JP6244946B2 - Propylene resin composition for injection molding and molded product - Google Patents

Description

  The present invention relates to a propylene-based resin composition for injection molding and a molded product, and more particularly, when injection molding is performed using a mold that has excellent transparency and mechanical properties such as rigidity and generates welds. The present invention relates to a propylene-based resin composition for injection molding and a molded product excellent in suppressing weld whitening.

  A propylene-based (co) polymer is a resin excellent in moldability, lightness, chemical resistance and rigidity. Moreover, since it is excellent also in recyclability and heat resistance, since melting | fusing point is comparatively low, the molded product of a complicated shape can be obtained by shape | molding by various methods. Specifically, it is widely used for various uses such as food containers, caps, medical instruments, medical containers, packaging films, stationery sheets, clothes cases, daily necessities, automobile parts, electrical parts and the like.

  Furthermore, in order to make use of the above characteristics, replacement of other transparent resins typified by polystyrene, polyethylene terephthalate and polycarbonate with polypropylene resins is also active. In that case, imparting transparency to the polypropylene resin is a very big problem. Moreover, since the polypropylene resin tends to have lower rigidity than other transparent resins, the improvement thereof is also desired.

Propylene-based (co) polymers are propylene homopolymers in terms of rigidity, heat resistance and gas barrier properties, and random copolymerization of propylene with ethylene, butene, etc. in terms of transparency and impact resistance. From the viewpoint of heat resistance and impact resistance, the copolymer is preferably a block copolymer of ethylene, butene or the like and propylene, and is selectively used as appropriate depending on the situation.
However, it is difficult for the block copolymer to exhibit sufficient performance in terms of transparency. In addition, propylene homopolymer is not as good as block copolymer, but it is inferior in transparency and it is difficult to exert sufficient performance in terms of impact resistance. Although it is most rigid among the three (co) polymers, it does not reach other transparent resins. Furthermore, although the random copolymer has the highest transparency among the three (co) polymers, the random copolymer does not reach other transparent resins.

For this reason, not only the modification of the propylene-based (co) polymer but also the improvement of transparency and molding processability by utilizing a clearing nucleating agent for the propylene-based (co) polymer has been widely attempted.
As the clarification nucleating agent, an organophosphate nucleating agent (for example, see Patent Document 1), a dimethylbenzylidene sorbitol-based nucleating agent (for example, see Patent Document 2), etc. are most commonly used. . Recently, new nucleating agents such as nonitol nucleating agents (see, for example, Patent Document 3) have been used. Furthermore, the addition of a nonitol nucleating agent to a special propylene-based (co) polymer polymerized using a metallocene catalyst further improves transparency (for example, (See Patent Document 4).

  However, according to the knowledge of the present inventors, a combination of the above-mentioned nonitol nucleating agent and a propylene-based (co) polymer polymerized using a metallocene catalyst may cause a new problem of weld whitening during injection molding. found. That is, as a result of the marked increase in the adhesion between the resin and the mold surface, the phenomenon that the air that was originally present in the mold becomes difficult to escape after filling with the resin, that is, the so-called degassing becomes apparent. It was.

  This phenomenon becomes particularly apparent in the welded portion, that is, the portion where the molten resin is abutted in a mold having a multipoint gate, and the portion where the molten resin flows once split into two or more locations and then merges again. In the case of molding a resin having high adhesion to the mold, the air in the mold loses its place at the weld and becomes a fine bubble that is pressed between the mold surface and the resin. The traces of the bubbles form fine voids of about several μm on the surface of the molded product, but the voids are observed as white streaks because they diffusely reflect light. Such streaks are very conspicuous when the transparency of the molded product is high, so that the appearance of the molded product is remarkably impaired (see the photograph in FIG. 1).

  A propylene-based (co) polymer polymerized using a metallocene catalyst has a narrow molecular weight distribution and composition distribution, and a molded product produced using this has a very good transparency because the crystal size is uniform. Has characteristics. On the other hand, the narrow molecular weight distribution has a negative effect on weld whitening. That is, a copolymer having a narrow molecular weight distribution tends to sharpen the flow front (melt front) in the mold during injection molding. When such a copolymer is used to mold with a mold having a weld, the effect of extruding gas out of the mold is weak, and when a plurality of flow fronts are united, the molded product is affected. The surface area also increases. As a result, the number of fine voids and the area of the void generation region are increased, and the weld whitening is more conspicuous.

Japanese Patent Laid-Open No. 05-140466 JP-A-53-117044 Special table 2007-534827 gazette JP 2009-120281 A

  In view of the above-mentioned problems of the prior art, an object of the present invention is injection molding that is superior in transparency and rigidity, and has excellent deterrence to whitening of a weld portion when injection molding is performed using a mold in which a weld is generated. It is to provide a propylene-based resin composition for use and a molded product obtained by molding the resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have developed a specific long-chain branched structure for a specific propylene-based (co) polymer (X) polymerized using a metallocene-based catalyst. By using a specific amount of the propylene polymer (Y) having a specific transparency and a specific clearing nucleating agent (Z), it is possible to obtain a propylene resin composition for injection molding excellent in transparency, rigidity and suppression of weld whitening. The headline and the present invention were completed.

That is, according to the first invention of the present invention, it is produced using a metallocene catalyst on the basis of a total of 100 parts by weight of the (co) polymer (X) and the polymer (Y), and has the following properties (X- i) to 75-97 parts by weight of a propylene-based (co) polymer (X) having (X-iii) and the following characteristics (Yi) to (Y-iv), and having a long-chain branched structure: Propylene polymer for injection molding containing 3 to 25 parts by weight of propylene polymer (Y) and 0.01 to 2.0 parts by weight of a nucleating agent (Z) represented by the following chemical structural formula (1) A composition is provided.
Characteristic (Xi): The ethylene content in the (co) polymer (X) is in the range of 0 to 3.0% by weight.
Characteristic (X-ii): The melt flow rate (MFR) (230 ° C., 2.16 kg load) of the (co) polymer (X) is in the range of 2 to 100 g / 10 min.
Characteristic (X-iii): Ratio (molecular weight distribution) (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) in GPC measurement of (co) polymer (X) is in the range of 2 to 4. is there.
Characteristic (Y-i): MFR (230 ° C., 2.16 kg load) is 0.1 to 30 g / 10 min.
Characteristic (Y-ii): GPC molecular weight distribution (Mw / Mn) is 3.0 to 10, and Mz / Mw is 2.5 to 10.
Characteristic (Y-iii): Melt tension (MT) (unit: g)
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (Y-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to the propylene polymer (Y) whole quantity.

[In formula (1), n is an integer of 0 to ^2, R 1 to R ⁵ are the same or different, each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, It is a carbonyl group, a halogen group or a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

According to the second invention of the present invention, in the first invention, the propylene polymer (Y) further has the following characteristics (Yv): a polypropylene-based resin for injection molding A composition is provided.
Furthermore, according to the third invention of the present invention, in the first or second invention, the propylene polymer (Y) further has the following property (Y-vi): A resin composition is provided.
Characteristic (Yv): The branching index g ′ when the absolute molecular weight (Mabs) is 1,000,000 is 0.30 or more and less than 1.00.
Characteristic (Y-vi): mm fraction of propylene unit 3 chain by ¹³ C-NMR is 95% or more.

  According to the fourth invention of the present invention, the propylene-based resin composition for injection molding according to any one of the first to third inventions is injection-molded using a mold in which a weld is generated. A propylene-based resin molded product is provided.

As described above, the present invention relates to a propylene-based resin composition for injection molding and the like, and preferred embodiments include the following.
(1) In the first invention, the transparent nucleating agent (Z) is a compound represented by the following chemical structural formula (2) {3,5: 4,6-bis [4-propylbenzylidenebis (oxy)]- 1,2-nonanediol or the commonly used name 1,2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol} for injection molding Propylene-based resin composition.
(2) In the first invention, the propylene polymer (Y) has a characteristic (Y-iv) 25 ° C. paraxylene-soluble component amount (CXS) of 3.0 wt% with respect to the total amount of the propylene polymer (Y). % Propylene-based resin composition for injection molding, characterized in that it is at most%.

  The propylene-based resin composition for injection molding of the present invention is a propylene polymer having a long-chain branched structure that satisfies a specific condition with respect to a specific propylene-based (co) polymer (X) polymerized using a metallocene catalyst. (Y) is a propylene-based resin composition for injection molding containing a specific amount of a specific transparent nucleating agent (Z) represented by the chemical structural formula (1), while realizing excellent transparency and rigidity, Even if injection molding is performed using a mold that generates welds, it is possible to obtain molded products having very excellent characteristics that cannot be realized with conventional propylene-based resin compositions in which whitening does not occur in the welds. Can do.

It is a photograph explaining the phenomenon of the weld whitening at the time of injection molding which is the subject of the propylene-type resin composition for injection molding of this invention.

The present invention relates to a specific propylene polymer (X) 75 to 97 parts by weight based on a total of 100 parts by weight of the (co) polymer (X) and the polymer (Y), and a specific propylene polymer. (Y) 3 to 25 parts by weight of a propylene-based resin composition for injection molding containing 0.01 to 2.0 parts by weight of the clarified nucleating agent (Z) represented by the chemical structural formula (1), and It is a molded product obtained by injection molding a propylene-based resin composition for injection molding using a mold that generates welds.
Hereinafter, the component which comprises the propylene-type resin composition for injection molding, the manufacturing method of the propylene-type resin composition for injection molding, and a molded article are demonstrated in detail for every item.

I. Components constituting propylene resin composition for injection molding Propylene-based (co) polymer (X)
The propylene-based (co) polymer (X) used in the propylene-based resin composition for injection molding of the present invention (hereinafter also referred to as a propylene-based resin composition) is obtained by polymerization using a metallocene catalyst. Is used. Those using metallocene catalysts have a narrower molecular weight distribution and narrower crystallinity distribution than those using Ziegler-Natta catalysts, resulting in uniform, fine and dense crystals, resulting in significantly better transparency. Propylene-based (co) polymers can be produced.
The proper form for producing the propylene-based (co) polymer (X) used in the present invention will be described in detail below.

1-1. Metallocene catalyst The type of the metallocene catalyst used in the production of the propylene-based (co) polymer (X) used in the present invention is not particularly limited.

As a typical example of the metallocene catalyst that can be used in the present invention, a metallocene catalyst comprising the following components (a) and (b) and an optional component (c) can be mentioned.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (3) Component (b): At least selected from the following (b-1) to (b-4) One solid component (b-1) A particulate carrier on which an organoaluminum compound is supported (b-2) An ionic compound capable of reacting with component (a) to convert component (a) into a cation Or a particulate carrier on which a Lewis acid is supported (b-3) a solid acid particulate (b-4) an ion-exchange layered silicate Component (c): an organoaluminum compound

(1) Component (a)
The component (a) is at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (3).

［式（３）中、ＡおよびＡ’は、置換基を有していてもよい共役五員環配位子、Ｑは、二つの共役五員環配位子間を任意の位置で架橋する結合性基、ＸおよびＹは、成分（ｂ）と反応してオレフィン重合能を発現させるσ共有結合性補助配位子、Ｍは、周期表第４族の遷移金属である。］

[In Formula (3), A and A ′ are conjugated five-membered ring ligands which may have a substituent, and Q bridges between two conjugated five-membered ring ligands at an arbitrary position. The bonding group, X and Y are σ covalent bonding auxiliary ligands that react with the component (b) to develop olefin polymerization ability, and M is a transition metal of Group 4 of the periodic table. ]

In the general formula (3), the conjugated five-membered ring ligand is a cyclopentadienyl group derivative that may have a substituent. When it has a substituent, examples of the substituent include a hydrocarbon group having 1 to 30 carbon atoms (which may contain a heteroatom such as halogen, silicon, oxygen, sulfur, etc.), and this hydrocarbon. Even if the group is bonded to the cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form a cyclopentadienyl group. A ring may be formed together with a part.
Examples of such a conjugated five-membered ring ligand include an indenyl group, a fluorenyl group, or a hydroazurenyl group, and these groups may further have a substituent, and among them, an indenyl group or a hydroazurenyl group. Groups are preferred. These groups may further have a substituent.

