JP4892392B2 - Low gloss container - Google Patents

Description

  The present invention relates to a low-gloss container, and more particularly to a low-gloss container that has good moldability and excellent scratch resistance and low gloss in a deep-drawn container obtained by thermoforming.

Thermoplastic resins such as polystyrene, polyethylene terephthalate, and polypropylene are preferably used as raw materials for various containers. There are many methods for manufacturing these containers by extruding a thermoplastic resin into a sheet and then reheating it and performing secondary processing using a thermoforming method such as vacuum forming or vacuum / pressure forming. It has been adopted. Such a thermoforming method is widely used as a molding method suitable for mass production because of its high productivity and easy multilayering.
Among thermoplastic resins, propylene polymers are excellent in heat resistance, rigidity, impact resistance, or hygiene, and are excellent materials for container materials for foods, etc. The range of use is expanding to range-up containers in microwave ovens and containers that require high-temperature filling.
On the other hand, in recent years, containers having characteristics of transparency and gloss have been demanded in order to enhance the high-class feeling of containers, and improvements in various methods such as materials and molding methods have been performed for high transparency and low gloss. ing.

Regarding a method for obtaining a low-gloss container, a method for blending polypropylene and high-density polyethylene with a specified MFR ratio (see, for example, Patent Document 1), and a blend ratio between an ethylene-propylene block copolymer and high-density polyethylene are specified. (For example, refer to Patent Document 2), a method of blending a polypropylene homopolymer with a specified MFR and high-density polyethylene in a certain ratio (for example, refer to Patent Document 3), and the like.
However, these are inventions related to blow-molded products, and can give low gloss and frost to containers obtained by blow molding. It could not be said that the obtained container was a composition capable of giving sufficient performance.

In the case of a thermoformed container made of a sheet, since the molten resin is sandwiched and formed between rolls and sleeves with high gloss when the sheet is first formed, the sheet has high gloss. On the other hand, if solid-phase thermoforming (pressure forming or vacuum / pressure forming at a temperature lower than the melting point of the sheet) is performed in order to obtain a container having a large drawing ratio, the sheet will be formed while maintaining the gloss of the sheet. It becomes very difficult to obtain a glossy container. Further, even if a method of obtaining a low gloss sheet by applying processing or the like to the roll surface is used, if a container is molded at a temperature below the melting point, it becomes a high gloss container.
Japanese Patent Laid-Open No. 3-197541 JP-A-4-86260 JP-A-10-315358

  The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a low-gloss container having good formability and scratch resistance by solid phase thermoforming from a sheet and having a high-class feeling. .

  As a result of repeating various studies to solve the above problems, the present inventors have high demand and importance in polypropylene containers in the conventional technical situation represented by the prior art in the previous patent documents and the like. In order to solve the above-described problems of the present invention, the results of various studies and considerations on raw materials and molding conditions in consideration of the prior art, a specific propylene-based block copolymer in solid-phase thermoforming The present inventors have found that a low-gloss container can be obtained by using a sheet made of a propylene-based resin composition containing an ethylene-based polymer and the present invention.

That is, according to the first invention of the present invention, at least the outer surface layer satisfies the following conditions (i) to ( iii ): 50 to 90% by weight of the propylene-based block copolymer (A), and the melt flow rate (MFR) 2.16 kg 190 ° C.) is molded from a resin composition containing 0.1 to 15 g / 10 min and an ethylene polymer (B) having a density of 0.950 g / cm ³ or more and 50 to 10% by weight. A low-gloss container having a depth / caliber ratio of 1.0 times or more and a gloss value of 10% or less obtained by thermoforming a sheet is provided.
(I) The propylene homopolymer component (A1) is 40 to 90% by weight in the first step, and the propylene-ethylene random copolymer component (A2) containing 35 to 100% by weight of ethylene in the second step is 60 to 10%. (Ii) Melt flow rate (MFR; 2.16 kg 230 ° C.) is in the range of 0.5 to 5 g / 10 min.
(Iii) The ratio MFR (A) / MFR (A1) of MFR (A) of the propylene block copolymer (A) and MFR (A1) of the propylene homopolymer component (A1) obtained in the first step is 3 .0 or more

