JP5509030B2 - Molded product using propylene resin composition - Google Patents

Description

  The present invention relates to a molded article using a propylene-based resin composition, and particularly relates to a molded article of a propylene-based resin composition excellent in impact resistance-stiffness balance, transparency, and surface scratch resistance.

  Propylene polymers are excellent in moldability, rigidity, recyclability and heat resistance, so they are molded and processed by various methods to produce food containers, caps, medical instruments, medical containers, and packaging. Widely used in various applications such as film, stationery sheet, costume case, daily necessities, automobile parts, electrical parts. In these applications, more excellent impact resistance-stiffness balance, transparency, scratch resistance, molding processability, and the like are required for the propylene polymer or the composition thereof. Excellent scratch resistance means that it is difficult to notice when the surface is scratched.

  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 impact resistance and heat 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 random polymer may not be sufficient in terms of impact resistance. In such a case, the impact resistance is improved by adding a modifier or the like to the propylene polymer. Currently. For example, Patent Document 1 attempts to improve impact strength by blending crystalline polypropylene with an ethylene copolymer having a density of 0.93 to 0.88 g / cm ³ . However, when a modifier is added to the random copolymer, the transparency is deteriorated and the scratch resistance is also deteriorated.
Thus, at present, sufficient propylene-based resin materials having both impact resistance-stiffness balance, transparency, and scratch resistance have not yet been found.

JP 2000-72938 A

  The object of the present invention is to solve the above-mentioned problems and to provide a molded product formed from a propylene-based resin composition excellent in impact resistance-stiffness balance, transparency and scratch resistance.

  As a result of intensive research to solve the above-mentioned problems, the present inventors have used a specific modifier for the propylene-based polymer, thereby improving impact resistance-stiffness balance, transparency, and scratch resistance. The inventors have found that it can be an excellent resin composition, and have completed the present invention.

That is, according to the first invention of the present invention, the propylene-ethylene block copolymer (A) 40 satisfying 60 to 99 parts by weight of the propylene-based copolymer (A) and the following (i) to (v): to 1 part by weight (provided that (a) and (total 100 parts by weight of b)) observed contains a ethylene content in the propylene-based copolymer (a), a propylene - ethylene block copolymer (a) in the A molded article using the propylene-based resin composition is provided , wherein the difference from the ethylene content of the component (A) is 3 wt% or less .
(I) Using a metallocene-based catalyst, 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene homopolymer or ethylene content of 7 wt% or less in the first step, and from 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 (ii) Melt flow The rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5 to 100 g / 10 min. (Iii) The melting peak temperature (Tm) measured by the DSC method is in the range of 110 to 150 ° C. (Iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (v) obtained by solid viscoelasticity measurement. In the temperature-loss tangent curve, the tan δ curve has a single peak below 0 ° C.

  According to the second invention of the present invention, in the first invention, the propylene copolymer (a) is a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. A molded product characterized in that the content of ethylene and / or α-olefin having 4 to 12 carbon atoms is 0.01 to 7 wt%.

Furthermore, according to the third invention of the present invention, in the first or second invention, the molded product is a food container, a beverage container, a cap, a cosmetic container, a medical container, a daily product, a film or a sheet. A featured article is provided.

  A molded article comprising the propylene resin composition of the present invention is obtained by molding a polypropylene resin composition in which the propylene-ethylene block copolymer (A) is blended with the propylene copolymer (A). It is a molded article, and it is possible to obtain a molded article having an excellent impact resistance-rigidity balance and transparency and scratch resistance balance that could not be realized by a conventional propylene-based resin material.

It is a figure which shows the elution amount and elution amount integration | accumulation of the component (A) and component (B) by TREF.

The present invention comprises 60 to 99 parts by weight of a propylene-based copolymer (a) and 40 to 1 part by weight of a propylene-ethylene block copolymer (a) satisfying the above (i) to (v). Is a molded product obtained by molding the propylene-based resin composition.
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.

