JP2010121119A - Propylenic resin composition and its molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylenic resin composition excellent in impact resistance, rigidity, transparency, and moldability, and to provide a molded article molded from the resin composition. <P>SOLUTION: This propylenic resin composition comprises (1) (α) 60-99 pts.wt. of a propylenic polymer and (2) (β) 1-40 pts.wt. of propylene-ethylene block copolymer satisfying requirements: (a) propylene-ethylene block copolymer obtained by sequentially polymerizing 30-95 wt.% of propylene homopolymer or propylene-ethylene random copolymer component (A) having an ethylene content of ≤7 wt.% in the first process and 70-5 wt.% of propylene-ethylene random copolymer component (B) containing ethylene in a larger amount by 3-20 wt.% than that of the component (A) in the second process in the presence of a metallocene-based catalyst; (b) a melt flow rate of 0.5-100 g/10 min; (c) a melt peak temperature (Tm) of 110-150°C, (d) a mol.wt. distribution (Mw/Mn) of 1.5-4; and (e) a tanδ curve has a single peak at 0°C or lower, and its molded article. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a propylene-based resin composition and a molded product thereof, and particularly relates to a propylene-based resin composition excellent in impact resistance and a molded product thereof.

Propylene polymers are excellent in moldability, rigidity, recyclability and heat resistance, so they are molded and processed by various methods, and like other resins such as polyvinyl chloride and polystyrene. Widely used in various applications such as containers, caps, medical instruments, medical containers, packaging films, stationery sheets, clothing cases, daily necessities, automobile parts, electrical parts, etc. In these applications, more excellent impact resistance, rigidity, transparency, molding processability and the like are strongly demanded for the propylene polymer or the composition thereof.

Propylene polymers are propylene homopolymers in terms of rigidity, heat resistance, and gas barrier properties, and random copolymers of propylene polymers with ethylene, butene, etc. in terms of transparency, and ethylene in terms of heat resistance and impact resistance. In addition, a block copolymer of butene or the like and propylene is preferable, and is selectively used as appropriate depending on the situation.
However, the propylene polymer may not be sufficient in terms of impact resistance. In such a case, the current situation is that the impact resistance is improved by adding a modifier or the like to the propylene polymer. However, it has been impossible to find a balance with excellent impact resistance, rigidity, transparency, molding processability, and heat resistance.

  An object of the present invention is to provide a propylene-based resin composition excellent in impact resistance, rigidity, transparency and molding processability, and a molded product formed from the resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors are excellent in impact resistance, rigidity, transparency, and moldability by using a specific modifier for the propylene-based polymer. The present inventors have found that the resin composition can be obtained and completed the present invention.

That is, according to the first invention of the present invention, (i) propylene-ethylene block satisfying the following conditions (Ai) to (Av) with respect to 60 to 99 parts by weight of the propylene polymer. A propylene-based resin composition characterized by adding 1 to 40 parts by weight of a copolymer.
(Ai) 30 to 95 wt% of propylene-ethylene random copolymer component (A) having a metallocene catalyst in the first step or propylene-ethylene random copolymer component (A) of 7 wt% or less in the first step, and component (A) in the second step A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% of ethylene more than (A-ii) ) Melt flow rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5-100 g / 10 min (A-iii) Melting peak temperature (Tm) measured by DSC method is in the range of 110-150 ° C. (A-iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (Av) Solid viscoelasticity measurement More resulting temperature - in the loss tangent curve, tan [delta curve has a single peak at 0 ℃ below.

  Moreover, according to the 2nd invention of this invention, the molded article characterized by using the said propylene-type resin composition is provided.

  The propylene-based resin composition of the present invention is a polypropylene-based resin composition in which the propylene-based polymer is blended with the (i) propylene-ethylene block copolymer, and by using such a modifier. Thus, it is possible to obtain a material having an excellent balance of transparency, molding processability, rigidity, and impact resistance that could not be realized by a conventional propylene-based resin composition.

It is a figure which shows the elution amount by TREF, and elution amount integration.

The present invention comprises (a) 1 to 40 parts by weight of a propylene-ethylene block copolymer satisfying the above conditions (Ai) to (Av) with respect to 60 to 99 parts by weight of a propylene polymer. It is a propylene-based resin composition characterized by being added, and is a molded product obtained by molding by various methods. Hereinafter, the component which comprises a propylene-type resin composition, the manufacturing method of a resin composition, and a molded article are demonstrated in detail.
(A) The propylene polymer may be at least 50 parts by weight, usually in the range of 60 to 99 parts by weight, in order to maintain the characteristics of the polymerization value. Specifically, embodiments of 65 parts by weight, 70 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, and 95 parts by weight can be exemplified, while (a) a blend of propylene-ethylene block copolymer The amount may be 50 parts by weight or less, usually 1 to 40 parts by weight. Specifically, the propylene-type resin composition which mix | blended each embodiment of 35 weight part, 30 weight part, 20 weight part, 10 weight part, and 5 weight part can be illustrated, respectively.

(B) If the blend amount of the propylene-ethylene block copolymer is reduced to 0.08 parts by weight, 0.05 parts by weight, 0.01 parts by weight, or 0.005 parts by weight, impact resistance, heat resistance, etc. The effect monotonously decreases and the effect of the present invention cannot be expected. On the other hand, when the blend amount is monotonously increased to 45 parts by weight, 50 parts by weight, and 60 parts by weight, (a) the propylene polymer tends to lose its rigidity, heat resistance, and gas barrier properties, and is slightly sticky. Tend to occur,
Thus, it is based on the knowledge of the present inventors that the properties of (a) propylene polymer are modified by blending a specific amount of (a) propylene-ethylene block copolymer. Propylene containing 60 to 99 parts by weight of this (a) propylene-based polymer and 1 to 40 parts by weight of (a) propylene-ethylene block copolymer satisfying specific conditions (Ai) to (Av) The resin-based resin composition is a material which is critically technically significant in combination with a specific polymer and also in the blend amount.

