JP5796539B2 - Thermoformed body - Google Patents

Description

  The present invention relates to a thermoformed article, and more particularly, to a thermoformed article excellent in rigidity and gloss, and further excellent in heat seal characteristics, thermoformed using a laminated sheet using a propylene-based polymer.

Propylene polymer is a general-purpose resin that combines excellent moldability, mechanical properties, heat resistance, and chemical stability, and is molded by methods such as extrusion and injection molding to take advantage of its characteristics. It is used.
However, the propylene-based polymer has a drawback that the rigidity is remarkably inferior particularly to polystyrene, polyvinyl chloride and the like.
As a method for improving the rigidity of the propylene-based polymer, for example, a high melting point polypropylene is used, and further, an inorganic filler such as talc is added to improve the rigidity. It is used for molded containers for packaging and the like by thermoforming.

In recent years, an extruded sheet of a composition in which a nucleating agent is blended with a propylene homopolymer or a copolymer of propylene and an α-olefin is thermoformed to produce a lid-like thermoformed article with good transparency. Although it is used as a lid for a separately thermoformed container body, it is necessary to prevent the lid and the container body from separating in actual use.
For example, in a convenience store or the like, in order to bond a lunch box main body and a lid, methods such as bonding them with an adhesive tape or packaging with a wrap film are performed.

On the other hand, when the container body is covered, when it is covered with a film, it can be completely bonded by heat bonding (heat sealing). However, when a thermoformed body by thermoforming is used as the lid, it is difficult to heat seal at low temperatures, and complicated methods such as adhesive tape and wrap film have to be taken. When covering with a film, the contents cannot be protected due to poor rigidity.
Thus, there is a strong demand for a thermoformed container that can be heat-sealed with a lid.

  An object of the present invention is to provide a thermoformed article which is excellent in rigidity and gloss and can be heat-sealed using an extruded sheet of a propylene-based polymer in view of the above-mentioned problems of the prior art.

As a result of intensive studies to solve the above-mentioned problems, the present inventors used a specific propylene-ethylene block copolymer by multistage polymerization using a metallocene-based catalyst for the heat seal layer, and blended an inorganic filler. It has been found that by using a laminated sheet with a specific polypropylene resin, a thermoformed body that can be heat-sealed while having rigidity and gloss can be obtained, and the present invention has been completed.
The present invention provides the following thermoformed bodies.

[1] For 100 parts by weight of propylene-ethylene block copolymer (A) satisfying the following conditions (Ai) to (A-iii) in the first layer, more than 0 parts by weight of polyethylene and 100 parts by weight or less using compositions containing, Ri Do at least two-layer structure with a composition containing 5 to 100 parts by weight of an inorganic filler relative to polypropylene 100 parts by weight of higher than the melting point 0.99 ° C. in the second layer, the laminated sheet the thickness was 200 to 1,000, the heat molded article thickness of the first layer is formed by thermoforming a polypropylene laminated sheet Ru 10~100μm der.
(Ai) Using a metallocene catalyst, 30 to 95% by weight of a propylene-ethylene random copolymer component (A1) having an ethylene content of 0.3 to 7% by weight in the first step and a component ( A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5% by weight of a propylene-ethylene random copolymer component (A2) containing 3 to 20% by weight of ethylene more than A1) .
(A-ii) The melt flow rate (2.16 kg 230 ° C.) is in the range of 0.1 to 30 g / 10 minutes.
(A-iii) The temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) has a single peak at 0 ° C. or lower.
[ 2 ] The thermoformed body according to the above [1 ], wherein the thermoformed body is a container.
[ 3 ] The thermoformed body according to the above [ 2 ], wherein the lid is heat sealed to the first layer of the container.

  The thermoformed article of the present invention is extremely excellent in rigidity and gloss, can be heat-sealed and can be surely sealed, can be used particularly suitably for packaging containers for various foods, daily necessities, etc. It can also be suitably used for packaging for use or containers for storage.

It is a graph which shows the elution amount curve and elution amount integration of PP-1 used for the Example of this invention. It is a graph which shows the solid viscoelasticity measurement of PP-1 used for the Example of this invention. It is a graph which shows the solid-viscoelasticity measurement of PP-3 used for the Example of this invention.

The thermoformed article of the present invention uses a propylene-ethylene block copolymer (A) satisfying the conditions (Ai) to (A-iii) for the first layer, and a polypropylene having a melting point of 150 ° C. or higher for the second layer. It is a thermoformed body formed by thermoforming a polypropylene-based laminated sheet having at least a two-layer structure using a composition in which 5 to 100 parts by weight of an inorganic filler is blended with 100 parts by weight.
Below, resin to be used, a layer structure, a shaping | molding method, etc. are demonstrated in detail.

[1. Propylene-ethylene block copolymer (A)]
Propylene-ethylene block copolymer (A) satisfying the conditions of (Ai) to (A-iii) is used for the first layer of the laminated sheet used in the thermoformed article of the present invention.
(Ai) Using a metallocene catalyst, 30 to 95% by weight of a propylene-ethylene random copolymer component (A1) having an ethylene content of 0.3 to 7% by weight in the first step and a component ( A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5% by weight of a propylene-ethylene random copolymer component (A2) containing 3 to 20% by weight of ethylene more than A1) (A-ii) Melt flow rate (2.16 kg, 230 ° C.) is in the range of 0.1-30 g / 10 minutes (A-iii) Temperature-loss tangent (tan δ) obtained by solid viscoelasticity measurement (DMA) ) In the curve, the tan δ curve has a single peak below 0 ° C

As described above, the propylene-ethylene block copolymer (A) is obtained by using the metallocene catalyst and adding 30 to 30% of the propylene-ethylene random copolymer component (A1) having an ethylene content of 0.3 to 7% by weight in the first step. It is obtained by sequentially polymerizing 70 to 5% by weight of a propylene-ethylene random copolymer component (A2) containing ~ 95% by weight and 3 to 20% by weight of ethylene in the second step as compared with the first step.
Such a propylene-ethylene block copolymer is commonly referred to as a so-called block copolymer, and includes a blended state of the component (A1) and the component (A2). It may be bonded by polymerization to form a real block structure.