[1] Propylene polymer (A)
In the present invention, the propylene-based copolymer (a) used in the propylene-based resin composition may be any propylene-based copolymer, but is preferably propylene and ethylene and / or It is a propylene-α-olefin random copolymer with an α-olefin having 4 to 12 carbon atoms.
Examples of such copolymers include propylene-ethylene copolymers, propylene-ethylene-diene copolymers, propylene-butene-1 copolymers, propylene-pentene-1 copolymers, propylene-hexene-1 Preferred are binary or ternary copolymers such as copolymers and propylene-4-methylpentene-1 copolymers.

  The content of ethylene and / or α-olefin having 4 to 12 carbon atoms as a copolymer component is preferably 0.01 to 7 wt%, and more preferably 1 to 5 wt%.

  The propylene copolymer (a) preferably has a melt flow rate of 0.3 to 200 g / 10 min in accordance with JIS K7210 (230 ° C., 2.16 kg load). 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 is significantly higher than the above, the uniform dispersibility in the propylene-based copolymer in the case where the clearing nucleating agent is blended may be deteriorated, and the transparency may be hardly exhibited.

The catalyst used for obtaining the propylene-based copolymer (a) 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, those described in JP-A-5-295022), which is a combination of a titanium compound and organic aluminum, can be used.
The polymerization process used for producing the propylene-based copolymer (a) 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, or 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] Propylene-ethylene block copolymer (I)
The propylene-ethylene block copolymer (a) used in the present invention is a propylene-ethylene random copolymer component (A) having a propylene homopolymer or ethylene content of 7 wt% or less in the first step using a metallocene catalyst. After polymerization of 30 to 95 wt%, it is obtained by sequentially polymerizing 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene than the first step in the second step. Propylene-ethylene block copolymer.
The propylene-ethylene block copolymer 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.

(I) Ethylene content in component / component (A) of propylene-ethylene block copolymer (A): [E] A
In order to obtain the rigidity of the molded product, the propylene-ethylene random copolymer component (A) produced in the first step has a relatively high melting point, a crystalline propylene homopolymer, or an ethylene content of 7 wt%. It is necessary to be the following propylene-ethylene random copolymer. If the ethylene content exceeds 7 wt%, the melting point becomes too low, and the rigidity of the molded product may become too low. The ethylene content is preferably 5 wt% or less, more preferably 3 wt% or less. When the rigidity is too low, the molded product cannot obtain an excellent impact resistance-stiffness balance.

  When the difference between the ethylene content ([E] a) of the propylene-based copolymer (A) and the ethylene content [E] A of the component (A) in the component (A) exceeds 3 wt%, The dispersion of the component (a) in the propylene-based copolymer (a) becomes poor, and there is a risk that transparency cannot be obtained and impact strength cannot be obtained. Preferably, the difference between [E] a and [E] A is 3 wt% or less.

-Ethylene content in component (B): [E] B
The propylene-ethylene random copolymer component (B) produced in the second step has a role of a rubber elastic component in the propylene-ethylene block copolymer and is a component necessary for imparting impact resistance. is there.
The range of the ethylene content of component (B) depends on the difference [E] B- [E] A (also referred to as [E] gap) with respect to the ethylene content of component (A) in order to fully exhibit the above effect. It is prescribed. [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 less than 3 wt%, 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.

-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 (I), and W (B), which is the proportion of the component (B), is 30 for W (A). ˜95 wt% and W (B) needs to be in the range of 70˜5 wt%.
If the ratio of W (A) is less than 30 wt%, the rigidity may decrease, and the product may become sticky and the heat resistance may decrease. 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 in the range of 40 to 90 wt%, more preferably 50 to 80 wt%.

・ Specification of [E] A and [E] B and each component amount W (A) and W (B) Each ethylene content and amount of component (A) and (B) is the material balance at the time of manufacture (material balance) However, in order to specify these more accurately, it is desirable to use the following analysis.

..Specification of each component amount W (A) and W (B) by temperature rising elution fractionation (TREF) The technique for evaluating the crystallinity distribution of a propylene-ethylene random copolymer by TREF 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 (a) in the present invention has a large difference in crystallinity between the components (A) and (B), and each crystallinity distribution is produced by using a metallocene catalyst. Therefore, it is possible to distinguish both of them 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 at the measurement temperature lower limit (that is, −15 ° C.) is detected.
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.

.. 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.