Q is preferably a methylene group, an ethylene group, a silylene group, a germylene group, a group in which these are substituted with a hydrocarbon group, a silafluorene group, or the like.
The auxiliary ligands X and Y are those which react with a cocatalyst such as component (b) to produce an active metallocene having olefin polymerization ability, and each of them is a hydrogen atom, a halogen atom, a hydrocarbon group, or The hydrocarbon group which may have hetero atoms, such as oxygen, nitrogen, and silicon, can be illustrated. Among these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable.
M is a transition metal of Group 4 of the periodic table, preferably titanium, zirconium or hafnium. In particular, zirconium and hafnium are preferable.

  Further, among the above transition metal compounds, those in which stereoregular polymerization of propylene proceeds and the obtained propylene polymer has a high molecular weight are preferable. Specifically, JP-A-1-301704, JP-A-4-221694, JP-A-6-1005909, JP-T 2002-535339, JP-A-6-239914, JP-A-10-226712. Preferably, transition metal compounds described in JP-A No. 3-193396 and JP-A No. 2001-504824 are listed.

Non-limiting examples of the transition metal compound include the following.
(1) Dichloro [1,1′-dimethylsilylenebis (2-methylcyclopentadienyl)] zirconium (2) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-phenylcyclopentadienyl) Zirconium (3) Dichloro [1,1′-dimethylsilylenebis (2,4,5-trimethylcyclopentadienyl)] zirconium (4) Dichloro [1,1′-dimethylsilylenebis (2-methyl-4-) Phenyl-indenyl)] zirconium (5) dichloro [1,1′-dimethylsilylenebis (2-ethyl-4-phenyl-indenyl)] zirconium (6) dichloro [1,1′-dimethylsilylene (2-methyl-4) -Phenyl-indenyl) (2-isopropyl-4-phenyl-indenyl)] zirconium (7) dichloro [1,1'- Dimethylsilylene (2-methyl-4-t-butylphenyl-indenyl) (2-isopropyl-4-t-butylphenyl-indenyl)] zirconium (8) dichloro [1,1′-dimethylsilylenebis {2- (5 -Methyl-2-furyl) -4-phenyl-indenyl}] zirconium (9) dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] zirconium (10) Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] zirconium (11) dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] zirconium (12) dichloro {1,1 '-Dimethylsilylenebis (2-methyl-4-phenyl-4H-azurenyl)} zirconium (13) dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl} ] Zirconium (14) dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4H-azulenyl}] zirconium (15) dichloro [1,1'-dimethylsilylenebis] {2-Ethyl-4- (2-fluoro-4-biphenyl) -4H-azurenyl}] zirconium (16) dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H -5,6,7,8-tetrahydroazurenyl}] zirconium (17) dichloro {1,1'-dimethylsilylene (2,3-dimethyl) Cyclopentadienyl) (2-methyl-4-phenyl-4H-azulenyl)} zirconium (18) dichloro {1,1′-dimethylsilylene (2-methyl-4-phenylcyclopentadienyl) (2-methyl- 4-phenyl-4H-azurenyl)} zirconium (19) dichloro {1,1′-dimethylsilylene (2,3,4-trimethylcyclopentadienyl) (2-methyl-4-phenyl-4H-azurenyl)} zirconium (20) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) fluorenyl) zirconium (21) dichlorodimethylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7- Di-t-butylfluorenyl) zirconium (22) dichlorodimethylmethylene (3-t-butyl) 5-methylcyclopentadienyl) (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzofluorene Nyl) zirconium

  For the preferred compounds represented above, only representative exemplary compounds are described avoiding many complicated examples. Although a compound whose central metal is zirconium has been described, it goes without saying that similar hafnium compounds can be used, and various conjugated five-membered ring ligands, binding groups, or auxiliary ligands are optionally used. It is obvious what can be done.

(2) Component (b)
As the component (b), at least one solid component selected from the components (b-1) to (b-4) described above is used. Each of these components is a well-known thing, and can be used selecting it suitably from well-known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, and the like.

  Examples of the particulate carrier used for the component (b-1) and the component (b-2) include inorganic oxides such as silica, alumina, magnesia, silica alumina, and silica magnesia, magnesium chloride, magnesium oxychloride, aluminum chloride, and chloride. Examples thereof include inorganic halides such as lanthanum, and porous organic carriers such as polypropylene, polyethylene, polystyrene, styrene divinyl benzene copolymer, and acrylic acid copolymer.

  Further, as a non-limiting specific example of the component (b), as the component (b-1), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl and the like are supported As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Silica alumina and pentafluorophenol calcined after treating a particulate carrier carrying anilinium tetrakis (pentafluorophenyl) borate or the like as component (b-3) with alumina, silica alumina, magnesium chloride or fluorine compound And diethyl sub After reacting with an organometallic compound such as, and further reacting with water, silica or the like carrying the product is used as component (b-4) as montmorillonite, zakonite, beidellite, nontronite, saponite, hectorite, stevensite. , Bentonite, teniolite and other smectites, vermiculite, mica and the like. These may form a mixed layer.

  Particularly preferred among the above components (b) is the ion-exchange layered silicate of component (b-4), and more preferred are chemical treatments such as acid treatment, alkali treatment, salt treatment, and organic matter treatment. It is an ion exchange layered silicate applied.

(3) Component (c)
The organoaluminum compound used as the component (c) as necessary is preferably an organoaluminum compound represented by the following general formula, and a trialkyl such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trioctylaluminum. Preferred examples include aluminum or halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride and diethylaluminum monomethoxide.
General formula: AlR _a X _3-a
(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, X is a hydrogen atom, a halogen atom or an alkoxy group, and a is a number satisfying 0 <a ≦ 3.)
In addition, aluminoxanes such as methylaluminoxane can also be used.
Of these, trialkylaluminum is particularly preferable as component (c).

(4) Formation of catalyst Component (a), component (b) and, if necessary, component (c) are brought into contact to form a catalyst. Although the contact method is not specifically limited, Contact can be made in the following order. Further, this contact may be performed not only at the time of catalyst preparation but also at the time of preliminary polymerization with olefin described later.
(I) The component (a) is contacted with the component (b).
(Ii) After contacting the component (a) and the component (b), the component (c) is added.
(Iii) After contacting the component (a) and the component (c), the component (b) is added.
(Iv) Component (b) and component (c) are contacted, and then component (a) is added.
(V) contacting the three components simultaneously.

The amounts of components (a), (b) and (c) used are arbitrary. For example, the amount of component (a) used relative to component (b) is preferably in the range of 0.1 μmol to 500 μmol, particularly preferably 0.5 μmol to 100 μmol, relative to 1 g of component (b). The amount of component (c) used relative to component (b) is preferably in the range of 0.001 mmol to 100 mmol, particularly preferably 0.005 mmol to 50 mmol, with respect to 1 g of component (b). It is. Therefore, the amount of component (c) to component (a) is within the range of 0.002 to 10 ⁶ , preferably 0.02 to 10 ⁵ , particularly preferably 0.2 to 10 ⁴ in terms of the molar ratio of transition metal. is there.

The metallocene catalyst is preferably preliminarily subjected to a prepolymerization treatment consisting of a small amount of polymerization by contacting with an olefin.
The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, and the like can be used. It is possible to use, and it is particularly preferable to use propylene.

In the prepolymerization treatment, any method can be used for supplying the olefin, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. . The temperature and time of the prepolymerization are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100 g / g, more preferably 0.1 to 50 g / g, based on 1 gram of the component (b). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

1-2. Production method of propylene-based (co) polymer (X) The propylene-based (co) polymer (X) used in the present invention is either a propylene homopolymer or a propylene-ethylene random copolymer. Use of a propylene-based copolymer other than this, for example, a block copolymer is not suitable because the transparency is remarkably lowered. Among these, a propylene-ethylene random copolymer is more preferable because high transparency can be obtained.

(1) Polymerization process Any polymerization process can be used, and single-stage polymerization or multi-stage polymerization may be used. Further, any reaction phase can be used, but a bulk method or a gas phase method is generally used. Although supercritical conditions can be used as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without any particular distinction.
In the case of a multi-tank continuous polymerization process, a gas phase polymerization reactor may be attached after a bulk polymerization reactor. In this case, the bulk method will be referred to as a bulk method according to the practice in the art. In the case of the batch method, the first step may be performed by a bulk method, and the second step may be performed by a vapor phase method. This case is also referred to as a bulk method.
Various processes have been proposed in each of the bulk method and the gas phase method. Although there is a difference in the stirring (mixing) method and the heat removal method, in this aspect, the process type is not particularly limited in the present invention.

(2) General polymerization conditions The polymerization temperature can be used without any particular problem as long as it is within a commonly used temperature range. Specifically, a range of 0 ° C to 200 ° C, preferably 40 ° C to 100 ° C can be used.
Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, preferably 0.1 to 50 MPa can be used. At this time, there is no problem even if an inert gas such as nitrogen coexists.

(3) Organoaluminum compound Unlike a Ziegler catalyst, the metallocene catalyst does not necessarily use an organoaluminum compound as a promoter. Therefore, it is not always necessary to add an organoaluminum compound to the polymerization reactor in terms of forming an activated catalyst. However, the polymerization reaction of olefins is unique in that an extremely large number of catalyst cycles rotate in a very short time compared to other catalytic reactions, and therefore there is a technical problem that it is easily affected by impurities. . In order to solve this problem, it is a well-known fact that various contrivances have been made, such as using raw materials that are much higher in purity than ordinary chemical products, or further purifying and using the raw materials. From this point of view, a method is often used in which a highly reactive organoaluminum compound is added to the polymerization reactor and reacted with the organoaluminum compound before the impurities react with the metallocene catalyst to render them harmless.
Also in the present invention, it is desirable to use an organoaluminum compound from this viewpoint. Although any compound can be used as the organoaluminum compound, examples of suitable compounds are the same as those of the component (c) (organoaluminum compound) which is an optional component of the metallocene catalyst described above. Trioctyl aluminum is preferred.

  The amount of the organoaluminum compound used can be arbitrarily set according to the level of impurities. Generally, it adds so that it may become in the range of 0.001-1000 mmol-Al / kg as a mole number of the aluminum atom of the organoaluminum compound with respect to the weight of the propylene-type (co) polymer (X) to manufacture. Preferably, it is added in a range of 0.01 to 100 mmol-Al / kg, more preferably 0.1 to 20 mmol / kg.

1-3. Method for controlling each characteristic of propylene-based (co) polymer (X) The propylene-based (co) polymer (X) used in the present invention needs to be a propylene homopolymer or a propylene-ethylene random copolymer. is there.

(1) Characteristic (Xi): Ethylene content When using a propylene-ethylene random copolymer as the propylene-based (co) polymer (X), the propylene-based (co) polymer (X) The ethylene content needs to be 3.0% by weight or less.
When the ethylene content exceeds 3.0% by weight, the rigidity is remarkably lowered, the crystallization rate is slowed, and the moldability is remarkably deteriorated.
The ethylene content of the propylene-based (co) polymer (X) can be adjusted by the ethylene ratio in the gas component in the polymerization tank. Specifically, when the ethylene ratio is increased, E (X) is increased. The reverse is also true. In order to increase the ethylene ratio in the polymerization tank, it is only necessary to increase the amount of ethylene supplied to the polymerization tank, and adjustment is extremely easy for those skilled in the art.

(2) Characteristic (X-ii): Melt flow rate (MFR)
The propylene-based (co) polymer (X) used in the present invention needs to have a melt flow rate (MFR) of 2 to 100 g / 10 minutes in accordance with JIS K7210 (230 ° C., 2.16 kg load).
If the MFR is less than 2 g / 10 min, the melt viscosity becomes high, so that a large product cannot be molded, stress during molding remains, warping deformation after molding occurs, and surface smoothness is impaired. The appearance of the molded product may deteriorate. On the other hand, if the MFR exceeds 100 g / 10 min, the uniform dispersibility of the clearing nucleating agent (Z) in the propylene (co) polymer (X) deteriorates, making it difficult to develop transparency, or a molded product. There is a risk that the impact resistance of the material may be reduced. The MFR is more preferably 3 to 80 g / min, and further preferably 5 to 50 g / min.
The MFR of the propylene-based (co) polymer (X) can be adjusted by using hydrogen as a chain transfer agent. Specifically, MFR increases as the concentration of hydrogen, which is a chain transfer agent, is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is very easy for those skilled in the art.