-About propylene-ethylene random copolymer component (A1)-Ethylene content E (A1) in component (A1)
The component (A1) produced in the first step has a relatively high melting point and propylene-ethylene having a crystallinity of 0.3 to 7% by weight in order to suppress stickiness and develop heat resistance. Must be a random copolymer. When the ethylene content is less than 0.3% by weight, the adhesiveness is insufficient, and when the ethylene content exceeds 7% by weight, the melting point becomes too low to deteriorate the heat resistance. Is 0.5 to 6% by weight.
Component (A1) exhibits improved adhesion, gloss and heat resistance even with propylene homopolymer, but when component (A1) is propylene homopolymer, it exhibits sufficient adhesion while maintaining gloss. Therefore, it is necessary to extremely increase the proportion of the component (A2) to be described later, which may cause remarkable deterioration such as heat resistance, stickiness and blocking.
On the other hand, when component (A1) is a propylene-ethylene random copolymer, although the melting point of component (A1) itself seems to deteriorate, the heat resistance seems to deteriorate, but it is necessary for exhibiting sufficient adhesiveness. Since the amount of the component (A2) can be suppressed, the heat resistance of the block copolymer as a whole is rather improved, and stickiness and blocking are less deteriorated, which is preferable.
Further, by reducing the melting point, it is possible to obtain an excellent sheet with very little generation of odor due to heating, etc., by obtaining sufficient molding stability even if the molding temperature during sheet molding is lowered.
From these viewpoints, the ethylene content in the component (A1) is preferably 0.5% by weight or more, more preferably 1.5% by weight or more.

.. Ratio of component (A1) in block copolymer (A) If the ratio of component (A1) in propylene-ethylene block copolymer (A) is too large, propylene-ethylene block copolymer ( The effect of improving the adhesiveness of A) cannot be sufficiently exhibited. Therefore, the proportion of component (A1) is 95% by weight or less, preferably 85% by weight or less, more preferably 70% by weight or less.
On the other hand, if the proportion of component (A1) is too small, stickiness increases, so the proportion of component (A1) is 30% by weight or more, preferably 40% by weight or more.

-About propylene-ethylene random copolymer component (A2)-Ethylene content E (A2) in component (A2)
The propylene-ethylene random copolymer component (A2) produced in the second step is a component necessary for improving the adhesiveness of the propylene-ethylene block copolymer (A).
Here, the component (A2) needs to have an ethylene content in a specific range in order to sufficiently exhibit the above effects. That is, in the block copolymer (A), the lower the crystallinity of the component (A2) relative to the component (A1), the greater the effect of improving the adhesion, and the crystallinity is the ethylene content in the propylene-ethylene random copolymer. Therefore, the ethylene content E (A2) in the component (A2) cannot be effective unless the ethylene content E (A1) in the component (A1) is 3% by weight or more, preferably 6% by weight or more, more preferably 8% by weight or more, and more ethylene than component (A1).
Here, when the difference in ethylene content between the component (A1) and the component (A2) is defined as E (gap) (= E (A2) −E (A1)), E (gap) is 3% by weight or more, Preferably it is 6 weight% or more, More preferably, it is 8 weight% or more.

  On the other hand, if the ethylene content is excessively increased to lower the crystallinity of the component (A2), the difference E (gap) between the ethylene content of the component (A1) and the component (A2) increases, and the phase is divided into a matrix and a domain. The separation structure is taken, and the transparency is lowered. This is because polypropylene originally has low compatibility with polyethylene, and even in the propylene-ethylene random copolymer, although the ethylene content is different, the mutual compatibility decreases as the difference in ethylene content increases. The upper limit of E (gap) may be within a range in which the peak of tan δ is single by solid viscoelasticity measurement described later. For this purpose, E (gap) is 20% by weight or less, preferably 18% by weight. % Or less, more preferably 16% by weight or less.

.. Ratio of component (A2) in block copolymer (A) If the ratio of component (A2) is too large, stickiness increases and deterioration of blocking occurs, so the ratio of component (A2) is 70% by weight or less It is necessary to keep it at a minimum.
On the other hand, if the proportion of component (A2) is too small, the effect of improving adhesiveness cannot be obtained. Therefore, the proportion of (A2) needs to be 5% by weight or more, preferably 15% by weight or more. Preferably it is 30 weight% or more.

-Melt flow rate (MFR) of block copolymer (A)
The MFR of the propylene-ethylene block copolymer (A) needs to be in the range of 0.1 to 30 g / 10 min. If the MFR is too low, surface roughness called shark skin or melt fracture occurs on the surface of the sheet, and the gloss and appearance are significantly impaired. On the other hand, if the MFR is too high, the molding stability of the sheet is impaired and the impact resistance is lowered, which is not preferable.
Therefore, in the present invention, the MFR of the component (A) must be in the range of 0.1 to 30 g / 10 min, and the range of 0.5 to 10 g / 10 min is the balance of molding stability, sheet appearance, and physical properties. From the viewpoint of
The melt flow rate (MFR) in the present invention is measured under the conditions of test temperature: 230 ° C., nominal load: 2.16 kg, die shape: diameter 2.095 mm, length 8.00 mm in accordance with JIS K7210 A method condition M. It is a thing.

-Peak regulation of tan δ curve by solid viscoelasticity Propylene-ethylene block copolymer (A) is a temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA). It is necessary to have one peak.
When the propylene-ethylene block copolymer has a phase separation structure, the glass transition temperature of the amorphous part contained in the component (A1) is different from the glass transition temperature of the amorphous part contained in the component (A2). , There will be multiple peaks. In this case, there arises a problem that the transparency is remarkably deteriorated.
Whether or not the phase separation structure is taken can be discriminated in the tan δ curve in the measurement of solid viscoelasticity. The avoidance of the phase separation structure that affects the transparency of the molded body has a single peak at 0 ° C. or less. Is brought about by having.
In the present invention, it is necessary that the tan δ curve in the solid viscoelasticity measurement has a single peak in order to exhibit transparency.
In addition, the example of the peak of the tan-delta curve of this invention, and the example of the tan-delta curve in case it does not have a single peak for a comparison are the polymerization manufacture example-1 (PP-1) and the polymerization manufacture example-3 ( Examples of PP-3) are shown in FIGS.

・ ・ Measurement method 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 and the loss elastic modulus are obtained by a known method, and the loss tangent (= loss elastic modulus G ″ / storage elastic modulus G ′) defined by the ratio is plotted against the temperature. Then, a tan δ curve is obtained, and in the present invention, a sharp peak is shown in a temperature range of 0 ° C. or lower. Generally, the peak of the tan δ curve at 0 ° C. or lower is for observing the glass transition of the amorphous part, and here, this peak temperature is defined as the glass transition temperature Tg (° C.).

