JP6079378B2 - Propylene resin master batch - Google Patents

Description

  The present invention relates to a masterbatch composition for adding to a propylene-based resin, and particularly to a masterbatch composition part characterized by containing a high concentration of inorganic filler and pigment.

  Propylene resins are excellent in molding processability, mechanical properties, product appearance, recyclability, heat resistance, and chemical resistance, so they are molded by various methods and used in a wide range of applications. Yes. Moreover, it is often performed that the rigidity and heat resistance are further improved by adding an inorganic filler to the propylene-based resin, or the design properties are improved by coloring by adding a pigment. In that case, melt-kneading may be carried out after adding an inorganic filler or pigment to the propylene-based resin, but there is a problem that the processing cost increases due to an increase in the number of steps. Therefore, it is widely practiced to prepare a master batch composition in which an inorganic filler or a pigment is dispersed in a resin, and blend and use it before molding.

  Since it is desirable for the master batch composition to contain more inorganic fillers and pigments, the resin used in the present composition needs to be excellent in dispersibility with the inorganic fillers and pigments. Therefore, those using a polyethylene component having a low melting point (for example, see Patent Document 1), those using a modified polyolefin having high compatibility with inorganic fillers and pigments (for example, see Patent Document 2), and having high fluidity Those using a polyolefin wax (for example, see Patent Document 3) and those using a propylene resin and an elastomer component in combination (for example, see Patent Documents 4 and 5) have been proposed and used in practice.

  Among these, polyethylene is very widely used because it is inexpensive and easily available. However, polyethylene is not compatible with the main material polypropylene. Therefore, when polyethylene is used as the base resin of the masterbatch composition, when the molded product is subjected to external factors such as impact, cyclic stress, thermal history, peeling occurs at the interface between polypropylene and polyethylene, There is a problem that it can lead to destruction.

  The modified polyolefin is excellent as a base resin for a masterbatch composition in that it has compatibility with inorganic fillers and pigments by a polar group and maintains compatibility with polypropylene, which is a main material, in a polyolefin skeleton. Has characteristics. However, there are cases where there are problems such as odor, and there are problems that a process and cost required for modification are required.

  In recent years, polyolefin waxes have been widely used as base resins for masterbatch compositions. While it has the advantage of very high fluidity, its molecular weight is small, so there is a possibility of high mobility in the molded product, and there is a risk of bleed out during long-term storage and use at high temperatures.

  The combined use of the propylene-based resin and the elastomer component makes it possible to increase the concentration of the inorganic filler and pigment in the master batch composition and to impart impact strength to the main material. However, since the elastomer component generally has low compatibility with the propylene-based resin, both components have a phase separation structure. As a result, when a masterbatch composition prepared using an elastomer is added to a propylene resin composition, the destruction due to interfacial delamination between the propylene resin and the elastomer component is the same as when polyethylene is used as the base resin. There is a problem that may cause.

  Thus, in the masterbatch composition, there is no technology that achieves compatibility with the main propylene-based resin, cost, and bleed-out properties while allowing the addition of high-concentration inorganic fillers and pigments. The development of new technology was desired.

JP 9-302099 A JP 9-31206 A Special table 2003-525329 gazette JP 2004-168876 A JP 2008-133376 A

  In view of the above problems, the object of the present invention is to reduce a propylene-based masterbatch composition that has a high concentration of inorganic fillers and pigments and is compatible with the propylene-based material and bleed-out properties. It is to provide at a cost.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a propylene-ethylene block obtained by sequentially polymerizing two specific types of propylene-ethylene random copolymer components using a metallocene catalyst. By using a copolymer as a base resin and adding an appropriate amount of inorganic fillers or pigments, and if necessary, an appropriate dispersant, compatibility with the main propylene resin and bleeding out properties Has been found to be feasible at low cost, and the present invention has been completed.

That is, according to the first invention of the present invention, the inorganic filler or pigment is used with respect to 100 parts by weight of the propylene-ethylene block copolymer (a) satisfying the following conditions (a-i) to (a-iii). (A) A polypropylene-based masterbatch composition characterized by containing 50 to 400 parts by weight and a fatty acid metal salt (U) 0 to 50 parts by weight is provided.
Propylene-ethylene block copolymer (A)
(A-i) Using a metallocene-based catalyst, 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene alone or ethylene content of 7 wt% or less in the first step, and component (A) in the second step It is a propylene-ethylene block copolymer obtained by successively polymerizing 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene.
(A-ii) The melting peak temperature (Tm) measured by the DSC method is in the range of 110 to 150 ° C.
(A-iii) In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.

  According to the second invention of the present invention, the polypropylene master batch characterized in that the propylene-ethylene block copolymer (a) in the first invention has an MFR of 5 or more at 230 ° C. and a load of 2.16 kg. A composition is provided.

  According to 3rd invention of this invention, the molded article obtained by adding the polypropylene-type masterbatch composition in 1st or 2nd invention to propylene-type resin is provided.

  The polypropylene-based masterbatch composition of the present invention is compatible with propylene-based materials and bleed-out properties at a low cost while containing a high concentration of inorganic filler and pigment. Moreover, the molded article using the polypropylene-based masterbatch composition of the present invention can realize high rigidity, heat resistance, and an appearance excellent in design at low cost.

It is a figure which shows the elution amount by TREF, and elution amount integration. It is a figure which shows the flow sheet of the superposition | polymerization apparatus used in the Example.

  In the present invention, the inorganic filler or pigment (I) 50 to 400 parts by weight and the fatty acid metal salt (c) 0 to 50 parts by weight per 100 parts by weight of the propylene-ethylene block copolymer (A) satisfying specific conditions. Part of a polypropylene-based masterbatch composition and a molded product. Hereinafter, a method for producing such a propylene-based resin composition and a molded product will be described in detail.