Further, according to the second invention of the present invention, the propylene-based block copolymer (A) having at least an outer surface layer satisfying the following conditions (i) to (iii ): 50 to 90% by weight, a melt flow rate (MFR) 2.16 kg 190 ° C.) is molded from a resin composition containing 0.1 to 5 g / 10 min and an ethylene polymer (B) having a density of 0.950 g / cm ³ or more and 50 to 10 % by weight. A low gloss container having a depth / caliber ratio of 1.15 times or more and a gloss value of 5% or less obtained by plug-assisted pressure forming of a sheet is provided.
(I) The propylene homopolymer component (A1) is 40 to 90% by weight in the first step, and the propylene-ethylene random copolymer component (A2) containing 35 to 75% by weight of ethylene in the second step is 60 to 10%. The ethylene content obtained by sequential polymerization by weight% exceeds 10% by weight.
(Ii) Melt flow rate (MFR; 2.16 kg, 230 ° C.) is in the range of 0.5 to 3.0 g / 10 min. (Iii) MFR (A) of propylene-based block copolymer (A) and The ratio MFR (A) / MFR (A1) of the MFR (A1) of the propylene homopolymer component (A1) obtained in one step is 3.0 or more.

  According to the present invention, a low-gloss container excellent in moldability, scratch resistance and low gloss can be obtained even in a deep-drawn thermoformed container.

  The low gloss container of the present invention is obtained by molding a resin composition containing a propylene-based block copolymer (A) and an ethylene-based polymer (B) into a sheet shape, and thermoforming the sheet using the sheet. can get. The low gloss container of the present invention will be described in detail below.

1. Component of resin composition (1) Propylene-based block copolymer (A)
The propylene block copolymer (A) used in the present invention is a propylene ethylene block copolymer composed of a propylene homopolymer component (A1) and a propylene-ethylene random copolymer component (A2). It has characteristics.

(I) Melt flow rate (MFR)
The melt flow rate (MFR) of the propylene-based block copolymer (A) used in the present invention is 0.5 to 5 g / 10 minutes, preferably 0.5 to 3 g / 10 minutes, more preferably 1.0 to 2 g. / 10 minutes. When MFR exceeds 5 g / 10 minutes, drawdown property will deteriorate and sheet shaping | molding will become difficult. When the MFR is less than 0.5 g / 10 min, the polymerization activity is lowered, the cost is increased, and the extrudability at the time of sheet forming is lowered, thereby reducing the productivity.
Here, the melt flow rate (MFR) is in accordance with JIS K7210 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate I (MVR) of thermoplastics”, test condition M: 230 ° C., 2. A value measured at a load of 16 kg.
In order to adjust the MFR of the polymer, for example, there are a method of appropriately adjusting a polymerization temperature, a catalyst amount, a supply amount of hydrogen as a molecular weight regulator, or a method of adjusting by adding a peroxide after the polymerization is completed.

(Ii) Component ratio of (A1) and (A2) The proportion of the propylene homopolymer component (A1) is 40 to 90% by weight, preferably 45 to 85% by weight. When the proportion of (A1) is less than 40% by weight, the scratch resistance of the container deteriorates, and when it exceeds 90% by weight, the gloss becomes high. The proportion of the propylene-ethylene random copolymer component (A2) is 60 to 10% by weight, preferably 55 to 15% by weight. When the proportion of (A2) exceeds 60% by weight, the scratch resistance of the container deteriorates, and when it is less than 10% by weight, the gloss becomes high.

(Iii) Ethylene content of (A2) The ethylene content in the propylene-ethylene random copolymer component (A2) is 35 to 100% by weight, preferably 35 to 75 % by weight. When the ethylene content is less than 35% by weight, the gloss of the resulting container is high.

(Iv) Ethylene content of (A) The ethylene content of the propylene-based block copolymer (A) is more than 10 wt%, preferably 12 to 25 wt%. When the ethylene content is 10% by weight or less, the gloss of the container becomes high.

Here, specification of ethylene content E (A2) and each component amount W (A1) and W (A2) is a value measured by the following method.
Although it is possible to specify by component amount of components (A1) and (A2), ethylene content E (A2) of component (A2), and material balance (material balance) at the time of polymerization, these are specified more accurately. Therefore, it is desirable to use the following analysis (fractionation method).