・ Ethylene content E (A1) and E (A2) of each component (A1) and (A2) and specific amount of each component W (A1) and W (A2) Each ethylene of component (A1) and (A2) The content and the amount of components can be specified by the material balance at the time of polymerization (material balance), but in order to specify these more accurately, it is desirable to use the following analysis (fractionation method).

..Specification of each component amount W (A1) and W (A2) by temperature-temperature elution fractionation method (TREF) ... Temperature-temperature elution fractionation method Temperature rise of crystallinity distribution of propylene-ethylene random copolymer The technique of evaluation by elution fractionation (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) has a large difference in crystallinity between the components (A1) and (A2), and each crystallinity distribution is narrow by being produced using a metallocene catalyst. Therefore, there are very few intermediate components between the two, and both can be accurately separated by TREF.

In the TREF elution curve obtained as a plot of elution amount (dWt% / dT) against temperature by the temperature rising elution fractionation method (TREF) in the temperature range of −15 ° C. to 140 ° C. using o-dichlorobenzene solvent, (A1) and (A2) show their elution peaks at the respective temperatures T (A1) and T (A2) due to the difference in crystallinity, and since the difference is sufficiently large, the intermediate temperature T (A3) (= {T Separation is almost possible at (A1) + T (A2)} / 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 (A2) is very low or an amorphous component, There may be no peak within the range (at this time, the concentration of the component (A2) dissolved in the solvent is detected at the lower limit of the measurement temperature (ie, −15 ° C.)). In this case, T (A2) is considered to exist below the lower limit of the measurement temperature, but the value cannot be measured. In such a case, T (A2) is the lower limit of the measurement temperature − It is defined as 15 ° C.
Here, if the integrated amount of the components eluted up to T (A3) is defined as W (A2) wt%, and the integrated amount of the portion eluted at T (A3) or higher is defined as W (A1) wt%, W (A2) Almost corresponds to the amount of the low-crystalline or amorphous component (A2), and the integrated amount W (A1) of the component eluted at T (A3) or higher is the component (A1) having a relatively high crystallinity. Almost corresponds to the amount of. In addition, the example of a TREF elution curve is illustrated by FIG. 1 as an example in superposition | polymerization manufacture example A-1.

... TREF measurement method In the present invention, specifically, measurement is performed 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. Then, a component of -15 ° C o-dichlorobenzene (containing 0.5 mg / ml BHT), which is a solvent, flows through the column at a flow rate of 1 ml / min, and is dissolved in -15 ° C o-dichlorobenzene in the TREF column. Is eluted for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.

..Specification of ethylene content E (A1) and E (A2) in each component: Separation of components (A1) and (A2) Preparative type based on T (A3) obtained by TREF measurement Using a temperature rising column fractionation method using a fractionation device, the soluble component (A2) in T (A3) and the insoluble component (A1) in T (A3) are fractionated, and the ethylene content of each component by NMR Ask for.
The temperature rising column fractionation method is a measurement method disclosed in, for example, Macromolecules 21 314-319 (1988). Specifically, the following method was used in the present invention.

... Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 ml of a sample o-dichlorobenzene solution (10 mg / ml) 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 (A3) 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 (A3), 800 ml of o-dichlorobenzene of T (A3) is allowed to flow at a flow rate of 20 ml / min, whereby components soluble in T (A3) present 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 o-dichlorobenzene as a solvent at 140 ° C. is flowed at a flow rate of 20 ml / min. , T (A3) is eluted and recovered.
The polymer-containing solution 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 collected by filtration and dried overnight in a vacuum dryer.

· · · ¹³ C-NMR according to the measurement the fractionated by components obtained ethylene content (A1) (A2) an ethylene content of each was measured according to the following conditions by complete proton decoupling ^method, 13 C- It is determined by analyzing the NMR spectrum.
Model: GSX-400 manufactured by JEOL Ltd. or equivalent device (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 follow the notation of Carman et al. (Macromolecules 10 536 (1977)), P represents a methyl carbon, S represents a methylene carbon, and T represents a methine carbon.

Hereinafter, when “P” is a propylene unit in a copolymer chain and “E” is an ethylene unit, six types of triads of PPP, PPE, EPE, PEP, PEE, and EEE may exist in the chain. As described in Macromolecules 15 1150 (1982) and the like, 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 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 a minute peak shown in Table 2.

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 obtained by using the relational expressions (1) to (7) as in the analysis of the copolymer produced with a Ziegler-Natta catalyst that does not substantially contain a heterogeneous bond. I will do it.
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 entire block copolymer is calculated from the ethylene contents E (A1), E (A2) and TREF of the components (A1) and (A2) measured above. Is calculated by the following formula from the weight ratio W (A1) and W (A2)% by weight.
E (W) = {E (A1) × W (A1) + E (A2) × W (A2)} / 100 (% by weight)

[2. Producing method of propylene-ethylene block copolymer (A)]
(1) Metallocene catalyst The method for producing the propylene-ethylene block copolymer (A) of the present invention 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 block copolymer, but also in the propylene-ethylene block copolymer used in the present invention, In order to suppress stickiness and bleed-out and to exhibit sufficient transparency in sheet molding, it is necessary to polymerize using a metallocene catalyst that can narrow the molecular weight and crystallinity distribution, and Ziegler-Natta The fact that the excellent propylene-ethylene block copolymer of the present invention cannot be obtained with the system catalyst is also apparent from the comparison of Examples and Comparative Examples described later.

The type of the metallocene-based catalyst is not particularly limited as long as the block copolymer (A) having the performance of the present invention can be produced. In order to satisfy the requirements of the present invention, for example, the following is shown. It is preferable to use a metallocene catalyst comprising such components (a) and (b) and optionally used component (c).
Component (a): At least one metallocene transition metal compound selected from the transition metal compounds represented by the general formula (1) Component (b): At least one selected from the following (b-1) to (b-4) (B-1) an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation, or (B-3) Solid acid fine particles (b-4) Ion exchange layered silicate Component (c): Organoaluminum compound.