(3) Characteristic (X-iii): Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) in GPC measurement (Mw / Mn)
The propylene-based (co) polymer (X) used in the present invention needs to have a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) in the GPC measurement in the range of 2 to 4. is there.
By using a metallocene catalyst, the Mw / Mn can be made smaller than when using a Ziegler-Natta catalyst, but when controlling the Mw / Mn, select an appropriate metallocene catalyst for the target value. At the same time, it is also effective to devise polymerization conditions. For example, if a two-tank continuous polymerization process is adopted and a propylene-ethylene copolymer having a different molecular weight is produced in the first-stage polymerization tank and the second-stage polymerization tank, the value originally given by the metallocene catalyst used is Mw / Mn can be increased. At this time, the relationship between the polymerization conditions to be used, particularly the hydrogen concentration and the molecular weight of the resulting propylene-ethylene copolymer is known in advance, and the Mw / Mn is set to a desired value by appropriately adjusting the hydrogen concentration in each tank. It is easy for those skilled in the art to adjust the value.

The definitions of Mn, Mw and Mz are described in “Basics of Polymer Chemistry” (edited by Polymer Society, Tokyo Kagaku Dojin, 1978) and can be calculated from molecular weight distribution curves by GPC.
And the specific measuring method of GPC is as follows.
・ Apparatus: GPC (ALC / GPC 150C) manufactured by WATERS
Detector: manufactured by FOXBORO, MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
・ Mobile phase solvent: o-dichlorobenzene ・ Measurement temperature: 140 ° C.
・ Flow rate: 1.0 ml / min ・ Injection volume: 0.2 ml
Sample preparation: Prepare a 1 mg / ml solution using o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. for about 1 hour.

Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78

2. Propylene polymer (Y)
The propylene polymer (Y) used in the present invention has the following characteristics (Yi) to (Y-iv) and needs to have a long chain branched structure.
Characteristic (Y-i): MFR (230 ° C., 2.16 kg load) is 0.1 to 30 g / 10 min.
Characteristic (Y-ii): GPC molecular weight distribution (Mw / Mn) is 3.0 to 10, and Mz / Mw is 2.5 to 10.
Characteristic (Y-iii): Melt tension (MT) (unit: g)
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (Y-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to the propylene polymer (Y) whole quantity.

2-1. Each characteristic (1) Characteristic (Y-i): MFR
The melt flow rate (MFR) of the propylene polymer (Y) used in the present invention is measured in accordance with JIS K7210 (230 ° C., 2.16 kg load) and is 0.1 to 30 g / 10 min. The range is preferably 0.3 to 20 g / 10 min, and more preferably 0.5 to 10 g / 10 min. Below this range, fluidity is insufficient, and problems such as poor appearance and rough surfaces occur during injection molding. On the other hand, if it exceeds this range, the effect of suppressing weld whitening does not appear.
The MFR of the propylene polymer (Y) used in the present invention can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen which is a chain transfer agent is increased, MFR is increased. The reverse is also true. In order to increase the concentration of hydrogen in the polymerization tank, it is sufficient to increase the amount of hydrogen supplied to the polymerization tank, and adjustment is very easy for those skilled in the art.

(2) Characteristic (Y-ii): Molecular weight distribution by GPC The propylene polymer (Y) used in the present invention needs to have a relatively wide molecular weight distribution, and is obtained by gel permeation chromatography (GPC). The molecular weight distribution (Mw / Mn) (where Mw is the weight average molecular weight and Mn is the number average molecular weight) must be 3.0 or more and 10 or less. The molecular weight distribution (Mw / Mn) of the propylene polymer (Y) is preferably in the range of 3.5 to 8.0, more preferably 4.1 to 6.0.
Furthermore, it is necessary that Mz / Mw (where Mz represents the Z average molecular weight), which is a parameter that more significantly represents the breadth of the molecular weight distribution, is 2.5 or more and 10 or less. The preferable range of Mz / Mw is 2.8 to 8.0, more preferably 3.0 to 6.0.
The broader the molecular weight distribution, the better the effect of suppressing weld whitening. However, when Mw / Mn and Mz / Mw are in this range, the effect of suppressing weld whitening is particularly excellent.

  In order to adjust Mw / Mn to 3.0 to 10 and Mz / Mw to 2.5 to 10, the temperature and pressure conditions of propylene polymerization are changed, or the most common technique is hydrogen or the like The chain transfer agent can be easily adjusted by adding the chain transfer agent during propylene polymerization. Furthermore, when using 2 or more types of the metallocene catalyst mentioned later and a catalyst, it can control by changing the quantity ratio.

(3) Characteristic (Y-iii): Melt tension (MT)
The propylene polymer (Y) used in the present invention has the following relationship between melt tension (MT) and MFR:
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Need to meet any of

Here, MT is Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd. Capillary: diameter 2.0 mm, length 40 mm, cylinder diameter: 9.55 mm, cylinder extrusion speed: 20 mm / min, take-off speed: 4. The melt tension when measured under the conditions of 0 m / min and temperature: 230 ° C. is expressed in grams.
However, when the MT of the propylene polymer (Y) is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed is lowered and Let MT be the tension at the highest possible speed. The measurement conditions and units of MFR are as described above.

This regulation regarding the melt tension is an index for the propylene polymer (Y) having a long-chain branched structure to have a sufficient melt tension in order to exhibit the effect of suppressing weld whitening. Is defined by a relational expression with MFR.
The method of defining the melt tension (MT) with the relational expression with MFR as described above is a normal method for those skilled in the art. For example, JP 2003-25425 discloses the definition of polypropylene having a high melt tension. The following relational expression has been proposed.
log (MS)> − 0.61 × log (MFR) +0.82
(Here, MS is synonymous with MT.)
Japanese Unexamined Patent Application Publication No. 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension.
11.32 × MFR−0.7854 ≦ MT
Furthermore, Japanese Patent Laid-Open No. 2003-94504 proposes the following relational expression as a definition of polypropylene having a high melt tension.
MT ≧ 7.52 × MFR−0.576

In the present invention, the propylene polymer (Y) having a long-chain branched structure has a relational formula:
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
If any one of the above is satisfied, it can be said that the resin has a sufficiently high melt tension, and is useful for exhibiting an effect of suppressing weld whitening.
The propylene polymer (Y) has the following relational formula:
log (MT) ≧ −0.9 × log (MFR) +0.9 or MT ≧ 15
It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill the following relational expressions.
log (MT) ≧ −0.9 × log (MFR) +1.1 or MT ≧ 15

  Although it is not necessary to provide the upper limit value of MT in particular, when MT exceeds 40 g, the above-described measurement method makes the take-up speed extremely slow and makes measurement difficult. In such a case, since it is considered that the spreadability of the resin is also deteriorated, it is preferably 40 g or less, more preferably 35 g or less, and most preferably 30 g or less.

  In order to satisfy the relational expression of MT and MFR described above, the long chain branching amount of the propylene polymer (Y) may be increased to increase the melt tension. Selection of a preferable metallocene catalyst described later and a combination thereof, It is possible by introducing a lot of long chain branches by controlling the amount ratio thereof and the prepolymerization conditions.

(4) Characteristic (Y-iv): 25 ° C. paraxylene soluble component amount (CXS)
It is preferable that the propylene polymer (Y) used in the present invention has high stereoregularity and has few low crystalline components that cause stickiness and bleed out of the molded product. This low crystallinity component is evaluated by the amount of xylene soluble component (CXS) at 25 ° C. In the present invention, it is necessary to be less than 5.0% by weight based on the total amount of the propylene polymer (Y). Preferably, it is 3.0 weight% or less, More preferably, it is 1.0 weight% or less, More preferably, it is 0.5 weight% or less. The lower limit is not particularly limited, but is usually 0.01% by weight or more, preferably 0.03% by weight or more.

In addition, the detail of the measuring method of 25 degreeC xylene soluble component amount (CXS) is as follows.
A 2 g sample (propylene polymer (Y)) is dissolved in 300 ml of p-xylene (containing 0.5 mg / ml BHT) at 130 ° C. to form a solution, and then left at 25 ° C. for 12 hours. Thereafter, the precipitated polymer is separated by filtration, p-xylene is evaporated from the filtrate, and further dried under reduced pressure at 100 ° C. for 12 hours to recover xylene-soluble components at room temperature. The ratio (% by weight) of the weight of the recovered component to the charged sample weight is defined as CXS.

  In order to make CXS less than 5% by weight, it can be produced by using a metallocene catalyst, as will be described later. It is necessary that the reaction conditions are not extremely high and that the amount ratio of the organoaluminum compound to the metallocene complex is not increased too much.

  The propylene polymer (Y) used in the present invention preferably satisfies the following properties (Yv) to (Y-vii) in addition to the properties (i) to (iv).

(5) Characteristic (Yv): Branch index g ′
As a direct indicator that the propylene polymer (Y) used in the present invention has long chain branching, a branching index g ′ can be mentioned. g ′ is given by the ratio of the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight as the intrinsic viscosity [η] br of the polymer having a long chain branched structure, that is, [η] br / [η] lin. When a long chain branched structure is present, the value is smaller than 1.
The definition is described in, for example, “Developments in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and is an index known to those skilled in the art.
The branching index g ′ can be obtained as a function of absolute molecular weight (Mabs), for example, by using GPC with a light scatterometer and viscometer in the detector.

  The propylene polymer (Y) used in the present invention preferably has a g ′ of 0.30 or more and less than 1.00, more preferably 0, when the absolute molecular weight (Mabs) obtained by light scattering is 1,000,000. 0.55 or more and 0.98 or less, more preferably 0.75 or more and 0.96 or less, and particularly preferably 0.78 or more and 0.95 or less.

  The propylene polymer (Y) used in the present invention is preferably considered to have a comb chain formed as a molecular structure, and when the branching index g ′ is less than 0.30, the main chain is less. The chain ratio is extremely large. In such a case, the melt tension may not be improved, or a gel or white spot may be generated due to poor dispersion, which is not preferable. On the other hand, when the branching index g ′ is 1.00 or more, this means that there is no long chain branching, and the effect of suppressing weld whitening does not appear.

In addition, it is preferable for the following reasons that the lower limit of g ′ is the above value.
According to the document “Encyclopedia of Polymer Science and Engineering vol. 2” (John Wiley & Sons 1985 p. 485), the g ′ value of the comb polymer is represented by the following formula.

  Here, g is a branching index defined by the rotation radius ratio of the polymer, and ε is a constant determined by the shape of the branched chain and the solvent. According to Table 3 of 487, a value of about 0.7 to 1.0 is reported for the comb chain in a good solvent. λ is the ratio of the main chain in the comb chain, and p is the average number of branches. According to this formula, the number of branches is extremely large for a comb chain, that is, p is infinite, and g ′ = gε = λε, which is not less than the value of λε. There will be a value.

  On the other hand, a conventionally known random branched chain formula that is considered to occur in the case of electron beam irradiation or peroxide degradation is given by the formula (19) on page 485 in the same document. In the branched chain, as the number of branch points increases, g ′ and g value monotonously decrease without any lower limit value. That is, in the present invention, the fact that the g ′ value has a lower limit means that the propylene polymer (Y) having a long chain branched structure used in the present invention has a structure close to a comb chain. This makes the distinction from random branched chains generated by conventional electron beam irradiation or peroxide degradation more clear.

  Further, in a branched polymer having a structure close to a comb chain in which g ′ is in the above range, when the kneading is repeated, the degree of decrease in melt tension is small. The decrease in physical properties and moldability is reduced.

A specific method for calculating the branching index g ′ is as follows.
Waters Alliance GPCV2000 is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). As the light scattering detector, a DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (an antioxidant “Irganox 1076” manufactured by BASF Japan Ltd. is added at a concentration of 0.5 mg / mL).
The flow rate is 1 mL / min, and two columns of Tosoh Corporation GMHHR-H (S) HT are connected and used. The temperature of the column, sample injection section, and each detector is 140 ° C. The sample concentration is 1 mg / mL and the injection volume (sample loop volume) is 0.2175 mL.

In order to obtain the absolute molecular weight (Mabs) obtained from MALLS, the mean square inertia radius (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer, the data processing software ASTRA (version 4.73.04) attached to MALLS is used. The calculation is performed with reference to the following documents.
1. "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1.)
2. Polymer, 45, 6495-6505 (2004).
3. Macromolecules, 33, 2424-2436 (2000).
4). Macromolecules, 33, 6945-6925 (2000).