(A) Identification of each component amount W (A1) and W (A2) by temperature-temperature elution fractionation (TREF) The crystallinity distribution of the propylene-ethylene random copolymer is evaluated by temperature-temperature elution fractionation (TREF). The technique 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)

Since the propylene-ethylene block copolymer (A) in the present invention has a large difference in crystallinity between the components (A1) and (A2), there are very few intermediate components between them, and both of them can be accurately processed by TREF. It is possible to sort.
In the TREF elution curve (plot of elution amount versus temperature), components (A1) and (A2) show their elution peaks at T (A1) and T (A2), respectively, due to differences in crystallinity and composition. Since it is large, separation is possible at an intermediate temperature T (A3) (= {T (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, In some cases, no peak is shown. (At this time, the concentration of the component (A2) dissolved in the solvent is detected at the measurement temperature lower limit (ie, −15 ° C.).)
At this time, T (A2) is considered to exist below the lower limit of the measurement temperature, but its value cannot be measured. In such a case, T (A2) is the lower limit of the measurement temperature. Defined as ° C.
Here, if the integrated amount of the component eluted before T (A3) is defined as W (A2) wt%, and the integrated amount of the component 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 cumulative amount W (A1) of the component eluted at T (A3) or higher is the propylene homopolymer component (A1) having high crystallinity. ).

(A) 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 (with 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 o-dichlorobenzene at −15 ° C. 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.

(C) Specificity of ethylene content E (A2) of component (A2) (C-1) Separation of components (A1) and (A2) Based on T (A3) determined by the previous TREF measurement, preparative fractionation Using a temperature rising column fractionation method with an apparatus, the soluble component (A2) in T (A3) and the insoluble component (A1) in T (A3) are separated, and the ethylene content of each component is determined by NMR. Ask.
The temperature rising column fractionation method is a measurement method disclosed in, for example, Macromolecules 21 314-319 (1988). Specifically, the following method is used in the present invention.

(U-2) Fractionation conditions A cylindrical column having a diameter of 50 mm and a height of 500 mm is filled with a glass bead carrier (80 to 100 mesh) and maintained at 140 ° C. Next, 200 mL of the o-dichlorobenzene solution (10 mg / mL) of the sample dissolved at 140 ° C. is introduced into the column. Thereafter, the temperature of the column is cooled to 0 ° C. at a rate of temperature decrease of 10 ° C./hour. After holding at 0 ° C. for 1 hour, the column temperature is heated to T (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), by flowing 800 mL of o-dichlorobenzene of T (A3) at a flow rate of 20 mL / min, components soluble in T (A3) existing in the column are obtained. Elute and collect.
Next, the column temperature was raised to 140 ° C. at a rate of temperature increase of 10 ° C./min, allowed to stand at 140 ° C. for 1 hour, and then 800 mL of 140 ° C. solvent o-dichlorobenzene was allowed to flow at a flow rate of 20 mL / min. Insoluble components are eluted with T (A3) and collected.
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 collected by filtration and dried overnight in a vacuum dryer.

(U-3) Measurement of ethylene content by ¹³ C-NMR The ethylene content of the component (A2) obtained by the above fractionation was measured by the proton complete decoupling method according to the following conditions, and the ¹³ C-NMR spectrum was analyzed. To find out.
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 number: 5,000 times or more The attribution of the spectrum 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
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 the weight ratio W (A1) and W (W) of each component calculated from the ethylene content E (A2) and TREF of the component (A2) measured above. A2) It is calculated by the following formula from wt%.
E (W) = E (A2) × W (A2) / 100 (wt%)

(V) MFR ratio of (A) and MFR of component (A1) Ratio of MFR (A) of propylene-based block copolymer (A) to MFR (A1) of propylene homopolymer MFR (A) / MFR (A1) ) Is 3.0 or more , preferably 3.3 or more. When MFR (A) / MFR (A1) is less than 3.0, the difference in fluidity between the propylene homopolymer component (A1) and the propylene-ethylene random copolymer component (A2) is small, and both components are the same during container molding. The resulting container has a high gloss.
In addition, MFR (A1) can be adjusted with the amount of hydrogen supplied to the 1st process in the below-mentioned sequential polymerization. MFR (A) is determined by the MFR and production ratio of the propylene homopolymer component (A1) obtained in the first step and the ethylene polymer component or propylene-ethylene random copolymer component (A2) obtained in the second step. Therefore, it can be adjusted by adjusting the amount of hydrogen supplied to the first step and the second step. The MFR of the component (A1) can be measured by extracting the powder that has undergone the polymerization in the first step.

