JP2013071953A - Method for producing propylene-based block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a propylene-based block copolymer as a reactor TPO, which has extremely low crystallinity, forms polymer particles having high flowability and easy handleability, has excellent transparency and no stickiness, and exhibits a high balance between flexibility and heat resistance.SOLUTION: The method for producing a propylene-based block copolymer by multi-step polymerization includes producing a crystalline polypropylene component (A) by a first step of polymerizing a propylene-based monomer in the presence of a metallocene catalyst (M) and an organoaluminum compound (C) and then producing a propylene-based elastomer component (B) by a second step of adding a ≥4C hydroxo compound (D) to it and performing polymerization in the presence of it.

Description

  The present invention relates to a method for producing a propylene-based block copolymer. Specifically, the present invention relates to a method for producing a propylene-based block copolymer having excellent transparency and high balance between flexibility and heat resistance, and relates to a method for forming polymer particles having high fluidity and easy handling. .

  Olefin-based thermoplastic elastomers or plastomers are blends of polymer components such as random copolymers typified by ethylene-α-olefin copolymer elastomers. They have moderate flexibility and strength and are suitable for environments such as recycling and incineration disposal. Since it is highly adaptable to problems and is lightweight and excellent in moldability and economic efficiency, it is widely used in a wide range of fields such as films and sheets, fibers and nonwoven fabrics, various containers and molded products, and modifiers.

  Among such thermoplastic elastomers, what is made of a propylene block copolymer, that is, a so-called block type in which crystalline polypropylene is produced in the first step and propylene-ethylene copolymer elastomer is produced in the second step. The so-called reactor TPO is superior in heat resistance, strength and productivity as compared with a random copolymer type elastomer. Also, compared to elastomers produced by mechanical mixing, the quality of the product is stable, production costs are reduced by shortening the production process, heat resistance and strength are excellent, and the dispersibility of the elastomer is good. Since it has an advantageous feature such that the composition can be widely varied, it has been widely used in recent years.

Technological development to produce a more flexible reactor TPO with lower crystallinity is also underway. As a method of increasing the flexibility of the propylene-based block copolymer as the reactor TPO, the method of reducing the crystallinity of the crystalline polypropylene produced in the first step, the ratio of the propylene-ethylene copolymer elastomer produced in the second step Examples thereof include a method of increasing the crystallinity of the elastomer and the like.
In order to produce such a propylene-based block copolymer, a study example using a metallocene-based catalyst instead of a conventionally used Ziegler catalyst is increasing (see Patent Documents 1 and 2). Metallocene catalysts have a uniform active site and narrow crystallinity distribution and molecular weight distribution compared to Ziegler catalysts. Even so, it has the advantage that the product is less sticky than when a Ziegler catalyst is used. In addition to the use of a metallocene catalyst, a method in which both the first step and the second step are performed by gas phase polymerization is often used.

  As a method for lowering the crystallinity of the elastomer produced in the second step, a method is known in which an α-olefin other than propylene and ethylene is used in combination to form a propylene-ethylene-α-olefin copolymer elastomer (Patent Document 3). reference). By using such an α-olefin, a reactor TPO having excellent transparency and a high balance between flexibility and heat resistance can be produced. However, when the crystallinity of the elastomer is lowered by using an α-olefin, the mobility of the elastomer is higher than that of the propylene-ethylene copolymer elastomer, so that the propylene-based block copolymer particles as the reactor TPO There was a technical problem that the fluidity of the liquid was reduced, and problems such as adhesion and blockage were likely to occur in the inner wall of the reactor and the transfer pipe. Even with metallocene catalysts, this problem has not been solved.

On the other hand, not only the reactor TPO but also a method of performing the second step of producing a copolymer elastomer in the presence of a polymerization inhibitor is known for the purpose of improving the particle properties of the propylene-based block copolymer ( Patent Documents 4 to 7). Oxygen molecules, methanol, ethanol, isopropanol, and acetone are disclosed as polymerization inhibitors, but the effect is not sufficient to obtain propylene block copolymer particles having sufficiently low crystallinity and good particle properties. There was no need for further technological development.

  An object of the present invention is a method for producing a propylene-based block copolymer as a reactor TPO that is excellent in transparency and has a high balance between flexibility and heat resistance, and is extremely crystalline. The object is to develop a method for forming polymer particles having high fluidity and easy handling even for propylene block copolymers having a low viscosity.

  In the production of a propylene-based block copolymer having very low crystallinity, the present inventor considered the relationship between the structure of the polymerization inhibitor and the particle properties of the resulting polymer particles, the polymerization inhibitor, the metallocene catalyst, and the organic aluminum. As a result of intensive studies on the relationship with chemical reactions that can occur with the compound, the use of an alkoxo compound having a specific structure as a polymerization inhibitor yields polymer particles that are extremely fluid and easy to handle. The present invention has been found.

  In the production of a propylene-based block copolymer as a reactor TPO, in which a crystalline polypropylene is produced in the first step and a copolymer elastomer of propylene and ethylene and / or α-olefin is produced in the second step, The novel present invention characterized in that the second step is carried out in the presence of an alkoxo compound having a structure basically comprises the following invention units (1) to (7).

The first feature of the present invention is a first step of producing a crystalline polypropylene component (A) satisfying the following property (i) in the presence of a metallocene catalyst and an organoaluminum compound (C):
A second step of producing a propylene-based elastomer component (B) satisfying the following property (ii) in the presence of the metallocene catalyst, the organoaluminum compound (C) and the crystalline polypropylene component (A). A method for producing a block copolymer, comprising:
In the method, the hydroxo compound (D) having 4 or more carbon atoms is added to the second step.
(I) a propylene homopolymer, or a random copolymer of propylene with at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, wherein ethylene and α- The total content of olefins is 10 wt% or less.
(Ii) a random copolymer of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, wherein the total content of ethylene and α-olefin is a crystal It is that it is higher than the sum total of the content of ethylene and α-olefin of the functional polypropylene component (A).

A second feature of the present invention is that the propylene block is characterized in that the weight ratio of the crystalline polypropylene component (A) and the propylene elastomer component (B) is in the range of 10:90 to 90:10. A method for producing a polymer.
The third feature of the present invention is that the propylene-based elastomer component (B) is a random copolymer of propylene and 1-butene, or a propylene-based block copolymer in which a random copolymer of propylene, ethylene, and 1-butene is used. A method for producing a coalescence.
The fourth feature of the present invention is that the ratio of the amount of the hydroxo compound (D) used to the amount of the organoaluminum compound (C) used per aluminum atom is within the range of 0.001 to 10 mol / mol-Al. A process for producing a propylene-based block copolymer.
A fifth feature of the present invention resides in a method for producing a propylene-based block copolymer, wherein the hydroxo compound (D) is a linear aliphatic alcohol.
A sixth feature of the present invention resides in a method for producing a propylene-based block copolymer, wherein the hydroxo compound (D) is a cyclic aliphatic alcohol.

A seventh feature of the present invention resides in a method for producing a propylene-based block copolymer, wherein the hydroxo compound (D) is an aromatic alcohol.
An eighth feature of the present invention resides in a method for producing a propylene-based block copolymer, wherein the second step is performed by a gas phase method.
By means of the achievement means of the present invention having the respective characteristic points, the problems of the invention can be solved.

  By the method for producing a propylene-based block copolymer of the present invention, a propylene-based block copolymer as a reactor TPO having excellent transparency and a high balance between flexibility and heat resistance can be produced very stably. In particular, the propylene-based block copolymer of the present invention not only has excellent transparency, flexibility and heat resistance, but also has no stickiness in the copolymer after polymerization and excellent fluidity of polymer particles. Therefore, it is not necessary to consider the prevention of the adhesion of the copolymer to the reaction peripheral device, and when it is made into particles by drying, it becomes a powder having a smooth particle size. In addition, since these particles are not sticky, they can be used as powders, particles, and pellets without sticking or agglomerating during time-consuming handling such as packing, storage, distribution and stacking. Therefore, the raw material powder form for molding that is easy to handle is maintained. When supplying this powder to a hopper or feeder for granulation or processing, it is easy to handle because it has good fluidity, and a constant amount that is stable in quantity can be constantly supplied, and the discharge amount is also stable. A stable product with good quality can be made. Even when this copolymer powder, particles, pellets, etc. are molded by conventional equipment, there is little adhesion and adhesion to the mold, and the molded product has no adhesion or blocking to molding peripheral equipment, High moldability and molding efficiency can be expected, and it is expected to produce molded products with good appearance and quality. In addition, in the case of a good quality powder, it is expected to dry blend with the additive, so the appearance and quality are good due to the uniform blending effect due to the fact that the powder has an approximate particle size. In addition to being able to mold, it can be expected to streamline moldability and increase molding efficiency.

Hereinafter, the best mode for carrying out the present invention will be described in detail.
In the present invention, a propylene-based monomer containing at least one comonomer selected from the group consisting of propylene alone or propylene and ethylene and an α-olefin having 4 to 8 carbon atoms is converted into a metallocene catalyst (M) and an organoaluminum compound ( C) In the first step of polymerizing in the presence of C), (i) a propylene homopolymer, or at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms and propylene A crystalline polypropylene component (A), which is a random copolymer and has a total content of ethylene and α-olefin of 10 wt% or less, and then further polymerizes a hydroxo compound (D) having 4 or more carbon atoms. Metallocene catalyst (M), organic aluminum compound (C) and hydroxy In the second step of polymerizing the propylene monomer in the presence of the compound (D), (ii) at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms and propylene A propylene-based elastomer component (B) having a characteristic of being a random copolymer, wherein the total content of ethylene and α-olefin is higher than the total content of ethylene and α-olefin of the crystalline polypropylene component (A) A method for producing a propylene-based block copolymer by two-stage polymerization consisting of at least a first step and a second step, or a multistage polymerization in which this polymerization step is repeated, for example, 2 to 6 steps, is carried out.

  The propylene block copolymer of the present invention improves the physical properties by controlling the morphology by introducing an elastomer component (soft segment) into the crystalline phase (hard segment) of the crystalline polypropylene component (A) at the polymerization stage. To do. In carrying out the present invention, the following 1- (3) constituting the metallocene catalyst (M) used in the first step of polymerization in the polymerization system in which the metallocene catalyst (M) and the organoaluminum compound (C) are present. ) The organoaluminum compound component (c) which is an optional component represented by the component (c) and the organoaluminum compound (C) represented by the following 2- (4) organoaluminum (C) term may be the same compound. Although it is possible, the environment and the state of the catalyst and polymer particles are different depending on whether the catalyst is used during the preparation of the catalyst or the polymerization, and therefore (c) and (C) perform different functions. The organoaluminum compound (C) mainly has a function as a scavenger for detoxifying impurities, and the polymerization of propylene monomer proceeds stably by performing the first step in the polymerization system in which this compound is present. In the second step, in the second step, the hydroxo compound (D), which is a specific compound that acts as a kind of polymerization inhibitor, is present in the polymerization system. It is based on the knowledge that the aluminum compound (C) plays a significant role in contributing to the action mode of the hydroxo compound (D) compound in the subsequent stage, for example, to exert the effect in controlling the diffusion into the polymer particles. is there. On the other hand, the organoaluminum compound (c), which is an optional component used in preparing the catalyst, is used in terms of how to stably produce a highly active catalyst, and it is clear that the functions of both are different. is there.