(1-1) Component (a)
As the component (a), at least one metallocene transition metal compound selected from transition metal compounds represented by the following general formula (1) can be used.
_{Q (C 5 H 4 -aR 1} ) (C 5 H 4 -bR 2) MeXY (1)
Here, Q represents a divalent binding 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 hydrogen atoms. , A halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, and X and Y are each independently, that is, the same or different Good. R ₁ and R _{2 each} represent hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . 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 or 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 represent hydrogen, a hydrocarbon group, a halogenated hydrocarbon group, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. . 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, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group or phosphorus-containing hydrocarbon group include methoxy group, ethoxy group, phenoxy group, trimethylsilyl group. Typical examples include a group, a diethylamino group, a diphenylamino group, a pyrazolyl group, an indolyl group, a dimethylphosphino group, a diphenylphosphino group, a diphenylboron group, and a dimethoxyboron group. In these, it is preferable that it is a C1-C20 hydrocarbon group, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, and a butyl group. By the way, adjacent R ₁ and R ₂ may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.
Me is a metal atom selected from titanium, zirconium and hafnium, preferably zirconium and hafnium.

  Among the components (a) described above, preferred for the production of the propylene polymer of the present invention is a substituted cyclopentadienyl group crosslinked with a silylene group, a germylene group or an alkylene group having a hydrocarbon substituent. A transition metal compound comprising a ligand having a substituted indenyl group, a substituted fluorenyl group, or a substituted azulenyl group, particularly preferably a 2,4-position crosslinked by a silylene group having a hydrocarbon substituent or a germylene group It is a transition metal compound comprising a ligand having a substituted indenyl group and a 2,4-position substituted azulenyl group.

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.

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

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

(1-4) Formation of catalyst Component (a), component (b) and, if necessary, component (c) are brought into contact to form a catalyst. The contact method is not particularly limited, but the contact can be made in the following order. 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) 5) Contact three components simultaneously

(1-5) Component Amount The amount of component (a), (b) and (c) 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.

(1-6) Prepolymerization It is preferable that the catalyst is subjected to a prepolymerization treatment in which a small amount of the olefin is brought into contact with the catalyst 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, but may be dried if necessary.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

(2) Production method (2-1) Sequential polymerization In producing the propylene-ethylene block polymer (A), the crystalline propylene-ethylene random copolymer component (A1) and the low crystalline or amorphous propylene- It is necessary to sequentially polymerize the ethylene random copolymer component (A2) for the reasons described above.
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 (A1) and component (A2) 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 the continuous method, 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 (A1) and the component (A2), but 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 (A1) and component (A2).

(2-2) Polymerization process As the polymerization process (polymerization method), 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 the low crystalline or amorphous propylene-ethylene random copolymer component (A2) is easily soluble in organic solvents such as hydrocarbons and liquefied propylene, it is desirable to use a gas phase method for the production of the component (A2).
Any process may be used for the production of the crystalline propylene-ethylene random copolymer component (A1), but in the case of producing the component (A1) having a relatively low crystallinity, adhesion, etc. In order to avoid this problem, it is desirable to use a vapor phase method.
Therefore, the crystalline propylene-ethylene random copolymer component (A1) is first polymerized by a bulk method or a gas phase method using a continuous method, followed by a low crystalline or amorphous propylene-ethylene random copolymer elastomer. It is most desirable to polymerize component (A2) by a gas phase method.

(2-3) 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.
Although the polymerization pressure varies depending on the process to be selected, it can be used without any problem as long as it is in a pressure range usually used. Specifically, a range of greater than 0 to 200 MPa, more preferably 0.1 MPa to 50 MPa can be used. At this time, an inert gas such as nitrogen can be coexisted.
In the case where the sequential polymerization of the component (A1) in the first step and the component (A2) 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 a reactor that performs 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 technical studies have been made on this technique, and examples thereof include Japanese Patent Publication Nos. 63-54296, 7-25960, and 2003-2939. It is desirable to apply the method to the present invention.

[3. Method for controlling component of propylene-ethylene block copolymer (A)]
Each element of the propylene-ethylene block copolymer (A) is controlled as follows, and can be manufactured to satisfy the constituent requirements required for the propylene-ethylene block copolymer (A) of the present invention. .

(1) About component (A1) About crystalline propylene-ethylene random copolymer component (A1), it is necessary to control ethylene content E (A1).
In the present invention, in order to control E (A1) 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 (A1) having the ethylene content E (A1) required by adjusting the supply ratio is added. Can be manufactured. For example, when E (A1) is controlled to 0 to 7% by weight, the supply weight ratio of ethylene to propylene may be in the range of 0 to 0.3, preferably in the range of 0 to 0.2.

(2) Component (A2) For the low crystalline or amorphous propylene-ethylene random copolymer component (A2), it is necessary to control the ethylene content E (A2).
In the present invention, in order to control E (A2) within a predetermined range, the ratio of ethylene supply to propylene in the second step may be controlled in the same manner as E (A1).
For example, when E (A2) is controlled to 5 to 20% by weight, the supply weight ratio of ethylene to propylene may be in the range of 0.01 to 5, preferably in the range of 0.05 to 2.

(3) About W (A1) and W (A2) The amount W (A1) of component (A1) and the amount W (A2) of component (A2) are the production amounts of the first step for producing component (A1). It can be controlled by changing the ratio of the production amount of the component (A2). For example, in order to increase W (A1) and decrease W (A2), the production amount of the second step may be reduced while maintaining the production amount of the first step, which shortens the residence time of the second step. It can be easily controlled by lowering the polymerization temperature or increasing the amount of the polymerization inhibitor. The reverse is also true.
When actually setting the conditions, it is necessary to consider the activity decay. That is, in the range of the ethylene content E (A1) and E (A2) carried out in the present invention, generally, the polymerization activity increases when the ratio of ethylene supply to propylene is increased in order to increase the ethylene content. 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, the production amount W (A1) is lowered in the first step, and the polymerization is performed as necessary. Lower the temperature and / or shorten the polymerization time (residence time), or increase the ethylene content E (A2) in the second step, increase the production W (A2), and raise the polymerization temperature as necessary And / or conditions may be set in such a way as to increase the polymerization time (residence time).