In the first step, the propylene-based block copolymer (A) used in the present invention is a so-called Ziegler-Natta catalyst or metallocene catalyst, which contains magnesium, titanium, halogen, and electron donor as essential components. Propylene homopolymer component (A1) is polymerized and produced in a sequential polymerization method in which a propylene-ethylene random copolymer is polymerized in the second step.
As the polymerization method, general-purpose processes such as a slurry method, a bulk method, a solution method, and a gas phase method can be applied. Examples of these polymerization methods include a method in which sequential polymerization is performed continuously in a single reactor and a method in which sequential polymerization is performed using a plurality of reactors. These polymerization methods may be used in combination. it can. Especially, since the propylene-based block copolymer (A) can be produced efficiently, a polymerization method using a plurality of gas phase reactors is preferable.

  In the propylene block copolymer (A), the propylene homopolymer component (A1) is polymerized in the first step and the propylene-ethylene random copolymer component (A2) is polymerized in the second step so as to satisfy the above-described characteristics. Polymerized.

The propylene-based block copolymer (A) may be used as one type or a mixture of two or more types as long as the above characteristics are satisfied.
In the present invention, commercially available products can be used as the propylene-based block copolymer (A), and examples thereof include Novatec PP and Newcon manufactured by Nippon Polypro Co., Ltd.

(2) Ethylene polymer (B)
Examples of the ethylene-based polymer (B) used in the present invention include homopolymers of ethylene, random copolymers of ethylene and α-olefin, and the like, and may be used as one kind or a mixture of two or more kinds. it can.
Examples of the α-olefin used in the copolymer include propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, octene-1, and the like. Alternatively, two or more multi-component copolymers may be used. Among these (co) polymers, a homopolymer of ethylene having a high density is preferable.

The ethylene polymer (B) used in the present invention has the following physical properties.
(I) MFR
The MFR of the ethylene polymer (B) used in the present invention is 0.1 to 15 g / 10 minutes, preferably 0.1 to 10 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes, particularly preferably. 0.1-1 g / 10 min. When the MFR exceeds 15 g / 10 minutes, the gloss becomes high, and when the MFR is less than 0.1 g / 10 minutes, the sheet is blurred and the appearance is deteriorated.
Here, the melt flow rate (MFR) conforms to JIS K7210 “Plastics—Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics”, and test condition D: 190 ° C., 2 It is a value measured with a 16 kg load.

(Ii) Density The density of the ethylene polymer (B) used in the present invention is 0.950 g / cm ³ or more. If the density is less than 0.950 g / cm ³ , a satisfactory low gloss container cannot be obtained.
Here, the density is a value measured by A method (underwater substitution method) in accordance with JIS K7112 “Plastics—Method of measuring density and specific gravity of non-foamed plastic”.

The ethylene-based polymer (B) used in the present invention can be produced by a known method using a conventionally known Ziegler type catalyst, chromium catalyst, metallocene catalyst or the like.
As a method for polymerizing the ethylene polymer (B) used in the present invention, general-purpose processes such as a slurry method, a bulk method, a solution method, a gas phase method and the like can be applied. In these polymerization methods, not only a single reactor but also a plurality of polymerization methods can be used, and a plurality of polymerization methods can also be used in combination.

  In the present invention, a commercially available product can be used as the ethylene polymer (B), and examples thereof include Novatec PE manufactured by Nippon Polyethylene Co., Ltd.

(3) Composition ratio of component (A) and component (B) The resin composition used in the present invention is a propylene block copolymer (A) of 50 to 90% by weight, preferably 60 to 80% by weight. The union (B) comprises 50 to 10% by weight, preferably 40 to 20% by weight. If the propylene-based block copolymer (A) exceeds 90% by weight, a satisfactory low gloss container cannot be obtained, and if it is less than 50% by weight, the scratch resistance deteriorates.