... Specification of ethylene content [E] A and [E] B in each component ... Separation of component (A) and component (B) Based on T (C) determined by TREF measurement at the previous point, Using a preparative type fractionation device, the soluble component (B) in T (C) and the insoluble component (A) in T (C) are separated by a temperature rising column separation method, and the ethylene content of each component is determined by NMR. Ask.
The temperature rising column fractionation method refers to a measurement method disclosed in, for example, Macromolecules, 21 314 to 319 (1988). Specifically, the following method was used in the present invention.

··· Separation 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 rate of temperature increase of 10 ° C./min, left at 140 ° C. for 1 hour, and then 800 mL of a 140 ° C. solvent (o-dichlorobenzene) is flowed at a flow rate of 20 mL / min. , And eluting and recovering insoluble components at T (C).
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.

.. Measurement of ethylene content by 13C-NMR The ethylene content of each of the components (A) and (B) obtained by the above fractionation was analyzed by a 13C-NMR spectrum measured according to the following conditions by the proton complete decoupling method. Ask for it.
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, 10536 (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), 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 (Tββ) (1)
[PPE] = k × I (Tβδ) (2)
[EPE] = k × I (Tδδ) (3)
[PEP] = k × I (Sββ) (4)
[PEE] = k × I (Sβδ) (5)
[EEE] = k × [I (Sδδ) / 2 + I (Sγδ) / 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). 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 Tββ.

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
In addition, the propylene random copolymer of the present invention contains a small amount of a propylene hetero bond (2,1-bond and / or 1,3-bond), thereby producing the following minute peak.

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 performed 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 mol%.
In addition, the ethylene content [E] W of the entire propylene-ethylene block copolymer (A) is determined from the ethylene contents [E] A, [E] B, and TREF of the components (A) and (B) measured above. From the weight ratios W (A) and W (B) wt% of each component calculated from the above, the following formula is used.
[E] W = {[E] A × W (A) + [E] B × W (B)} / 100 (wt%)

(Ii) Melt flow rate (MFR)
The melt flow rate (MFR) of the propylene-ethylene block copolymer (i) used in the present invention is 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, more preferably 2 to 2. 35 g / 10 min. 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 propylene-ethylene block copolymer (a), and by controlling the amount of hydrogen added during the polymerization of a chain transfer agent such as hydrogen. 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.

(Iii) Melting peak temperature (Tm)
The melting peak temperature (Tm) measured by the differential scanning calorimeter (DSC) of the propylene-ethylene block copolymer (A) used in the present invention needs to be in the range of 110 to 150 ° C., 120 to It is preferable that it is 140 degreeC. 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.).

(Iv) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method of the propylene-ethylene block copolymer (I) used in the present invention needs to be in the range of 1.5 to 4, It is preferably 1.8 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.
The method for adjusting the molecular weight distribution of the propylene-ethylene block copolymer (I) is to use a metallocene catalyst, which will be described later, or after polymerization of the propylene-ethylene block copolymer (I) and then organic peroxide. It can be adjusted by melt kneading using the product. 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 calibration curve prepared in advance with 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.
Apparatus: 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: 0.2 ml
Sample preparation: Prepare a 1 mg / ml solution using o-dichlorobenzene (containing 0.5 mg / ml BHT) and dissolve it at 140 ° C. for about 1 hour.

(V) Definition by peak of tan δ curve In the present invention, in order to maintain good compatibility and maintain transparency, component (A) and component constituting propylene-ethylene block copolymer (a) to be used It is necessary that (B) is not 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 (I) has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A) and the glass transition temperature of the amorphous part contained in the component (B) are Since each is different, there are a plurality of 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 necessary.

  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.

(3) Producing method of propylene-ethylene block copolymer (I) The method of producing the propylene-ethylene block copolymer (I) used in the present invention essentially requires the use of a metallocene catalyst.
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.