  The propylene-based resin composition of the present invention consists essentially of 1) 100 parts by weight of a propylene-ethylene block copolymer (a), 2) 50 to 400 parts by weight of an inorganic filler or pigment (ii), and 3) a fatty acid. It is comprised from 0.0-50 weight part of metal salts (c).

[1] Propylene-ethylene block copolymer (A)
In the first step, the propylene-ethylene block copolymer (a) used in the present invention is obtained by polymerizing 30 to 95 wt% of propylene alone or a propylene-ethylene random copolymer component (A) having an ethylene content of 7 wt% or less. Thereafter, in the second step, the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene than in the first step is obtained by sequential polymerization of 70 to 5 wt%.

The propylene-ethylene block copolymer (A) as used herein means a propylene-ethylene random copolymer component (A) (hereinafter referred to as component (A)) and a propylene-ethylene random copolymer component ( B) (hereinafter referred to as “component (B)”) is a block copolymer as a general name obtained by sequential polymerization, and the component (A) and the component (B) are not necessarily combined in a block form. It does not have to be.
The said requirements are demonstrated in detail by the following (1-1)-(1-8).

(1-1) Ethylene content in component (A): [E] A
The component (A) produced in the first step is a component for ensuring compatibility between the propylene-based resin as the main material and the master batch composition of the present invention. If the compatibility between the main material and the master batch composition is impaired, not only the dispersibility of the inorganic filler or pigment (I) in the main material is deteriorated, but also a phase separation structure is formed in the main material. When the product is subjected to external factors such as impact, cyclic stress, and thermal history, peeling may occur at the interface, leading to destruction.
The propylene resin usually used as the main material is a propylene homopolymer, ethylene and / or a random copolymer of α-olefin having about 4 to 8 carbon atoms and propylene, ethylene and / or α having about 4 to 8 carbon atoms. It is a block copolymer of olefin and propylene. In order to ensure compatibility with these polymers, the component (A) needs to be a propylene homopolymer or a propylene-ethylene random copolymer having an ethylene content of 7 wt% or less. When the ethylene content exceeds 7 wt%, compatibility with a general propylene-based resin is impaired.

  Furthermore, the component (A) also functions as a component that facilitates cutting in the granulation step of the master batch composition. Therefore, it is necessary to be a propylene homopolymer having a relatively high melting point and crystallinity, or a propylene-ethylene random copolymer having an ethylene content of 7 wt% or less. If the ethylene content exceeds 7 wt%, the crystallinity becomes too low and cutting may be extremely difficult. The ethylene content is preferably 5 wt% or less, more preferably 3 wt% or less.

(1-2) Ethylene content in component (B): [E] B
The component (B) produced in the second step has a role of a rubber elastic component in the propylene-ethylene block copolymer (a), and improves the mixing property with the inorganic filler or the pigment (a). This is a necessary ingredient.

  The range of the ethylene content of component (B) is defined by the difference [E] B- [E] A ([E] gap) from the ethylene content of component (A). [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 effect of improving the mixing property with the inorganic filler or pigment (I) is not sufficient, which is not preferable. On the other hand, if it exceeds 20 wt%, the compatibility with the component (A) produced in the first step is deteriorated, so that the dispersibility of the inorganic filler or pigment (A) is deteriorated and the master batch of the present invention is mainly used. It is not preferable because there is a possibility that breakage due to interfacial peeling occurs when converted into a material. [E] When the gap is 6 to 18 wt%, further 8 to 16 wt%, the balance between the compatibility of the components (A) and (B) and the dispersibility of the inorganic filler or pigment (I) is improved. More preferable.

(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 (a), and W (B), which is the proportion of the component (B), is such that W (A) is It is 30 to 95 wt%, and W (B) needs to be in the range of 70 to 5 wt%. When the ratio of W (A) is less than 30 wt%, the compatibility of the masterbatch composition with the main material is lowered, and the crystallinity of the masterbatch composition is lowered, which may make cutting difficult. On the other hand, if the ratio of W (A) exceeds 95 wt%, the effect of improving dispersibility with the inorganic filler or pigment (A) 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, it is necessary that the component (A) and the component (B) constituting the propylene-ethylene block copolymer (a) to be used are not phase-separated. It is. If the two components are phase-separated, the inorganic filler or pigment (i) is not preferable because it is difficult to uniformly disperse in the masterbatch composition. Furthermore, when the phase-separated masterbatch composition is added to a propylene-based resin that is a main material, there is a problem that breakage due to interfacial peeling may occur. Therefore, it is very important that the two components are 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 (a) 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. In order to maintain the dispersibility and transparency of the inorganic filler or pigment (a), tan δ It is necessary for the curve to have a single peak below 0 ° C.

  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 the amount of each component W (A) and W (B) The ethylene content and amount of each component (A) and (B) depend on the mass 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 component amounts W (A) and W (B) by temperature-temperature elution fractionation (TREF) Method for evaluating the crystalline distribution of propylene-ethylene random copolymer (a) 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.M. E. Hamielec, Polymer; 36, 8, 1639-1654 (1995)

  The propylene-ethylene block copolymer (a) in the present invention is greatly different in the crystallinity of each of the components (A) and (B), and each crystallinity distribution is produced by being produced 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 measurement temperature lower limit. However, since the value cannot be measured, T (B) is defined as −15 ° C. which is the lower limit of the measurement temperature in such a case.

  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) Specificity of ethylene content [E] A and [E] B in each component (I) 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 disclosed in, for example, Macromolecules, 21 314 to 319 (1988). Specifically, the following method was used in the present invention.