(4) Glass transition temperature Tg In the propylene-ethylene block copolymer used in the present invention, as described above, the glass transition temperature Tg needs to have a single peak. In order for Tg to have a single peak, the difference [E] gap between the ethylene content E (A1) in component (A1) and the ethylene content E (A2) in component (A2), ie, E (A2) -E (A1) is set to 20% by weight or less, preferably 18% by weight, more preferably 16% by weight or less, and E (gap) is reduced to a range where Tg becomes a single peak in actual measurement. That's fine.
Depending on the ethylene content E (A1) of the crystalline copolymer component (A1), the ethylene content E (A2) of the low crystalline or non-crystalline copolymer component (A2) is within an appropriate range. By setting the supply weight ratio of ethylene to propylene during the polymerization of component (A2), it is possible to obtain a polymer having a predetermined [E] gap.
The Tg in the case of a block copolymer that does not have a phase separation structure as in the present invention is the ethylene content E (A1) in the component (A1) and the ethylene content E (A2) in the component (A2). , And the amount ratio of both components. In the present invention, the amount of the component (A2) is 5 to 70% by weight, but in this range, Tg is more strongly affected by the ethylene content E (A2) in the component (A2).
That is, Tg reflects the glass transition of the amorphous part. In the block copolymer (A) of the present invention, the component (A1) has crystallinity and relatively few amorphous parts. This is because the component (A2) is low crystalline or amorphous and most of it is an amorphous part.
Therefore, the value of Tg is almost controlled by E (A2), and the control method of E (A2) is as described above.

(5) Melt Flow Rate (MFR) In the propylene-ethylene block copolymer (A) used in the present invention, the crystalline copolymer component (A1) and the low crystalline or non-crystalline are used in order to maintain transparency. Since it is essential that the crystalline copolymer elastomer component (A2) is compatible, the viscosity of the component (A1) ([η] A1), the viscosity of the component (A2) ([η] A2), An apparent viscosity mixing rule is generally established between the viscosity of the entire propylene-ethylene block copolymer (A) ([η] W). That is,
Log [η] W = {W (A1) × Log [η] A1 + W (A2) × Log [η] A2} / 100
Is generally established. Generally, since there is a certain correlation between MFR and [η], from the viewpoint of adhesiveness and heat resistance, [η] A2, W (A1), and W (A2) are set first. The MFR can be freely controlled by changing [η] A1 according to the above equation.

[4. Polyethylene for first layer compounding]
In the first layer of the present invention, a composition in which 0 to 100 parts by weight of polyethylene is blended with 100 parts by weight of the propylene-ethylene block copolymer (A) is also preferable. By blending a predetermined amount of polyethylene, it is possible to control the peel strength when heat-sealing.
The polyethylene used here may be high-pressure low-density polyethylene, linear low-density polyethylene, high-density polyethylene, or the like, but high-pressure low-density polyethylene is preferred from the viewpoint of not impairing transparency.
As a specific example of the high-pressure method low-density polyethylene, trade name Novatec (registered trademark) LD manufactured by Nippon Polyethylene Co., Ltd. can be used.
If the blending ratio of polyethylene exceeds the above range, the sealing strength is insufficient and the performance of the present invention cannot be exhibited, which is not preferable.

[5. Polypropylene for second layer]
The polypropylene (B) having a melting point of 150 ° C. or higher used for the second layer of the present invention can be a propylene homopolymer, or a propylene-α-olefin random or block copolymer containing 95% by weight or more of propylene. As the α-olefin, ethylene is preferable.
Polypropylene (B) can be used with any of the Ziegler-Natta catalyst or metallocene catalyst, and can be used with any of the production methods such as slurry method, bulk method and gas phase method.
The melting point of polypropylene (B) is 150 ° C. or higher, preferably 155 ° C. or higher, more preferably 158 ° C. or higher, and usually about 170 ° C. or lower. When the melting point is lower than 150 ° C., not only the rigidity is lowered, but also melted at the time of heat sealing, and the shape of the molded body is impaired.

The MFR of polypropylene (B) is preferably 0.1 to 20 g / 10 minutes, more preferably 0.2 to 10 g / 10 minutes, and further preferably 0.3 to 5 g / 10 minutes.
If the MFR exceeds 20 g / 10 minutes, the drawdown becomes large at the time of extrusion sheet molding, and the molding tends to be difficult. If the MFR is less than 0.1 / 10 minutes, the surface of the extruded sheet has a sharkskin-like appearance abnormality. Tends to occur, and transparency is easily impaired.
As specific products of polypropylene (B), for example, product names Novatec (registered trademark) PP and WINTEC (registered trademark) manufactured by Nippon Polypro Co., Ltd. can be preferably used.

[6. Inorganic filler for second layer]
As the inorganic filler used for the second layer, talc, calcium carbonate, mica, glass fiber, barium sulfate and the like are preferably mentioned. Among these, talc is most preferable in terms of price and rigidity.
The compounding ratio of the inorganic filler is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, and particularly preferably 20 to 70 parts by weight with respect to 100 parts by weight of the polypropylene (B).
If the blending amount of the inorganic filler is less than 5 parts by weight, the rigidity is insufficient and the effect of the present invention is not achieved. On the other hand, if the blending amount exceeds 100 parts by weight, the impact strength is undesirably lowered.

[7. Other additives]
In addition to these essential components, additional components can be added to the first layer and the second layer of the laminated sheet in the present invention as long as the effects of the present invention are not impaired. As these additional components, antioxidants, nucleating agents, light stabilizers, UV absorbers, lubricants, antistatic agents, antifogging agents, neutralizing agent colorants, fillers usually used for propylene resins And other additives, synthetic resins such as other polyolefins and polystyrene, and the like.

[8. Molded body and manufacturing method thereof]
The thickness of the laminated sheet in the present invention is preferably 200 to 1000 μm, and the thickness of the first layer is preferably 10 to 100 μm.
When the laminated sheet thickness is less than 200 μm, the rigidity of the thermoformed product tends to be impaired, and when the thickness exceeds 1000 μm, the heating time for thermoforming becomes long and the thermoformability tends to be poor.
Further, when the thickness of the first layer is less than 10 μm, the adhesive strength is easily impaired, and when the thickness is more than 100 μm, the rigidity of the molded body is likely to be insufficient.

The laminated sheet is preferably obtained by a multilayer extrusion sheet forming method usually used for forming polypropylene.
The multilayer extrusion sheet forming method is a method of extruding a sheet from a coat hanger die through a feed block or a multi-manifold from two or more single or twin screw extruders. The extruded sheet is cooled and solidified by pressing with an air knife, an air chamber, a hard rubber roll, a steel belt, and a metal roll on the surface of the metal roll (in which cooling water and oil are circulated). It is also possible to cool and solidify both sides of the sheet with a steel belt.

As long as the effect of this invention is not impaired, another layer, such as a candle, a gas barrier, oxygen adsorption, light shielding, and a regeneration process, can also be added to a laminated sheet.
The laminated sheet may be coated with a coating agent such as an antistatic agent, an antifogging agent, or a lubricant as long as the effect of the present invention is not impaired.