The propylene block copolymer of the present invention improves the physical properties by controlling the morphology by introducing an elastomer component (soft segment) into the crystalline phase (hard segment) of the crystalline polypropylene component (A) at the polymerization stage. To do. In particular, according to the present invention, in the case where the metallocene catalyst (M) is of a type composed of a catalyst component in which a metallocene compound and an aluminoxane (c) are combined, a metallocene catalyst ( The organoaluminum compound (C) to be present with M) is preferably one that can be recognized as a different form from the catalyst component (c) in the form, amount and function of the compound. In the polymerization system in which the organoaluminum compound (C) is present in the metallocene catalyst (M), it is not only useful for properly carrying out the polymerization of the propylene monomer in the first step, but also in the second step. The hydroxo compound (D), which is a specific compound that acts as a kind of polymerization inhibitor, is added to the system, in which case the organoaluminum compound (C) in the former stage is effective for stabilizing the hydroxo compound (D) in the latter stage It is based on the knowledge that it plays a meaningful role of contributing even in demonstrating.
Specific specifications of the propylene monomer, catalyst, polymerization conditions, additives and the like for carrying out the method for producing a propylene block copolymer of the present invention will be described in detail below.

When the crystalline polypropylene component (A) is a propylene homopolymer, the propylene monomer alone is used as the propylene monomer to be polymerized in the first step, but it is a random copolymer of propylene. In this case, at least one selected from the group consisting of ethylene and an α-olefin such as 1-butene, 1-hexene and 1-octene having 4 to 8 carbon atoms as a comonomer constituting the copolymer. A monomer mixture having specifications in which various types of comonomers are contained in propylene is used as a raw material for the first step as a propylene monomer.
Similarly, as the propylene monomer that is polymerized in the second step, since the main structural unit constituting the propylene-based elastomer component (B) is propylene, ethylene and 1-butene having 4 to 8 carbon atoms, 1-butene, A monomer-specific mixture containing a predetermined amount of at least one comonomer selected from the group consisting of α-olefins such as hexene and 1-octene is used as the raw material propylene monomer in the second step.
Of course, for the crystalline polypropylene component (A) produced in the first step and the propylene-based elastomer component (B) produced in the second step, predetermined propylene and comonomer are supplied as needed. Other comonomers such as butadiene, isoprene and styrene can be optionally used in combination as long as they do not affect the properties of A) and (B) and the polymerizability.
Such a polymerization operation of the first step and then the second step can be referred to as multi-stage polymerization. On the other hand, the multi-stage polymerization is carried out by repeating this unit sequentially with the polymerization of the first step and the second step as a basic unit. . The so-called [first step + second step] n, where n is 1 to 40 times, is recommended. Although it is multistage polymerization, usually, polymerization is repeated about n = 1 to 10 times to achieve a method for producing a propylene block copolymer of a predetermined grade.
Alternatively, multistage polymerization may be performed in which the first step is performed by single-stage polymerization or multistage polymerization, and then the second step is performed by singlestage polymerization or multistage polymerization. The specification, adjustment, and handling of the hydroxy compound (D) having 4 or more carbon atoms added in the second step, which is an important aspect of the present invention, are carried out in detail by using the 2- (6) hydroxy compound (D) described later. A mode is demonstrated.

  The propylene block copolymer of the present invention is described in detail in the section of 3- (3) propylene block copolymer below. Specifically, propylene homopolymer / propylene-ethylene- Random copolymer, propylene homopolymer / propylene block copolymer of propylene-butene-random copolymer, or propylene homopolymer / propylene block copolymer of propylene-ethylene-butene-random copolymer It is. Also, ethylene-propylene copolymer / propylene-ethylene-random copolymer, ethylene-propylene copolymer / propylene-butene-random copolymer, ethylene-propylene copolymer / propylene-ethylene-butene-random copolymer Coalescence is mentioned. It is preferable to use an ethylene-propylene copolymer / propylene-butene-random copolymer or an ethylene-propylene copolymer / propylene-ethylene-butene-random copolymer propylene-based block copolymer. Most preferred is an ethylene-propylene copolymer / propylene-based block copolymer of propylene-ethylene-butene-random copolymer. Similarly, a propylene-based block copolymer of propylene-1-butene copolymer / propylene-butene-random copolymer, or ethylene-1-butene-propylene copolymer / propylene-ethylene-butene-random copolymer Crystalline polypropylene component (A) and propylene-based elastomer component (propylene-based block copolymer, propylene-1-butene copolymer / propylene-ethylene-butene-random copolymer propylene-based block copolymer) When propylene or a predetermined comonomer is used in combination with B), various propylene-based block copolymers can be exemplified.

One of the problems of the present invention is that the propylene block copolymer has a problem of the stickiness of the polymer particles, which can be said to be a stickiness problem, and the stickiness of the polymerization apparatus, molding machine or processing machine. Thus, the propylene block copolymer having extremely advantageous characteristics in the polymerization stage, the distribution stage, the granulation stage, and the molding stage is provided. In particular, when the propylene-based block copolymer of the present invention after the polymerization in the second step is completed as particles by, for example, normal drying, there is no stickiness and good fluidity means that the reaction Copolymers are less likely to adhere to the reactor and reactor peripherals, and even in view of the efficiency of the polymerization stage, labor can be saved in the implementation and handling of the polymerization machine such as recovery, cleaning, and continuation. There is also a very advantageous ripple effect in terms of energy saving.
The present invention addresses such a technical problem, particularly in the stage of carrying out the polymerization for producing the propylene-based elastomer component (B) in the second step, and the hydroxo compound (D) having 4 or more carbon atoms in the polymerization vessel. Is added to the polymerization system in an appropriate amount and at least one compound belonging to the category of the hydroxo compound (D) is added. By polymerizing in the presence, the stickiness of the propylene block copolymer, particularly the polymer particles, and the problem of fluidity could be solved.

  As one of quantitative indicators representing the presence or absence of the stickiness of the polymer particles by the addition of the hydroxo compound (D) of the present invention, that is, the degree of fluidity, the polymer particles recovered after polymerization in the second step are: After recovery, the particles can be dried and the particles can be quantitatively displayed by examining the bulk density (g / cc) of the copolymer in accordance with ASTM D1895-69. When the index of the quantitative value of the fluidity state without stickiness is expressed by the term “polymer BD”, the following can be said. That is, when the polymerization in the second step is carried out by adding the hydroxo compound (D), the BD is usually in the range of about 0.35 to 0.50 g / cc, preferably 0.37 to 0.45 g. / Cc range can be arbitrarily produced. As an example, the product manufactured according to the specification of Example 1 has a BD of 0.38 g / cc. On the other hand, when the hydroxo compound (D) is not used under the same polymerization conditions, the BD is 0.36 g. More than / cc or less-not measurable. In any case, the degree of stickiness varies depending on the polymerization conditions of the propylene-based elastomer component (B) and the difference in the use of monomers, but the propylene-based block copolymer has the same monomer specifications and polymerization conditions. In the polymerization stage of the propylene-based elastomer component (B) in the second step, a difference of about 0.01 to 0.10 g / cc is observed in the BD depending on whether or not the hydroxo compound (D) is used. . Furthermore, even if the production conditions are the same, polymerization is carried out in the presence of a compound having only active hydrogen (D), for example, a compound having less than 4 carbon atoms, such as ethanol, instead of hydroxo compound (D). When carried out, those having a BD of about 0.30 g / cc to an unmeasurable one can be produced. In any case, when a propylene-based block copolymer is produced under the same polymerization conditions, the presence or absence of addition of the hydroxo compound (D) in the second step is a difference of about 0.01 to 0.10 g / cc in BD. In particular, when the hydroxo compound (D) is not present in the second step, the propylene-based block copolymer is produced with strongly sticky particles, and therefore does not flow at all. Then, as seen in the comparative example, in many cases, BD cannot be measured.

  Thus, in the method for producing a propylene-based block copolymer, the elastomer component (B) produced by the polymerization step for producing the propylene-based elastomer component (B) in the second step in particular has fluidity and sticky properties. It is often related to. The polymerization monomer in the second step is composed of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms. A random copolymer optionally containing a predetermined amount of a comonomer such as propylene, butene-1, 1-hexene and 1-octene. Depending on the selection and amount of propylene and comonomer, it can be assumed that the stickiness of the copolymer will be slightly affected, but the types and amounts of monomer specifications, catalyst, and polymerization conditions in the first and second steps are almost the same. Thus, if the stickiness (BD) of the propylene-based block copolymer produced under the condition of the presence or absence of the hydroxo compound (D) is compared, the presence of the hydroxo compound (D) and that it has 4 or more carbon atoms The difference in the bulk density of the polymer powder, that is, the difference in the BD of the particles appears remarkably.

  In the following, appropriate modes for carrying out the present invention will be sequentially described in detail.

1. Metallocene catalyst The method for producing a propylene-based block copolymer of the present invention requires the use of a metallocene catalyst. When a Ziegler catalyst is used, problems such as stickiness occur even in the production of a propylene-based block copolymer with relatively poor flexibility. This is as disclosed in the above-mentioned patent documents.
The gist of the present invention is to perform the second step of producing the propylene-based elastomer component (B) in a state where a hydroxo compound having a specific structure is added and mixed, and the type of metallocene catalyst 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 the transition metal compounds represented by the general formula (1) Component (b): At least one selected from the following (b-1) to (b-4) (B-1) an ionic compound capable of reacting with component (a) to convert component (a) into a cation or (B-3) Solid acid fine particles (b-4) Ion exchange layered silicate Component (c): Organoaluminum compound

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

(In the formula, A and A ′ are conjugated five-membered ring ligands which may have a substituent, Q is a bonding group which bridges between two conjugated five-membered ring ligands at an arbitrary position, X And Y is a σ covalent bond auxiliary ligand that reacts with component (b) to develop olefin polymerization ability, and M is a transition metal of Group 4 of the periodic table)
In the above general formula, the conjugated five-membered ring ligand is a cyclopentadienyl group derivative which 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 to each other at the other end (ω-end) to form one cyclopentadienyl group. A ring may be formed together with the 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.
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 react with a cocatalyst such as component (b) to produce an active metallocene having an olefin polymerization ability, and are each a hydrogen atom, a halogen atom, a hydrocarbon group, or oxygen. And hydrocarbon groups optionally having heteroatoms such as nitrogen and silicon. Among these, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is preferable.
M is titanium, zirconium, or hafnium. In particular, zirconium and hafnium are preferable.
Further, among the 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 The preferred compounds represented above are only representative exemplary compounds, avoiding many complicated examples. Although a compound in which the central metal is zirconium has been described, it goes without saying that similar hafnium compounds can also be used, and various ligands, cross-linking groups, or auxiliary ligands can be arbitrarily used. It is.

1- (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 known component, and can be appropriately selected from known technologies and used. 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.
Here, as the particulate carrier used for the component (b-1) and the component (b-2), inorganic oxides such as silica, alumina, magnesia, silica alumina, silica magnesia, magnesium chloride, magnesium oxychloride, chloride Examples thereof include inorganic halides such as aluminum and lanthanum chloride, 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.