The branching index g ′ is a ratio of the intrinsic viscosity ([η] _br ) obtained by measuring a sample with the above Viscometer and the intrinsic viscosity ([η] _lin ) obtained separately by measuring a linear polymer ([[eta] _lin ). η] _br / [η] _lin ).

When a long-chain branched structure is introduced into a polymer molecule, the radius of inertia becomes smaller than that of a linear polymer molecule having the same molecular weight. Since the intrinsic viscosity becomes smaller as the radius of inertia becomes smaller, the intrinsic viscosity ([η] _br ) of the branched polymer with respect to the intrinsic viscosity ([η] _lin ) of the linear polymer having the same molecular weight as the long-chain branched structure is introduced. ) Ratio ([η] _br / [η] _lin ) becomes smaller.
Therefore, when the branching index (g ′ = [η] _br / [η] _lin ) becomes a value smaller than 1, it means that a branch is introduced. Here, as a linear polymer for obtaining [η] _lin , a commercially available homopolypropylene (“Novatec PP (registered trademark)” manufactured by Nippon Polypro Co., Ltd., grade name: FY6) is used. Since it is known as the Mark-Houwink-Sakurada equation that the logarithm of [η] _lin of a linear polymer has a linear relationship with the logarithm of molecular weight, [η] _lin is on the low molecular weight side or the high molecular weight side. A numerical value can be obtained by extrapolating as appropriate.

  In order to make the branching index g ′ 0.30 or more and less than 1.00, it is achieved by introducing many long-chain branches, selection of preferred metallocene catalysts described later, a combination thereof, a quantitative ratio thereof, and prepolymerization This can be achieved by controlling the conditions for polymerization.

(6) Characteristic (Y-vi): mm fraction of propylene unit 3 chain by ¹³ C-NMR The propylene polymer (Y) used in the present invention is characterized by high stereoregularity. Stereoregularity of the ^height 13 that can be evaluated by ^{C-NMR, 13 C-NMR} mm fraction of the propylene unit triad sequences obtained by it is preferably 95% or more.
As for the mm fraction, the upper limit of the ratio of three propylene unit chains in which the direction of methyl branching in each propylene unit is the same in any three propylene unit chains composed of head-to-tail bonds in the polymer chain is 100%. This mm fraction is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and the higher the value, the higher the degree of control. If the mm fraction is smaller than this value, the mechanical properties tend to decrease.
Accordingly, the mm fraction is preferably 95% or more, more preferably 96% or more, and still more preferably 97% or more.

The detail of the measuring method of mm fraction of the propylene unit 3 chain | strand by ¹³ C-NMR is as follows.
A sample of 375 mg is completely dissolved in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), and then measured at 125 ° C. by a proton complete decoupling method. The chemical shift sets the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. The chemical shift of other carbon peaks is based on this.
・ Flip angle: 90 degrees ・ Pulse interval: 10 seconds ・ Resonance frequency: 100 MHz or more ・ Number of integrations: 10,000 or more ・ Observation range: −20 ppm to 179 ppm
-Number of data points: 32768

The analysis of the mm fraction is performed using the measured ¹³ C-NMR spectrum.
The spectrum is assigned with reference to Macromolecules, (1975) 8 pp. 687 and Polymer, 30, vol. 1, 1350 (1989).
Note that a more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of Japanese Patent Laid-Open No. 2009-275207, and the present invention is performed according to this method. .

  The mm fraction can be 95% or more by using a polymerization catalyst that achieves a highly crystalline polymer, and by using a preferred metallocene catalyst described later for polymerization.

(7) Characteristic (Y-vii): Strain hardening degree (λmax)
As a further additional feature of the propylene polymer (Y) used in the present invention, the strain hardening degree [λmax (0.1)] in the measurement of elongational viscosity at a strain rate of 0.1 s ⁻¹ is 6.0 or more. There are some.
The strain hardening degree [λmax (0.1)] is an index representing the strength at the time of melting, and when this value is large, there is an effect of improving the melt tension. As a result, the flow front (melt front) at the time of injection molding becomes dull, and the weld suppression effect is improved. The strain hardening degree is preferably 6.0 or more, and more preferably 8.0 or more.

Details of the calculation method of λmax (0.1) are as follows.
The elongational viscosity at a temperature of 180 ° C. and a strain rate = 0.1 s ⁻¹ is plotted on a logarithmic graph with the horizontal axis representing time t (seconds) and the vertical axis representing elongational viscosity ηE (Pa · seconds). On the log-log graph, the viscosity immediately before strain hardening is approximated by a straight line.
Specifically, first, the slope at each time when the extensional viscosity is plotted against time is obtained. In this case, considering that the measurement data of the extensional viscosity is discrete, various averaging methods are used. Is used. For example, there is a method of obtaining the slope of adjacent data and taking a moving average of several surrounding points.

  The elongational viscosity is a simple increasing function in the low strain region, gradually approaches a constant value, and if there is no strain hardening, it agrees with the Truton viscosity after a sufficient amount of time. From about 1 strain amount (= strain rate × time), the extensional viscosity starts to increase with time. That is, the slope tends to decrease with time in the low strain region, but tends to increase from about 1 strain, and there is an inflection point on the curve when the extensional viscosity is plotted against time. . Therefore, a point where the slope of each time obtained above takes the minimum value in the range of the distortion amount of about 0.1 to 2.5 is obtained, and a tangent line is drawn at the point, and the straight line has a distortion amount of 4.0. Extrapolate until The maximum value (ηmax) of the extensional viscosity ηE until the strain amount becomes 4.0 is obtained, and the viscosity on the approximate straight line up to that time is ηlin. ηmax / ηlin is defined as λmax (0.1).

2-2. Production method of propylene polymer (Y) having a long-chain branched structure The propylene polymer (Y) having a long-chain branched structure is not particularly limited as long as the above-described properties are satisfied. In addition, the preferred production method for satisfying all the conditions of low low crystalline component amount, high stereoregularity, relatively wide molecular weight distribution, range of branching index g ′ and high melt tension uses a combination of metallocene catalysts. This method uses the macromer copolymerization method. As an example of such a method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 2009-57542 can be given.
This method produces a polypropylene having a long-chain branched structure using a catalyst in which a catalyst component having a specific structure having macromer-producing ability and a catalyst component having a specific structure having high molecular weight and macromer copolymerization ability are combined. According to this, industrially effective methods such as bulk polymerization and gas phase polymerization, particularly single-stage polymerization under practical pressure-temperature conditions, and using hydrogen as a molecular weight regulator. It is possible to produce a polypropylene resin having a long-chain branched structure having the desired physical properties.

In the past, it was necessary to increase the branching efficiency by lowering the crystallinity by using a polypropylene component having a low stereoregularity. However, in the above method, a polypropylene component having a sufficiently high stereoregularity is required. It can be introduced into the side chain by a simple method, and is preferable as the propylene polymer (Y) used in the present invention. It is suitable for satisfying the characteristics relating to the fraction and the amount of paraxylene-soluble component (CXS).
In addition, by using the above-mentioned method, it is possible to broaden the molecular weight distribution by using two types of catalysts having greatly different polymerization characteristics, and simultaneously satisfy the characteristics relating to the melt tension, the molecular weight distribution Mw / Mn, and the branching index g ′. It is preferable.

Then, the preferable manufacturing method of the propylene polymer (Y) which has a long chain branched structure used by this invention is described in detail below.
A preferred method for producing a propylene polymer (Y) having a long-chain branched structure includes a method for producing a propylene-based polymer using the following catalyst components (A), (B) and (C) as propylene polymerization catalysts. .
Catalyst component (A): at least one component from component [A-1] which is a compound represented by the following general formula (a1) and component [A-2] which is a compound represented by the following general formula (a2) To 4 or more transition metal compounds of Group 4 of the periodic table.
Catalyst component (B): ion-exchangeable layered silicate.
Catalyst component (C): an organoaluminum compound.

Hereinafter, the catalyst components (A), (B), and (C) will be described in detail.
(1) Catalyst component (A)
(I) Component [A-1]: Compound represented by the following general formula (a1)

[In General Formula (a1), R ¹¹ and R ¹² each independently represent a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. R ¹³ and R ¹⁴ each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these, having 6 to 16 carbon atoms An aryl group, a heterocyclic group containing 6 to 16 carbon atoms, nitrogen, oxygen or sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹¹ and R ¹² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, It is a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
Moreover, as a substituted 2-furyl group, a substituted 2-thienyl group, and a substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, Examples include halogen atoms such as fluorine atom and chlorine atom, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, and trialkylsilyl groups. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.

Carbon atoms 6 to 16 of the R ¹³ and R ^14, halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or may contain a plurality of hetero elements selected from these, the aryl group In the range of 6 to 16 carbon atoms, one or more hydrocarbon group having 1 to 6 carbon atoms, silicon-containing hydrocarbon group having 1 to 6 carbon atoms, 1 to 6 carbon atoms on the aryl cyclic skeleton It may have a halogen-containing hydrocarbon group as a substituent.
At least one of R ¹³ and R ¹⁴ is preferably a phenyl group, a 4-methylphenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, or 2,3-dimethyl. A phenyl group, 3,5-di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably a phenyl group, 4-i-propylphenyl group, 4- t-butylphenyl group, 4-trimethylsilylphenyl group, 4-chlorophenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

In the general formula (a1), X ¹¹ and Y ¹¹ are auxiliary ligands, and react with the co-catalyst of the catalyst component (B) to generate an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹¹ and Y ¹¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. A C1-C20 silicon-containing hydrocarbon group, a C1-C20 halogenated hydrocarbon group, a C1-C20 oxygen-containing hydrocarbon group, an amino group, or a C1-C20 nitrogen-containing hydrocarbon Indicates a group.

In the general formula (a1), Q ¹¹ is a silylene that may have a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms that connects two five-membered rings. Represents either a group or a germylene group. When two hydrocarbon groups are present on the silylene group or the germylene group, they may be bonded to each other to form a ring structure.
Specific examples of Q ¹¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene and 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di ( n-propyl) silylene, di (i-propyl) silylene, alkylsilylene groups such as di (cyclohexyl) silylene, (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; arylsilylene groups such as diphenylsilylene; tetra An alkyl oligosilylene group such as methyldisilylene; a germylene group; an alkylgermylene group in which the silicon of the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) germylene Group; arylgermylene group And so on. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

Of the compounds represented by the general formula (a1), preferred compounds are specifically exemplified below.
Dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-thienyl) -4-phenyl -Indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-diphenylsilylenebis {2 -(5-Methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl} ] Hafnium, dichloro [1,1'-dimethylgermylenebis {2- (5-methyl-2-thienyl) -4-phenyl-indenyl}] hafnium, dic B [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5- Trimethylsilyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-phenyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (4,5-dimethyl-2-furyl) -4-phenyl-indenyl}] hafnium dichloride, dichloro [1,1′-dimethylsilylenebis {2- (2-benzofuryl) ) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- ( -Methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2 -Furfuryl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-fluorophenyl) -indenyl}] Hough , Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trifluoromethylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylene Bis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4 -(1-Naphtyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1 ′ -Dimethylsilylenebis {2- (2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (2-furyl) -4- (9-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (1-naphthyl) -indenyl}] hafnium, Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- ( 5-methyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (9- Phenanthryl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (1-naphthyl) -indenyl}] ha Nitrogen, dichloro [1,1′-dimethylsilylenebis {2- (5-tert-butyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-t-butyl-2-furyl) -4- (2-phenanthryl) -indenyl}] hafnium, dichloro [1,1'-dimethylsilylenebis {2- (5-t-butyl-2- Furyl) -4- (9-phenanthryl) -indenyl}] hafnium.

  Of these, more preferred are dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylene. Bis {2- (5-methyl-2-furyl) -4- (4-methylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-trimethylsilylphenyl) -indenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-chlorophenyl) -indenyl}] hafni Dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (2-naphthyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -(5-Methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl}] hafnium.

  Particularly preferred is dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4-phenyl-indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2- (5-Methyl-2-furyl) -4- (4-ipropylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)- 4- (4-Trimethylsilylphenyl) -indenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-t-butylphenyl) -indenyl} ] Hafnium.