(II) Fractionation condition 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.

(III) Measurement of ethylene content by ¹³ C-NMR The ethylene content of each of component (A) and component (B) obtained by the above fractionation was measured by a proton complete decoupling method according to the following conditions. 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

Spectral assignment may be performed with reference to Macromolecules, 17 1950 (1984), for example. The spectral attributions measured under the above conditions are shown in Table 1. 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 (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

  In addition, the propylene-ethylene random copolymer (a) of the present invention contains a small amount of a propylene heterogeneous bond (2,1-bond and / or 1,3-bond). A peak is produced.

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 (% by weight) = (28 × X / 100) / {28 × X / 100 + 42 × (1−X / 100)} × 100
(Where X is the ethylene content in mol%)

Further, the ethylene content [E] W of the propylene-ethylene block copolymer (a) as a whole is the ethylene content [E] A and [E] B of each of the component (A) and the component (B) measured above. The weight ratio W (A) and W (B) wt% of each component calculated from TREF is calculated by the following formula.
[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 propylene-ethylene block copolymer (a) used in the present invention is preferably 2 g / 10 min or more, more preferably 5 g / 10 min or more, further preferably 15 g / 10 min or more. It is. In general, the higher the MFR, the better the compatibility with the inorganic filler or pigment (I) and the lowering of fluidity that occurs when a high concentration of inorganic filler or pigment (A) is added is preferable.
The melt flow rate (MFR) is adjusted by adjusting the temperature and pressure, which are the polymerization conditions of the propylene-ethylene block copolymer (a), or by controlling the amount of chain transfer agent such as hydrogen during polymerization. Adjustment can be made easily.
Here, MFR is a value measured at a heating temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

(1-7) 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., and 120 to It is preferable that it is 140 degreeC. Those having a Tm of less than 110 ° C. are not preferable because the cooling and solidification rate is slow and the cutting property during granulation may be deteriorated. On the other hand, if it exceeds 150 ° C., the dispersibility of the inorganic filler or pigment (I) may be deteriorated, which is not preferable. Tm can be easily adjusted 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 a 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 the propylene-ethylene block copolymer (a) used in the present invention is preferably in the range of 1.5 to 4, More preferably, it is 1.8 or more and less than 3. Those having Mw / Mn of less than 1.5 are difficult to obtain with the current polymerization technology. On the other hand, when Mw / Mn exceeds 4, low molecular weight and high molecular weight components increase, but when the low molecular weight component increases, when the molded product to which the masterbatch composition is added is stored for a long time or at a high temperature. In addition, the phenomenon that the low molecular weight component bleeds out on the surface of the molded product may occur, which may unfavorably impair the commercial value. On the other hand, an increase in the high molecular weight component is not preferable because the dispersibility of the inorganic filler or the pigment (a) may be deteriorated.

  When narrowing the molecular weight distribution of propylene-ethylene block copolymer (a), use a metallocene catalyst described later, or polymerize propylene-ethylene block copolymer and then melt using organic peroxide. It can be adjusted by kneading. 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 a 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 (measured wavelength: 3.42 μm) manufactured by FOXBORO
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 (a) production method (2-1) Metallocene catalyst When producing the propylene-ethylene block copolymer (a) used in the present invention, use of a metallocene catalyst Is required.
As described above, the master batch composition of the present invention needs to have a narrow molecular weight distribution. However, even when the composition distribution is wide, the quality may be similarly impaired. That is, when the highly crystalline component increases, the dispersibility of the inorganic filler or the pigment (I) may be deteriorated, which is not preferable. On the other hand, when the amount of low crystal components increases, when a molded product to which a master batch composition is added is stored for a long period of time or at a high temperature, this low molecular weight component bleeds out to the surface of the molded product. This is not preferable because there is a risk of serious loss of value. Therefore, the composition distribution as well as the molecular weight distribution needs to be narrow, but in order to obtain such a polymer, it is indispensable to polymerize using a metallocene-based catalyst with 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), component (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) Particulate carrier carrying an organoaluminoxy compound (b-2) An ionic compound or Lewis 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 thereof include a silylene group, an oligosilylene group, and 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. , Chlorine, methyl, isobutyl, phenyl, dimethylamide, diethylamide group and the like. X and Y may be each independently, 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 R1 and R2 may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon A substituent comprising a 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, dimethylsilylenebis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis (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 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 thereby. 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 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), as the component (b-1), a particulate carrier on which methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl and the like are supported As component (b-2), triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl 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.

(2-4) Component (c)
Examples of organoaluminum compounds used as component (c) as needed are those of the 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, and a is a number of 0 <a ≦ 3)
Or a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, or triisobutylaluminum, or a halogen- or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or diethylaluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred.

(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. Further, this contact may be performed not only at the time of catalyst preparation but also at the time of preliminary polymerization with olefin or at the time of polymerization of olefin.
1) A component (a) and a component (b) are made to contact.
2) Add component (c) after contacting component (a) and component (b).
3) Component (b) is added after contacting component (a) and component (c).
4) Component (a) is added after contacting component (b) and component (c).
In addition, you may 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.

