be produced by a known blow-molding apparatus. As the molding conditions, known conditions can be adopted. For example, in the case of extrusion blow molding,
A tubular parison is extruded from a die in a molten state at a resin temperature of 100 to 300 ° C., and then the parison is held in a mold of a shape to be imparted, and then air is blown to the resin temperature of 130 to 300 ° C. Then, it is attached to a mold to obtain a hollow molded product. The draw ratio is preferably 1.5 to 5 times in the transverse direction.

In the case of injection blow molding, the resin temperature is 10
The propylene-based polymer composition is injected into a mold at 0 to 300 ° C. to form a parison, and then the parison is held in a mold having a shape to be imparted, and then air is blown into the mold to obtain a resin temperature of 1
It is attached to a mold at 20 to 300 ° C to obtain a hollow molded product. The stretching ratio is preferably 1.1 to 1.8 times in the machine direction and 1.3 to 2.5 times in the cross direction. Such a blow-molded body has a high crystallization rate and is excellent in rigidity, heat resistance rigidity, transparency, luster, surface hardness and the like.

The propylene-based polymer composition of the present invention is
It can be used as a base material in a method (mold stamping molding) for producing a molded body in which both of the skin material and the base material are press-molded at the same time to form a composite. The mold stamping molding obtained by this molding method is suitably used as an interior material for automobiles such as door trim, rear package trim, seat back garnish, instrument panel and the like. Such a mold stamping molding has a high crystallization rate and is excellent in rigidity, heat resistance rigidity, transparency, gloss, surface hardness and the like.

[0139]

INDUSTRIAL APPLICABILITY The polyolefin of the present invention, particularly the propylene-based polymer composition, is a polyolefin obtained by using a metallocene catalyst, especially the propylene-based polymer (A).
In addition, since the nucleating agent (B) is mixed in, the crystallization rate is high, and the rigidity, heat resistance rigidity, transparency, gloss, surface hardness, etc. are excellent. Since the molded product of the present invention is a molded product obtained by molding the above-mentioned polyolefin, particularly a propylene-based polymer composition, it has a high crystallization rate and is excellent in rigidity, heat resistance rigidity, transparency, gloss, surface hardness and the like.

[0140]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples. The methods for measuring physical properties and the polymers used in each example are as follows.

<< Physical Property Measuring Method >> (1) Melt Flow Rate (MFR) 230 ° C. according to ASTM D1238-65T.
2. Measured under a load of 16 kg. (2) Intrinsic viscosity ([η]) Measured in 135 ° C. decahydronaphthalene. (3) Molecular weight distribution (Mw / Mn) It was determined by measuring with gel permeation chromatography (GPC) at 140 ° C. using o-dichlorobenzene as a solvent.

(4) Crystallinity (Xc) The crystallinity (Xc) was measured by an X-ray diffractometer using a press sheet having a thickness of 0.5 mm formed at 200 ° C. (5) Polymer composition In a 10 mmφ sample tube, about 200 mg of polymer is 1 m
A sample uniformly dissolved in 1 liter of hexachlorobutadiene was measured at a measurement temperature of 120 ° C. and a measurement frequency of 25.02 MHz,
Spectral width 1500Hz, pulse repetition time 4.2s
It was determined by ¹³ C-NMR spectrum measurement under the conditions of ec and pulse width of 6 μsec. (6) Melting point (Tm) 10 ° C / min after melting once with a differential scanning calorimeter
The sample solidified at the cooling rate of 10 ° C / min
It was determined by measuring at the rate of temperature rise.

(7) Flexural Modulus (FM) Two injection-molded test pieces were prepared according to ASTM D790.
The test was performed at 3 ° C., a span interval of 32 mm, and a bending speed of 5 mm / min. (8) Haze A press sheet having a thickness of 0.5 mm formed at 200 ° C. was measured according to ASTM D1003.

Table 1 shows the physical properties of the propylene-based polymer used in each example and produced by a conventional method using the metallocene-based catalyst. In the table, A-1 is a homopolymer, A-1
-2 is a random copolymer and A-3 is a block copolymer.

[Table 1]

Examples 1 to 5 For 100 parts by weight of each propylene-based polymer in Table 1,
Nucleating agents of the types shown in Tables 2 and 3 were blended or prepolymerized in the amounts shown in Tables 2 and 3, and tetrakis [methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane 0.1 part by weight, 3,5-di-
0.1 parts by weight of t-butyl-4-hydroxytoluene,
And 0.1 parts by weight of calcium stearate,
A sample was prepared by melt-kneading at 230 ° C. with a twin-screw extruder. The results are shown in Tables 2 and 3.

Comparative Examples 1-3 With respect to 100 parts by weight of each propylene-based polymer in Table 1,
0.1 parts by weight of tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and 0.1 part of 3,5-di-t-butyl-4-hydroxytoluene. Parts by weight and 0.1 parts by weight of calcium stearate, and mixed by a twin-screw extruder at 230 ° C.
A sample was prepared by melt-kneading at. The results are shown in Tables 2 and 3.

[0147]

[Table 2]

[0148]

[Table 3]

Note to Tables 2 and 3 * 1 B-1: 1,3,2,4-di (p-methylbenzylidene) sorbitol * 2 B-2: Sodium-2,2'-methylenebis (4,6) -Di-t-butylphenyl) phosphate * 3 B-3: aluminum hydroxy-pt-butylbenzoate * 4 B-4: poly-3-methyl-1-butene

Claims (3)

[Claims] 1. A propylene polymer composition comprising a propylene polymer (A) obtained by using a metallocene catalyst and a nucleating agent (B). 2. The propylene polymer composition according to claim 1, wherein the amount of the nucleating agent (B) is 0.001 to 5 parts by weight based on 100 parts by weight of the propylene polymer (A). 3. A molded product comprising the composition according to claim 1.