[1] (A) Propylene polymer (a) The propylene polymer used in the propylene resin composition of the present invention may be a propylene homopolymer or a propylene copolymer (random copolymer, A block copolymer) or a mixture thereof. In the case of a copolymer, it is common to use one or more selected from the group consisting of α-olefins other than ethylene or propylene as a comonomer, but is not limited thereto. .
However, in order to develop excellent transparency, a propylene homopolymer, a propylene random copolymer, or a propylene block copolymer having a comonomer content of 10% by weight or less is preferable, and a propylene random copolymer is more preferable.
Examples of the copolymer included in the specific propylene-based polymer are usually a propylene-ethylene copolymer containing about 0.5 to 20% by weight, preferably about 1 to 8% by weight of a comonomer. , Propylene-ethylene-diene copolymer, propylene-butene-1 copolymer, propylene-pentene-1 copolymer, propylene-hexene-1 copolymer, propylene-4-methylpentene-1 copolymer, etc. A binary or ternary copolymer can be exemplified.

  Moreover, the propylene-type polymer whose melt flow rate based on JISK7210 (230 degreeC, 2.16kg load) is 0.3-200 g / 10min is preferable. When the melt flow rate is significantly lower than 0.3 g / 10 min, the extrusion load at the time of extrusion molding increases, the surface smoothness may be impaired, and the appearance of the molded product may be deteriorated. If the amount exceeds significantly, the uniform dispersibility of the clearing nucleating agent in the propylene-based polymer may be deteriorated, and transparency may be hardly exhibited.

The catalyst used for obtaining the propylene-based polymer used in the present invention is not particularly limited, and a known catalyst can be used. For example, a so-called Ziegler-Natta catalyst or a metallocene catalyst (for example, described in JP-A-5-295022) in which a titanium compound and organoaluminum are combined can be used.
The polymerization process used to obtain the propylene-based polymer used in the present invention is not particularly limited, and a known polymerization process can be used. For example, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used. Moreover, it can also superpose | polymerize by performing multistage polymerization combining the 1 type (s) or 2 or more types of these polymerization methods. Further, it can also be produced by mechanically melting and kneading two or more kinds of propylene polymers.

[2] (A) Propylene-ethylene block copolymer (I) The propylene-ethylene block copolymer used in the present invention is a propylene-ethylene block copolymer having propylene alone or an ethylene content of 7 wt% or less in the first step. After the polymer component (A) is polymerized in an amount of 30 to 95 wt%, in the second step, the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene than the first step is added in an amount of 70 to 5 wt%. Obtained by sequential polymerization.
The propylene-ethylene block copolymer referred to here is a propylene-ethylene random copolymer component (A) (hereinafter referred to as component (A)) and a propylene-ethylene random copolymer component (B) ( Hereinafter, it is a block copolymer in a general name obtained by sequentially polymerizing component (B)), and component (A) and component (B) are not necessarily combined in a block form. It is not necessary.

(1-1) Ethylene content in component (A): [E] A
The component (A) produced in the first step suppresses stickiness of the product (pellet) and expresses heat resistance, so that the propylene homopolymer having a relatively high melting point and crystallinity, or ethylene content is high. The propylene-ethylene random copolymer must be 7 wt% or less. If the ethylene content exceeds 7 wt%, the melting point becomes too low and the heat resistance of the product may be deteriorated. The ethylene content is preferably 5 wt% or less, more preferably 3 wt% or less. In addition, if the pellets are sticky, the pellets may stick together during storage of the pellet bag, which is not preferable.

(1-2) Ethylene content in component (B): [E] B
The component (B) produced in the second step has a role as a rubber elastic component in the propylene-ethylene block copolymer and is a component necessary for imparting impact resistance.
The range of the ethylene content of the component (B) is defined by the difference [E] B- [E] A ([E] gap) from the ethylene content of the component (A) in order to fully exhibit the above effect. . [E] B- [E] A needs to be in the range of 3 to 20 wt%, preferably 6 to 18 wt%, and more preferably 8 to 16 wt%.
[E] When the gap is 3 wt% or less, the impact resistance is not sufficient, which is not preferable. On the other hand, when the content exceeds 20 wt%, the compatibility with the component (A) produced in the first step is deteriorated, so that the transparency is undesirably deteriorated.

(1-3) Ratio of component (A): W (A) and ratio of component (B): W (B)
The content ratio of W (A), which is the proportion of the component (A) constituting the propylene-ethylene block copolymer, and W (B), which is the proportion of the component (B), is 30 to 95 wt% for W (A). And W (B) needs to be in the range of 70 to 5 wt%.
If the ratio of W (A) is less than 30 wt%, the product may become sticky and the heat resistance may be reduced. On the other hand, if the ratio of W (A) exceeds 95 wt%, the rubber elasticity is insufficient and the impact resistance may be insufficient. Preferably, the ratio of W (A) is 40 to 90 wt%, more preferably 50 to 80 wt%.

(1-4) Specification by peak of tan δ curve In the present invention, in order to maintain good compatibility and maintain transparency, the component (A) and the component (A) constituting the propylene-ethylene block copolymer to be used ( B) must not be phase separated. The phase separation conditions are affected not only by the ethylene content but also by the molecular weight and composition. Therefore, in addition to the above-mentioned regulations regarding the ethylene content, a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) Therefore, it is necessary to define the peak of the tan δ curve.
When the propylene-ethylene block copolymer has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A) is different from the glass transition temperature of the amorphous part contained in the component (B). , There will be multiple peaks. Conversely, when they are compatible, both components are mixed in the order of molecules and have a single peak at a temperature intermediate between the glass transition temperatures of both components. That is, whether or not the phase separation structure is taken can be determined in the temperature-tan δ curve in the solid viscoelasticity measurement, and in order to maintain transparency, the tan δ curve has a single peak at 0 ° C. or lower. is required.
Specifically, solid viscoelasticity measurement is performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress. Here, the frequency is 1 Hz and the measurement temperature is raised stepwise from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus G ′ and the loss elastic modulus G ″ are obtained by a known method, and the loss tangent (= loss elastic modulus / storage elastic modulus) defined by this ratio is plotted against the temperature. It shows a sharp peak in the temperature range below 0 ° C. Generally, the peak of the tan δ curve below 0 ° C. is for observing the glass transition of the amorphous part, and here the peak temperature is defined as the glass transition temperature Tg (° C.). Define.