Further, the extruded sheet-molded laminated sheet is processed into various thermoformed bodies by thermoforming such as hot platen pressure forming, vacuum forming, vacuum pressure forming, and solid phase pressure forming.
Since the thermoformed body using the laminated sheet of the present invention is extremely excellent in rigidity, it is a packaging product for foods, cosmetics, daily necessities, and electronic parts such as IC chips and liquid crystal panels that particularly require shape retention and heat resistance. Ideal for industrial components such as trays, plastic cardboards, and display boxes.

As the thermoformed body using the laminated sheet of the present invention, a packaging container formed by thermoforming the laminated sheet into a container shape is preferable.
The shape and size of the packaging container are not particularly limited, and the planar shape can be various shapes such as a quadrilateral, a circle, and an ellipse, and the three-dimensional shape is also a box shape (particularly a lunch box shape), a tray. Various shapes such as a shape and a bowl shape can be used. Furthermore, a type in which the lid and the container main body are separate is also preferable.

In the case where the lid and the container main body are separate types, the lid material is preferably a lid material made of a laminated sheet provided with a heat-adhesive resin (heat seal) layer on the container main body side. It is preferable to use a layer using a propylene-ethylene copolymer as the (heat seal) layer.
Furthermore, the heat adhesive resin layer of the lid material is made of the same material as that of the first heat adhesive resin layer, so that when the lid material is heat sealed to the opening of the container body, the seal portion is deformed. The container package that can be reduced, can perform clean and stable heat sealing, stores contents such as cooked foods, and is heat-sealed with a lid material is extremely excellent in hermeticity.

  There are no particular restrictions on the use of such packaging containers, but lunch boxes, sugar beet containers, trays, cups, cases, food packs, range-up containers, frozen food containers, fitting containers, steaming containers, general containers, Etc. can be suitably used. Moreover, it can be suitably used in the general packaging field as the food packaging field and others.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, the measuring method and evaluation method of the physical property values used in each example and comparative example are as follows.

1) Melt flow rate (MFR, unit: g / 10 min)
According to JIS K7210 A method condition M, it measured on condition of the following.
Test temperature: 230 ° C
Nominal weight: 2.16kg
Die shape: Diameter 2.095mm Length 8.00mm

2) TREF
A sample is dissolved in o-dichlorobenzene (containing 0.5 mg / ml BHT) at 140 ° C. to prepare 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 caused to flow through the column at a flow rate of 1 ml / min, and components dissolved in o-dichlorobenzene at −15 ° C. in the TREF column. Elution is performed for 10 minutes, and then the column is linearly heated to 140 ° C. at a heating rate of 100 ° C./hour to obtain an elution curve.

[Device used]
(TREF part)
TREF column: 4.3 mmφ × 150 mm stainless steel column Column filler: 100 μm Surface inactive glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is cooled by water)
Temperature distribution: ± 0.5 ° C
Temperature controller: Chino Corporation Digital Program Controller KP1000 (Valve Oven)
Heating method: Air bath oven Measurement temperature: 140 ° C
Temperature distribution: ± 1 ° C
Valve: 6-way valve 4-way valve (sample injection part)
Injection method: Loop injection method Injection amount: Loop size 0.1ml
Inlet heating method: Aluminum heat block Measurement temperature: 140 ° C
(Detection unit)
Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Detection wavelength: 3.42 μm
High-temperature flow cell: LC-IR micro flow cell Optical path length 1.5mm
Window shape 2φ × 4mm oval synthetic sapphire window Measurement temperature: 140 ° C
(Pump part)
Liquid feed pump: SSC-3461 pump manufactured by Senshu Kagaku Co. [Measurement conditions]
Solvent: o-dichlorobenzene (containing 0.5 mg / ml BHT)
Sample concentration: 5 mg / ml
Sample injection volume: 0.1 ml
Solvent flow rate: 1 ml / min

3) Measurement of solid viscoelasticity A sample cut into a strip of 10 mm width × 18 mm length × 2 mm thickness from a 2 mm thick sheet injection-molded under the following conditions was used. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised stepwise from −60 ° C., and the measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.
[Preparation of specimen]
Standard number: JIS-7152 (ISO294-1)
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)

4) Melting point (Tm)
Using a Seiko DSC, take 5.0 mg of sample, hold at 200 ° C. for 5 minutes, crystallize to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further melt at a rate of temperature increase of 10 ° C./min. The melting peak temperature was Tm. (Unit: ° C)
5) Content of ethylene The content of ethylene is a value measured by ¹³ C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene

6) Tensile modulus (unit: MPa)
The tensile elastic modulus of the sheet was measured in both the MD direction and the TD method according to JIS K7127.
7) Surface gloss (unit:%)
For the surface gloss, the gloss on the first layer side of the thermoformed container was measured at a 60 ° angle in accordance with JIS Z8741.
8) Seal strength of the container (unit: kgf)
It carried out by the method of a postscript.

<Production of propylene-ethylene block copolymer>
[Production Example PP-1]
[Polymerization Production Example A-1]
・ Preparation of catalyst for pre-polymerization (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 (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing solution (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.

(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer. Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical inner diameter 50mm Heating zone 550mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt 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. To this, 200 g of dry silicate was introduced, 1,160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added and stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry. Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 ML) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, 187 ml of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium and 2,180 mg (0.3 mM) of mixed heptane Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.

(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 ML) and 5600 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then 5600 ml of the supernatant was removed. This operation was further repeated 3 times. When the component analysis of the final supernatant was conducted, the concentration of the organoaluminum component was 1.23 mmol / liter, the Zr concentration was 8.6 × 10 ⁻⁶ g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 ML) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.

· In the first step the first step, propylene using a stirring device with liquid phase polymerization vessel having an internal volume of 0.4 m ³ - was carried ethylene random copolymer. Liquefied propylene, liquefied ethylene, and triisobutylaluminum were continuously fed at 90 kg / hour, 4.2 kg / hour, and 21.2 g / hour, respectively. The hydrogen supply amount was adjusted so that the MFR in the first step became a target value. Further, the above prepolymerized catalyst was supplied as a catalyst (excluding the weight of the prepolymerized polymer) so as to be 6.9 g / hour. The polymerization tank was cooled so that the polymerization temperature was 45 ° C.
When the propylene-ethylene random copolymer obtained in the first step was analyzed, BD (bulk density) was 0.46 g / cc, MFR was 2.0 g / 10 min, and ethylene content was 3.7% by weight. It was.