Metallocene-based catalyst The type of metallocene-based catalyst is not particularly limited as long as it can produce a copolymer having the performance of the present invention, but in order to satisfy the requirements of the present invention, for example, the following is shown: It is preferable to use a metallocene catalyst composed of such catalyst components (a) and (b) and a catalyst 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

..Catalyst 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 the same or different from each other. 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 represent 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. Among these, hydrogen is preferable , 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. Among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable. 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, those preferable for the production of the propylene-ethylene random block copolymer (a) used in the present invention are 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, dimethylsilylene bis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylene bis (2-propyl-4-phenanthrylindenyl) zirconium dichloride, dimethyl Silylene bis (2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylene bis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylene bi (2-Ethyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2-isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium Dichloride, dimethylsilylenebis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride, and the like can be given. 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 thereby. It is.

..Catalyst 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, 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., component (b-3), alumina, silica alumina, magnesium chloride, etc., 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.

..Catalyst 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 preferable.

.. Formation of catalyst The catalyst component (a) is contacted with the component (b) and, if necessary, the 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 (a) after contacting component (b) and component (c). Alternatively, the other three components may be contacted simultaneously.

The used amount of the catalyst components (a), (b) and (c) to be used 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 production of the propylene-ethylene block copolymer (I) is preferably subjected to a prepolymerization treatment comprising previously contacting an olefin and polymerizing a small amount.
The olefin used for the prepolymerization 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, 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.

-Polymerization method-Sequential polymerization In order to produce a propylene-ethylene block copolymer (I), it is necessary to sequentially polymerize the component (A) and the component (B). In the conventional propylene-ethylene copolymer, there is no well-considered balance of the propylene-ethylene copolymer obtained in the first step and the second step, and the flexibility, impact resistance and transparency are improved in a well-balanced manner. There was nothing to let me.
Therefore, in the present invention, the propylene-ethylene block copolymer (i) is a block copolymer obtained by sequentially polymerizing components having different ethylene contents in the first step and the second step. Necessary for balancing impact resistance 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), the component (A) is polymerized in order to prevent problems such as adhesion to the reactor. It is necessary to use a method of 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 effects of the present invention are 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 individually polymerize the component (A) and the component (B), but the effect of the present invention is not impaired. As long as each of the component (A) and the component (B) is used, a plurality of reactors may be connected in series and / or in parallel.

..Polymerization process As the polymerization process, an arbitrary 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 readily 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).
The production of component (A) is not particularly problematic regardless of which process is used, but when producing component (A) having relatively low crystallinity, a vapor phase method is used to avoid problems such as adhesion. It is desirable.
Therefore, it is most desirable to polymerize component (A) first by the bulk method or gas phase method and then polymerize component (B) by the gas phase method using the continuous method.

.. Other polymerization conditions The polymerization temperature can be applied without any particular problem as long as it is in a normally 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 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 sequential polymerization of the component (A) in the first step and the component (B) in the second step is performed, it is desirable to add a polymerization inhibitor into the system in the second step. In the case of producing a propylene-ethylene block copolymer, if a polymerization inhibitor is added to the reactor for carrying out the ethylene-propylene random copolymerization in the second step, the particle properties (fluidity, etc.) of the resulting powder, gel, etc. Product quality can be improved. Various methods have been proposed for this method, and examples include JP-B-63-54296, JP-A-7-25960, JP-A-2003-2939, and the like. desirable.

(4) Method for Controlling Components of Propylene-Ethylene Block Copolymer (A) Each component of propylene-ethylene block copolymer (A) used in the present invention is controlled as follows. It can be manufactured to meet the structural requirements required for the polymer.

・ Ingredient (A)
For component (A), it is necessary to control the ethylene content [E] A and the elution peak temperature 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.

・ Ingredient (B)
For component (B), it is necessary to control ethylene content [E] B and elution peak temperature T (B).
In the present invention, in order to control [E] B within a predetermined range, the ratio of ethylene supply to propylene in the second step may be controlled as in [E] A. 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 with the increase of the ethylene content, T (B) is decreased with the increase of [E] B, similarly to the component (A). Therefore, in order to satisfy T (B) within 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.

・ 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), it is only necessary to reduce the production amount of the second step 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 content [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 increases. 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).

・ Single peak of tan δ curve The propylene-ethylene block copolymer (a) used in the present invention has a glass transition at which the tan δ curve obtained in the temperature-loss tangent curve obtained by solid viscoelasticity measurement shows a peak. The temperature Tg needs to have a single peak at 0 ° C. or lower. In order for Tg to have a single peak, the difference between the ethylene content [E] A in component (A) and the ethylene content [E] B in component (B) [E] gap (= [E ] 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.