It is preferable that the catalyst used in the propylene-ethylene block copolymer (a) of the present invention is 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. It is possible to use, and it is particularly preferable to use propylene. The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change. The prepolymerization temperature and time are not particularly limited, but are preferably in the range of −20 ° C. to 100 ° C. and 5 minutes to 24 hours, respectively. The amount of prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 with respect to the component (b). After completion of the prepolymerization, the catalyst can be used as it is, depending on the usage form of the catalyst. However, if necessary, drying can be performed.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

(2-6) Polymerization method (2-6-1) Sequential polymerization In producing the propylene-ethylene block copolymer (a) used in the present invention, the component (A) and the component (B) are sequentially polymerized. It is necessary.
Among the prior arts, there is also a technique that uses a composition obtained by individually polymerizing component (A) and component (B) and then melt-kneading them. However, even if a masterbatch composition is produced using such a composition, it is difficult to uniformly disperse the inorganic filler or pigment (a), and the blending concentration may be increased. was difficult.
In addition, there is no conventional propylene-ethylene copolymer in which the balance of the propylene-ethylene copolymer obtained in the first step and the second step is sufficiently considered, and the dispersibility of the inorganic filler or pigment (I) In addition, none improved the compatibility with the main material in a well-balanced manner.
On the other hand, in the present invention, the propylene-ethylene block copolymer (a) is a block copolymer obtained by sequentially polymerizing components having appropriate ethylene contents in the first step and the second step, so that the two components are It became compatible at the molecular level, and it became possible to realize the dispersibility of the inorganic filler or pigment (i) in the propylene-ethylene block copolymer (a) and the compatibility with the main material.
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) individually 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 the 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), 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 in the production of component (B).
For the production of component (A), there is no particular problem even if any process is used. However, when producing component (A) having relatively low crystallinity, in order to avoid problems such as adhesion, the gas phase It is desirable to use the method.
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.

(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 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 (a), the addition of a polymerization inhibitor to the reactor for carrying out the ethylene-propylene random copolymerization in the second step results in particle properties (fluidity, etc.) of the resulting powder. Product quality such as gel and gel can be improved. 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) 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.

(3-1) Component (A)
For component (A), it is necessary to control the ethylene content [E] 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 (a) varies depending on the type of metallocene catalyst used, but the component having the ethylene content [E] A required by adjusting the supply ratio ( A) can be produced.
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.

(3-2) Component (B)
For component (B), it is necessary to control the ethylene content [E] 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.

(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), 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 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 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 reduced 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 to increase the production amount W (B). The conditions may be set by a method that raises the polymerization temperature and / or lengthens the polymerization time (residence time) as necessary.

(3-4) MFR (A) and MFR (B)
The melt flow rate MFR (W) of the propylene-ethylene block copolymer (a) includes a melt flow rate MFR (A) of the component (A) and a melt flow rate MFR (B) of the component (B). This value is determined by the contribution. That is, the following equation is established between MFR (W), MFR (A), and MFR (B) and the weight ratios W (A) and W (B) of each component.
log {MFR (W)} = W (A) × log {MFR (A)} + W (B) × log {MFR (B)}

By using this formula, the melt flow rate MFR (A) of the polymer obtained after the first step, the melt flow rate MFR (W) of the polymer obtained after the second step, W (A), W (B) From the above, the melt flow rate of the component (B) can be calculated.
The melt flow rate MFR (A) of component (A) and the melt flow rate MFR (B) of component (B) are the first step for producing component (A) and the second for producing component (B). In each step, the temperature and pressure, which are polymerization conditions, can be adjusted, or the amount of chain transfer agent such as hydrogen can be controlled to easily adjust. That is, the adjustment of MFR (A) and MFR (B) can be performed independently as long as they are within a range that satisfies the provisions of the present invention. Especially, when MFR (B) is smaller than MFR (A), even if the molded product is stored or heated for a long time, stickiness and appearance deterioration due to bleed-out can be almost completely prevented.
Here, MFR is a value measured at a heating temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

(3-5) Glass transition temperature Tg
The propylene-ethylene block copolymer (a) 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 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 (a) 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, but 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.

[2] Inorganic filler or pigment (I)
As the inorganic filler or pigment (I) in the present invention, any inorganic filler or pigment can be used. Depending on the type of inorganic filler, it is possible to impart a unique performance to the propylene-based resin that is the main material, and depending on the type of pigment, it is possible to impart a unique color tone to the main material. Any inorganic filler or pigment can be used depending on the required performance.

  Non-limiting specific examples of inorganic fillers include calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, sulfurous acid. Examples include calcium, talc, mica, clay, dolomite, basic magnesium carbonate, and glass.

Non-limiting specific examples of pigments include, for example, inorganic pigments such as titanium oxide, iron oxide (eg, bengara), chromic acid (eg, chrome lead), molybdic acid, selenide sulfide, ferrocyanide, carbon black, Soluble azo lakes, soluble azo lakes, insoluble azo chelates, condensable azo chelates, other azo chelates such as azo chelates, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, slen pigments such as anthraquinone, perinone, perylene, thioindigo, quinacridone, dioxazine And organic pigments such as isoindolinone and functional pigments that impart glossiness such as aluminum flakes and pearl pigments.
The composition ratio of the inorganic filler or the pigment (A) is 50 to 400 parts by weight with respect to 100 parts by weight of the propylene-ethylene block copolymer (A). If the composition ratio of the inorganic filler or pigment in the masterbatch is high, the compounding amount of the masterbatch with respect to the main material can be reduced. Therefore, in general, the composition ratio of the inorganic filler or pigment (b) should be high. The higher the better. However, the composition ratio can be arbitrarily set within the scope of the present invention due to circumstances such as the respective uses, required physical properties, and restrictions on manufacturing equipment.

[3] Fatty acid metal salt (U)
In this invention, a fatty-acid metal salt (u) can be added in the ratio of 0-50 weight part with respect to 100 weight part of a propylene-ethylene block copolymer (a) as needed. Use of the fatty acid metal salt (U) has an effect of promoting the dispersion of the inorganic filler or the pigment (I) in the propylene-ethylene block copolymer (A) and suppressing aggregation. Any type of dispersant can be blended at any concentration depending on the type of inorganic filler or pigment (A) and the required performance.