(1-5) Specificity of [E] A and [E] B and each component amount W (A) and W (B) The ethylene content and amount of each component (A) and (B) are the material balance at the time of manufacture. Although it is possible to specify by (material balance), in order to specify these more accurately, it is desirable to use the following analysis.

(1-5-1) Identification of each component amount W (A) and W (B) by temperature rising elution fractionation (TREF) The method for evaluating the crystallinity distribution of a propylene-ethylene random copolymer by TREF This method is well known to those skilled in the art. For example, detailed measurement methods are shown in the following documents.
G. Glockner, J. et al. Appl. Polym. Sci. : Appl. Polym. Symp. 45, 1-24 (1990)
L. Wild, Adv. Polym. Sci. 98, 1-47 (1990)
J. et al. B. P. Soares, A .; E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)

The propylene-ethylene block copolymer in the present invention is greatly different in the crystallinity of each of the components (A) and (B), and each crystallinity distribution is narrowed by being produced using a metallocene catalyst. Therefore, there are very few intermediate components between the two, and both can be discriminated with high accuracy by TREF.
A specific method will be described with reference to the figure showing the elution amount and the elution amount integration by TREF in FIG. In the TREF elution curve (plot of elution amount versus temperature), components (A) and (B) show their elution peaks at T (A) and T (B), respectively, due to the difference in crystallinity, and the difference is sufficiently large. Separation is possible at an intermediate temperature T (C) (= {T (A) + T (B)} / 2).

In addition, the lower limit of the TREF measurement temperature is −15 ° C. in the apparatus used for this measurement, but in the case where the crystallinity of the component (B) is very low or an amorphous component, There may be no peak in the range. (In this case, the concentration of the component (B) dissolved in the solvent is detected at the measurement temperature lower limit (ie, −15 ° C.).)
At this time, T (B) is considered to exist below the lower limit of the measurement temperature, but the value cannot be measured. In such a case, T (B) is the lower limit of the measurement temperature. Defined as ° C.
Here, if the integrated amount of the component eluted before T (C) is defined as W (B) wt%, and the integrated amount of the component eluted at T (C) or higher is defined as W (A) wt%, W (B) Almost corresponds to the amount of the component (B) having low crystallinity or amorphousness, and the integrated amount W (A) of the component eluted at T (C) or higher is the component (A) having relatively high crystallinity. Almost corresponds to the amount of. The elution amount curve obtained by TREF and the above-described methods for calculating the various temperatures and amounts obtained therefrom are performed as illustrated in FIG.

(1-5-2) TREF measuring method In the present invention, the TREF is specifically measured as follows.
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 flowed through the column at a flow rate of 1 mL / min, and components dissolved in o-dichlorobenzene at −15 ° C. are eluted in the TREF column for 10 minutes. Next, the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.

(1-5-3) Identification of ethylene content [E] A and [E] B in each component (a) Separation of component (A) and component (B) T (C) determined by the previous TREF measurement Based on the temperature-separated column separation method using a preparative separation apparatus, the soluble component (B) in T (C) and the insoluble component (A) in T (C) are separated, and each component is analyzed by NMR. Determine the ethylene content.
The temperature rising column fractionation method refers to a measurement method as disclosed in, for example, Macromolecules, 21 314-319 (1988). Specifically, the following method was used in the present invention.

(B) Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 mL of the o-dichlorobenzene solution (10 mg / mL) of the sample dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (C) at a heating rate of 10 ° C./hour and held for 1 hour. Note that the temperature control accuracy of the column through a series of operations is ± 1 ° C.
Next, while maintaining the column temperature at T (C), 800 mL of o (dichlorobenzene) of T (C) is allowed to flow at a flow rate of 20 mL / min, whereby components soluble in T (C) existing in the column are obtained. Elute and collect.
Next, the column temperature is increased to 140 ° C. at a temperature rising rate of 10 ° C./min, and after leaving still at 140 ° C. for 1 hour, by flowing 800 mL of a 140 ° C. solvent (o-dichlorobenzene) at a flow rate of 20 mL / min, Elute insoluble components with T (C) and collect.
The solution containing the polymer obtained by fractionation is concentrated to 20 mL using an evaporator and then precipitated in 5 times the amount of methanol. The precipitated polymer is recovered by filtration and then dried overnight in a vacuum dryer.

(C) Measurement of ethylene content by ¹³ C-NMR The ethylene content of each of the components (A) and (B) obtained by the above fractionation was measured by a proton complete decoupling method according to the following conditions: ¹³ C-NMR spectrum It is obtained by analyzing.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent equipment (carbon nuclear resonance frequency of 100 MHz or more)
Solvent: o-dichlorobenzene / heavy benzene = 4/1 (volume ratio)
Concentration: 100 mg / mL
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more The attribution of the spectrum may be performed with reference to, for example, Macromolecules, 17 1950 (1984). The attribution of spectra measured under the above conditions is as shown in the table below. In the table, symbols such as S _αα are in accordance with the notation of Carman et al. (Macromolecules, 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six kinds of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules, 15 1150 (1982), etc., the concentration of these triads and the peak intensity of the spectrum are linked by the following relational expressions (1) to (6).
[PPP] = k × I (T _ββ ) (1)
[PPE] = k × I (T _βδ ) (2)
[EPE] = k × I (T _δδ ) (3)
[PEP] = k × I (S _ββ ) (4)
[PEE] = k × I (S _βδ ) (5)
[EEE] = k × [I (S _δδ ) / 2 + I (S _γδ ) / 4} (6)
Here, [] indicates the fraction of triads, for example, [PPP] is the fraction of PPP triads in all triads. Therefore,
[PPP] + [PPE] + [EPE] + [PEP] + [PEE] + [EEE] = 1
(7)
It is. Further, k is a constant, I indicates the spectral intensity, and for example, I (T _ββ ) means the intensity of the peak at 28.7 ppm attributed to T _ββ .

By using the relational expressions (1) to (7) above, the fraction of each triad is obtained, and the ethylene content is obtained from the following expression.
Ethylene content (mol%) = ([PEP] + [PEE] + [EEE]) × 100
Note that the propylene random copolymer of the present invention contains a small amount of propylene heterogeneous bonds (2,1-bonds and / or 1,3-bonds), thereby producing the following minute peaks.