(4) Other components In addition to the propylene-based block copolymer (A) and the ethylene-based polymer (B), the resin composition used in the present invention has an additional component (arbitrary component) having the effect of the present invention. It can also mix | blend in the range which is not impaired remarkably. As this additional component, a nucleating agent, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, a neutralizer, a lubricant, an antistatic agent, a dispersion used as an ordinary polyolefin resin compounding agent Agent, inorganic pigment, organic pigment, metal deactivator, peroxide, filler, and resins other than those used in the present invention, ethylene / propylene rubber, ethylene / butene rubber, ethylene / hexene rubber, ethylene -Examples include octene rubber.

  Specific examples of the phenolic antioxidant as the antioxidant include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3-tris (2-methyl- 4-hydroxy-5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro 5,5] undecane, etc. 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.

  Specific examples of phosphorus antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, bis (2, 4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t -Butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di Phosphite can be mentioned.

  Specific examples of the sulfur-based antioxidant include di-stearyl-thio-di-propionate, di-myristyl-thio-di-propionate, pentaerythritol-tetrakis- (3-lauryl-thio-propionate), and the like. it can.

  Specific examples of the neutralizing agent include calcium stearate, zinc stearate, hydrotalcite, and Mizukarak (manufactured by Mizusawa Chemical Co., Ltd.).

  Specific examples of hindered amine stabilizers include polycondensates of dimethyl oxalate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis (1,2 , 2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, N, N- Bis (3-aminopropyl) ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5 -Triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5- Triazine , 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], poly [(6- Morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) Imino}] and the like.

  Specific examples of the nucleating agent include sodium 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphate, talc, 1,3,2,4-di (p-methylbenzylidene) sorbitol, etc. Sorbitol-based compound, hydroxy-di (aluminum t-butylbenzoate, 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphoric acid and aliphatic monocarboxylic acid lithium salt mixture having 8 to 20 carbon atoms (Trade name NA21 manufactured by Asahi Denka Co., Ltd.).

Specific examples of the lubricant include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like as the saturated fatty acid monoamide.
Examples of the unsaturated fatty acid monoamide include oleic acid amide, erucic acid amide, ricinoleic acid amide and the like.
Specific examples of the substituted amide include N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide and the like. Is mentioned.

As saturated fatty acid bisamide, methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, ethylene bis behenic acid amide, Examples include hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bishydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sepacic acid amide and the like. .
Examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepacic acid amide and the like.
Examples of the aromatic bisamide include m-xylylene bis stearic acid amide and N, N′-distearylisophthalic acid amide.

2. Production of Resin Composition The resin composition used in the present invention is produced by blending the propylene-based block copolymer (A), the ethylene-based polymer (B) and, if necessary, an additional component by a known method. be able to.
As a specific example of the blending method, polymerized propylene block copolymer powder and / or ethylene polymer powder is melt-kneaded by separately preliminarily mixing additional components individually or in a mixture powder thereof. The blend can be obtained by a method of mixing, a method of blending a master batch in which the concentration of the additional component is high, or the like. Examples of the mixer or kneader used for the mixing or melt kneading include, for example, Henschel mixer, super mixer, V blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, Brabender plastograph, roll, single screw extrusion Examples thereof include a granulator and a twin screw extrusion granulator. The melt kneading temperature is generally 100 to 300 ° C.

3. Sheet The sheet used in the present invention can be produced by a known molding method, for example, an extrusion molding method, a calendar molding method, a compression molding method, or the like, using the above-described resin composition.
Of these, the extrusion method is preferable, and specific examples include an extrusion method using a T-die method, an inflation method, or the like.
The obtained sheet is cooled and solidified by a known method such as a polishing method, an air knife method, or a metal mirror belt method.