The fatty acid metal salt (c) is a fatty acid metal salt represented by the following general formula (8).
M (RCOO) n (8)
[Wherein, R 1 represents a carboxyl group from a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms (preferably 10 to 22 carbon atoms) which may have one or more hydroxyl groups in the molecule. Represents residues obtained by removing. n represents an integer of 1 or 2, and when n = 2, two Rs may be the same or different. M represents a metal belonging to Group 1, Group 2, Group 12, or Group 13 of the periodic table. ]

Specifically, a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms (preferably 10 to 22 carbon atoms) which may have one or more hydroxyl groups in the molecule, and a periodic table. It consists of metals belonging to Group 1, Group 2, Group 12 or Group 13.
The fatty acid metal salt (c) includes a compound or a mixture of the fatty acid metal salt or the basic fatty acid metal salt and a metal oxide or / and a metal hydroxide.

  As the aliphatic monocarboxylic acid in the above formula (8), caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, Margaric acid, oleic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, succinic acid, lindelic acid, tuzic acid, palmitoleic acid, petraceric acid, elaidic acid, vacsen Examples thereof include acid, linoleic acid, linoelaidic acid, γ-linolenic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid, naphthenic acid, and abietic acid. Preferably, at least one selected from lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, behenic acid, montanic acid and 12-hydroxystearic acid is used.

  Examples of the metal belonging to Group 1, Group 2, Group 12 or Group 13 of the periodic table in the above formula (8) include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, strontium, barium). Etc.), magnesium, zinc, aluminum and the like, and preferably at least one selected from magnesium, calcium, zinc, lithium, sodium and potassium.

Preferred fatty acid metal salts (U) include at least one aliphatic monocarboxylic acid selected from lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, behenic acid, montanic acid and 12-hydroxystearic acid, Examples include fatty acid metal salts composed of at least one metal selected from magnesium, calcium, zinc, lithium, sodium and potassium.
Specifically, magnesium palmitate, magnesium oleate, magnesium stearate, magnesium behenate, 12-hydroxy magnesium stearate, calcium stearate, calcium behenate, 12-hydroxy calcium stearate, zinc stearate, zinc behenate, 12 -Zinc hydroxystearate, sodium stearate, sodium 12-hydroxystearate, potassium stearate, potassium 12-hydroxystearate, lithium stearate, lithium 12-hydroxystearate and the like.

  Among them, particularly preferred fatty acid metal salts (c) are those in which the metal is composed of at least one metal selected from magnesium, calcium or zinc, specifically magnesium oleate, magnesium stearate, behenic acid. Examples thereof include magnesium, magnesium 12-hydroxystearate, calcium oleate, calcium stearate, calcium behenate, calcium 12-hydroxystearate, zinc oleate, zinc stearate, zinc behenate, and zinc 12-hydroxystearate.

The melting point of the fatty acid metal salt (U) is not particularly limited. For example, when the metal is magnesium, the melting point is preferably 116 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher. When the melting point is less than 116 ° C., the dispersibility, the balance of physical properties and the molded appearance of the inorganic filler or pigment (I) in the MB of the present invention, the resin composition comprising the same, and the injection molded product tend to be lowered.
For example, when the metal is calcium, the temperature is preferably 140 ° C. or higher, more preferably 142 ° C. or higher, and particularly preferably 145 ° C. or higher. When the melting point is less than 140 ° C., the dispersibility, physical properties and molded appearance tend to be lowered.
Furthermore, for example, when the metal is zinc, one having a temperature of 116 ° C. or higher is preferable, one having a temperature of 120 ° C. or higher is more preferable, and one having a temperature of 125 ° C. or higher is particularly preferable. When the melting point is less than 116 ° C., the dispersibility, physical properties and molded appearance tend to be lowered. Here, the melting point is a value measured using a differential scanning calorimeter or the like.

The content of each metal in the fatty acid metal salt (c) is not particularly limited. For example, when the metal is magnesium, it is preferably 3.2% by mass or more, more preferably 3.6% by mass or more. An amount of 3.8% by mass or more is particularly preferable. When the magnesium content is less than 3.2% by mass, the dispersibility, physical properties, and molded appearance of the inorganic filler or pigment (I) in the masterbatch composition of the present invention and molded articles using the same are reduced. Tend.
For example, when the metal is calcium, 5.0% by mass or more is preferable, 5.5% by mass or more is more preferable, and 6.0% by mass or more is particularly preferable. When the calcium content is less than 5.0% by mass, the dispersibility, physical properties and molded appearance tend to be lowered.
Furthermore, for example, when the metal is zinc, it is preferably 10.0% by mass or more, more preferably 10.4% by mass or more, and particularly preferably 11.0% by mass or more. When the zinc content is less than 10.0% by mass, the dispersibility, physical properties and molded appearance tend to be lowered. Here, the metal content is a value measured using a thermogravimetric measuring device or the like.

(4) Other additives In the polypropylene masterbatch composition of the present invention, propylene-ethylene block copolymer (A), inorganic filler or pigment (I), fatty acid metal salt (U), propylene Additives such as various antioxidants, neutralizers, lubricants, UV absorbers, light stabilizers, nucleating agents, and antistatic agents that are used as stabilizers for polymer polymers can adversely affect required performance and color tone. It can mix | blend in the range which does not give.

  Specifically, as the antioxidant, for example, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, Bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) Phosphorus-based antioxidants such as -4,4'-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite Agent, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxy) Benzyl) isocyanurate phenolic antioxidants, di-stearyl-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ'-thio-di-propionate And thio antioxidants.