In order to obtain an accurate ethylene content, it is necessary to include these peaks derived from heterogeneous bonds in the calculation, but it is difficult to completely separate and identify the peaks derived from heterogeneous bonds, and the amount of heterogeneous bonds is small. Therefore, the ethylene content of the present invention is determined using the relational expressions (1) to (7) as in the analysis of the copolymer produced with the Ziegler catalyst that does not substantially contain heterogeneous bonds. .
Conversion from mol% to wt% of ethylene content is carried out using the following formula: ethylene content (wt%) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100) } × 100
Here, X is the ethylene content in terms of mol%. The ethylene content [E] W of the entire propylene-ethylene block copolymer is the ethylene content of each of the components (A) and (B) measured from the above. It is calculated by the following formula from the weight ratios W (A) and W (B) wt% of each component calculated from [E] A, [E] B and TREF.
[E] W = {[E] A × W (A) + [E] B × W (B) / 100 (wt%)

(1-6) Melt flow rate (MFR)
The melt flow rate (MFR) of the (a) propylene-ethylene block copolymer used in the present invention is 0.5 to 100 g / 10 min, preferably 1 to 50 g / 10 min, more preferably 2 to 35 g / 10 min. It is. If the MFR is less than 0.5 g / 10 min, molding becomes difficult, and if it exceeds 100 g / 10 min, impact resistance cannot be expected.
Melt flow rate (MFR) is easily controlled by adjusting the temperature and pressure, which are the polymerization conditions for (i) propylene-ethylene block copolymerization, or by controlling the amount of hydrogen added to the chain transfer agent such as hydrogen during polymerization. Adjustments can be made.
Here, MFR is a value measured at a heating temperature of 230 ° C. and a load of 21.2 N in accordance with JIS K7210.

(1-7) Melting peak temperature (Tm)
The melting peak temperature (Tm) measured by the differential scanning calorimeter (DSC) of (i) propylene-ethylene block copolymer used in the present invention needs to be in the range of 110 to 150 ° C., and 120 to 140 It is preferable that the temperature is C. Those having a Tm of less than 110 ° C. are not preferred because the cooling and solidification rate of the molten propylene resin is slow and may deteriorate the moldability, and those exceeding 150 ° C. are not preferred because the impact resistance may be deteriorated. . The Tm can be adjusted easily by controlling the amount of ethylene supplied to the polymerization reaction system.
Here, the specific measurement of Tm is performed using a differential scanning calorimeter (DSC), taking a sample amount of 5 mg, holding at 200 ° C. for 5 minutes, and then crystallizing to 40 ° C. at a rate of temperature decrease of 10 ° C./min. Further, the peak position of the curve drawn when the film is melted at a temperature rising rate of 10 ° C./min is defined as a melting peak temperature Tm (° C.).

(1-8) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method of (i) propylene-ethylene block copolymer used in the present invention must be in the range of 1.5-4. It is preferably 8 or more and less than 3. When Mw / Mn is less than 1.5, it is difficult to obtain with the current polymerization technique, and when it exceeds 4, the product (pellet) may be sticky, which is not preferable. When narrowing the molecular weight distribution of the propylene-ethylene block copolymer, use a metallocene catalyst described later, or polymerize the propylene-ethylene block copolymer and then melt knead using an organic peroxide. Can be adjusted. When making it wide, it can adjust by superposing | polymerizing using the catalyst system which used together 2 or more types of metallocene catalyst components, or the catalyst system which used 2 or more types of metallocene complexes together.
Here, the molecular weight distribution is obtained by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and is obtained by measurement by a gel permeation chromatography (GPC) method.
Conversion from the retention volume to the molecular weight is performed using a standard curve prepared in advance by standard polystyrene.

The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is prepared by injecting 0.2 ml of a solution dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml.
The calibration curve uses a cubic equation obtained by approximation by the least square method. The following numerical value is used for [η] = K × Mα in the viscosity formula used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ α = 0.7
PP: K = 1.03 × 10 ⁻⁴ α = 0.78
The measurement conditions for GPC are as follows.
Equipment: GPC (ALC / GPC 150C) manufactured by WATERS
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
Mobile phase solvent: o-dichlorobenzene Measurement temperature: 140 ° C.
Flow rate: 1.0 ml / min
Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / ml solution using o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. for about 1 hour.

(2) Propylene-ethylene block copolymer production method (2-1) Metallocene catalyst The method for producing a propylene-ethylene block copolymer used in the present invention requires the use of a metallocene catalyst. To do.
It is well known to those skilled in the art that stickiness and bleedout deteriorate when the molecular weight and crystallinity distribution are wide in the propylene-ethylene random copolymer, but also in the propylene-ethylene block copolymer used in the present invention, In order to suppress stickiness and bleed-out, it is necessary to polymerize using a metallocene catalyst that has a narrow molecular weight and crystallinity distribution.

The type of the metallocene-based catalyst is not particularly limited as long as it can produce a copolymer having the performance of the present invention. However, in order to satisfy the requirements of the present invention, for example, the following components ( It is preferable to use a metallocene catalyst comprising a), (b), and component (c) used as necessary.
Component (a): At least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula Component (b): At least one selected from the following (b-1) to (b-4) (B-1) a particulate carrier on which an organoaluminoxy compound is supported,
(B-2) Particulate carrier carrying an ionic compound or Lewis acid capable of reacting with component (a) to convert component (a) into a cation (b-3) Solid acid fine particles (b- 4) Ion exchange layered silicate,
Component (c): Organoaluminum compound.