The sheet used in the present invention is not limited to a single layer and may be a multilayer sheet.
In the case of a multilayer sheet, a low-gloss layer (propylene-based composite resin layer) comprising a propylene-based block copolymer (A), an ethylene-based polymer (B), and additional components blended as necessary is a surface layer. Specific examples of suitable layer configurations include propylene-based composite resin layer / main layer two-type two-layer configuration and propylene-based composite resin layer / recycled layer / main layer three-type three-layer configuration. As mentioned.
Moreover, a laminated sheet in which a gas barrier resin layer is arranged to add gas barrier properties can also be mentioned. As the layer configuration, for example, propylene-based composite resin layer / main layer / adhesive resin layer / gas barrier resin layer / adhesive resin layer / main layer, six-layer configuration of propylene-based composite resin layer / main layer / recycled layer / adhesion A suitable layer configuration includes five types and seven layers of resin layer / gas barrier resin layer / adhesive resin layer / regeneration layer / main layer.
In the case of a multilayer sheet, the method of laminating each layer is preferably a method of laminating the above-described resin materials forming each layer in a molten state in terms of interlayer adhesion. In general, a multi-manifold system in which each material is melted and kneaded in each extruder and then laminated in a die, or a feed block system (combining adapter system) in which the material is laminated before flowing into the die is preferable.

4). Container (1) Molding Method of Container The sheet obtained above is shaped into various containers such as cups by thermoforming. Thermoforming is generally vacuum forming in which a plastic sheet is softened by heating and pressed against a desired mold, the air in the gap between the mold and the material is removed and closely adhered to the mold by atmospheric pressure, and the pressure above atmospheric pressure Compressed air or compressed air forming that uses vacuum in combination is used. As a method, vacuum or compressed air is used, and if necessary, a method of forming into a mold shape using a plug together (straight method, A drape method, an air slip method, a snapback method, a plug assist method, a plug assist reverse draw molding method, a match mold molding method, etc.), and solid phase press molding and stamping molding. Although it is not particularly limited as long as it is a molding method using a combination of these thermoforming methods, the ratio of depth / caliber (the maximum diameter passing through the center point when the shape is complicated) is 1 in the low gloss container of the present invention. Since it is a deep-drawn low-gloss container of 0.0 times or more, preferably 1.15 times or more, more preferably 1.25 times or more, it is essential that the sheet is in an unmelted state, and plug-assisted pressure forming is suitable. is there. Various conditions such as the thermoforming temperature, the degree of vacuum, the pressure of compressed air, and the forming speed are appropriately set depending on the plug shape, the die shape, the nature of the material sheet, and the like.

(2) Physical Properties of Container The low gloss container of the present invention is a container having a gloss value of 10% or less, preferably 8% or less , more preferably 5% or less, and particularly preferably 4% or less . If the gloss value exceeds 10%, the low glossiness is lacking, so that the high-class feeling of the container is lost and the commercial value is lowered.
Here, the gloss value is a value measured in accordance with JIS K7105 “Testing methods for optical properties of plastics”.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The evaluation methods and resins used in the examples are as follows.

1. Evaluation method (1) Melt flow rate (MFR)
(I) Polypropylene Measured according to test condition M of Method A of JIS K7210 (ISO 1133) “Plastics—Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Thermoplastic Plastics” under the following conditions: .
Test temperature: 230 ° C
Nominal load: 2.16kg
Die shape: 2.095mm diameter, 8.00mm length
(Ii) Polyethylene JIS K7210 (ISO 1133) Measured under the following conditions in accordance with Test Condition D of Method A of “Plastics—Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Thermoplastic Plastics” .
Test temperature: 190 ° C
Nominal load: 2.16kg
Die shape: 2.095mm diameter, 8.00mm length
(2) Ethylene content of each component and each component ratio It measured by the above-mentioned method.
(3) Gloss value of the container The gloss of the container was evaluated under the following conditions.
Standard number: JIS K7105 "Testing method for optical properties of plastics"
Measuring machine: Digital variable angle gloss meter UGV-5K manufactured by Suga Test Instruments
Test piece thickness: 200 μm
Preparation method of test piece: Cut out a 50 × 50 mm test piece from a container Condition adjustment: After molding, left in a constant temperature room adjusted to room temperature 23 ° C. and humidity 50% Number of test pieces: 3
Evaluation item: 60 degree specular gloss (4) Moldability of container The moldability of the container was evaluated under the following conditions.
○: Can be molded without any problem Others: The cause of failure in visual confirmation is listed in the table. (5) Scratch property of container The scratch property of the container was evaluated under the following conditions.
After the containers were rubbed together, they were visually judged and judged according to the following criteria.
○: Scratches are hardly recognized.
Δ: Slightly damaged.
X: Scratches are conspicuous.