1- (3) Component (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlRaX3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3)
Or a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or trioctylaluminum, or a halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

1- (4) Formation of catalyst Component (a), component (b) and, if necessary, component (c) are brought into contact to form a catalyst. The contact method is not particularly limited, but the 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 prepolymerization with olefin. In addition, when using an organoaluminum compound at the time of superposition | polymerization of an olefin, it treats as below-mentioned organoaluminum (C), and does not treat as an arbitrary component (c) of a catalyst. This is because even if the same compound is used, the environment and process used are different, so the functions of both are different.
1) Contact component (a) and component (b) 2) Add component (c) after contacting component (a) and component (b) 3) Contact component (a) and component (c) 4) Add component (a) after contacting component (b) and component (c) 5) Contact three components simultaneously.
The amount of components (a), (b) and (c) used in the present invention is 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 such that the amount of transition metal is 0.001 mmol to 100 mmol, particularly preferably 0.005 mmol to 50 mmol, relative to 1 g of component (b). Therefore, the amount of component (c) to component (a) is in the range of 0.002 to 106, preferably 0.02 to 105, particularly preferably 0.2 to 104, in terms of the molar ratio of transition metal.

It is preferable that the catalyst of the present invention is subjected to a prepolymerization treatment comprising a small amount of polymerization by contacting an olefin in advance. 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. The olefin can be supplied by any method, 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 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 with respect to 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.

2. Production Method 2- (1) Sequential Polymerization In carrying out the present invention, it is necessary to sequentially polymerize the crystalline polypropylene component (A) and the propylene-based elastomer component (B). Specifically, it is necessary to polymerize the propylene-based elastomer component (B) in the second step after polymerizing the crystalline polypropylene component (A) in the first step. As long as the effects of the present invention are not hindered, there is no problem even if other polymerization is carried out at any point before the first step, between the first step and the second step, and after the second step.
When performing sequential polymerization, either a batch method or a continuous method can be used, but it is generally desirable to use a continuous method from the viewpoint of productivity.
In the case of the batch method, it is possible to individually polymerize the crystalline polypropylene component (A) and the propylene-based elastomer component (B) using a single polymerization reactor by changing the polymerization conditions with time. . As long as the effects of the present invention are not impaired, a plurality of polymerization reactors may be connected in parallel.
In the case of a continuous process, it is necessary to use a production facility in which two or more polymerization reactors are connected in series because it is necessary to individually polymerize the crystalline polypropylene component (A) and the propylene-based elastomer component (B). The polymerization reactor corresponding to the first step for producing the crystalline polypropylene component (A) and the polymerization reactor corresponding to the second step for producing the propylene-based elastomer component (B) must be in series. A plurality of polymerization reactors may be connected in series and / or in parallel for each of the first step and the second step.

While the crystalline propylene component (A) is produced by polymerization in the first step and the propylene elastomer component (B) is produced by polymerization in the second step, it is essential to employ at least two-stage polymerization. The first step and the second step are preferably performed in a directly connected line, but can also be performed in a so-called batch method in which each step is independent. First, the detailed mode for carrying out the first step is not limited to a mode in which only the single polymerization reactor is used. For example, a plurality of individual polymerization reactors are used as the first polymerization reactor and the second polymerization reactor. In addition, it is also possible to carry out by a so-called series arrangement polymerization apparatus arbitrarily arranged as a third polymerization reactor. It can also be implemented in a so-called complex polymerization reactor in which the series reactors are implemented by a parallel polymerization apparatus that is arbitrarily arranged in parallel, such as one row, two rows, or three rows. In the individual reactor constituting the composite polymerization reactor, the propylene monomer specifications to be supplied are, for example, at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, and If the composition ratio of propylene is seen in the example of ethylene content, the ethylene content of the first polymerization reactor is 1 wt%, the ethylene content of the first polymerization reactor is 16 wt%, and the ethylene content of the first polymerization reactor is 8 wt%. Thus, it is also possible to make a difference in the monomer content. When the composite reactor is implemented by a technique belonging to the category of polymerization production of the crystalline propylene component (A) in the first step, the ethylene contained in the propylene-based polymerization product of each reactor Content is calculated | required, The ethylene content of each reactor will be averaged, and the characteristic of following (i) prescribed | regulated by the crystalline polypropylene component (A) of a 1st process must be satisfy | filled.
Similarly, in the case of producing the propylene-based elastomer component (B) in the second step, not only an embodiment in which only one polymerization reactor is used, but also a series type, as in the method of performing the first step. The reaction can be carried out by a so-called composite polymerization reactor that optionally employs a reactor and a series reactor. The same can be said for the monomer specifications supplied to the polymerization as in the first step. In the case where the second step is performed by a composite polymerization reactor, it is necessary to take measures to prevent stickiness by adding a hydroxo compound (D) having an important carbon number of 4 or more to each reactor. In any case, the propylene-based elastomer component (B) must satisfy the following property (ii) when it is carried out by a method using a composite polymerization reactor belonging to the category of the second step.
The crystalline propylene component (A) in the first step and the propylene-based elastomer component (B) in the second step are the same as those of the crystalline polypropylene component (A) in the polymerization stage. Introducing an elastomer component (soft segment) into the crystalline phase (hard segment), and even if some of the types and contents of monomer specifications in the first and second steps may be common, the component ( Both A) and component (B) are not confused because they are clearly different in physical properties or structure from the technical common sense of polymers.
(I) a propylene homopolymer, or a random copolymer of propylene with at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, wherein ethylene and α- The total content of olefins is 10 wt% or less.
(Ii) a random copolymer of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, wherein the total content of ethylene and α-olefin is a crystal Higher than the total content of ethylene and α-olefin of the conductive polypropylene component (A).

2- (2) Polymerization process The polymerization process can use a bulk method or a gas phase method. 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 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. In the case of the batch method, the first step may be performed by the bulk method and the second step may be performed by the vapor phase method. This case is also referred to as the 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, the present invention does not limit the particular process type in this respect.
Since the propylene-based elastomer component (B) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is preferable to use a gas phase method in the second step of producing the propylene-based elastomer component (B).
The first step for producing the crystalline polypropylene component (A) may be a bulk method or a gas phase method, but there is no problem, but a relatively low crystallinity is required to produce a more flexible product. When producing the conductive polypropylene component (A), it is desirable to use a gas phase method in order to avoid problems such as adhesion.
Therefore, using the continuous method, first, the first step for producing the crystalline polypropylene component (A) is carried out by the gas phase method, and the second step for producing the propylene-based elastomer component (B) is subsequently carried out by the gas phase method. This is most desirable.

2- (3) 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.
The polymerization pressure varies depending on the process to be selected, but 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.

2- (4) Organoaluminum compound (C)
Unlike Ziegler catalysts, metallocene catalysts do not require the use of organoaluminum compounds as promoters. 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 catalyst 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 raw materials. From this point of view, a technique is often used in which a highly reactive organoaluminum compound is added to a polymerization reactor and reacted with the organoaluminum compound before the impurities react with the metallocene catalyst to render it harmless.
In the present invention, it is necessary to use the organoaluminum compound (C). If the organoaluminum compound (C) is not used, the activity suppression reaction by the hydroxo compound (D) described later cannot be stably controlled, and the effects of the present invention cannot be obtained. Moreover, since the effect of detoxifying impurities can be expected as described above, it is extremely important from the viewpoint of stable operation.
Although any compound can be used as the organoaluminum compound (C) of the present invention, examples of suitable compounds are the same as those of the component (c) which is an optional component of the metallocene catalyst, and in particular, triisobutylaluminum and trioctyl. Aluminum is preferred.
The amount of the organoaluminum compound (C) 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 the number-of-moles of aluminum atom with respect to the weight of the propylene-type block copolymer 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.

2- (5) Hydroxo compound (D)
The gist of the present invention is to perform the second step of producing the propylene-based elastomer component (B) in the presence of a hydroxo compound having a specific structure. The hydroxo compound (D) of the present invention is a hydroxo compound having 4 or more carbon atoms, and a hydroxo compound having 3 or less carbon atoms such as ethanol and isopropanol has a small effect on improving particle properties, and in some cases, on the contrary, the particle properties. It is not preferable because it has an effect of worsening. Specific examples of the hydroxo compound (D) include alcohols, silanols, carboxylic acids, sulfonic acids, hydroxycarbonyl compounds, and the like. Of these, alcohols are most preferred. As the alcohol, any of a linear aliphatic alcohol, a cyclic aliphatic alcohol, and an aromatic alcohol can be used. The hydroxo compound (D) has 4 or more carbon atoms, preferably 6 or more, and more preferably 8 or more. If the number of carbon atoms of the hydroxo compound (D) is too large, the proportion remaining in the product propylene-based block copolymer becomes too high, and therefore it is preferably 30 or less. More preferably, it is 20 or less, More preferably, it is 15 or less. Specific examples of preferred compounds as the hydroxo compound (D) include n-butanol, i-butanol, t-butanol, n-hexanol, octanol, 2-ethylhexanol, decanol, dodecanol, undecanol, stearyl alcohol, cyclohexanol, Examples include methylcyclohexanol, phenol, cresol, dimethylphenol, t-butylphenol, di-t-butylphenol, di-t-butylmethylphenol, naphthyl alcohol, methoxyphenol, and the like. Although there are examples in which geometric isomers (n, i, t, o, m, p, etc.) are not described, the above illustrations include all geometric isomers, so any geometric isomers are excluded. Not what you want.

The reason why the hydroxo compound (D) having the specific structure as described above is effective is currently under intensive research. The reactivity with the metallocene catalyst and the organoaluminum compound (C), and propylene The inventor believes that two phenomena of diffusion into the interior of the system block copolymer particles are important. The inventor's idea will be outlined below.
In the first place, a method for improving the particle properties of a propylene-based block copolymer using a suitable amount of a hydroxo compound such as alcohol as a polymerization inhibitor has been developed in a production technique using a Ziegler catalyst. A Ziegler catalyst is a catalyst obtained by activating a solid catalyst component having a titanium atom with an organoaluminum compound, and a monomer such as propylene is formed on the alkyl-Ti bond formed by the reaction of the titanium compound and the organoaluminum compound in the solid catalyst. It is believed that polymerization proceeds by coordination and insertion. In general, when propylene is polymerized, the alkoxy-Ti compound is not a preferred solid catalyst component, and an organoaluminum compound having an alkoxy-Al bond is not a preferred cocatalyst. Therefore, when an alcohol compound is allowed to coexist in a propylene-based polymerization reaction field using a Ziegler catalyst, the alkyl-Ti bond having a polymerization catalyst ability reacts with the alcohol compound to form an inactive alkoxy-Ti compound, or a promoter. It is considered that the essential organic aluminum compound reacts with the alcohol compound to become an alkoxyaluminum compound having a poor promoter ability and the polymerization reaction is stopped. Since the propylene block copolymer is produced as particles, the alcohol compound present in the polymerization field is thought to gradually diffuse from the outside of the particle toward the inside of the particle. Since it reacts with the aluminum compound and is consumed on the spot, it can be considered that the polymerization reaction mainly at the polymerization active site outside the particle is stopped and the polymerization reaction at the polymerization active site inside the particle is maintained and continued. Accordingly, in the production of a propylene block copolymer using a Ziegler catalyst, although it is a production of a propylene block copolymer that is harder than the flexibility of the propylene block copolymer of the present invention, propylene- When alcohols are present in the production of easily sticky polymers such as ethylene copolymer elastomers, the amount of propylene-ethylene copolymer elastomer produced on the particle surface can be suppressed, and stickiness on the particle surface can be suppressed. The particle properties can be improved.