-Second step In the second step, propylene-ethylene random copolymerization was carried out using a stirred gas phase polymerization tank having an internal volume of 0.5 m ³ . The slurry containing polymer particles was continuously withdrawn from the liquid phase polymerization tank in the first step, flushed with liquefied propylene, and then pressurized with nitrogen and continuously supplied to the gas phase polymerization tank.
The polymerization tank was controlled so that the temperature was 80 ° C. and the total partial pressure of propylene, ethylene, and hydrogen was 1.5 MPa. At that time, the concentrations of propylene, ethylene, and hydrogen in the total partial pressure of propylene, ethylene, and hydrogen were controlled to be 66.99 vol%, 32.99 vol%, and 150 volppm, respectively.
Furthermore, ethanol was supplied to the gas phase polymerization tank as an activity inhibitor. The supply amount of ethanol was set to 0.3 mol / mol with respect to aluminum in TIBA supplied along with the polymer particles supplied to the gas phase polymerization tank.
When the propylene-ethylene block copolymer thus obtained was analyzed, the activity was 7.6 kg / g-catalyst, the BD was 0.41 g / cc, the MFR was 2.0 g / 10 min, and the ethylene content was 8.7. % By weight.

(Production of composition)
The following antioxidant and neutralizing agent were added to 100 parts by weight of the block copolymer powder obtained in Polymerization Production Example A-1 using a Henschel mixer, and mixed at 750 rpm for 1 minute at room temperature.
Antioxidant:
Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (trade name “Irganox 1010” manufactured by Ciba Specialty Chemicals Co., Ltd.) 05 parts by weight Tris (2,4-di-t-butylphenyl) phosphite (Ciba Specialty Chemicals, trade name “IRGAFOS 168”) 0.10 parts by weight Neutralizing agent:
Calcium stearate (Nippon Yushi Co., Ltd., trade name “Calcium stearate G”)
0.05 parts by weight

  Furthermore, in a PCM twin screw extruder manufactured by Ikegai Seisakusho with a screw diameter of 30 mm, the melted resin extruded from the strand die is melt-kneaded at a screw rotation speed of 200 rpm, a discharge rate of 10 kg / hr, and an extruder temperature of 190 ° C. The solution was taken up while being cooled and solidified, and the strand was cut using a strand cutter to obtain a propylene-ethylene block copolymer composition (PP-1).

(analysis)
Using the obtained PP-1, TREF, ethylene content, DSC, GPC, and solid viscoelasticity were measured.
Table 4 shows each data obtained by the measurement.
From the measurement results obtained, it can be said that PP-1 satisfies all the requirements as component (A).
Here, with respect to the TREF measurement result of PP-1, in order to show the positioning of each parameter, an elution curve is illustrated in FIG. Similarly, in order to show the position of each parameter in the solid viscoelasticity measurement results, FIG. 2 illustrates changes in storage elastic modulus G ′, loss elastic modulus G ″ and loss tangent tan δ with respect to temperature.

[Production Examples PP-2 to 3]
[Polymerization Production Examples A-2 to 3]
In the same manner as in Polymerization Production Example A-1, the polymerization conditions were changed to produce a propylene-ethylene block copolymer. The polymerization conditions and polymerization results are shown in Table 3.
Using the obtained polymer powder, PP-2 to 3 were obtained by the same additive formulation and mixing kneading conditions as in Production Example PP-1. Various analysis results are shown in Table 4.

[Production Example PP-4]
[Polymerization Production Example A-4]
In Polymerization Production Example A-1, polymerization was carried out in the same manner as in Polymerization Production Example A-1, except that only the first step was carried out without carrying out the second step, to produce a propylene-ethylene random copolymer. went. The polymerization conditions and polymerization results are shown in Table 3.
Using the obtained polymer powder, PP-4 was obtained by the same additive formulation and granulation conditions as in Production Example PP-1. Various analysis results are shown in Table 4.

[Production Example PP-5]
[Polymerization Production Example A-5]
(Preparation of solid catalyst component)
2,000 milliliters of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly purged with nitrogen, and then 2.6 mol of MgCl ₂ and 5.2 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. The mixture was introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 320 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.
Next, 4,000 milliliters of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 1.46 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 25 ml of n-heptane was mixed with 2.62 mol of SiCl ₄ , introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.15 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 11.4 mol of TiCl ₄ was introduced and reacted at 110 ° C. for 3 hours. After completion of the reaction, the solid component (A1) was obtained by washing with n-heptane. The titanium content of this solid component was 2.0% by weight.
Next, the autoclave having an internal volume of 16 liters having a stirring and temperature control device was sufficiently replaced with nitrogen, and 5,000 milliliters of n-heptane purified in the same manner as above was introduced into the solid component (A1 ) Was introduced, and 0.875 mol of SiCl ₄ was introduced and reacted at 90 ° C. for 2 hours. After completion of the reaction, 0.15 mol of (CH ₂ ═CH) Si (CH ₃ ) ₃ , 0.075 mol of (t-C ₄ H ₉ ) (CH ₃ ) Si (OCH ₃ ) ₂ and Al (C ₂ H ₅ ) ₃ 0.4 mol was sequentially introduced and contacted at 30 ° C. for 2 hours. After completion of the contact, the solid catalyst component (A) mainly composed of magnesium chloride was obtained by thoroughly washing with n-heptane. The titanium content of this product was 1.8% by weight.

(Preliminary polymerization)
An autoclave with an internal volume of 16 liters equipped with a stirring and temperature control device was sufficiently replaced with nitrogen. Here, 100 g of the n-heptane slurry of the solid catalyst component (A) prepared above was introduced as the solid catalyst component (A), and n-heptane was further introduced to adjust the liquid level to 5000 ml. Next, the temperature in the tank was adjusted to 15 ° C., and 0.1 mol of triethylaluminum / n-heptane solution (10 wt%) was added as Al (C ₂ H ₅ ) ₃ . Thereafter, prepolymerization was performed by supplying propylene at a rate of 50 g / hour for 2 hours. After completion of the prepolymerization, the residual monomer was purged and the solid catalyst was thoroughly washed with n-heptane. After the washing, drying under reduced pressure was performed to obtain a prepolymerized catalyst. The prepolymerized catalyst contained 2.0 g of polypropylene per 1 g of the catalyst.
Polymerization Production Example A-1 except that the prepolymerization catalyst thus obtained was used, and triethylaluminum was continuously fed at 10 g / hour instead of triisobutylaluminum, and the polymerization conditions shown in Table 3 were used. Propylene-ethylene block copolymer was produced in the same manner as described above. The polymerization results are shown in Table 3.
Using the obtained polymer powder, PP-5 was obtained by the same additive formulation and granulation conditions as in Production Example PP-1. Various analysis results are shown in Table 4.