  Specific examples of the neutralizing agent include, for example, hydrotalcite (trade name: magnesium aluminum composite hydroxide salt represented by the following general formula (9) of Kyowa Chemical Industry Co., Ltd.), Mizukarak (the following general formula ( And lithium aluminum composite hydroxide salt represented by 10).

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (9)
[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 (10)
[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 fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, and behenic acid amide, butyl stearate, and silicone oil.

  Specific examples of the ultraviolet absorber include, for example, 2-hydroxy-4-n-octoxybenzophenone and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole. And ultraviolet absorbers such as 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole.

  Specific examples of the light stabilizer include, for example, 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-succinate-2- (4-hydroxy-2,2,6,6-tetra Methyl-1-piperidyl) ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2 , 6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine -2,4-bis [N They include butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate of light stabilizers.

  Specific examples of the nucleating agent include, for example, aluminum benzoate, potassium benzoate, sodium benzoate, lithium benzoate, aluminum di-pt-butyl benzoate, titanium di-pt-butyl benzoate, di- Aromatic carboxylic acid metal salt nucleating agents such as chromium p-t-butylbenzoate, aluminum hydroxy-di-t-butylbenzoate, aluminum-p-butylbenzoate, sodium β-naphthoate, bis (4-t- Butylphenyl) sodium phosphate, lithium bis (4-t-butylphenyl) phosphate, aluminum bis (4-t-butylphenyl) phosphate, 2,2′-methylene-bis (4,6-di) -T-butylphenyl) phosphate sodium salt, 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate lithium salt, 2,2′-methylene-bis (4,6-di-t-butylphenyl) aluminum phosphate, 2,2′-methylidene-bis (4,6-di-t-butylphenyl) calcium phosphate, 2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate sodium salt, 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate lithium, 2,2 Aromatic metal phosphate nucleating agents such as' -ethylidene-bis (4,6-di-t-butylphenyl) aluminum phosphate, bis- (4-t-butylphenyl) calcium phosphate, dibenzylidene sorbitol, 1,3-di (methylbenzylidene) sorbitol, 2,4-di (methylbenzylidene) sorbitol, 1,3-di (ethylbenzylidene) sorbitol, 2,4-di (ethylbenzene) Nidylidene) sorbitol, 1,3-di (butylbenzylidene) sorbitol, 2,4-di (butylbenzylidene) sorbitol, 1,3-di (methoxybenzylidene) sorbitol, 2,4-di (methoxybenzylidene) sorbitol, Sorbitol-based nucleating agents such as 3-di (ethoxybenzylidene) sorbitol, 2,4-di (ethoxybenzylidene) sorbitol, 1.3-chlorobenzylidene, 2.4-methylbenzylidenesorbitol, mono (methyl) dibenzylidenesorbitol, 1 , 2,3-trideoxy-4,6: 5,7-bis-[(4-propylphenyl) methylene] -nonitol and the like.

  Examples of the antistatic agent include, for example, glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monobehenate, glycerol monooleate, diglycerol monolaurate, diglycerol monomyristate. Glycerin fatty acid esters such as state, diglycerin monopalmitate, diglycerin monostearate, diglycerin monobehenate, diglycerin monooleate, or sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan mono Polyhydric alcohol fatty acid ester antistatic agents such as sorbitan fatty acid esters such as stearate, sorbitan monobehenate, sorbitan monolaurate, lauryl diethanol Amine-based antistatic agents such as mine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine, oleyl diisopropanolamine, lauryl Diethanolamide, myristyl diethanolamide, palmityl diethanolamide, stearyl diethanolamide, behenyl diethanolamide, oleyl diethanolamide, lauryl diisopropanolamide, myristyl diisopropanolamide, palmityl diisopropanolamide, stearyl diisopropanolamide, oleyl diisopropanol Higher alcohol antistatic agents such as amide antistatic agents such as uramide, linear alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, or branched alcohols such as isostearyl alcohol Agents and the like.

  Further, an amine-based antioxidant represented by the following chemical structural formula (11) or the following general formula (12), 5,7-di-t-butyl-3- (3,4-di-methyl-phenyl)- Examples thereof include lactone antioxidants such as 3H-benzofuran-2-one and vitamin E antioxidants such as the following chemical structural formula (13).

［但し、式（４）中、Ｒ^１とＲ^２は、炭素数１４〜２２のアルキル基である。］

[However, in Formula (4), R < ¹ > and R < ² > is a C14-C22 alkyl group. ]

  In addition to these, organic peroxides, high density polyethylene, low density polyethylene, linear low density polyethylene, olefinic elastomers, non-olefinic elastomers, and the like can be blended.

[2] Method for Producing Polypropylene Masterbatch Composition The propylene resin composition of the present invention comprises a propylene-ethylene block copolymer (A), an inorganic filler or pigment (I), a fatty acid metal salt (U), and Other additives to be used as needed are put into a Henschel mixer, super mixer, ribbon blender, etc., and mixed (dry blended), and then a normal single screw extruder, twin screw extruder, Banbury mixer, It can be obtained by further melt-kneading (melt blending) in a temperature range of about 180 to 280 ° C. with a lavender or roll.

[3] Propylene resin molded product The molded product of the present invention is obtained by adding the above-mentioned polypropylene master batch composition to an arbitrary propylene resin composition in an arbitrary ratio, and then, a known injection molding machine, extrusion molding machine, It is obtained by molding with various molding machines such as a film molding machine, a blow molding machine, and a fiber molding machine.