In turn, let's consider a propylene-based block copolymer using a metallocene catalyst. As mentioned in the description of the metallocene catalyst, the organic aluminum compound (C) added to the polymerization field is not a promoter of the metallocene catalyst, but merely added for the purpose of detoxifying impurities. The polymerization active site in a metallocene catalyst is said to be an alkyl-transition metal bond that has undergone alkylation and cationization with an activator such as component (b), but has a structure different from that of a Ziegler catalyst. Therefore, it must be considered that the reactivity with various chemical species is also different. Although concretely illustrated in the Examples and Comparative Examples, the alcohol compound is not necessarily a catalyst poison and may have an effect of increasing the activity. In other words, since the structure and reactivity of the polymerization active site having polymerization ability are different and the role of the organoaluminum compound (C) coexisting in the polymerization field is different, the particle property improvement of the propylene block copolymer using the metallocene catalyst is improved. In the development of polymerization inhibitors for this purpose, the known technology of polymerization inhibitors for improving the particle properties of propylene-based block copolymers using Ziegler catalysts is completely non-referenced, and new technology development was started from scratch. Must-have.
Since an alcohol compound does not necessarily become a catalyst poison, when a relatively large hydroxo compound (D) having 4 or more carbon atoms is present in the range of the amount used later in a polymerization field using a metallocene catalyst, this hydroxo compound (D ) Directly acting on the polymerization active site to stop the polymerization reaction is very small, or the frequency of occurrence is considered to be low enough not to consider the effect. Possibly, it reacts with the organoaluminum compound (C) that is adjacent to or near the polymerization active site to form an alkoxyaluminum compound, and the polymerization reaction is suppressed by the steric hindrance of this alkoxyaluminum compound. It is. Further, in order to selectively suppress the polymerization reaction on the particle surface, it is necessary to cause a reaction locally on the particle surface, and the hydroxo compound (D) must be large enough to slow the diffusion into the particle. it is conceivable that. By such a mechanism, it is considered that a hydroxo compound (D) having 4 or more carbon atoms is specifically effective, and a small hydroxo compound having 3 or less carbon atoms may be insufficiently effective.

2- (6) Method of using hydroxo compound (D) Hydroxo compound (D) may be present when performing the second step of producing propylene-based elastomer component (B), and the addition method is particularly limited. It is not a thing. For example, when using the batch method, the hydroxo compound (D) may be added after completion of the first step, and then the second step may be performed, or the hydroxo compound (D) may be added simultaneously with the start of the second step. May be. In the case of using the continuous method, the hydroxo compound (D) is added through a transfer path (for example, a transfer pipe or a degassing tank in the middle) from the polymerization reactor performing the first step to the polymerization reactor performing the second step. Alternatively, the hydroxo compound (D) may be added to the polymerization reactor that performs the second step.
The hydroxo compound (D) may be added after being diluted with a saturated hydrocarbon solvent or may be added as it is without being diluted. A single hydroxo compound (D) may be used, or a plurality of hydroxo compounds (D) may be mixed and used.
The use amount of the hydroxo compound (D) is preferably in the range of 0.001 to 10 mol / mol-Al in terms of a molar ratio with respect to the use amount of the organoaluminum compound (C) per aluminum atom. More preferably, it is 0.01-5 mol / mol-Al, More preferably, it exists in the range of 0.1-2 mol / mol-Al. The organoaluminum compound (c) that can be used as an optional component of the catalyst is not included in the calculation of the amount of the hydroxo compound (D) used.

3. Propylene-based block copolymer The propylene-based block copolymer of the present invention is used as a reactor TPO,
It has excellent transparency and high balance between flexibility and heat resistance. Specifically, it is produced by multistage polymerization including a first step for producing a crystalline polypropylene component (A) and a second step for producing a propylene-based elastomer component (B) thereafter. Details will be described below.
3- (1) Crystalline polypropylene component (A)
The crystalline polypropylene component (A) of the present invention is a random copolymer of propylene with a propylene homopolymer or at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms. It is a coalescence. The crystalline polypropylene component (A) is a component for developing the heat resistance of the product reactor TPO, and it is preferable that the melting point is somewhat high. On the other hand, in order to make the reactor TPO flexible enough, it is preferable that the crystallinity of the crystalline polypropylene component (A) is not too high, and therefore the melting point corresponding to the crystallinity is preferably not too high. . Therefore, in order to obtain a higher balance between flexibility and heat resistance, a random copolymer is preferable to a propylene homopolymer, and the degree of crystallinity of the propylene homopolymer is determined by the metallocene catalyst used. It is preferable to carry out copolymerization of propylene and a comonomer according to the level to control the melting point and crystallinity.
When the crystalline polypropylene component (A) is a random copolymer of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, The total content needs to be 10 wt% or less. More preferably, the total content of ethylene or α-olefin is 0.1 wt% or more and 5 wt% or less, and more preferably 1 wt% or more and 3 wt% or less. From the viewpoint of heat resistance, it is preferable that the content of ethylene or α-olefin is not too high and the melting point is not lowered too much. Preferred comonomers are ethylene and 1-butene, with ethylene being particularly preferred. An α-olefin having 9 or more carbon atoms cannot be used because its boiling point becomes too high and production becomes difficult.

The melting point of the crystalline polypropylene component (A) can be measured as a melting peak temperature Tm (A) by a differential scanning calorimeter (DSC) as is well known in the art. From the viewpoint of heat resistance, the melting peak temperature Tm (A) is preferably not too low, and Tm (A) is preferably 105 ° C. or higher, particularly preferably 110 ° C. or higher.
On the other hand, as the melting point becomes higher, the crystallinity of the crystalline polypropylene component (A) increases accordingly, so that the rigidity becomes higher, and the propylene-based elastomer component (B) needs to be increased in order to impart flexibility. In order to obtain a higher balance between flexibility and heat resistance, it is preferable to keep the amount of the propylene-based elastomer component (B) within a range in which the propylene-based elastomer component (B) does not become a matrix, and the Tm (A) increases. It is preferable that it is not too much. For this reason, it is preferable that Tm (A) is 145 degrees C or less, Especially preferably, it is 140 degrees C or less.

When the crystalline polypropylene component (A) is a random copolymer of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, ethylene or carbon atoms is 4 The content of α-olefin of ˜8 can be controlled by the ratio of monomers supplied to the polymerization tank. The case of ethylene will be described as an example. If the amount ratio of ethylene to propylene supplied to the polymerization tank (ethylene supply amount ÷ propylene supply amount) is increased, the ethylene content of the resulting ethylene-propylene copolymer is increased. The reverse is also true. The relationship between the amount ratio of propylene and ethylene supplied to the polymerization tank and the ethylene content in the resulting propylene-ethylene random copolymer varies depending on the type of metallocene catalyst used, but the purpose is to adjust the supply amount ratio appropriately. It is very easy for those skilled in the art to obtain an ethylene-propylene copolymer having an ethylene content of 5%.
The melting point of the crystalline polypropylene component (A) can be controlled by the comonomer content. Although the relationship between the comonomer content and the melting point varies depending on the metallocene catalyst used, the melting point can be controlled to a desired value by examining this relationship in advance and adjusting the comonomer content as appropriate. The higher the comonomer content, the lower the melting point of the crystalline polypropylene component (A), the lower the crystallinity, and the higher the flexibility. The reverse is also true.

  When the first step is performed by multistage polymerization, it is preferable that the polymer produced in each stage satisfies the properties of the crystalline polypropylene component (A).

3- (2) Propylene-based elastomer component (B)
The propylene-based elastomer component (B) of the present invention is a random copolymer of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, and further comprises ethylene. Alternatively, the sum of the α-olefin contents is higher than the sum of the ethylene or α-olefin contents of the crystalline polypropylene component (A). Since the propylene-based elastomer component (B) is a component that imparts flexibility to the reactor TPO that is a product, it needs to be a softer component than the crystalline polypropylene component (A). As described in 3- (1), the higher the comonomer content, the higher the flexibility. Therefore, the total comonomer content of the propylene-based elastomer component (B), that is, the ethylene or α-olefin content, is the crystalline polypropylene component (A ) Of ethylene or α-olefin.

As the comonomer of the propylene-based elastomer component (B), ethylene and an α-olefin having 4 to 8 carbon atoms can be used. An α-olefin having 9 or more carbon atoms cannot be used because its boiling point becomes too high and production becomes difficult. Preferred comonomers are ethylene, 1-butene, 1-hexene, 1-octene. Among these, 1-butene can be particularly preferably used because it can improve the balance between flexibility and transparency. Specifically, the propylene-based elastomer component (B) is preferably a propylene-butene-random copolymer or a propylene-ethylene-butene-random copolymer. Most preferred is a propylene-ethylene-butene-random copolymer. However, when 1-butene is used as the comonomer of the propylene-based elastomer component (B), a softer propylene-based block copolymer can be obtained, but the polymer particles are easily sticky and it is difficult to ensure fluidity. In that respect, it can be said that the hydroxo compound (D) of the present invention is useful for producing a softer propylene-based block copolymer having a propylene-based elastomer component (B) using 1-butene as a comonomer.
The total content of ethylene or α-olefin in the propylene-based elastomer component (B) may be higher than the total content of ethylene or α-olefin in the crystalline polypropylene component (A), but preferably the crystalline polypropylene component It is higher than the total content of ethylene or α-olefin in (A) and is 10 wt% or more and 90 wt% or less.

When ethylene is used as a comonomer, it is preferable that the ethylene content be 1 wt% or more and 60 wt% or less regardless of whether an α-olefin is used as another comonomer. More preferably, they are 3 wt% or more and 40 wt% or less, Especially preferably, they are 4 wt% or more and 20 wt% or less, Most preferably, they are 5 wt% or more and 14 wt% or less. In order to achieve high flexibility, it is preferable to lower the crystallinity of the propylene-based elastomer component (B), and for that purpose, a higher ethylene content is preferable. Conversely, from the viewpoint of increasing transparency, it is preferable that the crystalline polypropylene component (A) and the propylene-based elastomer component (B) are not phase-separated, and the propylene-based elastomer component (B) has a lower ethylene content. Is preferred. From these two viewpoints, it is desirable to use the above preferred range.
When 1-butene is used as the comonomer, the 1-butene content is preferably 5 wt% or more and 95 wt% or less regardless of whether ethylene or another α-olefin is used in combination as another comonomer. More preferably, they are 10 to 90 wt%, More preferably, they are 20 to 85 wt%, Most preferably, they are 30 to 75 wt%. Since 1-butene rarely deteriorates transparency unlike ethylene, the range in which it can be suitably used is wide. Therefore, in order to obtain a more flexible propylene block copolymer while maintaining transparency, it is preferable that the content of 1-butene in the propylene elastomer component (B) is larger than the ethylene content. From the viewpoint of increasing flexibility, a higher 1-butene content is preferable because the crystallinity of the propylene-based elastomer component (B) decreases. Conversely, considering that 1-butene has a high monomer unit cost and a burden on the recovery system during production, it is preferable to set the 1-butene content of the propylene-based elastomer component (B) not so high. .
The content of ethylene and the α-olefin having 4 to 8 carbon atoms in the propylene elastomer component (B) is the same as the content of ethylene and the α-olefin having 4 to 8 carbon atoms in the crystalline polypropylene component (A). Can be adjusted.