(2-2) Component (a)
As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula can be used.
^{_{Q (C 5 H 4 -aR 1}} ) (C 5 H 4 -bR 2) MeXY
[Wherein Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, and X and Y represent a hydrogen atom, a halogen atom, An atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group is shown, and X and Y may be independently, that is, the same or different. R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Show. a and b are the number of substituents. ]

Specifically, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, and has, for example, a divalent hydrocarbon group, a silylene group, an oligosilylene group, or a hydrocarbon group as a substituent. Examples include a silylene group, an oligosilylene group, or a germylene group having a hydrocarbon group as a substituent. Among these, preferred is a silylene group having a divalent hydrocarbon group and a hydrocarbon group as a substituent.
X and Y each represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group. And chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide group and the like. X and Y may be independent, that is, may be the same or different.
R ¹ and R ² are hydrogen, hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group. Represents. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. In addition, as halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group, methoxy group, ethoxy group, phenoxy group Typical examples include trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group, and dimethoxyboron group. In these, it is preferable that it is a C1-C20 hydrocarbon group, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, and a butyl group. By the way, adjacent R ¹ and R ² may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.
Me is a metal atom selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

Among the components (a) described above, (i) a propylene-ethylene random block copolymer used in the present invention is preferably a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. It is a transition metal compound comprising a ligand having a bridged substituted cyclopentadienyl group, substituted indenyl group, substituted fluorenyl group, substituted azulenyl group, particularly preferably a silylene group having a hydrocarbon substituent or a germylene group It is a transition metal compound comprising a ligand having a 2,4-position-substituted indenyl group and a 2,4-position-substituted azulenyl group which are cross-linked by
Non-limiting specific examples include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl). Benzoindenyl) zirconium dichloride, dimethylsilylenebis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethyl Silylenebis (2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylenebi (2-Ethyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium Examples thereof include dichloride and dimethylsilylenebis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride. A compound in which the silylene group of these specific examples is replaced with a germylene group and zirconium is replaced with hafnium is also exemplified as a suitable compound. In addition, since the catalyst component is not an important element of the present invention, it avoids complicated listing and is limited to a representative example, but it is obvious that the effective range of the present invention is not limited by this. It is.

(2-3) 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 known and can be used by appropriately selecting from known techniques. Specific examples and manufacturing methods thereof are described in detail in JP-A No. 2002-284808, JP-A No. 2002-53609, JP-A No. 2002-69116, JP-A No. 2003-105015, 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), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl, etc. are supported as the component (b-1). As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl Particulate carrier carrying anilinium tetrakis (pentafluorophenyl) borate, etc. as component (b-3), alumina, silica alumina, magnesium chloride, etc. as component (b-4), montmorillonite, zakonite, beidellite , Nontronic , Saponite, hectorite, stevensite, bentonite, smectite group such as taeniolite, vermiculite, and the like mica group. 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.

(2-4) Component (c)
Examples of organoaluminum compounds used as component (c) as needed are:
General formula AlR _a P _3-a
(Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, P is hydrogen, halogen, alkoxy group, a is a number of 0 <a ≦ 3), trimethylaluminum, triethylaluminum, tripropylaluminum, tri Trialkylaluminum such as isobutylaluminum or halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

(2-5) Formation of catalyst Component (a) is contacted with component (b) and, if necessary, component (c) to form a catalyst. The contact method is not particularly limited, but the contact can be made in the following order. Moreover, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.
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 (b) after contact 4) Add component (a) after contacting component (b) and component (c), or 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 1,000 μmol, particularly preferably 0.5 μmol to 500 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 to 100 μmol, particularly preferably 0.005 to 50 μmol, relative to 1 g of component (b). Therefore, the amount of the component (c) to the component (a) is preferably in the range of 10 ⁻⁵ to 50, particularly preferably 10 ^{−4 to} 5 in terms of the molar ratio of the transition metal.

The catalyst used in the (i) propylene-ethylene block copolymer of the present invention is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with 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. In particular, it is 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.

(2-6) Polymerization Method (2-6-1) Sequential Polymerization (i) When the propylene-ethylene block copolymer used in the present invention is produced, component (A) and component (B) are polymerized sequentially. It is necessary to.
(I) In the conventional propylene-ethylene copolymer, there is no thing in which the balance of the propylene-ethylene copolymer obtained in the first step and the second step is sufficiently considered, and flexibility, impact resistance and transparency are not obtained. None improved in a balanced manner.
Therefore, in the present invention, (i) the propylene-ethylene block copolymer is a block copolymer obtained by sequentially polymerizing components having different ethylene contents in the first step and the second step. It is necessary to balance all properties and heat resistance.
In the present invention, since a copolymer having a low molecular weight and easily sticking alone may be used as the component (B), in order to prevent problems such as adhesion to the reactor, the component (A) is polymerized. It is necessary to use a method for polymerizing component (B).
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 a batch method, it is possible to polymerize component (A) and component (B) separately using a single reactor by changing the polymerization conditions with time. As long as the effect of the present invention is not impaired, a plurality of 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 reactors are connected in series because it is necessary to polymerize component (A) and component (B) separately, as long as the effect of the present invention is not impaired. A plurality of reactors may be connected in series and / or in parallel for each of component (A) and component (B).

(2-6-2) Polymerization process As the polymerization process, any polymerization method such as a slurry method, a bulk method, or a gas phase method can be used. Although supercritical conditions can be used as intermediate conditions between the bulk method and the gas phase method, they are substantially the same as the gas phase method, and are therefore included in the gas phase method without particular distinction.
Since component (B) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method for the production of component (B).
There is no particular problem in using any process for the production of component (A). However, when producing component (A) having relatively low crystallinity, a vapor phase method is used to avoid problems such as adhesion. It is desirable to use
Therefore, it is most desirable to first polymerize component (A) by the bulk method or gas phase method using the continuous method, and then polymerize component (B) by the gas phase method.

(2-6-3) Other 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., more preferably 40 ° C. to 100 ° C. can be used.
The polymerization pressure varies depending on the process to be selected, but it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, more preferably 0.1 MPa to 50 MPa can be used. At this time, an inert gas such as nitrogen may coexist.
When the component (A) is sequentially polymerized in the first step and the component (B) is sequentially polymerized in the second step, it is desirable to add a polymerization inhibitor to the system in the second step. In the case of producing a propylene-ethylene block copolymer, if a polymerization inhibitor is added to a reactor that performs ethylene-propylene random copolymerization in the second step, the particle properties (fluidity, etc.) of the resulting powder, gel, etc. Can improve the product quality. Various technical studies have been made on this method, and examples thereof include Japanese Patent Publication No. 63-54296, Japanese Patent Application Laid-Open No. 7-25960, Japanese Patent Application Laid-Open No. 2003-2939, and the like. It is desirable to apply the method to the present invention.