The molded product thus obtained can be applied to uses that require high rigidity, high heat resistance, low shrinkage, low linear expansion coefficient, and all uses that require coloring.
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.), pharmaceutical containers (infusion bags, blood) Bags, prefilled syringes, kit formulations, eye drops containers, drug containers, drug containers, liquid long-term storage containers, press-through packages, strip packages, sachets, plastic vials, etc., and other various containers (ink containers, cosmetic containers, shampoo containers) , Detergent containers, etc.) Medical devices (Disposable syringes and parts thereof, catheters and tubes, vacuum blood collection tubes, surgical nonwovens, blood filters, disposable devices such as blood circuits, parts of artificial organs such as artificial lungs and colostomy, dialyzers, test tubes , Inspection kits, sutures, poultice base materials, parts for dental materials, parts for orthopedic materials, contact lens cases, etc., daily necessities (costume cases, buckets, washbasins, bath / toiletries, writing utensils, stationery, etc. , Toys, cooking utensils, other cases, etc.), automotive parts (instruments, bumpers, trims, interior parts, lamps, etc.), electrical / electronic parts (members / housing for various electrical equipment, semiconductor transport containers, optical parts, Various information media cases, solar cell encapsulants, etc.), industrial materials (containers, pallets, etc.), building materials, physics and chemistry equipment, stretched films -Time, non-stretched film, sheet, such as fibers 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, and propylene-ethylene block copolymer (A), inorganic filler or pigment (I), fatty acid metal salt (U), and As other additives (antioxidants and the like), 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 inert treatment 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 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) Peak of tan δ curve A sample cut from a 2 mm thick sheet injection-molded under the following conditions into a strip shape of 10 mm width × 18 mm length × 2 mm thickness 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 solid viscoelasticity was measured until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
<Conditions for creating specimens>
Molding machine: TU-15 injection molding machine manufactured by Toyo Machine Metal Co., Ltd. Molding machine set temperature: 80, 80, 160, 200, 200, 200 ° C. from below the hopper
Mold temperature: 40 ℃
Injection speed: 200 mm / sec (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 (thickness 2 mm, width 30 mm, length 90 mm)

(5) MFR
According to JIS K7210, the measurement was performed at a temperature of 230 ° C. and a load of 2.16 kg.

(6) Melting peak temperature Using a Seiko Instruments RDC220U as a DSC tester, taking 5.0 mg of sample, holding at 200 ° C. for 5 minutes, and then crystallizing to 40 ° C. at a rate of 10 ° C./min. Further, the melting peak temperature when melted at a heating rate of 10 ° C./min was measured.

(7) Molecular weight distribution It measured by the above-mentioned method.

(8) Master batch suitability Propylene-ethylene block copolymer (A), inorganic filler or pigment (I), fatty acid metal salt (U), and other additives (antioxidants) are dry blended with a super mixer. After that, melt kneading was performed under the following conditions, and the strand was discharged. The state of the strand obtained at that time was determined according to the following criteria.
<Strand discharge conditions>
Extruder: TEM-35B extruder manufactured by Toshiba Machine Extruder set temperature: 50, 100, 200, 250, 250, 250 ° C. from below the hopper
Discharge rate: 15kg / h
Screw rotation speed: 200rpm
Cooling water bath temperature: 10 ° C
<Strand take-off criteria>
○: The strand can be taken up to the cutter.
X: The strand was cut in the middle of drawing the strand to the cutter.
<Strand surface roughness>
○: The strand surface is smooth.
X: Many unevenness | corrugations exist in the strand surface (it can detect by hand).

[2. Materials used]
(1) Propylene-ethylene block copolymer (A)
According to the following Production Example 1, a propylene-ethylene block copolymer (PP1) satisfying the requirements of the present invention was obtained.

(Production Example 1: Production of PP1)
・ Manufacture of 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 (Mizusawa Chemical Co., Ltd. Benclay SL; average particle size = 50 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 liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g. The chemically treated silicate was dried by a kiln dryer.

Catalyst preparation:
200 g of the dry silicate obtained above was introduced into a glass reactor with an internal volume of 3 liters, and 1160 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 2.0 l of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] (according to Examples in JP-A-10-226712) 33.1 ml of a triisobutylaluminum heptane solution (0.71 M) was added to 2180 mg (3 mmol) and 870 ml of mixed heptane, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. Stir for hours.

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

-Polymerization (i) 1st superposition | polymerization process The superposition | polymerization apparatus of the flow sheet shown in FIG. 2 was used.
After introducing 35 kg of seed polymer in advance into a horizontal polymerization vessel 1 (L / D = 3.7, internal volume 100 L) having a stirring blade, nitrogen gas was circulated for 3 hours. Thereafter, the temperature was raised to 65 ° C. while introducing propylene, ethylene and hydrogen. The pressure of the reactor was set to 2.2 MPaG, and the conditions were adjusted so that ethylene / propylene (molar ratio) = 0.06 and hydrogen / propylene (molar ratio) = 0.005 in the gas, and then the prepolymerized catalyst 0.6 g / hr (amount including the prepolymerized polymer) and triisobutylaluminum as an organoaluminum compound were fed so as to be constant at 15 mmol / hr. Propylene-ethylene random copolymer (A) was produced while maintaining the reaction temperature of 65 ° C., the reaction pressure of 2.2 MPaG, and the above conditions of ethylene / propylene and hydrogen / propylene.
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 3. The unreacted gas discharged from the polymerization reactor was cooled and condensed outside the reactor system through the pipe 4 and refluxed to the polymerization reactor 1. The propylene-ethylene random copolymer (A) obtained by the main polymerization is intermittently withdrawn from the polymerization vessel 1 through the pipe 5 so that the retained level of the polymer is 65% by volume of the reaction volume. The polymerization vessel 10 was supplied. At this time, the production amount of the propylene-ethylene random copolymer (A) was 7 kg / hr. A part of the propylene-ethylene random copolymer (A) was extracted from the pipe 5 and used as a sample for analysis.