  When the second step is performed by multistage polymerization, the polymer produced in each stage preferably satisfies the properties of the propylene-based elastomer component (B).

3- (3) Propylene-Based Block Copolymer The propylene-based block copolymer of the present invention comprises a crystalline polypropylene component (A) and a propylene-based elastomer component (B) as essential components. The weight ratio of the crystalline polypropylene component (A) and the propylene-based elastomer component (B) is preferably in the range of 10:90 to 90:10. Preferably, the weight ratio of the crystalline polypropylene component (A) to the propylene-based elastomer component (B) is 15:85 to 85:15, more preferably 25:75 to 75:25, particularly preferably 35:65. It is in the range of 65:35. From the viewpoint of increasing flexibility, it is preferable that the crystalline polypropylene component (A) is not too much. On the other hand, from the viewpoint of increasing heat resistance, it is preferable that the crystalline polypropylene component (A) is not too small. From these two viewpoints, it is desirable to use the above preferred range.
The weight ratio of the crystalline polypropylene component (A) and the propylene-based elastomer component (B) is the production amount in the first step for producing the crystalline polypropylene component (A) and the second step for producing the propylene-based elastomer component (B). Control by production volume. For example, in order to increase the amount of the crystalline polypropylene component (A) and reduce the amount of the propylene-based elastomer component (B), the production amount of the second step may be reduced while maintaining the production amount of the first step, That is, the residence time in the second step may be shortened or the polymerization temperature may be lowered. It can also be controlled by increasing the amount of the hydroxo compound (D) of the present invention and other polymerization inhibitors such as oxygen. The reverse is also true.

  Usually, the weight ratio of the crystalline polypropylene component (A) and the propylene-based elastomer component (B) is the same as the production amount in the first step for producing the crystalline polypropylene component (A) and the first for producing the propylene-based elastomer component (B). It is defined by the ratio of production in two steps. If the crystalline polypropylene component (A) and the propylene-based elastomer component (B) are sufficiently different in crystallinity, they can be separated and identified using analytical techniques such as TREF (temperature rising elution fractionation method) You may ask for. A technique for evaluating the crystallinity distribution of a propylene-based block copolymer by TREF measurement is well known to those skilled in the art. Glokner, J. et al. Appl. Polym. Sci: Appl. Poly. Symp. 45, 1-24 (1990), L .; Wild, Adv. Polym. Sci. 98, 1-47 (1990), J .; B. P. Soares, A .; E. Detailed measurement methods are shown in documents such as Hamielec, Polymer; 36, 8, 1639-1654 (1995).

The MFR of the propylene-based block copolymer of the present invention can be set to an arbitrary value depending on the molding method and application, but generally it is preferably in the range of 0.1 to 1000 g / 10 min. When used for extrusion molding of films and sheets, it is preferable that the MFR is in the range of 0.2 to 20 g / 10 min. More preferably, MFR is in the range of 0.5 to 10 g / 10 min, and still more preferably in the range of 1.0 to 7.0 g / 10 min. When used for injection molding, the MFR is preferably in the range of 1.0 to 200 g / 10 min. More preferably, MFR is in the range of 10 to 100 g / 10 min, and still more preferably in the range of 20 to 50 g / 10 min. When used for fibers, the MFR is preferably in the range of 10 to 1000 g / 10 min. More preferably, MFR is in the range of 50 to 500 g / 10 min, and still more preferably in the range of 80 to 200 g / 10 min.
As a method for controlling the MFR of the propylene-based block copolymer of the present invention, a method for controlling the MFR of the crystalline polypropylene component (A), a method for controlling the MFR of the propylene-based elastomer component (B), a crystalline polypropylene component ( A method for controlling the weight ratio of A) to the propylene-based elastomer component (B) can be exemplified.

Although arbitrary values can be used for MFR of a crystalline polypropylene component (A), generally it is preferable to set it as the range of 0.1-1000 g / 10min. More preferably, it is 1-100 g / 10min. In the first step of producing the crystalline polypropylene component (A), MFR of the crystalline polypropylene component (A) can be adjusted by using hydrogen as a chain transfer agent. Specifically, when the concentration of hydrogen as a chain transfer agent is increased, the MFR of the crystalline polypropylene component (A) is increased. The reverse is also true.
Although any value can be used for the MFR of the propylene-based elastomer component (B), it is generally preferable that the MFR is in the range of 0.1 to 1000 g / 10 min. More preferably, it exists in the range of 1-100 g / 10min, More preferably, it is in the range of 3-60 g / 10min. Unlike a Ziegler catalyst, a metallocene catalyst has a narrow molecular weight distribution, so even if a component having a very low molecular weight is produced, it is difficult to cause problems such as stickiness. The MFR of the propylene-based elastomer component (B) can be controlled in the same manner as the MFR of the crystalline polypropylene component (A).

The melting point of the propylene block copolymer can be measured as a melting peak temperature Tm (w) by a differential scanning calorimeter (DSC) as is well known in the art. From the viewpoint of increasing heat resistance, the melting peak temperature Tm (w) is preferably not too low, and Tm (w) is preferably 105 ° C. or higher, particularly preferably 110 ° C. or higher.
On the other hand, since the melting point Tm (w) of the propylene-based block copolymer is mainly governed by the melting point Tm (A) of the crystalline polypropylene component (A), the crystalline polypropylene component (A) increases as the melting point increases. As the crystallinity increases, the rigidity becomes high, and it is necessary to increase the propylene-based elastomer component (B) in order to impart flexibility. In order to obtain a higher balance between flexibility and heat resistance, it is preferable to keep the amount of the propylene-based elastomer component (B) within a range in which the propylene-based elastomer component (B) does not become a matrix, and Tm (w) becomes high. It is preferable that it is not too much. For this reason, it is preferable that Tm (w) is 145 degrees C or less, Especially preferably, it is 140 degrees C or less.
The melting point Tm (w) of the propylene block copolymer can be adjusted by controlling the melting point Tm (A) of the crystalline polypropylene component (A) by the method described above. Further, for the purpose of controlling the affinity (compatibility parameter) between the crystalline polypropylene component (A) and the propylene-based elastomer component (B), it can be prepared by appropriately setting the comonomer content of both components. In practice, it is easy for those skilled in the art to adjust Tm (w) to a desired value by grasping how Tm (w) changes by changing the comonomer content of both components.

4). Additional ingredients (additives)
In the propylene-based block copolymer of the present invention, in order to add various functions, an additive component (optional component) can be used as an additive within a range that does not significantly impair the effects of the present invention.
As this additional component, an antioxidant, a UV absorber, a light stabilizer, a metal deactivator, a stabilizer, a neutralizer, a lubricant, an antistatic agent, which are conventionally used as a polyolefin resin compounding agent, Various additives such as antifogging agents, nucleating agents, peroxides, fillers, antibacterial and antifungal agents, and optical brighteners can be added.
The amount of these additives is generally 0.0001 to 3 wt%, preferably 0.001 to 1 wt%.

Hereinafter, each additive will be described.
Oxidative degradation of polyolefin is a radical chain reaction via peroxide radicals or hydroperoxide compounds generated by the action of heat, light, mechanical force, metal ions, etc. and oxygen, and is generally called auto-oxidation. Antioxidants are used to suppress this auto-oxidation, and there are three types of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants depending on where they act in the chain reaction. It is common to be separated.
Phenol-based antioxidants are radical scavengers, and radicals generated by reaction with peroxide radicals and the like are relatively stable, so that the concentration of radicals in the system can be lowered. In general, a substituted phenol compound, particularly a substituted phenol compound having a bulky substituent at the ortho position is used.

  Hereinafter, typical compounds are exemplified as the phenolic antioxidant. In the monophenol type compound, 2,6-di-t-butyl-4-methylphenol (common name: BHT), tocopherol (vitamin E), n-octadecyl-3- (4′-hydroxy-3 ′, 5 ′) -Di-t-butylphenyl) propionate (trade name: Irganox 1076, Sumilizer BP-76) can be exemplified. Among the bisphenol type compounds, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) (trade name: Sumilizer MDP-S), 1,1-bis (2′-methyl-4′-hydroxy-5) '-T-Butylphenyl) butane (trade name: Sumilizer BBM-S, Adekastab AO-40), 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (trade names: Smither GA-80, Adeka Stab AO-80) can be exemplified. Among the triphenol type compounds, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane (trade name: ADK STAB AO-30), 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (trade name: Irganox 1330, Adeka Stab AO-330), Tris- (3,5-di-t-butyl-4- Hydroxybenzyl) -isocyanurate (trade name: Irganox 3114, Adeka Stab AO-20), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate (trade name: Sumilyzer) BP-179) can be exemplified. Examples of the tetraphenol type compound include tetrakis {methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate} methane (trade name: Irganox 1010).

The phosphorus-based antioxidant has an action of reducing the hydroperoxide compound and is also called a hydroperoxide decomposing agent. Even when used alone, it has an antioxidant effect, but when used in combination with the above-mentioned phenolic antioxidant, a synergistic effect is generated and the antioxidant effect is further enhanced. Therefore, both are usually used in combination. This synergistic effect occurs when the phenolic antioxidant is regenerated by reducing the phenoxy radical species generated by the reaction between the phenolic antioxidant and the radical species involved in auto-oxidation, thereby regenerating the phenolic antioxidant. It is considered.
Hereinafter, typical compounds are exemplified as the phosphorus-based antioxidant. Among the phosphite type compounds, tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgafos 168, Sumilizer P-16, Adeka Stab 2112), trisnonylphenyl phosphite (trade name: Sumilyzer TNP, Adeka Stab) 1178), tris (mixed, mono-dinonylphenyl phosphite) (trade name: ADK STAB 329K), tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphonite (common name: P-EPQ).
Sulfur-based antioxidants have the effect of reducing hydroperoxide compounds in the same way as phosphorus-based antioxidants, and are also called hydroperoxide decomposing agents. This is also said to have a synergistic effect in combination with a phenolic antioxidant as well as a phosphorus antioxidant.
Hereinafter, typical compounds are exemplified as the sulfur-based antioxidant. In the sulfide type compound, dilauryl-3,3′-thio-dipropionate (common name: DLTDP), di-myristyl-3,3′-thio-dipropionate (common name: DMTDP), distearyl-3,3′-thio- Examples include dipropionate (common name: DSTDP), pentaerythritol-tetrakis- (3-laurylthio-propionate) (trade name: Sumilizer TP-D, Adeka Stab AO-412S).