(3) (a) Method for controlling constituent elements of propylene-ethylene block copolymer Each element of the propylene-ethylene block copolymer used in the present invention is controlled as follows and is necessary for the copolymer of the present invention. It can be manufactured to meet the required configuration requirements.

(3-1) Component (A)
For component (A), it is necessary to control the ethylene content [E] A and T (A).
In the present invention, in order to control [E] A within a predetermined range, the amount ratio of propylene and ethylene supplied to the polymerization tank in the first step may be appropriately adjusted. The relationship between the supply ratio and the ethylene content in the resulting propylene-ethylene random copolymer varies depending on the type of metallocene catalyst used, but the component (A) having the ethylene content [E] A required by adjusting the supply ratio is selected. Can be manufactured.
For example, when [E] A is controlled to be less than 7 wt%, the supply weight ratio of ethylene to propylene may be in the range of 0.3 or less, preferably in the range of 0.2 or less.
At this time, the component (A) has a narrow crystallinity distribution, and T (A) decreases as [E] A increases.
Therefore, in order for T (A) to satisfy the scope of the present invention, [E] A and their relationship are grasped and adjusted so as to take a target range.

(3-2) Component (B)
For component (B), it is necessary to control the ethylene content [E] B, T (B) and [η] cxs.
In the present invention, in order to control [E] B within a predetermined range, similarly to [E] A, the ratio of ethylene supply to propylene in the second step may be controlled. For example, when [E] B is controlled to 3 to 27 wt%, the supply weight ratio of ethylene to propylene may be in the range of 0.005 to 6, preferably in the range of 0.01 to 3.
At this time, although the crystallinity distribution of the component (B) is slightly increased as the ethylene content is increased, the T (B) is decreased as [E] B is increased as in the case of the component (A).
Therefore, in order for T (B) to satisfy the scope of the present invention, the relationship between [E] B and T (B) is grasped, and [E] B is controlled to be within a predetermined range. That's fine.

(3-3) W (A) and W (B)
The amount W (A) of the component (A) and the amount W (B) of the component (B) change the ratio of the production amount of the first step for producing the component (A) and the production amount of the component (B). Can be controlled. For example, in order to increase W (A) and decrease W (B), the production amount of the second step may be reduced while maintaining the production amount of the first step, which shortens the residence time of the second step. It can be easily controlled by lowering the polymerization temperature or increasing the amount of the polymerization inhibitor. The reverse is also true.
When actually setting the conditions, it is necessary to consider the activity decay. That is, in the range of the ethylene contents [E] A and [E] B carried out in the present invention, generally, when the ratio of ethylene supply to propylene is increased in order to increase the ethylene content, the polymerization activity is increased. The activity decay tends to increase. Therefore, in order to maintain the activity of the second step, it is necessary to suppress the polymerization activity of the first step. Specifically, in the first step, the ethylene content [E] A is lowered and the production amount W (A ), And if necessary, lower the polymerization temperature and / or shorten the polymerization time (residence time), or increase the ethylene content [E] B in the second step and increase the production W (B). If necessary, the conditions may be set by a method that raises the polymerization temperature and / or lengthens the polymerization time (residence time).

(3-4) Glass transition temperature Tg
The (i) propylene-ethylene block copolymer used in the present invention has a glass transition temperature Tg of 0 ° C. or less, which is a temperature at which a tan δ curve obtained in a temperature-loss tangent curve obtained by solid viscoelasticity measurement shows a peak. Need to have a single peak. In order for Tg to have a single peak, the difference [E] gap (= [E] between the ethylene content [E] A in component (A) and the ethylene content [E] B in component (B) ] B- [E] A) may be 20 wt% or less, preferably 16 wt% or less, and [E] gap may be reduced to a range where Tg becomes a single peak in actual measurement.

According to the ethylene content [E] A in the component (A), the supply amount of ethylene to propylene during the polymerization of the component (B) so that the ethylene content [E] B in the component (B) falls within an appropriate range. By setting the ratio, a propylene-ethylene block copolymer having a predetermined [E] gap can be obtained.
Further, the Tg of the propylene-ethylene block copolymer which does not have a phase separation structure as used in the present invention is the ethylene content [E] A in the component (A) and the ethylene in the component (B). It is affected by the content [E] B and the quantity ratio of both components. In the present invention, the amount of the component (B) is 5 to 70 wt%, but in this range, Tg is more strongly affected by the ethylene content [E] B in the component (B).
That is, Tg reflects the glass transition of the amorphous part. In (i) the propylene-ethylene block copolymer used in the present invention, the component (A) has crystallinity and a relatively amorphous part. This is because the component (B) is low crystalline or amorphous, and most of it is an amorphous part. Therefore, the value of Tg is almost controlled by [E] B, and the control method of [E] B is as described above.

[3] Additives In the present invention, additives such as various antioxidants, nucleating agents, neutralizing agents, lubricants, ultraviolet absorbers, light stabilizers and the like used as stabilizers for propylene polymers are added. Can be blended.

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

  As a specific example of the nucleating agent, a known nucleating agent can be used. For example, a known nucleating agent such as a sorbitol-based transparent nucleating agent, an amide-based nucleating agent, an organic phosphate-based transparent nucleating agent, an aromatic phosphate ester, or talc can be used.

Specific examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate and magnesium stearate, hydrotalcite (trade name: magnesium represented by the following general formula (2) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (3)), and the like.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (2)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]

[Al ₂ Li (OH) ₆ ] _n X · mH ₂ O (3)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]

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

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

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

  Further, an amine-based antioxidant represented by the following general formula (4) or the following general formula (5), 5,7-di-t-butyl-3- (3,4-di-methyl-phenyl) -3H -Lactone type antioxidants, such as benzofuran-2-one, and vitamin E type antioxidants, such as following General formula (6), can be mentioned.