The Tg of the propylene-ethylene block copolymer (A) that 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. However, in the propylene-ethylene block copolymer (A) 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.

(5) Content of copolymer (a) and block copolymer (a) The blending amount of the propylene copolymer (a) and the propylene-ethylene block copolymer (a) is determined based on the propylene copolymer (a). A) 60 to 99 parts by weight, propylene-ethylene block copolymer (b) 40 to 1 part by weight. However, the sum of (a) and (b) is 100 parts by weight. Propylene-ethylene block copolymer (I) is preferably 3 to 30 parts by weight.
If the content of the propylene-ethylene block copolymer (a) is too small, the compatibilizing effect is reduced, so that the effect of improving the rigidity-impact resistance balance is lowered, and if it exceeds 40 parts by weight, the rigidity-impact resistance is obtained. The balance, wear resistance, etc. deteriorate.

(6) 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 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Phenolic antioxidants such as di-stearyl-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ'-thio-di-propionate An antioxidant etc. are mentioned.

  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 neutralizer include calcium fatty acid stearate, zinc stearate, magnesium stearate, aluminum stearate, lithium stearate and other metal fatty acid salts, hydrotalcite (trade name: Kyowa Chemical Industry Co., Ltd. (A magnesium aluminum composite hydroxide salt represented by (1)), Mizukarak (a lithium aluminum composite hydroxide salt represented by the following general formula (2)), and the like.
Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (1)
[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 (2)
[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) ethanol succinate Condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetra Methyl-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 formula (3) or the following general formula (4), 5,7-di-t-butyl-3- (3,4-di-methyl-phenyl) -3H- Examples include lactone antioxidants such as benzofuran-2-one, and vitamin E antioxidants such as the following general formula (5).

［式中のＲ^１とＲ^２は、炭素数１４〜２２のアルキル基］

[Wherein R ¹ and R ² are alkyl groups having 14 to 22 carbon atoms]

In addition, an antistatic agent, a dispersant such as a fatty acid metal salt, polyethylene, an olefin-based elastomer, and the like can be blended within a range that does not impair the object of the present invention.
The propylene-based resin composition comprising the propylene-based copolymer (A) and the propylene-ethylene block copolymer (I) of the present invention has other characteristics or functions while maintaining the maximum characteristics of the composition. In order to impart, 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.

(7) Propylene resin composition production method The propylene resin composition of the present invention comprises a propylene copolymer (A), a propylene-ethylene block copolymer (I), and other additives used as necessary. After mixing the agent with a Henschel mixer, super mixer, ribbon blender, etc., the mixture is mixed in a normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll, etc. at a temperature range of 180-280 ° C. It can be obtained by melt-kneading.

(8) Molded product The molded product of the present invention is obtained by molding the above-mentioned 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. Particularly, impact resistance is required, and at the same time, it is suitable for applications requiring scratch resistance, whitening resistance, gloss and transparency. 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.

  Specifically, food containers (pudding containers, jelly containers, yogurt containers, other dessert containers, side dish containers, tea bowl steamers, instant noodle containers, cooked rice containers, retort containers, lunch boxes, etc.), beverage containers (drink bottles, chilled containers, etc.) Coffee containers, one-hand cup containers, other beverage containers, etc.), caps (plastic bottle caps, 1-piece caps, 2-piece caps, instant coffee caps, seasoning caps, cosmetic container caps, etc.), cosmetic containers, pharmaceutical containers (infusion solutions) Bags, blood bags, prefilled syringes, kit preparations, eye drops containers, drug solution containers, drug containers, liquid long-term storage containers, press-through packages, strip packages, sachets, plastic vials, etc., medical instruments (disposable syringes and parts thereof) , Cate Tubes, vacuum blood collection tubes, surgical non-woven fabrics, blood filters, disposable devices such as blood circuits, parts of artificial organs such as artificial lungs and colostomy, dialyzers, test tubes, test kits, sutures, compresses , Parts for dental materials, parts for orthopedic materials, contact lens cases, etc.), daily necessities (costume cases, buckets, washbasins, bath / toiletries, writing utensils, stationery, containers, toys, cooking utensils, etc. Case, etc.), film, sheet 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 method. As propylene-based copolymer (a), propylene-ethylene block copolymer (ii), polyethylene and other additives, The following were used.