Additives for suppressing photodegradation are ultraviolet absorbers and light stabilizers. When polypropylene is exposed to ultraviolet rays, radicals are generated and auto-oxidation occurs. The ultraviolet absorber has an action of suppressing generation of radicals by absorbing ultraviolet rays, and the light stabilizer has an action of capturing and inactivating radicals generated by ultraviolet rays.
Ultraviolet absorbers are compounds having an absorption band in the ultraviolet region, and triazole, benzophenone, salicylate, cyanoacrylate, nickel chelate, inorganic fine particle, and the like are known. Of these, the triazole type is most widely used.
Hereinafter, typical compounds are exemplified as the ultraviolet absorber. Among triazole-based compounds, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole (trade name: Sumisorb 200, TinuvinP), 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (Trade names: Sumisorb 340, Tinuvin 399), 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole (trade names: Sumisorb 320, Tinuvin 320), 2- (2′-hydroxy) -3 ′, 5′-di-t-amylphenyl) benzotriazole (trade names: Sumisorb 350, Tinuvin 328), 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5 Chlorobenzotriazole (trade name: Sumisorb 300, Tinuvin 326) can be exemplified The Examples of the benzophenone compounds include 2-hydroxy-4-methoxybenzophenone (trade name: Sumisorb 110) and 2-hydroxy-4-n-octoxybenzophenone (trade name: Sumisorb 130). Examples of salicylate compounds include 4-t-butylphenyl salicylate (trade name: Seesorb 202). Examples of cyanoacrylate compounds include ethyl (3,3-diphenyl) cyanoacrylate (trade name: Seesorb 501). Examples of nickel chelate compounds include nickel dibutyldithiocarbamate (trade name: Antigen NBC). Examples of inorganic fine particles include TiO ₂ , ZnO ₂ , and CeO ₂ .

The light stabilizer is generally a hindered amine compound and is called HALS. HALS has a 2,2,6,6-tetramethylpiperidine skeleton and cannot absorb ultraviolet rays, but suppresses photodegradation by various functions. The main functions are said to be three of: scavenging radicals, decomposing hydroxy peroxide compounds, and capturing heavy metals that accelerate the decomposition of hydroxy peroxides.
Hereinafter, typical compounds are exemplified as HALS. In the sebacate type compound, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: ADK STAB LA-77, Tinuvin 770), bis (1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate (trade name: Tinuvin 765) can be exemplified. Among the butanetetracarboxylate type compounds, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (trade name: ADK STAB LA-57), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (trade name: ADK STAB LA-52), 1,2,3,4-butanetetra Condensation product of carboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol (trade name: Adeka Stab LA-67), 1,2,3,4-butanetetracarboxylic acid and 1, A condensate (trade name: Adeka Stab LA-62) with 2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol can be exemplified. Examples of the succinic polyester type compound include a condensation polymer of succinic acid and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine. In the triazine type compound, N, N′-bis (3-aminopropyl) ethylenediamine · 2,4-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino } -6-Chloro-1,3,5-triazine condensate (trade name: Chimasorb 199), poly {6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino} (trade name: Chimasorb944) ), Poly (6-morpholino-s-triazine-2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl) Til-4-piperidyl) imino} (trade name: Chimasorb 3346).

A metal deactivator is an additive that suppresses auto-oxidation, and is usually a compound having a chelating ability for metal ions. It is known that metal ions radically decompose hydroxyperoxide compounds in auto-oxidation and accelerate the chain reaction, but this reaction can be suppressed by adding compounds that can form chelates with metal ions. Can be expected. In particular, it is a stabilizer used when used for copper tube coating, and is generally used in combination with other antioxidants. A hydrazine type compound is often used as a metal deactivator. Specific examples include decanedicarboxylic acid disalicyloyl hydrazide.
The stabilizer is an additive for polyvinyl chloride (PVC) in the first place, and is used for the purpose of preventing the hydrochloric acid (HCl) from desorbing from PVC and deteriorating. Some of the various stabilizers also have a function as a neutralizing agent, and thus may be used as an additive for polyolefins. A neutralizer is a compound used to neutralize chlorine components derived from Ziegler catalysts used in the production of polyolefins. As the neutralizing agent, a carboxylate having a neutralizing ability is often used, but an inorganic compound having a chlorine ion capturing ability can also be used. Both are compounds used as stabilizers. Basically, it is an additive that is not necessary when using a metallocene catalyst that does not contain chlorine atoms. However, since chlorine atoms are easily contaminated chemical species, they may be used for insurance from the viewpoint of stable production. Many.
Hereinafter, typical compounds are exemplified as the neutralizing agent. Examples of the carboxylate type compound include calcium stearate and zinc stearate. Examples of inorganic compounds include hydrotalcite and inclusions of aluminum hydroxide and lithium carbonate (trade name: Mizukarak).

  A lubricant is an additive used to improve moldability and fluidity, and has an action of reducing friction force between polymer molecules and friction force between a polymer and a moldable inner wall in a molding machine or an extruder. Compounds used as lubricants include hydrocarbon compounds such as paraffin and wax, alcohols such as stearyl alcohol and propylene glycol, higher fatty acid esters such as n-butyl stearate, higher fatty acid amides such as oleic acid amide and stearic acid amide, stear Examples include higher fatty acid salts such as calcium phosphate, partial esters of polyhydric alcohols such as stearic acid monoglyceride, and silicone oil.

The antistatic agent is an additive used to weaken the electrical insulating properties of the polymer, and has an effect of preventing adhesion of dust and the like due to static electricity. Compounds used as antistatic agents are surfactants or surfactant analogues, and are generally quaternary ammonium salts, sulfonates, partial esters of polyhydric alcohols, alkyldiethanolamines, alkyldiethanolamides, and the like. Specific examples of the antistatic agent include (3-laurylamidopropyl) trimethylammonium methylsulfate, sodium alkyldiphenyl ether disulfonate, stearic acid monoglyceride, alkyldiethanolamine (trade name: electrostripper EA), polyoxyethylene alkylamine ( Product name: Ethomen), polyoxyethylene alkylamide (trade name: Ethomen O / 15), and the like.
The antifogging agent is an additive that changes the surface of the polymer to be hydrophilic and makes it difficult for water droplets to adhere thereto. Usually, the same surfactant as the antistatic agent is used.

The nucleating agent is an additive that improves the physical properties and transparency by promoting the formation of crystal nuclei, thereby increasing the crystallinity and decreasing the crystal size. Nucleating agents are roughly classified into three types: sorbitol, phosphate metal salt, and carboxylate metal salt, depending on structural features.
A sorbitol-based nucleating agent is a compound having a benzylidene sorbitol skeleton, which is a 1: 2 condensate of sorbitol, which is a hexavalent alcohol, and benzaldehydes. It is said to form an intermolecular assembly to form a three-dimensional network structure. When used in polypropylene, it is believed that polypropylene crystals grow from the surface of this network structure, and exhibits an excellent effect in improving transparency. Specific examples include 1,3,2,4-dibenzylidene sorbitol (trade name: Gelol D, EC-1), 1,3,2,4-di (p-methylbenzylidene) sorbitol (trade name) : Gelol MD), 1,3,2,4-bis (3,4-dimethylbenzylidene) sorbitol (trade name: Gelol MX, Millad 3988), 1,2,3-trideoxy-4,6,5,7-bis -O-{(4-n-propylphenyl) methylene} nonitol (trade name: MilladNX8000).

Metal phosphate nucleating agents promote the formation of crystal nuclei by dispersing fine crystals of a metal phosphate having a melting point higher than that of polypropylene, and generally have an alkylbenzene skeleton. Specific examples of the compound include sodium 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate (trade name: ADK STAB NA-11), 2,2-methylene-bis (4 , 6-di-t-butylphenyl) aluminum phosphate hydroxide and lithium stearate (trade name: ADK STAB NA-21).
Carboxylic acid metal salt-based nucleating agents are the oldest nucleating agent systems, and have a disadvantage that their effects are inferior compared to metal phosphate-based nucleating agents. An example of a specific compound is di (4-t-butylbenzoic acid) aluminum hydroxide (common name: AL-PTBBA).

Further, ethylene / propylene rubber, ethylene / butene rubber, ethylene / hexene rubber, ethylene / octene rubber, etc., which are resins other than the propylene block copolymer of the present invention, do not significantly impair the effects of the present invention. It can also be blended within. Resins other than those used in the present invention can be blended up to a maximum of 30 wt%, preferably 20 wt%.
These additional components can be directly added to the propylene block copolymer of the present invention obtained by polymerization and melt kneaded for use, or may be added during melt kneading. Furthermore, it can be added directly after melt-kneading, or can be added as a masterbatch within a range that does not significantly impair the effects of the present invention. Moreover, you may add by these composite methods.
In general, additives such as an antioxidant and a neutralizing agent are blended, mixed, melted and kneaded before being molded into a product. It is also possible to add and use other resins or other additional components (including a masterbatch) as long as the effects of the present invention are not significantly impaired during molding.
For the mixing, melting, and kneading, any conventionally known methods can be used. Usually, Henschel mixer, super mixer, V blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, uniaxial or biaxial kneading extrusion Can be implemented on the machine. Among these, it is preferable to perform mixing or melt-kneading with a uniaxial or biaxial kneading extruder.

4). Use and molding method of the present invention The propylene-based block copolymer of the present invention is excellent in flexibility and transparency, and can be molded at low temperatures while the product has heat resistance, and stickiness and bleed are suppressed. Therefore, it is suitably used for films, sheets, laminates, various containers, various molded products, various coating materials, and the like.
In particular, a film or sheet is suitable because bleeding is suppressed and the stickiness is remarkably reduced, so that blocking hardly occurs and the appearance is good.
Moreover, when used as various containers, the content contamination by bleed is very small, and it is suitable for food, medical and industrial fields.
Also as a molded article, there is no deterioration in appearance over time due to bleeding, and it can be suitably used.

As a molding method for these various products, a known molding method can be used without limitation.
Examples of film or sheet molding methods include air-cooled inflation molding, water-cooled inflation molding, non-stretching molding using a T-die, uniaxial stretching molding, biaxial stretching molding, and calendar molding.
Moreover, when using as a film or a sheet | seat, the use as a layer in a multilayer structure is also possible in a laminated body. That is, it can be used for the intermediate layer by taking advantage of its flexibility, and can also be used as a surface layer by taking advantage of its excellent strength without forming stickiness and bleed-out and enabling molding at low temperature.
As container molding, hot pressure molding, pressure molding, vacuum molding, vacuum pressure molding, blow molding, stretch blow molding, injection molding, or the like can be used.
In order to obtain a molded product, not only normal injection molding but also insert molding, sandwich molding, gas assist molding, and the like can be performed, and press molding, stamping molding, rotational molding, and the like can also be used.
Since these molded products have heat resistance, they are suitable for sterilization with hot water and use at relatively high temperatures, and not only do not deform, but also deteriorate transparency due to bleed-out when heat is applied. It also has the feature that it does not occur.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples.
Method and apparatus for measuring physical properties (1) Melt flow rate (MFR)
The MFT of the propylene block copolymer and the crystalline polypropylene component (A) was measured according to JIS K7210 A method condition M under the following conditions.
Test temperature: 230 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm
Since the MFR of the propylene-based elastomer component (B) cannot be directly measured, it was calculated using a viscosity law which is a method well known to those skilled in the art. A specific calculation formula is shown below.