(Ii) Component [A-2]: Compound represented by general formula (a2)

[In General Formula (a2), R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ²³ and R ²⁴ are each independently halogen, silicon, oxygen, It is a C6-C16 aryl group which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of heteroelements selected from these. X ²¹ and Y ²¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ²¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon number It represents a silylene group or a germylene group which may have 1 to 20 hydrocarbon groups. M ²¹ is zirconium or hafnium. ]

R ²¹ and R ²² are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, and preferably methyl. , Ethyl, n-propyl.

In addition, R ²³ and R ²⁴ each independently contain a halogen having 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms, silicon, or a plurality of hetero elements selected from these. It is a good aryl group. Preferable examples include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-fluoro-4-biphenylyl), 4- (2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dichloro-4-trimethylsilylphenyl, and the like.

Further, the X ²¹ and Y ²¹ are auxiliary ligands, it reacts with the cocatalyst of the catalyst component (B) to form an active metallocene having olefin polymerizability. Therefore, as long as this object is achieved, X ²¹ and Y ²¹ are not limited in the type of ligand, and are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, C1-C20 silicon-containing hydrocarbon group, C1-C20 halogenated hydrocarbon group, C1-C20 oxygen-containing hydrocarbon group, amino group, or C1-C20 nitrogen-containing hydrocarbon group Indicates.

Q ²¹ is a binding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. A silylene group or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon and germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked.
Specific examples of Q ²¹ include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, Examples include diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene, methylphenylgermylene, and the like.

Further, M ²¹ is zirconium or hafnium, preferably hafnium.

As a non-limiting example of the metallocene compound represented by the general formula (a2), the following can be preferably exemplified.
However, in the following, only representative exemplary compounds are described avoiding many complicated examples, and the present invention is not construed as being limited to these compounds, and various ligands, cross-linking groups or auxiliary groups are described. Obviously, any ligand can be used. In the following, a compound in which the central metal is hafnium is described, but a compound replacing zirconium is also treated as disclosed in this specification.

  Dichloro {1,1′-dimethylsilylenebis (2-methyl-4-phenyl-4-hydroazurenyl)} hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4 -Hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-methyl-4- (4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-t-butylphenyl)- 4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- ( -Methyl-4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl} ] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2 -Methyl-4- (1-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [ 1,1′-dimethylsilylenebis {2-methyl-4- (4-chloro-2-naphthyl)- -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Methyl-4- (2-chloro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (9-phenanthryl) -4-hydroazurenyl] }] Hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-n-propyl -4- (3-Chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] huff Nitrogen, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-chloro-4-tert-butylphenyl) -4-hydroazulenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis { 2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (2-fluoro-4-biphenylyl) ) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylgermylenebis {2-methyl-4- (4-t-butylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′- (9-silafluorene-9,9-diyl) bis {2-ethyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Funium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-fluoro-4-biphenylyl) -4-hydroazulenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3 5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium and the like.

  Of these, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2- Methyl-4- (3-chloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (2-fluoro-4-biphenylyl) -4 -Hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (4-chloro-2-naphthyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-Ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4-hydroazurenyl}] ha Dichloro, [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] hafnium, is there.

  Particularly preferably, dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl -4- (2-Fluoro-4-biphenylyl) -4-hydroazurenyl}] hafnium, dichloro [1,1′-dimethylsilylenebis {2-ethyl-4- (3-methyl-4-trimethylsilylphenyl) -4- Hydroazurenyl}] hafnium, dichloro [1,1 ′-(9-silafluorene-9,9-diyl) bis {2-ethyl-4- (3,5-dichloro-4-trimethylsilylphenyl) -4-hydroazurenyl}] Hafnium.

(2) Catalyst component (B)
The catalyst component (B) preferably used for producing the propylene polymer (Y) is an ion-exchange layered silicate.
(I) Types of ion-exchanged layered silicates Ion-exchanged layered silicates (hereinafter sometimes simply referred to as silicates) are surfaces formed by ionic bonds or the like that are parallel to each other with a binding force. A silicate compound having a stacked crystal structure and containing exchangeable ions. Most silicates are mainly produced as a main component of clay minerals in nature, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. Good. Depending on the type, amount, particle size, crystallinity, and dispersion state of these impurities, it may be preferable to pure silicate, and such a complex is also included in the catalyst component (B).
The silicate to be used is not limited to a natural product, and may be an artificial synthetic product or may contain them.

Specific examples of the silicate include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
That is, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stemite and other smectites, vermiculite and other vermiculites, mica, illite, sericite and sea chlorite and other mica, attapulgite, sepiolite and palygorskite , Bentonite, pyrophyllite, talc, chlorite group, etc.
The silicate is preferably a silicate in which the main component silicate has a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The type of interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easy and inexpensive to obtain as an industrial raw material.

(Ii) Chemical treatment of ion-exchangeable layered silicate The ion-exchangeable layered silicate of the catalyst component (B) can be used as it is without any particular treatment, but it is preferable to perform chemical treatment. Here, the chemical treatment of the ion-exchange layered silicate can be any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the structure of the clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like.

<Acid treatment>:
In addition to removing impurities on the surface, the acid treatment can elute some or all of cations such as Al, Fe, Mg, etc. in the crystal structure.
The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
Two or more salts (described in the next section) and acid may be used for the treatment. The treatment conditions with salts and acids are not particularly limited. Usually, the salt and acid concentrations are 0.1 to 50% by weight, the treatment temperature is room temperature to boiling point, and the treatment time is 5 minutes to 24 hours. It is preferable to carry out the process under the condition of selecting and eluting at least a part of the substance constituting at least one compound selected from the group consisting of ion-exchangeable layered silicates. In addition, salts and acids are generally used in an aqueous solution.

In addition, you may use what combined the following acids and salts as a processing agent. Moreover, the combination of these acids and salts may be sufficient.
<Salt treatment>:
Cations that are preferably 40% or more, more preferably 60% or more, of the exchangeable Group 1 metal cations contained in the ion-exchange layered silicate before being treated with salts, dissociated from the salts shown below. It is preferable to perform ion exchange.
The salt used in the salt treatment for the purpose of ion exchange is a group consisting of a cation containing at least one atom selected from the group consisting of group 1 to 14 atoms, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion selected from the group consisting of at least one anion selected from the group consisting of group 2 to 14 atoms, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ) At least one anion selected from the group consisting of OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₅ H ₅ O ₇ Is a compound consisting of

Preferred examples of such _{salts, LiF, LiCl, LiBr, LiI} , Li 2 SO 4, Li (CH 3 COO), LiCO 3, Li (C 6 H 5 O 7), LiCHO 2, LiC 2 O ₄ , LiClO ₄ , Li ₃ PO ₄ , CaCl ₂ , CaSO ₄ , CaC ₂ O ₄ , Ca (NO ₃ ) ₂ , Ca ₃ (C ₆ H ₅ O ₇ ) ₂ , MgCl ₂ , MgBr ₂ , MgSO ₄ , Mg (PO ₄ ) ₂ , Mg (ClO ₄ ) ₂ , MgC ₂ O ₄ , Mg (NO ₃ ) ₂ , Mg (OOCCH ₃ ) ₂ , MgC ₄ H ₄ O _{4 and the} like.
Further, Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , Zr (OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), HF (OOCCH ₃ ) ₄ , HF (CO ₃ ) ₂ , HF (NO ₃ ) ₄ , HF (SO ₄ ) ₂ , HFOCl ₂ , HFF ₄ , HFCl ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr _{3 and the} like.

Also, Cr (CH ₃ COCHCOCH ₃ ) ₃ , Cr (OOCCH ₃ ) ₂ OH, Cr (NO ₃ ) ₃ , Cr (ClO ₄ ) ₃ , CrPO ₄ , Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Mn (OOCCH ₃ ) ₂ , Mn (CH ₃ COCHCOCH ₃ ) ₂ , MnCO ₃ , Mn (NO ₃ ) ₂ , MnO, Mn (ClO ₄ ) ₂ , MnF ₂ , MnCl ₂ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeC ₆ H ₅ O _{7 and the} like.

In addition, Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr _{2 and the} like.
Furthermore, Zn (OOCCH ₃ ) ₂ , Zn (CH ₃ COCHCOCH ₃ ) ₂ , ZnCO ₃ , Zn (NO ₃ ) ₂ , Zn (ClO ₄ ) ₂ , Zn ₃ (PO ₄ ) ₂ , ZnSO ₄ , ZnF ₂ , ZnCl ₂ , AlF ₃ , AlCl ₃ , AlBr ₃ , AlI ₃ , Al ₂ (SO ₄ ) ₃ , Al ₂ (C ₂ O ₄ ) ₃ , Al (CH ₃ COCHCOCH ₃ ) ₃ , Al (NO ₃ ) ₃ , AlPO ₄ , GeCl ₄ , GeBr ₄ , GeI _{4 and the} like.

<Alkali treatment>:
In addition to acid and salt treatment, the following alkali treatment or organic matter treatment may be performed as necessary. Examples of the treating agent used in the alkali treatment include LiOH, NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (OH) _{2 and the} like.

<Organic treatment>:
Examples of the organic treatment agent used for the organic treatment include trimethylammonium, triethylammonium, N, N-dimethylanilinium, triphenylphosphonium, and the like.
Examples of the anion constituting the organic treatment agent include hexafluorophosphate, tetrafluoroborate, and tetraphenylborate other than the anion exemplified as the anion constituting the salt treatment agent. However, it is not limited to these.

  Moreover, these processing agents may be used independently and may be used in combination of 2 or more types. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment. The chemical treatment can be performed a plurality of times using the same or different treatment agents.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water and use them as the catalyst component (B).
The heat treatment method of the ion-exchange layered silicate adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is 0.5 hour or longer, preferably 1 hour or longer. At that time, the water content of the catalyst component (B) after the removal is 3% by weight or less when the water content when dehydrating for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight, It is preferably 1% by weight or less.

As described above, particularly preferable as the catalyst component (B) is an ion-exchange layered silicate having a water content of 3% by weight or less, which is obtained by performing a salt treatment and / or an acid treatment.
The ion-exchange layered silicate can be treated with a catalyst component (C) of an organoaluminum compound, which will be described later, before formation of a catalyst or use as a catalyst, which is preferable. Although there is no restriction | limiting in the usage-amount of the catalyst component (C) with respect to 1g of ion-exchange layered silicate, Usually, 20 mmol or less, Preferably it is 0.5 mmol or more and 10 mmol or less. There is no limitation on the treatment temperature and time, the treatment temperature is usually 0 ° C. or more and 70 ° C. or less, and the treatment time is 10 minutes or more and 3 hours or less. It is possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as that used in the preliminary polymerization and slurry polymerization described later is used.

The catalyst component (B) is preferably spherical particles having an average particle size of 5 μm or more. If the particle shape is spherical, a natural product or a commercially available product may be used as it is, or a particle whose particle shape and particle size are controlled by granulation, sizing, fractionation, or the like may be used.
Examples of the granulation method used here include a stirring granulation method and a spray granulation method, but commercially available products can also be used.
Moreover, you may use organic substance, an inorganic solvent, inorganic salt, and various binders in the case of granulation.
The spherical particles obtained as described above desirably have a compressive fracture strength of 0.2 MPa or more, particularly preferably 0.5 MPa or more, in order to suppress crushing and generation of fine powder in the polymerization process. In the case of such particle strength, the effect of improving the particle properties is effectively exhibited particularly when prepolymerization is performed.

(3) Catalyst component (C)
The catalyst component (C) is an organoaluminum compound. The organoaluminum compound used as the catalyst component (C) is preferably a compound represented by the following general formula.
General ^{_{formula: (AlR 31 q Z 3-}} q) p
(In the formula, R ³¹ represents a hydrocarbon group having 1 to 20 carbon atoms, Z represents a halogen, hydrogen, an alkoxy group or an amino group. Q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively. Represents.)