(Ii) Second polymerization step The propylene-ethylene random copolymer (A) from the first polymerization step is intermittently supplied to the horizontal polymerization vessel 10 (L / D = 3.7, internal volume 100 L) having a stirring blade. Then, copolymerization of propylene and ethylene was performed. The reaction conditions were a stirring speed of 18 rpm, a reaction temperature of 70 ° C., a reaction pressure of 2.1 MPaG, and the gas ethylene / propylene (molar ratio) = 0.4 and hydrogen / propylene + ethylene (molar ratio) = 0.0003. Adjusted. Oxygen gas was supplied from the piping 7 as a polymerization activity inhibitor for adjusting the polymerization amount of the propylene-ethylene random copolymer (B).
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the pipe 6. The unreacted gas discharged from the polymerization vessel was cooled and condensed outside the reactor system through the pipe 8 and refluxed to the polymerization vessel 10. The propylene-based block copolymer (PP1) produced in the second doubling step was intermittently withdrawn from the polymerizer 10 through the pipe 9 so that the retained level of the polymer was 50% by volume of the reaction volume.

(Iii) Analysis results of propylene-based block copolymer (PP1) The propylene-based block copolymer (PP1) obtained above has an MFR of 20 g / 10 minutes, a melting peak temperature Tm of 133 ° C., and component (A). The content is 56 wt%, the content of component (B) is 44 wt%, the MFR of component (A) is 42 g / 10 min, the ethylene content is 1.8 wt%, and the ethylene content in component (B) is 10 % By weight. Table 3 shows production conditions and physical properties of PP1.

(2) Polymer not corresponding to propylene-ethylene block copolymer (a) / propylene-ethylene random copolymer (hereinafter referred to as “PP2”):
Product name "Novatec PP MG3FQ" made by Nippon Polypro
Ziegler-Natta catalyst, MFR: 8 g / 10 min, ethylene content = 2.5 wt%

(3) Inorganic filler or pigment (I)
・ Talc (hereinafter referred to as “TALC”)
Product name "PKP-53" manufactured by Fuji Talc

(4) Fatty acid metal salt (U)
・ Zinc stearate (hereinafter referred to as “ZNST”)
NOF brand name "Zinc stearate"

(5) Antioxidants and hindered phenolic antioxidants:
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxylphenyl) propionate] methane Product name “Irganox 1010” (hereinafter referred to as “IR1010”) manufactured by BASF Corporation.
・ Phosphorus antioxidants:
Tris (2,4-di-tert-butylphenol) phosphite BASF's trade name “Irgaphos 168” (hereinafter referred to as “IF168”)

(Examples 1 to 3, Comparative Example 1)
Each above-mentioned component was prepared with the mixture ratio (all weight part) of Table 4, and the masterbatch suitability evaluation was implemented by the above-mentioned method.

  As is apparent from Table 4, Examples 1 to 3 are 100 to 300 parts by weight of the inorganic filler or pigment (ii) with respect to 100 parts by weight of the propylene-ethylene block copolymer (a) corresponding to the present invention. And 20 parts by weight of fatty acid metal salt (U). In Comparative Example 1 using a normal propylene-ethylene random copolymer, even when the blending amount of the inorganic filler or the pigment (I) is 100 parts by weight, there is a problem in the strand take-up property and the surface roughness of the strand. Compared to the difficulty in preparing the masterbatch, in the examples, even when the blending concentration of the inorganic filler or pigment (I) is increased to 300 parts by weight, the strand take-up property at the time of preparing the masterbatch and the surface roughness of the strand It can be seen that a very high concentration masterbatch can be produced by using the propylene-ethylene block copolymer (a).

  The polypropylene masterbatch composition of the present invention can contain a very high concentration of inorganic filler or pigment, and has a property that the propylene-ethylene block copolymer (a) is compatible with a propylene resin as a main material. Therefore, it has a great feature that it is difficult to break due to interface separation due to phase separation. Therefore, it is extremely useful for applications such as industrial materials, daily necessities, automobile parts, electrical parts, food containers, caps, packaging films, sheets and the like.

Claims (3)

For 100 parts by weight of the propylene-ethylene block copolymer (a) satisfying the following conditions (a-i) to (a-iii), 50 to 400 parts by weight of an inorganic filler or pigment (a), a fatty acid metal salt ( C) A polypropylene-based masterbatch composition containing 0 to 50 parts by weight.
Propylene-ethylene block copolymer (A)
(A-i) Using a metallocene-based catalyst, 30 to 95 wt% of propylene-ethylene random copolymer component (A) having propylene alone or ethylene content of 7 wt% or less in the first step, and component (A) in the second step It is a propylene-ethylene block copolymer obtained by successively polymerizing 70 to 5 wt% of the propylene-ethylene random copolymer component (B) containing 3 to 20 wt% more ethylene.
(A-ii) The melting peak temperature (Tm) measured by the DSC method is in the range of 110 to 150 ° C.
(A-iii) In the temperature-loss tangent curve obtained by solid viscoelasticity measurement, the tan δ curve has a single peak at 0 ° C. or lower.   2. The polypropylene-based masterbatch composition according to claim 1, wherein the propylene-ethylene block copolymer (a) has an MFR of 5 or more at 230 ° C. and a load of 2.16 kg. After addition of polypropylene masterbatch composition according to the propylene resin to claim 1 or 2, the manufacturing method of a molded article you mold the molded article by a molding machine.

Images