MFR−B = exp [{log (MFR−w) −W (A) × log (MFR−A)} ÷ W (B)]

(Variable definition)
MFR-w: MFR of propylene-based block copolymer
MFR-A: MFR of crystalline polypropylene component (A)
MFR-B: MFR of propylene-based elastomer component (B)
W (A): ratio of the weight of the crystalline polypropylene component (A) to the weight of the entire propylene-based block copolymer (g / g)
W (B): Ratio of the weight of the propylene-based elastomer component (B) to the weight of the entire propylene-based block copolymer (g / g)

(2) Polymer BD
The bulk density of the polymer was measured according to ASTM D1895-69.
(3) Measurement of powder particle size It measured using the particle size distribution measuring device camsizer by Lecce Technology.
(4) Weight ratio of crystalline polypropylene component (A) and propylene-based elastomer component (B) Using the obtained propylene-based block copolymer, TREF is measured according to the procedure described in (4) below. The amount eluted up to 40 ° C. (including 40 ° C.) was taken as the amount of the propylene-based elastomer component (B). The amount eluted at a temperature higher than 40 ° C. was defined as the amount of the crystalline polypropylene component (A). Naturally, the total elution amount corresponds to the amount of the propylene-based block copolymer. It is easy to determine the weight ratio from the amounts of both components thus obtained. Further, W (A) and W (B) can be obtained as values for the total elution amount.

(5) Method for measuring TREF A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / mL BHT) at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to −15 ° C. at a rate of 4 ° C./min, and held for 60 minutes. Thereafter, o-dichlorobenzene (containing 0.5 mg / mL BHT) as a solvent is allowed to flow through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. in the TREF column. Elution is performed for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.
[apparatus]
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column filler: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve

(Sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: Micro flow cell for LC-IR Optical path length 1.5mm Window shape 2φ x 4mm oval Synthetic sapphire window Measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-orthodichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(6) Ethylene content and butene content of each component The ethylene content contained in the crystalline polypropylene component (A) was determined by NMR using a sample collected after the first step. The contents of ethylene and 1-butene contained in the propylene-based block copolymer were determined by NMR using a sample obtained after completion of the second step. The contents of ethylene and 1-butene contained in the propylene-based elastomer component (B) were calculated by the following formula using the amounts of each component determined in (4).
(a formula)
[E] B = {[E] w- [E] AxW (A)} ÷ W (B)
[B] B = [B] w ÷ W (B)
(Variable definition)
[E] w; ethylene content of propylene-based block copolymer [E] A: ethylene content of crystalline polypropylene component (A) [E] B: ethylene content of propylene-based elastomer component (B) [B] w; propylene 1-butene content of block copolymer [B] B: 1-butene content of propylene-based elastomer component (B) The definitions of W (A) and W (B) are as described in (1).
In addition, the determination method of the content of ethylene and 1-butene by NMR is as follows.

(7) Determination method of ethylene and 1-butene contents by NMR Each comonomer content was determined from 13C-NMR spectrum. 13C-NMR measurement was performed using AVANCE-400 FT-NMR manufactured by Bruker BioSpin Inc. equipped with a 10 mmφ cryoprobe.
A 250 mg sample was uniformly dissolved in 2.5 ml of o-dichlorobenzene / benzene bromide-d5 mixed solvent (volume ratio: 8/2), and measurement was performed at 130 ° C. Accumulation was performed 512 times under a complete decoupling of 1H with a pulse angle of 90 ° and a pulse interval of 15 seconds. Spectral assignments are described in J. Polym. Sci. , Polym. Phys. Ed. 21, 573 (1983) and J. Org. Appl. Polym. Sci. , 80, 1880 (2001).
Each comonomer content was determined according to the following formula.
Butene content (mol%) = I (B) / {I (B) + I (P) + I (E)} × 100
Propylene content (mol%) = I (P) / {I (B) + I (P) + I (E)} × 100
Ethylene content (mol%) = I (E) / {I (B) + I (P) + I (E)} × 100
Here, I (B) is the integrated intensity of the signal derived from the methyl group of the butene unit generated near 11 ppm, and I (P) is the integrated intensity of the signal derived from the methyl group of the propylene unit generated near 19-22 ppm. And the integrated intensity of the signal derived from the methyl group of the 2,1-inserted propylene unit occurring in the vicinity of 17 to 18 ppm, and I (E) is all the values derived from the copolymer appearing between 10 ppm and 48 ppm. It is a numerical value obtained by subtracting 4 times I (B) and 3 times I (P) from the sum of signal intensities and then dividing by 2.
As is well known to those skilled in the art, heterogeneous bonds may be observed in olefin polymerization using a metallocene catalyst. Therefore, in the case of copolymerization containing propylene or 1-butene, there may be a 1,3-inserted propylene unit or a 1,4-inserted butene unit. Since all of these units have a structure in which a plurality of methylene chains are continuous, in the present invention, signals derived from these units are also treated as signals derived from ethylene units, and the calculation method of each monomer content is defined according to the above formula. .
(8) Melting peak temperature (Tm)
Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further melt at a rate of temperature increase of 10 ° C./min. The melting peak temperature was Tm (unit: ° C.).

Example 1
1. Production of Catalyst Carrier Particle Size Measurement In the examples, catalyst synthesis was performed using ion-exchange layered silicate (Montmorillonite: Benclay SL manufactured by Mizusawa Chemical Co., Ltd.) as a carrier. Prior to catalyst synthesis, the average particle size of the carrier was measured using a laser diffraction / scattering particle size distribution analyzer (“LA-920” manufactured by Horiba, Ltd.). In the measurement, ethanol was used as a dispersion medium, and the average particle diameter was determined with a shape factor of 1.0. The value obtained was 50 μm.

Silicate Chemical Treatment To a 10 liter glass separable flask equipped with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Mizusawa Chemical Co., Ltd. Benclay SL) was further dispersed, the temperature was raised to 90 ° C., and the temperature was maintained for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The mass after drying was 707 g. The chemically treated silicate thus obtained was further dried with a kiln dryer to obtain a dried silicate.

Preparation of catalyst 200 g of the dry silicate obtained above was introduced into a glass reactor equipped with a stirring blade with an internal volume of 3 liters, mixed with 1160 ml of mixed heptane, and further with 840 ml of a heptane solution of triethylaluminum (0.60 M) at room temperature. Stir with. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry at 2.0 liters. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] (synthesized in JP-A-10-226712) 33.1 ml of a triisobutylaluminum heptane solution (0.71 M) was added to 2180 mg (3 mmol) and 870 ml of mixed heptane (performed according to the example), and the mixture reacted at room temperature for 1 hour was added to the silicate slurry, Stir for 1 hour.

Prepolymerization Subsequently, 2.1 liters of n-heptane was introduced into a stirring autoclave having an internal volume of 10 liters that had been sufficiently substituted with nitrogen, and maintained at 40 ° C. The previously prepared silicate / metallocene complex slurry was introduced therein. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours. After completion of the prepolymerization, the remaining monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then about 3 liters of the supernatant was decanted. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5.6 liters of mixed heptane were added, and the mixture was stirred at 40 ° C. for 30 minutes and allowed to stand for 10 minutes. Removed liters. This operation was further repeated 3 times. When the component analysis of the final supernatant was performed, the concentration of the organoaluminum component was 1.23 mmol / L and the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 17.0 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. By this operation, a prepolymerized catalyst (catalyst-1) containing 2.2 g of polypropylene per 1 g of catalyst was obtained.

2. Production of propylene-based block copolymer Using the prepolymerized catalyst (catalyst-1) obtained above, a propylene-based block copolymer was produced according to the following procedure.

Step 1 After fully replacing an autoclave with an internal volume of 3 L having a stirring and temperature control device with propylene, 2.76 ml (2.0 mmol) of triisobutylaluminum / n-heptane solution was added, 19 g of ethylene, 40 ml of hydrogen, 750 g of liquid propylene was introduced, and the temperature was raised to 60 ° C. to maintain the temperature. The above prepolymerized catalyst (Catalyst-1) was slurried with n-heptane, and 9 mg (excluding the weight of the prepolymerized polymer) was injected as a catalyst to initiate polymerization. Polymerization was continued for 30 minutes while maintaining the temperature in the tank at 60 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen. When a part of the produced polymer was sampled and analyzed, the ethylene content was 1.8 wt%, the MFR was 6.0 g / 10 min, and the average particle size was 1,000 μm.

Addition of Hydroxo Compound (D) After a part of the polymer was sampled in the first step, n-heptane diluted solution of n-decanol as hydroxo compound (D) was autoclaved so that the amount of n-decanol was 0.05 mmol. Added and mixed well.

Second Step Separately, a mixed gas used in the second step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 85 ° C., and the mixed gas composition was ethylene 14 vol%, propylene 59 vol%, and 1-butene 27 vol%. After the hydroxo compound (D) was added and mixed well, this mixed gas was supplied to a 3 L autoclave to start polymerization in the second step. The polymerization was continued for 29 minutes at a polymerization temperature of 80 ° C. and a pressure of 1.5 MPaA. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization. The recovered polymer was sufficiently dried in an oven. The activity was 15.4 kg / g-catalyst, ethylene content was 2.9 wt%, butene content was 18 wt%, MFR was 11 g / 10 min, and BD was 0.38 g / cc.
As a result of the TREF measurement, the amount of the propylene elastomer component (B) produced in the second step was 35 wt%, and the weight ratio of the crystalline polypropylene component (A) to the propylene elastomer component (B) was 65 : 35. As described above, when the comonomer content of the propylene-based elastomer component (B) was calculated, the ethylene content was 5 wt% and the butene content was 40 wt%. Moreover, when the MFR of the propylene-based elastomer component (B) was calculated, it was 35 g / 10 min.

Comparative Example 1
A propylene-based block copolymer was produced in the same manner as in Example 1 except that the hydroxo compound (D) was not added. The results are shown in Table 1. The BD of the propylene-based block copolymer was 0.36 g / cc, and the particles were sticky but flowed as compared to Example 1.

Comparative Example 2
As the hydroxo compound (D), a propylene-based block copolymer was produced in the same manner as in Example 1 except that 0.05 mmol of ethanol was added. The results are shown in Table 1. The BD of the propylene-based block copolymer was 0.30 g / cc, and was much sticky compared to Example 1 and was a particle that hardly flowed.

Comparative Example 3
A propylene-based block copolymer was produced in the same manner as in Comparative Example 2 except that the amount of ethanol added was 0.8 mmol. The results are shown in Table 1. The propylene block copolymer was very sticky particles and did not flow at all, so BD could not be measured.

Example 2
1. Catalyst Preparation In the preparation of the catalyst, instead of [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] [(r) -Dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium] (synthesis was carried out in accordance with Examples of JP-A-11-240909) A catalyst (catalyst-2) was produced in the same manner as in Example 1 except for.

2. Production of propylene-based block copolymer Using the prepolymerized catalyst (Catalyst-2) obtained above, a propylene-based block copolymer was produced according to the following procedure.

Step 1 After fully replacing the 3 L autoclave with stirring and temperature control with propylene, 2.76 ml (2.0 mmol) of triisobutylaluminum / n-heptane solution was added, 18 g of ethylene, 20 ml of hydrogen, 750 g of liquid propylene was introduced, the temperature was raised to 50 ° C., and the temperature was maintained. The above prepolymerized catalyst (Catalyst-2) was slurried with n-heptane, and 100 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. Polymerization was continued for 15 minutes while maintaining the bath temperature at 50 ° C. Thereafter, the residual monomer was purged to normal pressure and further completely replaced with purified nitrogen. When a part of the produced polymer was sampled and analyzed, the ethylene content was 1.9 wt%, the MFR was 8.0 g / 10 min, and the average particle size was 450 μm.