<Other ingredients>
-The following polyethylene was used as polyethylene mix | blended with a 1st layer.
Polyethylene (PE-1):
Product name "Novatec (registered trademark) LD LB440HB", manufactured by Nippon Polyethylene
High pressure polyethylene, MFR = 2.8 g / 10 min, density = 0.925 g / cm ³
-The following polypropylene (B-1) was used as the polypropylene resin for the second layer, and the following talc was used as the inorganic filler to be blended in the second layer.
Polypropylene (B-1):
Product name “NOVATEC (registered trademark) PP EA9” manufactured by Nippon Polypro Co., Ltd.
Propylene homopolymer, MFR = 0.5 g / 10 min Talc:
Product name “PKP53S” manufactured by Fuji Talc Co., Ltd., average particle size 14 μm

(Example 1 (Reference Example 1) )
Manufacture of Extruded Sheet PP-1 is placed in the first extruder in a multi-layer extrusion sheet molding machine having two screw diameter 40 mm extruders heated to 230 ° C., and polypropylene B- 1 and the first extruder is extruded on the upper surface of the sheet and the second extruder is extruded on the lower surface of the sheet through the feed block, and is extruded horizontally from a coat hanger die having a width of 600 mm and a die lip interval of 0.8 mm. The sheet was cooled and solidified by being sandwiched between mirror-finished hard chrome-plated metal rolls in which water at 0 ° C. was circulated to produce a sheet having a thickness of 0.5 mm. Table 5 shows the measurement results of the physical properties of the obtained laminated sheet.

  Furthermore, the laminated sheet is heated from above and below with a ceramic heater at 450 ° C. using an indirectly heated vacuum / pressure forming machine (manufactured by Asano Laboratories, Cosmic forming machine), so that the first layer of the sheet is on the inside, A round container molded body was vacuum formed using a mold having a diameter of 10 cm and a depth of 3 cm. Table 5 shows the measurement results of the physical properties of the obtained molded container.

Separately, a single-layer sheet made of polypropylene (Nippon Polypro Co., Ltd., propylene-ethylene copolymer, trade name “WINTEC WEG5TF”, MFR = 3.5 g / 10 min) is vacuum-compressed and formed into a 10 cm diameter, depth A 2 cm round lid was prepared.
The container molded body was covered with a round lid (so that the first layer was in contact with the lid), and a temperature of 200 ° C., a pressure of 5 kg / cm ² , and a heating time of 5 with a semi-automatic pack sealer SN-1 manufactured by Shinwa Machinery Co., Ltd. Second, the container and the lid were heat-sealed at an adhesive width of 5 mm.
Further, the heat-sealed portion was cut out at a width of 15 mm, and the lid and the container were peeled off at a rate of 500 mm / min with a tensile tester Autograph 5KNG manufactured by Shimadzu Corporation, and the seal strength was measured.
The seal strength is preferably in the range of ^{2 to} 5 kg / cm ² when peeled.
If it is below this range, it may be peeled off at the stage of transportation or the like, and if it exceeds this range, it will be difficult for the user to peel off.
The results are shown in Table 5.

(Examples 2 to 4 (Example 4 is Reference Example 2) )
Evaluation was conducted in the same manner as in Example 1 except that the formulation and the addition amount thereof were changed as shown in Table 1.
The results are shown in Table 5.

(Comparative Examples 1-6)
Evaluation was conducted in the same manner as in Example 1 except that the formulation and the addition amount thereof were changed as shown in Table 5.
The results are shown in Table 6.

As is clear from these results, it can be seen that the thermoformed bodies of Examples 1 to 4 have high tensile elastic modulus (high rigidity), high gloss, and appropriate seal strength.
In contrast, the thermoformed body of Comparative Example 1 using a block copolymer having a plurality of peaks in the tan δ curve had extremely poor gloss. The thermoformed bodies of Comparative Examples 2 and 3 have a low sealing strength and cannot provide excellent packaging. In Comparative Example 4, talc was not used, but the rigidity was extremely low.
The comparative example 5 is a layer structure which does not use a 1st layer, and it turns out that the molded object obtained from this has low sealing strength, and cannot obtain the outstanding packaging. Comparative Example 6 is a sheet using only the first layer, but it can be seen that the thermoformed body obtained therefrom cannot be used because the thermoformed body is not only less rigid but also melted during sealing.

  The thermoformed article of the present invention is excellent in rigidity and gloss, and further has excellent heat sealing properties. Therefore, packaging products such as foods, cosmetics, and daily necessities that particularly require shape retention and heat resistance, and electronic components such as IC chips and liquid crystal panels. The present invention can also be used widely in industrial members such as packaging trays.

Claims (3)

The first layer contains more than 0 parts by weight of polyethylene and not more than 100 parts by weight with respect to 100 parts by weight of the propylene-ethylene block copolymer (A) satisfying the following conditions (Ai) to (A-iii): using a composition, Ri Do at least two-layer structure with a composition containing 5 to 100 parts by weight of an inorganic filler relative to polypropylene 100 parts by weight of higher than the melting point 0.99 ° C. in the second layer, the thickness of the laminated sheet 200 in ～1000Myuemu, thermoforming body thickness of the first layer is formed by thermoforming a polypropylene laminated sheet Ru 10~100μm der.
(Ai) Using a metallocene catalyst, 30 to 95% by weight of a propylene-ethylene random copolymer component (A1) having an ethylene content of 0.3 to 7% by weight in the first step and a component ( A propylene-ethylene block copolymer obtained by sequential polymerization of 70 to 5% by weight of a propylene-ethylene random copolymer component (A2) containing 3 to 20% by weight of ethylene more than A1) .
(A-ii) The melt flow rate (2.16 kg 230 ° C.) is in the range of 0.1 to 30 g / 10 minutes.
(A-iii) The temperature-loss tangent (tan δ) curve obtained by solid viscoelasticity measurement (DMA) has a single peak at 0 ° C. or lower. Thermoforming body, thermoformed article according to claim 1, wherein the container. The thermoformed body according to claim 2 , wherein the lid is heat sealed to the first layer of the container.

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