In this invention, it cannot be overemphasized that the compound represented by the said formula can be used individually, in mixture of multiple types or in combination.
In the above ^{formulas, R 31} represents a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen, hydrogen, an alkoxy group or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2, respectively.
R ³¹ is preferably an alkyl group, and Z is a chlorine atom when it is halogen, a C 1-8 alkoxy group when it is an alkoxy group, and a carbon atom number 1 when it is an amino group. An amino group of ˜8 is preferred.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum and alkylaluminum hydride having p = 1 and q = 3 are preferable. More preferably, it is trialkylaluminum in which R ³¹ is an alkyl group having 1 to 8 carbon atoms.

(4) Catalyst formation / preliminary polymerization In the catalyst, the above catalyst components (A) to (C) are contacted in the (preliminary) polymerization tank simultaneously or continuously, or once or multiple times. Can be formed.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but it is preferably performed between −20 ° C. and + 150 ° C. As the contact order, any desired combination can be used, but particularly preferable ones for each component are as follows.

When the catalyst component (C) is used, the catalyst component (A), the catalyst component (B), or the catalyst component (A) and the catalyst are brought into contact before the catalyst component (A) and the catalyst component (B) are brought into contact with each other. Contacting catalyst component (C) with both components (B), or contacting catalyst component (C) with catalyst component (A) and catalyst component (B), or catalyst component Although it is possible to contact the catalyst component (C) after bringing the catalyst component (B) into contact with (A), it is preferable that the catalyst component be brought into contact with the catalyst component (A) before contacting the catalyst component (B). It is a method of contacting any of the component (C).
Moreover, after contacting each component, it is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amount of catalyst components (A), (B), and (C) used is arbitrary. For example, the amount of the catalyst component (A) used relative to the catalyst component (B) is preferably in the range of 0.1 μmol to 1,000 μmol, particularly preferably 0.5 μmol to 500 μmol, relative to 1 g of the catalyst component (B). The amount of the catalyst component (C) relative to the catalyst component (A) is preferably a transition metal molar ratio of preferably 0.01 to 5 × 10 ⁶ , particularly preferably within a range of 0.1 to 1 × 10 ^4. .

  The component [A-1] (compound represented by the general formula (a1)) and the component [A-2] (compound represented by the general formula (a1)) are used in proportion to the propylene polymer (Y). The molar ratio of the transition metal of [A-1] to the total amount of the components [A-1] and [A-2] is preferably 0.30 or more, 0 .99 or less.

  By changing this ratio, it is possible to adjust the balance between melt physical properties and catalyst activity. That is, from the component [A-1], a low molecular weight terminal vinyl macromer is produced, and from the component [A-2], a high molecular weight body obtained by copolymerizing a part of the macromer is produced. Therefore, by changing the ratio of the component [A-1], the average molecular weight, molecular weight distribution, bias of the molecular weight distribution toward the high molecular weight side, very high molecular weight component, branch (amount, length, Distribution) can be controlled, whereby the melt properties such as branching index g ′, strain hardening degree λmax, melt tension, and spreadability can be controlled.

In order to produce the propylene polymer (Y), the molar ratio of the transition metal of the component [A-1] to the total amount of the components [A-1] and [A-2] is preferably 0.30 or more. Is required, more preferably 0.40 or more, and still more preferably 0.5 or more. Further, the upper limit is preferably 0.99 or less, and preferably 0.95 or less, more preferably 0.90 or less in order to efficiently obtain a propylene polymer (Y) with high catalytic activity. Range.
In addition, by using component [A-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the amount of hydrogen.

  The catalyst is preferably subjected to a prepolymerization treatment which consists of contacting it with an olefin and polymerizing it in a small amount. By performing the prepolymerization treatment, gel formation can be prevented when the main polymerization is performed. The reason is considered to be that long-chain branches can be uniformly distributed among the polymer particles when the main polymerization is performed, and the melt physical properties can be improved thereby.

  The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene and the like can be exemplified. The olefin feed method may be any method such as a feed method for maintaining the olefin at a constant rate or a constant pressure in the reaction tank, a combination thereof, or a stepwise change.

The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to + 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 in terms of a weight ratio with respect to the catalyst component (B). Moreover, a catalyst component (C) can also be added or added at the time of prepolymerization. It is also possible to wash after the prepolymerization.
In addition, a method of coexisting a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or titania, at the time of contacting or after contacting each of the above components is also possible.

(5) Use of Catalyst / Propylene Polymerization Any polymerization mode can be used as long as the olefin polymerization catalyst including the catalyst component (A), the catalyst component (B), and the catalyst component (C) is in efficient contact with the monomer. Can be adopted.
Specifically, a slurry method using an inert solvent, a so-called bulk method using a propylene as a solvent without using an inert solvent as a solvent, a solution polymerization method, or a monomer without using a liquid solvent substantially. A gas phase method can be used. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied. In addition to single-stage polymerization, it is possible to carry out multistage polymerization of two or more stages.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent.

The polymerization temperature is usually 0 ° C. or higher and 150 ° C. or lower. In particular, when bulk polymerization is used, the temperature is preferably 40 ° C or higher, more preferably 50 ° C or higher. The upper limit is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.
Furthermore, when using vapor phase polymerization, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. The upper limit is preferably 100 ° C. or lower, more preferably 90 ° C. or lower.
The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. In particular, when bulk polymerization is used, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, more preferably 3.5 MPa or less.
Furthermore, when using vapor phase polymerization, 1.5 MPa or more is preferable, and 1.7 MPa or more is more preferable. Further, the upper limit is preferably 2.5 MPa or less, and more preferably 2.3 MPa or less.

Furthermore, as a molecular weight regulator and for the activity improvement effect, hydrogen is supplementarily in a molar ratio with respect to propylene, preferably in the range of 1.0 × 10 ⁻⁶ or more and 1.0 × 10 ⁻² or less. Can be used.
Also, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer to be produced, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, very high molecular weight components, branching (amount, length, Distribution) can be controlled, whereby the melt physical properties characterizing polypropylene having a long chain branching structure such as MFR, branching index, strain hardening degree, melt tension MT, and spreadability can be controlled.
Therefore, hydrogen should be used at a molar ratio to propylene of 1.0 × 10 ⁻⁶ or more, preferably 1.0 × 10 ⁻⁵ or more, more preferably 1.0 × 10 ⁻⁴ or more. Is good. Moreover, regarding an upper limit, it is good to use at 1.0 * 10 ^<-2> or less, Preferably it is 0.9 * 10 ^<-2> or less, More preferably, it is 0.8 * 10 ^<-2> or less.

  Moreover, you may perform the copolymerization which uses a C2-C20 alpha olefin comonomer except propylene, for example, ethylene and / or 1-butene as a comonomer other than a propylene monomer.

  Therefore, in order to obtain a propylene polymer (Y) used in the present invention having a good balance between catalytic activity and melt properties, it is preferable to copolymerize ethylene and / or 1-butene. Is preferably used in an amount of not more than 15 mol%, more preferably not more than 10 mol%, still more preferably not more than 7 mol% with respect to propylene.

  When propylene is polymerized using the catalyst and polymerization method exemplified here, one end of the polymer is mainly propenyl from the active species derived from the catalyst component [A-1] by a special chain transfer reaction generally called β-methyl elimination. The structure is shown and so-called macromers are produced. This macromer can generate a higher molecular weight and is taken into the active species derived from the catalyst component [A-2] having a better copolymerization property, and it is considered that the macromer copolymerization proceeds. Therefore, it is considered that the comb chain is the main branch structure of the polypropylene resin having a long chain branch structure to be generated.

3. Proportion of propylene-based (co) polymer (X) and propylene polymer (Y) Ratio of propylene-based (co) polymer (X) and propylene polymer (Y) in the propylene-based resin composition for injection molding of the present invention. Is based on a total of 100% by weight of the propylene-based (co) polymer (X) and the propylene polymer (Y), and the propylene-based (co) polymer (X) is 75 to 97% by weight, and the propylene polymer (Y) 3 ~ 25% by weight. By setting it as such a range, the balance of transparency, mechanical physical properties, and the effect of suppressing weld whitening is improved, and a resin composition that can be suitably used in injection molding can be obtained.

4). Clearing nucleating agent (Z)
The transparent nucleating agent (Z) used in the propylene resin composition for injection molding of the present invention is a transparent nucleating agent represented by the following chemical structural formula (1).

[In formula (1), n is an integer of 0 to ^2, R 1 to R ⁵ are the same or different, each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, It is a carbonyl group, a halogen group or a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ]

In the chemical structural formula (1), preferably, n is an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are each a hydrogen atom, and R ³ and R ⁶ are the same or Differently, each is an alkyl group having 1 to 20 carbon atoms. More preferably, n is an integer of 0 to 2, R ¹ , R ² , R ⁴ and R ⁵ are each a hydrogen atom, and R ³ is —CH ₃ , —CH ₂ CH ₃ , —CH. _{2 CH 2 CH 3, -CH 2} CH 2 CH 2 CH 3, -CH 2 CH = CH 2, -CH (CH 3) CH = CH 2, -CH 2 CH-X 1 -CH 2 -X 2, - CH ₂ CH—X ³ —CH ₂ CH ₃ , —CH ₂ CH—X ⁴ —CH ₂ OH or —CH ₂ OH—CH (OH) —CH ₂ OH (where X ^{1 to} X ⁴ are each An independent halogen group), and R ⁶ is an alkyl group having 1 to 20 carbon atoms.

  As the transparent nucleating agent (Z), in the transparent nucleating agent represented by the chemical structural formula (1), specifically, for example, a nonitol type transparent nuclei which is a compound represented by the following chemical structural formula (2) An agent is mentioned and preferable. The compound represented by the following chemical structural formula (2) is 3,5: 4,6-bis [4-propylbenzylidenebis (oxy)]-1,2-nonanediol or the conventional name 1,2,3-trideoxy. -4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol.

  The clearing nucleating agent (Z) used in the present invention can give the molded article obtained very excellent transparency that is impossible to achieve with conventional clearing nucleating agents. In addition, since it is possible to give a higher crystallization temperature than the conventional clearing nucleating agent, it is possible to realize improvement in molding processability.

  The blending amount of the clearing nucleating agent (Z) used in the propylene-based resin composition of the present invention is 0 with respect to a total of 100 parts by weight of the propylene-based (co) polymer (X) and the propylene polymer (Y). 0.01 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight. When the blending amount is less than 0.01 parts by weight, it is difficult to obtain a sufficient effect. On the other hand, when the blending amount exceeds 2.0 parts by weight, the nucleating agent is aggregated and the transparency may be lowered. More preferably, it is 0.1-1.0 weight part, and 0.3-0.6 weight part is further more preferable.

  As a manufacturing method of the transparent nucleating agent (Z) used by this invention, the method as described in WO2005 / 111134 (or the special table 2007-534827 of the said patent document 3) gazette etc. can be mentioned. Commercially available products can also be easily obtained, and for example, MIRAD NX8000J (Milken & Company) can be mentioned.

  Moreover, in the propylene-type resin composition of this invention, you may use together at least 1 sort (s) of another nucleating agent other than the clearing nucleating agent (Z) shown by Chemical Structural Formula (1). Thereby, transparency, rigidity, moldability, etc. can be further improved. The nucleating agent used here is not particularly limited, and known nucleating agents can be used. For example, a known clearing nucleating agent such as a sorbitol-based clearing nucleating agent, an organic phosphate-based clearing nucleating agent, an aromatic phosphate ester, or talc may be added as long as the effect of the present invention is not significantly inhibited. it can.

5). Other additives In the propylene-based resin composition of the present invention, in addition to the propylene-based (co) polymer (X), the propylene polymer (Y), and the clearing nucleating agent (Z), propylene-based (co) heavy Additives such as various antioxidants, neutralizing agents, lubricants, ultraviolet absorbers, light stabilizers and the like used as a stabilizer for coalescence can be blended.

  Specifically, as the antioxidant, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis ( 2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4 Phosphorous antioxidants such as 4,4'-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 1 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Phenolic antioxidants such as di-stearyl-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ'-thio-di-propionate An antioxidant etc. are mentioned.

  Specific examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (trade name: magnesium represented by the following general formula (4) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (5)), and the like.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (4)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]
[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (5)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

  Specific examples of the lubricant include known lubricants, and examples thereof include fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, and behenic acid amide, butyl stearate, and silicone oil.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 And ultraviolet absorbers such as' -hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.

  Examples of the light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 ′. -Hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) succinate ) Ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine-2,4- Bis [N-butyl-N- ( , Mention may be made of a light stabilizer such as 2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.