Addition of Hydroxo Compound (D) After a part of the polymer was sampled in the first step, an n-heptane diluted solution of n-butanol as a hydroxo compound (D) was placed in an autoclave so that the amount of n-butanol was 0.8 mmol. Added and mixed well.

Second Step Separately, a mixed gas used in the second step was prepared using an autoclave having an internal volume of 20 L having a stirring and temperature control device. The preparation temperature was 85 ° C., and the mixed gas composition was ethylene 45 vol%, propylene 11 vol%, and 1-butene 44 vol%. After the hydroxo compound (D) was added and mixed well, this mixed gas was supplied to a 3 L autoclave to start polymerization in the second step. The polymerization was continued for 41 minutes at a polymerization temperature of 80 ° C. and a pressure of 1.0 MPaA. Thereafter, 10 ml of ethanol was introduced to terminate the polymerization. The recovered polymer was sufficiently dried in an oven. The activity was 2.6 kg / g-catalyst, the ethylene content was 4.5 wt%, the butene content was 58 wt%, the MFR was 39 g / 10 min, and the BD was 0.36 g / cc.
As a result of the TREF measurement, the amount of the propylene-based elastomer component (B) produced in the second step was 64 wt%, and the weight ratio of the crystalline polypropylene component (A) to the propylene-based elastomer component (B) was 36 : 64. As described above, when the comonomer content of the propylene-based elastomer component (B) was calculated, the ethylene content was 6 wt% and the butene content was 73 wt%. Moreover, when the MFR of the propylene-based elastomer component (B) was calculated, it was 96 g / 10 min.

Examples 3-8
A propylene-based block copolymer was produced in the same manner as in Example 2 except that the compounds shown in Table 2 were used as the hydroxo compound (D). The results are shown in Table 2. In the compounds shown in Table 2, 2,6-Me2PhOH means 2,6-dimethylphenol, and 2-t-BuPhOH means 2-t-butylphenol.

Comparative Example 4
A propylene-based block copolymer was produced in the same manner as in Example 2 except that the hydroxo compound (D) was not added. The results are shown in Table 2. The propylene block copolymer was very sticky particles and did not flow at all, so BD could not be measured.

Comparative Example 5
A propylene-based block copolymer was produced in the same manner as in Example 2 except that 0.8 mmol of acetone was used as the hydroxo compound (D). The results are shown in Table 2. The propylene block copolymer was very sticky particles and did not flow at all, so BD could not be measured.

3. Measurement of physical properties For reference, the propylene-based block copolymer obtained in Example 1 was pelletized by a general method, and the handling of the particles at that time was confirmed, and the obtained pellet was injection-molded. The physical properties were evaluated by the following methods.
Additive formulation The following additives were added to the propylene-based block copolymer obtained in Example 1 and mixed well in a plastic bag. The polymer particles were excellent in fluidity, and the additive was sufficiently stirred.
Additive formulation Antioxidant: tetrakis {methylene-3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate} methane (BASF Corp. Irganox1010) 500 ppm, tris (2,4-di - t-Butylphenyl) phosphite (Irgafos 168 manufactured by BASF) 500 ppm
Neutralizer: Calcium stearate 500ppm
-Granulation Granulated and pelletized under the following conditions. The polymer particles were excellent in fluidity, could be stably supplied to the extruder by a feeder, and could be easily pelletized.
Feeder: Kuma Engineering's Accurate Feeder (Model 100)
Extruder: KZW-15-45MG twin screw extruder manufactured by Technobel Co., Ltd. Screw: 15 mm in diameter L / D = 45
Extruder set temperature: (from below the hopper) 40, 80, 160, 180, 180, 180 (die temperature)
Screw rotation speed: 400rpm
Discharge rate: About 1.5kg / hr (adjusted with feeder)
Die: 3 mm diameter Strand die The pellets obtained with 2 holes were injection molded under the following conditions to obtain test pieces for evaluating physical properties.

・ (Injection molding)
Standard number: JIS K-7152 (ISO 294-1) compliant Reference molding machine: EC20P injection molding machine manufactured by Toshiba Machine Co., Ltd. Molding machine set temperature: (from under the hopper) 80, 210, 210, 200, 200 ° C
Mold temperature: 40 ℃
Injection speed: 52 mm / s (screw speed)
Holding pressure: 10 MPa
Holding pressure time: 15 seconds Cooling time: 60 seconds Mold shape: flat plate (thickness 4 mm, width 10 mm, length 80 mm x 2 picks)
And flat plate (thickness 2 mm, width 40 mm, length 80 mm)
About the obtained test piece, the physical property of the following item was evaluated.

Transparency The transparency of the test piece was evaluated under the following conditions. As a result of the evaluation, HAZE was 61% and total light transmittance was 90%, which was excellent in transparency.
Standard number: Conforms to JIS K-7361-1 Measuring instrument: Haze meter NDH2000 (Nippon Denshoku Industries Co., Ltd.)
Test piece thickness: 2 mm
Test piece preparation method: Injection molded flat plate Condition adjustment: After molding, left in a constant temperature room adjusted to room temperature 23 ° C. and humidity 50% Number of test pieces: 3
Evaluation items: Haze (HAZE), total light transmittance

Bending test The bending characteristics of the test piece were evaluated under the following conditions. As a result of the evaluation, the flexural modulus was 190 MPa, and the flexibility was excellent.
Standard number: Compliant with JIS K-7171 (ISO178) Testing machine: Fully automatic bending testing machine Bendgraph (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
Specimen sampling direction: Flow direction Specimen shape: Thickness 4 mm Width 10 mm Length 80 mm
Condition adjustment: left in a temperature-controlled room adjusted to room temperature 23 ° C. and humidity 50% for more than 24 hours Test room: temperature-controlled room temperature adjusted to 23 ° C. and humidity 50% Number of test pieces: 5
Distance between fulcrums: 64.0mm
Test speed: 2.0 mm / min Evaluation item: Flexural modulus

Heat resistance The Vicat softening point of the obtained block copolymer was evaluated under the following conditions. As a result of the evaluation, the Vicat softening point temperature was 122 ° C., which was excellent in heat resistance.
Standard number: JIS K7206 (Conforms to the 50 method except that the load is 250 g)
Measuring machine: Fully automatic HDT measuring machine (manufactured by Toyo Seiki)
Specimen shape: 2mm thickness 25mm x 25mm two flat plates Stacked test piece creation method: Injection molded flat plate is punched into the above shape (see the molding section for molding)
Condition adjustment: Leave in a temperature-controlled room adjusted to room temperature 23 ° C and humidity 50% for more than 24 hours (no annealing)
Test weight: 250g
Temperature increase rate: 50 ° C / h
Number of specimens: 3

The same evaluation was performed on the propylene-based block copolymer obtained in Comparative Example 1. These particles were sticky and difficult to handle, but somehow they could be granulated, shaped and evaluated. About the physical property, it corresponded with the case where the polymer particle obtained by Example 1 was used.
The same evaluation was attempted for the propylene-based block copolymer obtained in Comparative Example 2. However, these polymer particles have very poor fluidity, and the amount discharged from the feeder is not stable during granulation, making pelletization difficult.
Further, the propylene block copolymer obtained in Comparative Example 3 had extremely poor fluidity of particles, and the polymer particles could not be supplied to the extruder by the feeder.
As a result, these propylene-based block copolymers could not produce pellets, and injection molding and physical property evaluation could not be performed.

Consideration by contrast between Examples and Comparative Examples By contrasting the above Examples-1 to 8 and Comparative Examples-1 to 5, the present invention has excellent transparency and a balance between flexibility and heat resistance. It is clear that a high propylene-based block copolymer can be obtained as particles with very good fluidity.
Specifically, Example 1 has a high BD compared to Comparative Examples 1 to 3, and the same transparency, flexibility, and heat resistance are obtained as good particles. I understand. In particular, from the comparison with Comparative Examples 2 and 3 using ethanol, the significance of using the hydroxo compound (D) having 4 or more carbon atoms is clear.

Moreover, Examples 2-8 have high BD compared with the comparative example 4, and are excellent also in a softness | flexibility. In Comparative Example 5, acetone is used, but the fluidity of the particles is extremely poor as compared with Examples 2 to 8, and the difference between acetone and the hydroxo compound (D) is clear.
When all Examples and Comparative Examples are compared, it can be seen that the hydroxo compound (D) does not necessarily decrease the activity. For example, in Example 1, the polymerization time of the second step is 29 minutes, and the same polymerization amount is achieved in a short time compared to Comparative Example 1 in which nothing is added and Comparative Examples 2 and 3 in which ethanol is added. . That is, it can be seen that the polymerization activity is increased by adding n-decanol. There is no doubt that the particle surface is modified due to the improved fluidity of the particles, and the hydroxo compound in the present invention has two functions: a polymerization inhibiting function on the particle surface and an activation function inside the particle. It is thought to have. In this respect as well, the present invention is greatly different from conventional known techniques.

  By achieving a stable and advanced production method for propylene-based block copolymers, it contributes significantly to the progress of polymerization technology in the field of polymerization technology and the development of the industrial field of polymer production, and the propylene-based block copolymer with good performance. It can be said that it contributes to the expansion and promotion of the field of use of polymers, and the development of molded products and molding processes.

JP 2005-132992 A JP 2007-297505 A JP 2008-260826 A JP 2001-310907 A JP 2009-292879 A JP 2009-292882 A JP 2005-533138 A

Claims (8)

A first step of producing a crystalline polypropylene component (A) satisfying the following property (i) in the presence of a metallocene catalyst and an organoaluminum compound (C);
A second step of producing a propylene-based elastomer component (B) satisfying the following property (ii) in the presence of the metallocene catalyst, the organoaluminum compound (C) and the crystalline polypropylene component (A). A method for producing a block copolymer, comprising:
The method according to claim 1, wherein the hydroxo compound (D) having 4 or more carbon atoms is added to the second step.
(I) a propylene homopolymer, or a random copolymer of propylene with at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, wherein ethylene and α- The total content of olefins is 10 wt% or less.
(Ii) a random copolymer of propylene and at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 8 carbon atoms, wherein the total content of ethylene and α-olefin is a crystal Higher than the total content of ethylene and α-olefin of the conductive polypropylene component (A).   2. The production of a propylene-based block copolymer according to claim 1, wherein the weight ratio of the crystalline polypropylene component (A) and the propylene-based elastomer component (B) is in the range of 10:90 to 90:10. Method.   3. The propylene-based block copolymer according to claim 1 or 2, wherein the propylene-based elastomer component (B) is a random copolymer of propylene and 1-butene, or a random copolymer of propylene, ethylene, and 1-butene. Production method.   The ratio of the amount of the hydroxo compound (D) used to the amount of the organoaluminum compound (C) used per aluminum atom is in the range of 0.001 to 10 mol / mol-Al. The manufacturing method of the propylene-type block copolymer in any one.   The method for producing a propylene-based block copolymer according to any one of claims 1 to 4, wherein the hydroxo compound (D) is a linear aliphatic alcohol. The method for producing a propylene-based block copolymer according to any one of claims 1 to 4, wherein the hydroxo compound (D) is a cyclic aliphatic alcohol.
Production method. The method for producing a propylene-based block copolymer according to any one of claims 1 to 4, wherein the hydroxo compound (D) is an aromatic alcohol.
Production method. The method for producing a propylene-based block copolymer according to any one of claims 1 to 7, wherein the second step is performed by a gas phase method.