[1. Measurement method]
(1) TREF
The TREF measurement method is as described above, and the apparatus and conditions are as follows.
<Device>
(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: Digital program controller KP1000 (valve oven) manufactured by Chino Co., Ltd.
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: Infrared detector with fixed wavelength MIRAN 1A manufactured by FOXBORO
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 Scientific Co., Ltd. <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) Calculation of each component amount It calculated by the method mentioned above using TREF.
(3) 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 test piece used was a pellet made into a film having a thickness of about 500 microns by press molding.

(4) Preparation of test pieces Various test pieces were molded by a Toshiba Machine EC-100 injection molding machine at a molding temperature of 230 ° C and a mold temperature of 40 ° C using a JIS family mold.

(5) Peak of tan δ curve It was measured by intrinsic viscoelasticity measurement.
The sample used was cut out into a strip shape of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet injection-molded under the above conditions. 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%.

(6) Molecular weight distribution It measured by the above-mentioned method.
(7) MFR
Based on JIS K-7210-1995, it measured at the temperature of 230 degreeC by 21.18N load.

(8) DSC measurement Melting peak temperature:
Using a Seiko DSC, a 5.0 mg sample was taken, held at 200 ° C. for 5 minutes, crystallized to 40 ° C. at a temperature lowering speed of 10 ° C./min, and further melted at a temperature rising speed of 10 ° C./min. The melting peak temperature was measured.

(9) Flexural modulus Measured at 23 ° C. in accordance with JIS K7203 “Bending test method of hard plastic”.
(10) Izod impact strength Measured at 23 ° C. in accordance with JIS K-7110-1984.

(11) Haze value Using a sheet piece having a thickness of 2 mm, the haze value was measured in accordance with JIS K7105.
(12) Rockwell hardness Rockwell hardness was measured according to JIS K-7202-1982.

(13) Scratch resistance test A 12 cm × 12 cm × 2 mm flat plate was molded by an injection molding machine at a molding temperature of 230 ° C. and a mold temperature of 40 ° C., and the flat plate and a scratch tester (TRIBO GEAR TYPE 18L manufactured by HEIDON) were used at room temperature. The scratch resistance test was carried out.
The tip of a conical sapphire scratching needle with R processing (tip R: 0.05 (mm)) at the tip is brought into contact with a flat test piece perpendicularly and a fixed load (80 gf) is applied. By moving the moving table loaded with the flat test piece at a constant speed (600 mm / min), the scratching needle in contact with the surface of the test piece is slid linearly to scratch the surface of the test piece. Using a confocal laser microscope (V9700, manufactured by Keyence Corporation), the surface shape of the formed wound bottom was measured, and the surface roughness (Ra) of the wound bottom was calculated according to the ISO method, which was used as an index for judging scratch resistance.
If Ra is small, there are few irregularities in the groove of the resulting scratch, light reflection is less, and scratches are less noticeable. Conversely, if Ra is large, there are many irregularities, light is irregularly reflected, and scratches are easily noticeable. Therefore, a smaller Ra value means better scratch resistance. From the viewpoint of scratching properties, the smaller the Ra, the better.

(14) Evaluation of impact whitening resistance DuPont impact tester described in JIS K5600-5-3 in an environment of 20 to 25 ° C. ) Was placed on the strike cradle, and a weight of 100 g was dropped from a place with a height of 50 cm.
In the case where no crack was generated in the flat test piece in this impact test, the impact test was performed by further increasing the weight by 100 g and replacing it with a new test piece. When cracks did not occur in this way, the impact test was repeated in the same manner until the weight reached 1000 g.
In a DuPont whitening test using 200 g and 1000 g weights, a three-stage evaluation was performed on the test pieces that were not broken by visual judgment based on the following criteria.
○: Whitening is not noticeable △: Remarkable whitening is observed ×: Extremely whitening occurs