  Further, an amine-based antioxidant represented by the following chemical structural formula (6) or the following general formula (7), 5,7-di-t-butyl-3- (3,4-di-methyl-phenyl)- Examples thereof include lactone antioxidants such as 3H-benzofuran-2-one and vitamin E antioxidants such as the following chemical structural formula (8).

［但し、式（７）中、Ｒ^１とＲ^２は、炭素数１４〜２２のアルキル基である。］

[In the formula (7), R ¹ and R ² are alkyl groups having 14 to 22 carbon atoms. ]

  In addition, an antistatic agent, a dispersant such as a fatty acid metal salt, polyethylene, an olefin-based elastomer, and the like can be blended within a range that does not impair the object of the present invention.

II. Method for Producing Propylene Resin Composition for Injection Molding The propylene resin composition for injection molding of the present invention comprises a propylene-based (co) polymer (X), a propylene polymer (Y), and a clearing nucleating agent (Z), In addition, other additives used as necessary are mixed in a Henschel mixer, a super mixer, a ribbon blender, etc. It can be obtained by melt-kneading in a temperature range of 180 to 280 ° C.

III. Molded Product The molded product of the present invention is obtained by molding the above-described propylene-based resin composition for injection molding with a known injection molding machine. In particular, when molding is performed using a mold in which a weld portion is generated, that is, a mold having a multi-point gate, or a mold having a location where a once branched molten resin is merged, the weld portion is less whitened. It exhibits very good characteristics.
Examples of the molded article of the present invention include food containers, caps, medical instruments, medical containers, costume cases, daily necessities, automobile parts, electrical parts, industrial materials, containers, pallets and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these description.
In each example and comparative example, the physical properties used were measured by the following methods, and propylene-based (co) polymer (X), propylene polymer (Y), clearing nucleating agent (Z) and others. As the additives (neutralizing agent, lubricant, etc.), the following were used.

1. Test method (1) Ethylene content:
The ethylene content in the random copolymer was measured by infrared spectroscopy using a characteristic absorber of 733 cm ⁻¹ with an ethylene / propylene random copolymer whose composition was verified by ¹³ C-NMR as a reference substance. As the test piece, a pellet was formed into a film having a thickness of about 500 microns by press molding.
(2) Melt flow rate (MFR):
Based on JIS K7120, it measured on the conditions of 230 degreeC and a 2.16kg load.
(3) Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), Mz / Mw:
It was determined by GPC measurement according to the method described above.

(3) Melt tension (MT):
It measured on the following conditions using the Toyo Seiki Seisakusho Capillograph.
・ Capillary: Diameter 2.0mm, length 40mm
・ Cylinder diameter: 9.55mm
・ Cylinder extrusion speed: 20 mm / min ・ Pickup speed: 4.0 m / min ・ Temperature: 230 ° C.
When the MT is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed is lowered and the tension at the highest speed at which the take-up can be taken is MT. And The unit is gram.

(4) 25 ° C. paraxylene soluble component amount (CXS):
Measurement was performed by the method described above.
(5) Branch index g ′:
As described above, it was determined by GPC equipped with a differential refractometer (RI), a viscosity detector (Viscometer), and a light scattering detector (MALLS) as detectors.
(6) mm fraction of propylene unit 3 chain by ¹³ C-NMR As described above, using JSX-GSX-400 and FT-NMR, paragraphs [0053] to [0065] of JP-A-2009-275207 It was measured by the method described in the above.
The unit is%.

(7) Degree of strain hardening [λmax (0.1)]:
The extension viscoelasticity was measured under the following conditions.
・ Device: Ares manufactured by Rheometrics
・ Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 180 ℃
-Strain rate: 0.1 / sec
-Preparation of test piece: A sheet of 18 mm x 10 mm and a thickness of 0.7 mm was formed by press molding.
The details of the method of calculating λmax are as described above.

(8) Flexural modulus:
Using an EC-100 injection molding machine manufactured by Toshiba Machine, injection molding was performed in accordance with JIS K7152-1 to produce an A1 type dumbbell test piece. The parallel part was cut out to produce an 80 × 10 × 4 mmt strip-shaped test piece. Using this, the flexural modulus was measured at 23 ° C. in accordance with JIS K7171.
(9) Charpy impact strength:
Using an EC-100 injection molding machine manufactured by Toshiba Machine, injection molding was performed in accordance with JIS K7152-1 to produce an A1 type dumbbell test piece. The parallel part was cut out to produce an 80 × 10 × 4 mmt strip-shaped test piece. Using this, Charpy impact strength was measured at 23 ° C. in accordance with JIS K7111.
(10) Haze value:
Using a Toshiba Machine EC-100 injection molding machine, injection molding was performed in accordance with JIS K7152-3 to produce a D2 type small square plate having a thickness of 2 mm. Using this, haze was measured according to JIS K7136. It shows that transparency is so favorable that this value is small.

(11) Weld whitening:
Injection at a molding temperature of 220 ° C and a mold temperature of 40 ° C using a Toshiba Machine IS-170 injection molding machine and a mold in which resin is injected from both ends of a test piece of outer dimensions: 350mm x 100mm x 2mmt. Molded. Regarding the obtained test piece, the degree of whitening of the weld portion where the resin was united was visually determined. Judgment criteria are as follows.
(Double-circle): The whitening of a weld part cannot be distinguished visually.
○: The whitening of the weld is hardly discernable visually.
(Triangle | delta): The whitening of a weld part can be discriminate | determined visually.
X: The whitening of the weld portion can be distinguished very clearly visually.

(12) White spot:
Using a Toshiba Machine EC-100 injection molding machine, injection molding was performed in accordance with JIS K7152-3 to produce a D2 type small square plate having a thickness of 2 mm. This was visually observed to determine the presence or absence of white spots. Judgment criteria are as follows.
○: The white spot cannot be visually determined.
X: A white point can be visually discriminated.
XX: A large number of white spots can be identified visually.

2. 2. Propylene-based (co) polymer, propylene polymer, clearing nucleating agent and other additives 2-1. Propylene-based (co) polymer (X)
(1) Ethylene / propylene random copolymer (X-1):
Wintech WMG03 (manufactured by Nippon Polypro). Polymerized with a metallocene catalyst. Ethylene content 0.9% by weight, Mw / Mn 2.6, MFR 30 g / 10 min

(2) Ethylene / propylene random copolymer (X-2):
Novatec MG3F (manufactured by Nippon Polypro). Polymerized with Ziegler-Natta catalyst. Ethylene content 2.5% by weight, Mw / Mn 4.5, MFR 8 g / 10 min.
This is a propylene-based (co) polymer not corresponding to the propylene-based (co) polymer (X) according to the present invention.

2-2. Propylene polymer (Y)
As the propylene polymer (Y), the propylene polymer (Y-1) produced in Production Example 1 below was used.

(1) Production Example 1 (Production of Y-1)
[Synthesis Example 1 of Catalyst Component (A)]
Synthesis of dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium (component [A-1] (complex 1) Synthesis):
(I) Synthesis of 4- (4-i-propylphenyl) indene To a 500 ml glass reaction vessel, 15 g (91 mmol) of 4-i-propylphenylboronic acid and 200 ml of dimethoxyethane (DME) were added, and 90 g of cesium carbonate ( 0.28 mol) and 100 ml of water were added, 13 g (67 mmol) of 4-bromoindene and 5 g (4 mmol) of tetrakistriphenylphosphinopalladium were added in this order, and the mixture was heated at 80 ° C. for 6 hours.
After allowing to cool, the reaction solution was poured into 500 ml of distilled water, transferred to a separatory funnel, and extracted with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 15.4 g (yield 99%) of 4- (4-i-propylphenyl) indene as a colorless liquid.

(Ii) Synthesis of 2-bromo-4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 15.4 g (67 mmol) of 4- (4-i-propylphenyl) indene and distilled water were added. 7.2 ml and 200 ml of DMSO were added, and 17 g (93 mmol) of N-bromosuccinimide was gradually added thereto. The mixture was stirred at room temperature for 2 hours, poured into 500 ml of ice water, and extracted three times with 100 ml of toluene. The toluene layer was washed with saturated brine, 2 g (11 mmol) of p-toluenesulfonic acid was added, and the mixture was heated to reflux for 3 hours while removing moisture. The reaction mixture was allowed to cool, washed with saturated brine, and dried over sodium sulfate. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to obtain 19.8 g (yield 96%) of 2-bromo-4- (4-i-propylphenyl) indene as a yellow liquid. .

(Iii) Synthesis of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene In a 500 ml glass reaction vessel, 6.7 g (82 ml mol) of 2-methylfuran and DME were added. 100 ml was added and cooled to -70 ° C. in a dry ice-methanol bath. To this, 51 ml (81 mmol) of a 1.59 mol / L n-butyllithium-n-hexane solution was added dropwise and stirred as it was for 3 hours. The solution was cooled to −70 ° C., and a solution of 20 ml (87 mmol) of triisopropyl borate and 50 ml of DME was added dropwise thereto. After dropping, the mixture was stirred overnight while gradually returning to room temperature.
After the reaction solution was hydrolyzed by adding 50 ml of distilled water, a solution of 223 g of potassium carbonate and 100 ml of water, and 19.8 gg (63 mmol) of 2-bromo-4- (4-i-propylphenyl) indene were added in order. The mixture was heated at 0 ° C. and reacted for 3 hours while removing low-boiling components.
After allowing to cool, the reaction solution was poured into 300 ml of distilled water, transferred to a separatory funnel and extracted three times with diisopropyl ether. The ether layer was washed with saturated brine and dried over sodium sulfate. Sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column to give 19.6 g of 2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indene colorless liquid Yield 99%).

(Iv) Synthesis of dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane In a 500 ml glass reaction vessel, 2- (2-methyl-5- Furyl) -4- (4-i-propylphenyl) indene (9.1 g, 29 mmol) and THF (200 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. To this, 17 ml (28 mmol) of a 1.66 mol / L n-butyllithium-hexane solution was dropped, and the mixture was stirred as it was for 3 hours. The mixture was cooled to −70 ° C., 0.1 ml (2 mmol) of 1-methylimidazole and 1.8 g (14 mmol) of dimethyldichlorosilane were sequentially added, and the mixture was stirred overnight while gradually returning to room temperature.
Distilled water was added to the reaction solution, transferred to a separatory funnel and washed with brine until neutral, and sodium sulfate was added to dry the reaction solution. Sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified with a silica gel column, and dimethylbis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane pale 8.6 g (88% yield) of a yellow solid was obtained.

(V) Synthesis of dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride Into a 500 ml glass reaction vessel, dimethylbis (2- (2 -Methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) silane (8.6 g, 13 mmol) and diethyl ether (300 ml) were added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Thereto was added dropwise 15 ml (25 mmol) of a 1.66 mol / L n-butyllithium-n-hexane solution, and the mixture was stirred for 3 hours. The solvent of the reaction solution was distilled off under reduced pressure, 400 ml of toluene and 40 ml of diethyl ether were added, and the solution was cooled to −70 ° C. in a dry ice-methanol bath. Thereto was added 4.0 g (13 mmol) of hafnium tetrachloride. Thereafter, the mixture was stirred overnight while gradually returning to room temperature.
The solvent was distilled off under reduced pressure and recrystallized from dichloromethane-hexane to obtain a racemic dimethylsilylenebis (2- (2-methyl-5-furyl) -4- (4-i-propylphenyl) indenyl) hafnium dichloride. As a yellow crystal, 7.6 g (yield 65%) was obtained.

The identified value by ^{1 H-NMR} of the obtained racemates are described below.
1H-NMR (C6D6) identification results Racemate: δ 0.95 (s, 6H), δ 1.10 (d, 12H), δ 2.08 (s, 6H), δ 2.67 (m, 2H), δ 5.80 (D, 2H), δ 6.37 (d, 2H), δ 6.74 (dd, 2H), δ 7.07 (d, 2H), δ 7.13 (d, 4H), δ 7.28 (s, 2H) , Δ 7.30 (d, 2H), δ 7.83 (d, 4H).

[Synthesis Example 2 of Catalyst Component (A)]
Synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (synthesis of component [A-1] (complex 2)):
The synthesis of rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium is carried out according to the method described in Example 1 of JP-A-11-240909. It carried out like.