In addition, an antistatic agent, a dispersant such as a fatty acid metal salt, polyethylene, an olefin-based elastomer, and the like can be blended within a range not impairing the object of the present invention.
The propylene resin composition comprising (a) a propylene polymer and (i) a propylene-ethylene block copolymer of the present invention imparts other characteristics or functions while maintaining the characteristics of this composition to the maximum. Therefore, other polymers, copolymers, and elastomers can be arbitrarily blended. Specifically, polyethylene, ethylene-propylene copolymer or rubber, ethylene-propylene-diene copolymer or rubber, ethylene-acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylonitrile copolymer, natural Various resins or elastomers such as rubber, diene rubber, chloroprene rubber, nitrile rubber, polysaccharides and natural resins can be arbitrarily blended in an amount of about 1 to 30 parts by weight with respect to 100 parts by weight of the propylene diameter resin composition. Is possible.
Similarly, 1-30 parts by weight of various inorganic fillers such as alumina, carbon black, calcium carbonate, silica, gypsum, talc, mica, kaolin, clay, titanium oxide, and alumina as fillers, preferably 1-10 parts by weight. A part can also be added arbitrarily.

[4] Propylene resin composition production method The propylene resin composition of the present invention comprises (a) a propylene polymer, (b) a propylene-ethylene block copolymer, and other additives used as necessary. Are mixed into a Henschel mixer, super mixer, ribbon blender, etc., and then melted in a temperature range of 180 to 280 ° C. with a normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll, etc. It can be obtained by kneading.

[5] Molded product The molded product of the present invention is obtained by molding the propylene-based resin composition with various molding machines such as a known injection molding machine, extrusion molding machine, film molding machine, blow molding machine, and fiber molding machine. Can be obtained.
Examples of the molded article of the present invention include food containers, caps, medical instruments, medical containers, packaging films, stationery sheets, costume cases, daily necessities, automobile parts, electrical parts, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these description. In each Example and Comparative Example, the physical properties used were measured by the following methods, and the following were used as propylene-based polymers, nucleating agents, and other additives (neutralizing agents, lubricants).

1. Measurement method (1) TREF
The TREF measurement method is as described above.
[apparatus]
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column packing material: 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 volume: 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: 1.5 mm Window shape: 2φ x 4 mm long circle Synthetic sapphire window measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / mL BHT)
Sample concentration: 5 mg / mL
Sample injection volume: 0.1 mL
Solvent flow rate: 1 mL / min

(2) Measurement of solid viscoelasticity A sample cut into a strip of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet injection molded under the following conditions was used. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
(Creation of specimen)
Standard number: JIS-7152 (ISO294-1)
Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Setting temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / s (speed in the mold cavity)
Injection pressure: 800 kgf / cm ²
Holding pressure: 800 kgf / cm ²
Holding time: 40 seconds
Mold shape: Flat plate (2mm thickness, 30mm width, 90mm length)

(3) Calculation of each component amount It calculated by the method mentioned above using TREF.

(4) Calculation of ethylene content
The ethylene content in the random copolymer was measured by infrared spectroscopy using a characteristic absorber of 733 cm ⁻¹ with an ethylene / propylene random copolymer whose composition was verified by ¹³ C-NMR as a reference substance. The pellets were formed into a film having a thickness of about 500 microns by press molding.

(5) Measured by peak intrinsic viscoelasticity measurement of tan δ curve.

(6) MFR: Measured according to JIS K7210 at a heating temperature of 230 ° C. and a load of 21.2 N.

(7) Melting peak temperature: 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 10 ° C./min. The melting peak temperature was measured when melting at a heating rate.

(8) Molecular weight distribution: measured by the method described above.

(9) Haze value: Measured according to JIS K7105 using a sheet piece having a thickness of 1 mm.

(10) Flexural modulus: Measured at 23 ° C. in accordance with JIS K7203 “Bending test method for hard plastic”.

(11) Izod (IZOD) impact value: measured at 23 ° C. in accordance with JIS K7110: 1999 using a notched test piece.

2. Materials used (1) (A) Propylene polymer

(I) Propylene homopolymer (HPP2): Novatec MA5Q (manufactured by Nippon Polypro Co., Ltd.), catalyst: Ziegler catalyst, MFR: 5 g / 10 min, isotactic pentad fraction 0.96 (by ¹³ C-NMR Measurement).

(2) (I) Propylene-ethylene block copolymer According to the following Production Example 1, the propylene-ethylene block copolymer (PP-1) used in the present invention is used in the present invention according to the following Production Example 2. A propylene-ethylene block copolymer (PP-2) different from that obtained was obtained.

[Production Example PP-1]
Preparation of prepolymerization catalyst (chemical treatment of ion-exchange layered silicate)
To a 10-liter glass separable flask 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 (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature 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 it, 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 weight after drying was 707 g.
(Drying of ion-exchanged layered silicate) The silicate previously chemically treated was dried by a kiln dryer. Specifications and drying conditions are as follows. Rotating cylinder: Cylindrical inner diameter 50 mm Heating zone 550 mm (Electric furnace) Speed with rotating blade: 2 rpm Tilt angle: 20/520 Silicate feed rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying Temperature: 200 ° C (powder temperature)

(Preparation of catalyst) An autoclave having an internal volume of 16 liters having a stirring and temperature control device was sufficiently replaced with nitrogen. 200 g of the silicate was introduced, 1,160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 ML) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 187 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.

(Preliminary polymerization / washing) Subsequently, the temperature in the tank was raised by 40 ° C., and when the temperature was stabilized, 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 residual monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 ML) and 5600 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was conducted, the concentration of the organoaluminum component was 1.23 mmol / liter, 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, 170 ml of a heptane solution of triisobutylaluminum (0.71 ML) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained. Using this prepolymerized catalyst, a propylene-ethylene block copolymer was produced according to the following procedure.

First Step In the first step, propylene-ethylene random copolymerization was performed using a liquid phase polymerization layer with an agitator having an internal volume of 0.4 m ³ . Liquefied propylene, liquefied ethylene, and triisobutylaluminum were continuously fed at 90 kg / hour, 2.2 kg / hour, and 21.2 g / hour, respectively. The hydrogen supply amount was adjusted so that the MFR in the first step became a target value. Further, the above prepolymerized catalyst was supplied as a catalyst (excluding the weight of the prepolymerized polymer) so as to be 5.4 g / hour. The polymerization tank was cooled so that the polymerization temperature was 65 ° C.
When the propylene-ethylene random copolymer obtained in the first step was analyzed, BD (bulk density) was 0.46 g / cc, MFR was 7.0 g / 10 min, and ethylene content was 1.5 wt%. .