(Materials used)
(A) Propylene copolymer (PP1) Propylene-ethylene random copolymer 1:
Novatec MG03BQ (Nippon Polypro, trade name)
Ziegler-Natta catalyst, ethylene content 2.2 wt%, MFR 30 g / 10 min (PP2) propylene-ethylene random copolymer 2:
Novatec MX03ZQ (Nippon Polypro, trade name)
Ziegler-Natta catalyst, ethylene content 3.8% by weight, MFR 30 g / 10 min (PP3) propylene-ethylene random copolymer 3:
Wintech WMG03P (Nippon Polypro, trade name)
Metallocene catalyst, ethylene content 0.9% by weight, MFR 25 g / 10 min (PP4) propylene-ethylene random copolymer 4:
Wintech WSX02P (Nippon Polypro, trade name)
Metallocene catalyst, ethylene content 3.2% by weight, MFR 25 g / 10 min (PP5) propylene homopolymer:
Novatec MA5Q (trade name, manufactured by Nippon Polypro Co., Ltd.)
Ziegler catalyst, MFR 5 g / 10 min

(A) Propylene-ethylene block copolymer (PP-i)
A propylene-ethylene block copolymer (PP-i) was produced by the following method.
(I) Preparation of prepolymerized catalyst (chemical treatment of 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 (trade name “Benclay SL”, manufactured by Mizusawa Chemical Co., Ltd., average particle size 25 μm, particle size distribution 10-60 μm) was further 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 silicate)
The chemically treated silicate was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50 mm Heating zone 550 mm (electric furnace) With hoisting blades Rotation speed: 2 rpm Inclination angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)

(Preparation of catalyst)
An autoclave with an internal volume of 16 liters equipped with a stirring and temperature control device was thoroughly replaced with nitrogen. 200 g of the obtained dry silicate was introduced, 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was 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 M / L) 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.

(Prepolymerization / 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 remaining monomer was purged, the 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 M / L) and 5,600 ml of mixed heptane were further added, stirred for 30 minutes at 40 ° C., allowed to stand for 10 minutes, and then 5,600 ml of the supernatant was removed. It was. 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 mM / L and the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the charged amount Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) 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.

(Ii) First polymerization step A horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. While stirring at 30 rpm in the presence of a polypropylene powder bed, 0.568 g / hr of the above prepolymerized catalyst (as the amount of solid catalyst excluding the prepolymerized powder) and 15 triisobutylaluminum in the upstream part of the reactor. It was continuously supplied at 0.0 mmol / hr. The monomer mixed gas is continuously reacted so that the reactor temperature is maintained at 65 ° C., the pressure is maintained at 2.1 MPaG, the ethylene / propylene molar ratio in the reactor gas phase is 0.07, and the hydrogen concentration is 100 ppm. It was made to distribute | circulate in a container and vapor phase polymerization was performed. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, the amount of the polymer extracted when the steady state was reached was 10.0 kg / hr.
When the propylene-ethylene random copolymer (component (A)) obtained in the first polymerization step was analyzed, the MFR was 6.0 g / 10 min and the ethylene content was 2.2 wt%.

(Iii) Second polymerization step The propylene-ethylene copolymer extracted from the first step was continuously supplied to a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. While stirring at a rotational speed of 25 rpm, the temperature of the reactor is maintained at 70 ° C., the pressure is maintained at 2.0 MPaG, and the ethylene / propylene molar ratio in the gas phase in the reactor is 0.453, and the hydrogen concentration is 330 ppm. A monomer mixed gas was continuously passed through the reactor to carry out gas phase polymerization. The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 17.9 kg / hr, and the polymerization reaction amount in the second polymerization step was controlled. The activity was 31.429 kg / g-catalyst.
Table 3 shows various analysis results of the obtained propylene-ethylene block copolymer (PP-I).