[Catalyst Synthesis Example 1]
(I) Chemical treatment of ion-exchange layered silicate In a separable flask, 96% sulfuric acid (668 g) was added to 2,264 g of distilled water, and then montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL: average particle size 19 μm) as a layered silicate ) 400 g was added. The slurry was heated at 90 ° C. for 210 minutes. When 4,000 g of distilled water was added to the reaction slurry and filtered, 810 g of a cake-like solid was obtained.
Next, 432 g of lithium sulfate and 1,924 g of distilled water were added to the separable flask to make a lithium sulfate aqueous solution, and the entire amount of the cake-like solid was charged. The slurry was reacted at room temperature for 120 minutes. 4 L of distilled water was added to this slurry, followed by filtration, and further washing with distilled water to pH 5-6, followed by filtration to obtain 760 g of a cake-like solid.
The obtained solid was preliminarily dried overnight at 100 ° C. under a nitrogen stream, and then coarse particles of 53 μm or more were removed, followed by drying under reduced pressure at 200 ° C. for 2 hours to obtain 220 g of chemically treated smectite.
The composition of this chemically treated smectite is Al: 6.45 wt%, Si: 38.30 wt%, Mg: 0.98 wt%, Fe: 1.88 wt%, Li: 0.16 wt%, Al / Si = 0.175 [mol / mol].

(Ii) Catalyst preparation and prepolymerization In a three-necked flask (volume: 1 L), 20 g of the chemically treated smectite obtained above was placed, and heptane (132 mL) was added to form a slurry, which was triisobutylaluminum (25 mmol: concentration) 143 mg / mL heptane solution (68.0 mL) was added, and the mixture was stirred for 1 hour, washed with heptane until the residual liquid ratio became 1/100, and heptane was added so that the total volume became 100 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl)-] prepared in Synthesis Example 1 of the catalyst component (A) was used. 4- (4-i-propylphenyl) indenyl}] hafnium (210 μmol) is dissolved in toluene (42 mL) (solution 1), and the catalyst component (A) is synthesized in another flask (volume 200 mL). Rac-dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium (90 μmol) prepared in Example 2 was dissolved in toluene (18 mL) (solution 2 ).
Triisobutylaluminum (0.84 mmol: 1.2 mL of a heptane solution with a concentration of 143 mg / mL) was added to a 1 L flask containing the chemically treated smectite, and then the above solution 1 was added and stirred at room temperature for 20 minutes. Thereafter, triisobutylaluminum (0.36 mmol: 0.50 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.
Thereafter, 338 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 10 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the resulting catalyst slurry by decantation, triisobutylaluminum (6 mmol: 17.0 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 52.8 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 1.64.
Hereinafter, this is referred to as “preliminary polymerization catalyst 1”.

[polymerization]
After sufficiently replacing the inside of the stirring autoclave having an internal volume of 200 liters with propylene, 40 kg of sufficiently dehydrated liquefied propylene was introduced. To this was added 4.4 liters of hydrogen (as a standard volume) and 470 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, and the internal temperature was raised to 70 ° C. Next, 2.4 g of the prepolymerized catalyst 1 (by weight excluding the prepolymerized polymer) was injected with argon to initiate polymerization, and the internal temperature was maintained at 70 ° C. After 2 hours, 100 ml of ethanol was injected, purged of unreacted propylene, and the inside of the autoclave was purged with nitrogen to terminate the polymerization.
The obtained polymer was dried for 1 hour under a nitrogen stream at 90 ° C. to obtain 16.5 kg of the polymer (X-1). The catalytic activity was 6880 (g-PP / g-cat).

[Production of Propylene Polymer (Y-1) Pellets (Y-1)]
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4), which is a phenolic antioxidant, with respect to 100 parts by weight of the propylene polymer (Y-1) produced in Production Example 1. '-Hydroxyphenyl) propionate] methane (trade name “IRGANOX1010”, manufactured by BASF) 0.125 parts by weight, tris (2,4-di-t-butylphenyl) phosphite which is a phosphite antioxidant (Product name “IRGAFOS 168”, manufactured by BASF) 0.125 parts by weight was mixed and mixed at room temperature for 3 minutes using a high-speed agitating mixer (Henschel mixer, product name), and then into a twin screw extruder. And kneaded to obtain propylene polymer (Y) pellets (Y-1).
For the twin screw extruder, KZW-25 manufactured by Technobel was used, the screw rotation speed was 400 RPM, and the kneading temperature was 80, 160, 210, 230 from the bottom of the hopper (hereinafter, the same temperature up to the die outlet). did.
This pellet (Y-1) was evaluated for MFR, CXS, mm, Mw / Mn, Mz / Mw, branching index g ′, MT, and λmax.
The evaluation results are shown in Table 1.

Moreover, the following Y-2 which does not correspond to a preferable propylene polymer (Y) and the following Y-3 which does not correspond to a propylene polymer (Y) were used as a propylene polymer.
Y-2:
Product name “PF814” manufactured by Basel, which is a high melt tension polypropylene imparted with long chain branching by electron beam irradiation.
The evaluation results for Y-2 are shown in Table 1.
Y-3:
A product name "Novatec PP FY6H" manufactured by Nippon Polypro Co., Ltd., which is a propylene homopolymer having no long chain branching, MFR: 2 g / 10 min

2-3. Clearing nucleating agent (Z)
(I) Mirad NX8000J (Milliken & Company):
A compound represented by the following chemical structural formula (2), which is an equivalent of the transparent nucleating agent (Z) of the present invention.

(Ii) Gerol MD (GAMD; manufactured by Shin Nippon Rika Co., Ltd.):
Dimethylbenzylidene sorbitol-based clearing nucleating agent. This is a clearing nucleating agent not corresponding to the clearing nucleating agent (Z) of the present invention.

[Examples 1 to 4 and Comparative Examples 1 to 4]
Propylene-based (co) polymer (X), propylene polymer (Y), clearing nucleating agent (Z), and other additives (antioxidants, neutralizing agents) as shown in Table 2 (parts by weight) ), And dry blended with a super mixer, and then melt-kneaded using a TEM35 twin screw extruder manufactured by Toshiba Machine. Extruded pellets from the die at a die outlet temperature of 200 ° C.
Test pieces were prepared from the obtained pellets by the method described above, and the physical properties were measured. The results are shown in Table 2.

  As is clear from Table 2, Examples 1 to 3 are based on 80 to 95 parts by weight of X-1 corresponding to the propylene-based (co) polymer (X) within the specified range of the present invention. Add 5 to 20 parts by weight of Y-1 corresponding to the propylene polymer (Y) within the specified range of the invention, and further add NX8000J to 0.4 as the transparent nucleating agent (C) within the specified range of the present invention. It is a blended part by weight. It can be seen that weld whitening is suppressed and white spots are not generated while maintaining high transparency. Further, as the addition concentration of Y-1 increases, mechanical properties such as flexural modulus and Charpy impact strength are improved and transparency is improved, and the propylene polymer (Y) is effective in improving mechanical properties and transparency. I know that there is.

  In addition, Example 4 is a system using Y-2 instead of Y-1 of Example 2. As is clear from Table 1, Y-2 is roughly equivalent to Y-1 for the characteristics (Yi) to (Y-iii), which are requirements of the present invention, but the characteristic (Y-iv) CXS of 4.5% by weight is higher than Y-1, and g ′ of the characteristic (Yv) is 0.54, which is lower than Y-1. Also, the mm fraction of the characteristic (Y-iv) is 92.5%, which is lower than Y-1, and is out of the preferred range. When such Y-2 is used as the propylene polymer (Y), it can be seen that the effect of suppressing weld whitening is seen to some extent, but is not perfect. It can also be seen that the effects of improving the flexural modulus, Charpy impact strength, and transparency are slight.

  On the other hand, Comparative Example 1 is a system that does not contain a propylene-ethylene copolymer (Y). Although the transparency and the white point are good, it is understood that whitening of the weld part is observed and the design is inferior.

  Moreover, the comparative example 2 is a system using X-2 which is outside the specified range of the present invention instead of X-1 corresponding to the propylene-based (co) polymer (X) of Example 2. The propylene-based (co) polymer (X) of the present invention is a polymer produced using a metallocene catalyst, and Mw / Mn is also in the range of 2.0 to 4.0, whereas X- No. 2 is produced using a Ziegler-Natta catalyst, and Mw / Mn is also larger than the specified range. It can be seen that when such a polymer is used instead of the propylene-based (co) polymer (X), weld whitening or white spot does not occur, but transparency is inferior and design is deteriorated.

  Comparative Example 3 is a system using Y-3 which is outside the specified range of the present invention instead of Y-1 of Example 2. Since Y-3 is a propylene polymer having no branched structure, it can be seen that the weld improving effect is not exhibited at all. Moreover, although the bending elastic modulus is greatly improved, it can be seen that the Charpy impact strength and haze are deteriorated.

  Further, Comparative Example 4 is a system using GAMD that is outside the scope of the present invention instead of NX8000J corresponding to the clearing nucleating agent (Z) of Example 2. It can be seen that when such a clearing nucleating agent is used in place of the clearing nucleating agent (Z), although weld whitening and white spots do not occur, the transparency is remarkably lowered and cannot be practically used.

  The propylene-based resin composition for injection molding of the present invention and the molded product thereof are molded with a mold having a weld while having an excellent balance of transparency and rigidity that cannot be achieved by conventional propylene-based resin compositions. However, since no whitening is observed in the weld and no white spots are generated, it is possible to provide a molded product with extremely excellent appearance and design. In particular, it is extremely useful in a case where the shape is complicated, or in a molded product having a large size and in which the occurrence of welds is difficult to avoid, so that a great restriction on the design of the molded product can be removed. For this reason, it is extremely useful for uses such as food containers, caps, medical instruments, medical containers, costume cases, daily necessities, automobile parts, electrical parts, industrial materials, containers, and pallets.

Claims (4)

Propylene-based (based on a total of 100 parts by weight of (co) polymer (X) and polymer (Y)) using a metallocene catalyst and having the following characteristics (Xi) to (X-iii) (Co) polymer (X) 75 to 97 parts by weight and propylene polymer (Y) 3 to 25 parts by weight having the following characteristics (Yi) to (Y-iv) and having a long-chain branched structure: A propylene-based resin composition for injection molding containing 0.01 to 2.0 parts by weight of a nucleating agent (Z) represented by the following chemical structural formula (1).
Characteristic (Xi): The ethylene content in the (co) polymer (X) is in the range of 0 to 3.0% by weight.
Characteristic (X-ii): The melt flow rate (MFR) (230 ° C., 2.16 kg load) of the (co) polymer (X) is in the range of 2 to 100 g / 10 min.
Characteristic (X-iii): Ratio (molecular weight distribution) (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) in GPC measurement of (co) polymer (X) is in the range of 2 to 4. is there.
Characteristic (Y-i): MFR (230 ° C., 2.16 kg load) is 0.1 to 30 g / 10 min.
Characteristic (Y-ii): GPC molecular weight distribution (Mw / Mn) is 3.0 to 10, and Mz / Mw is 2.5 to 10.
Characteristic (Y-iii): Melt tension (MT) (unit: g)
log (MT) ≧ −0.9 × log (MFR) +0.7 or MT ≧ 15
Satisfy one of the following.
Characteristic (Y-iv): 25 degreeC paraxylene soluble component amount (CXS) is less than 5.0 weight% with respect to the propylene polymer (Y) whole quantity.

[In formula (1), n is an integer of 0 to ^2, R 1 to R ⁵ are the same or different, each a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, It is a carbonyl group, a halogen group or a phenyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms. ] The polypropylene resin composition for injection molding according to claim 1, wherein the propylene polymer (Y) further has the following characteristics (Yv).
Characteristic (Yv): The branching index g ′ when the absolute molecular weight (Mabs) is 1,000,000 is 0.30 or more and less than 1.00. The polypropylene-based resin composition for injection molding according to claim 1 or 2, wherein the propylene polymer (Y) further has the following characteristics (Y-vi).
Characteristic (Y-vi): mm fraction of propylene unit 3 chain by ¹³ C-NMR is 95% or more.   A propylene-based resin molded article obtained by injection-molding the propylene-based resin composition for injection molding according to any one of claims 1 to 3, using a mold that generates welds.

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