Second step
In the second step, propylene-ethylene random copolymerization was carried out using a stirred gas phase polymerization tank having an internal volume of 0.5 m ³ . The slurry containing polymer particles was continuously extracted from the liquid phase polymerization tank in the first step, and after liquefied propylene was flushed, the pressure was increased with nitrogen and continuously supplied to the gas phase polymerization tank. The polymerization tank was controlled so that the temperature was 80 ° C. and the total partial pressure of propylene, ethylene, and hydrogen was 1.5 MPa. At that time, the concentrations of propylene, ethylene, and hydrogen in the total partial pressure of propylene, ethylene, and hydrogen were controlled to be 73.99 vol%, 26.00 vol%, and 150 vol ppm, respectively. Furthermore, ethanol was supplied to the gas phase polymerization tank as an activity inhibitor. The supply amount of ethanol was set to 0.3 mol / mol with respect to aluminum in TIBA supplied along with the polymer particles supplied to the gas phase polymerization tank.
When the propylene-ethylene block copolymer thus obtained was analyzed, the activity was 7.6 kg / g-catalyst, the BD was 0.41 g / cc, the MFR was 2.0 g / 10 min, and the ethylene content was 6.5 wt. % PP-1 was obtained.
The PP-1 has an ethylene content of component (A) of 1.5 wt%, a composition ratio of 50 wt%, an ethylene content of component (B) of 11.5 wt%, a composition ratio of 50 wt%, and a tan δ curve of −12.3 ° C. Have a single peak. The production conditions are shown in Table 3.

[Production Example PP-2]
Except for the conditions described in Table 3, BD (bulk density) is 0.46 g / cc, MFR is 2.0 g / 10 min, and ethylene content is 1st step in accordance with Production Example PP-1. Obtained 3.7 wt% of propylene-ethylene random copolymer, and in the second step, PP-4 with 0.41 g / cc of BD, 2.0 g / 10 min of MFR, and 11.7 wt% of ethylene content was obtained. .
The PP-4 has an ethylene content of component (A) of 3.7 wt%, a composition ratio of 50 wt%, an ethylene content of component (B) of 19.7 wt%, a composition ratio of 50 wt%, and a tan δ curve of −12.4 ° C. And two peaks at −33 ° C.

(3) Nucleating agent (i) Organophosphate metal salt compound nucleating agent ADK STAB NA-11 (NA-11; manufactured by ADEKA Corporation)

(4) Neutralizing agent (i) CAST: calcium stearate (5) peroxide (i) PHA25B: Perhexa 25B manufactured by Nippon Oil & Fats (6) Antioxidant (i) Hindered phenol antioxidant: Irganox 1010 ( IR1010; manufactured by Ciba), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxylphenyl) propionate] methane (ii) phosphorus antioxidant: Irgaphos 168 (IF168; Ciba) ), Tris (2,4-di-tert-butylphenol) phosphite

(Examples 1-4, Comparative Examples 1-3)
A propylene polymer, a nucleating agent and other additives (antioxidants, neutralizing agents, etc.) were prepared in the blending ratios (parts by weight) shown in Table 4, and after dry blending with a super mixer, the diameter of 35 mm Were melt-kneaded using a twin-screw extruder. Extruded pellets from the die at a die outlet temperature of 230 ° C. The obtained pellets were injection molded by an injection molding machine at a resin temperature of 230 ° C., an injection pressure of 600 kg / cm ^2, and a mold temperature of 40 ° C. to prepare test pieces. The physical properties were measured using the obtained test pieces. The results are shown in Table 4.

As is apparent from Table 4, Examples 1 to 4 are blends of propylene homopolymer with 10 to 40 parts by weight of the propylene-ethylene block copolymer of the present invention (i), compared with Comparative Example 1. It can be seen that, while maintaining transparency, impact resistance is improved, and a material having an excellent balance of physical properties can be obtained.
In Comparative Example 2, (i) instead of the propylene-ethylene block copolymer, a propylene-ethylene block copolymer outside the scope of the present invention was used as an impact modifier, and the transparency was poor. I understand.
In Comparative Example 3, 50 parts by weight of the (i) propylene-ethylene block copolymer of the present invention is blended outside the scope of the present invention. The (i) propylene-ethylene block copolymer of the present invention is a material that is less sticky than other materials having the same rigidity balance, but when 50 parts by weight outside the range of the present invention is blended, the stickiness deteriorates. In addition, since the rigidity is excessively lowered, molding becomes difficult, which is not preferable.

  The propylene-based resin composition and its molded product of the present invention are particularly excellent in impact resistance, and a molded product with excellent transparency can be easily provided by a known molding method. In addition, the propylene-based resin composition of the present invention and the molded product thereof are excellent in the balance of transparency, rigidity, and impact resistance, so that food containers, caps, medical instruments, medical containers, packaging films It is extremely useful for applications such as stationery sheets, costume cases, daily necessities, automobile parts, and electrical parts.

1. JP-A-5-295022

Claims (2)

(A) 60 to 99 parts by weight of a propylene-based polymer and (i) propylene-ethylene block copolymer 1 to 40 parts by weight satisfying the following conditions (Ai) to (Av): A propylene-based resin composition.

(Ai) 30 to 95 wt% of propylene-ethylene random copolymer component (A) having a metallocene catalyst in the first step or propylene-ethylene random copolymer component (A) of 7 wt% or less in the first step, and component (A) in the second step A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% of ethylene more than (A-ii) ) Melt flow rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5-100 g / 10 min (A-iii) Melting peak temperature (Tm) measured by DSC method is in the range of 110-150 ° C. (A-iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (Av) Solid viscoelasticity measurement More resulting temperature - in the loss tangent curve, tan [delta curve has a single peak at 0 ℃ below.
A molded article using the propylene-based resin composition according to claim 1.