(PE) Metallocene low density polyethylene:
Product name Kernel KS571 manufactured by Japan Polytechnic Co., Ltd.
Density (JIS K7112) 0.907 g / cm ³
MFR (JIS K7210, 230 ° C., 2.16 kg load) 24 g / 10 min Mw / Mn 2.4

(Nucleating agent) Organophosphate metal nucleating agent:
Product name ADK STAB NA-21 manufactured by ADEKA Corporation

(Neutralizer) Neutralizer:
Calcium stearate

(Antioxidant A) Hindered phenolic antioxidant:
Product name Irganox 1010, manufactured by Ciba
Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxylphenyl) propionate] methane

(Antioxidant B) Phosphorous antioxidant:
Product name Irgafos 168 made by Ciba
Tris (2,4-di-tert-butylphenol) phosphite

(Examples 1-4, Comparative Examples 1-6)
Each component described above was prepared in the proportions (% by weight) shown in Tables 4 and 5 and dry blended with a super mixer, then melt-kneaded using a 35 mm diameter twin screw extruder, and the die outlet temperature 220 Extruded from the die at 0 ° C. and pelletized. The 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. Physical properties were measured using the prepared test pieces.
The results are shown in Tables 4 and 5.

As is clear from Tables 4 and 5, Examples 1 to 4 were prepared by blending the propylene-ethylene random copolymer (A) with the propylene-ethylene block copolymer (I) of the present invention. For 1 to 6, it can be seen that the material has a good balance of rigidity and impact resistance, a good balance of rigidity and transparency, and an excellent balance of physical properties.
Furthermore, it can be seen that Example 3 is superior to Comparative Examples 4 and 5 in the whitening property and the scratch resistance of the bending elastic modulus. The surface roughness Ra indicating the size of the scratch was 8.3 μm in Example 3, 10.5 μm in Comparative Example 4, and 9.2 μm in Comparative Example 5.

(Examples 5-7, Comparative Examples 7-10)
Each component described above was prepared in the proportions (% by weight) shown in Table 6 and dry blended with a super mixer, then melt kneaded using a 35 mm diameter twin screw extruder, and the die exit part temperature was 220 ° C. Was extruded into pellets. The 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. Physical properties were measured using the prepared test pieces.
The results are shown in Table 6.

  As is apparent from Table 6, Examples 5 to 7 were prepared by blending the propylene-ethylene random copolymer (A) with the propylene-ethylene block copolymer (I) of the present invention. Comparative Examples 7 to 10 Compared to the above, the rigidity-impact resistance balance is good, the rigidity-transparency balance is also good, and the physical property balance is excellent. Further, it can be seen that Example 6 is superior to Comparative Example 9 in whitening characteristics and scratch resistance.

  The propylene-based resin composition and the molded product thereof of the present invention are particularly excellent in impact resistance, and a molded product having excellent transparency can be easily provided by various molding methods. Further, since the propylene-based resin composition of the present invention and the molded product thereof are excellent in balance of transparency, rigidity, and impact resistance, food containers, caps, medical instruments, medical containers, packaging films, It is extremely useful for applications such as stationery seats, costume cases, daily necessities, automobile parts, and electrical parts.

Claims (3)

Propylene-based copolymer (a) 60 to 99 parts by weight and propylene-ethylene block copolymer (a) satisfying the following (i) to (v) (a) 40 to 1 part by weight (however, (a) and (a) total viewed contains 100 parts by weight) of the ethylene content of the propylene copolymer (a), propylene - the difference between the ethylene content of the components in the ethylene block copolymer (i) (a) is, 3 wt% The molded article using the propylene-type resin composition characterized by the following .
(I) Using a metallocene-based catalyst, 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene homopolymer or ethylene content of 7 wt% or less in the first step, and from 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 (ii) Melt flow The rate (MFR: 230 ° C. 2.16 kg) is in the range of 0.5 to 100 g / 10 min. (Iii) The melting peak temperature (Tm) measured by the DSC method is in the range of 110 to 150 ° C. (Iv) The molecular weight distribution (Mw / Mn) measured by the GPC method is in the range of 1.5 to 4 (v) obtained by solid viscoelasticity measurement. In the temperature-loss tangent curve, the tan δ curve has a single peak below 0 ° C.   The propylene copolymer (a) is a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms, and the content of ethylene and / or an α-olefin having 4 to 12 carbon atoms The molded article according to claim 1, wherein is 0.01 to 7 wt%. The molded article according to claim 1 or 2 , wherein the molded article is a food container, a beverage container, a cap, a cosmetic container, a medical container, a daily necessities, a film, or a sheet.

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