2. Resin used (1) Propylene block copolymer (A)
As the propylene-based block copolymer (A), (PP-1) to (PP-11) obtained in Production Examples 1 to 11 were used. Table 2 shows the characteristics of (PP-1) to (PP-11).

(Production Example 1)
(I) Production of Ti-based solid catalyst A 6 liters of n-hexane, 5.0 mol of diethylaluminum monochloride (DEAC), and 12.0 mol of diisoamyl ether were mixed at 25 ° C. for 5 minutes, and at the same temperature for 5 minutes. The reaction solution (I) (diisoamyl ether / DEAC molar ratio 2.4) was obtained by reaction. 40 moles of titanium tetrachloride was placed in a nitrogen-substituted reactor and heated to 35 ° C., and the entire amount of the reaction solution (I) was added dropwise to the reactor over 180 minutes, then kept at the same temperature for 30 minutes and heated to 75 ° C. The reaction was further continued for 1 hour, cooled to room temperature, the supernatant was removed, 30 liters of n-hexane was added, and decantation was repeated 4 times to obtain 1.9 kg of a solid product (II). In a state where the whole amount of (II) is suspended in 30 liters of n-hexane, 1.6 kg of diisoamyl ether and 3.5 kg of titanium tetrachloride are added at 20 ° C. over about 5 minutes, and 1 at 60 ° C. Reacted for hours. After completion of the reaction, the mixture was cooled to room temperature (20 ° C.), the supernatant was removed by decantation, 30 liters of n-hexane was added, stirred for 15 minutes, and allowed to stand to remove the supernatant 5 times. After repeating, it was dried under reduced pressure to obtain a Ti-based solid catalyst (A).
(Ii) Polymerization A stainless steel autoclave with a stirrer having an internal volume of 400 liters was sufficiently substituted with propylene gas at room temperature, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, 86 g of diethylaluminum chloride, 17 liters of hydrogen (standard condition conversion), and 18 g of the catalyst A were added under the condition of a temperature of 65 ° C.
After raising the internal temperature of the autoclave to 70 ° C., propylene was supplied at a rate of 20.3 kg / hour and hydrogen was supplied at a rate of 19.3 L / hour to initiate polymerization. After 190 minutes, the introduction of propylene and hydrogen was stopped. The pressure was 0.34 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 5.1 kg / cm ² G when the supply was stopped. Then, after residual polymerization was performed until the internal pressure decreased to 2.0 kg / cm ² G, unreacted gas was released to 0.5 kg / cm ² . During this time, the polymerization temperature was maintained in the range of 70 ± 1 ° C. (first stage polymerization step).
Next, after the autoclave was brought to an internal temperature of 65 ° C., propylene was supplied at a rate of 1.62 kg / hour and ethylene was supplied at a rate of 6.46 kg / hour to start two-stage polymerization. After 78 minutes, the introduction of propylene and ethylene was stopped. The pressure increased with time during the supply of propylene and ethylene, and increased to 0.7 kg / cm ² G when the supply was stopped. Thereafter, the unreacted gas in the vessel was released to 0.3 kg / cm ² . During this time, the polymerization temperature was maintained in the range of 65 ± 1 ° C. (second stage polymerization step).
The obtained slurry was transferred to the next tank with a stirrer, 5 liters of butanol was added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, and 100 liters of pure water in which 100 g of sodium hydroxide was dissolved. In addition, after treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry was treated with a centrifuge to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane, thereby obtaining 59.4 kg of a propylene-based copolymer (PP-1).
(Iii) Granulation With respect to 100 parts by weight of the propylene-based polymer (PP-1), pentaerythryl-tetrakis [3- (3,5-t-butyl-4-hydroxyphenyl) is used as a phenol-based antioxidant. ) Propionate] (Ciba Specialty Chemicals Co., Ltd .; Irganox 1010) 0.05 parts by weight, Tris- (2,4-di-t-butylphenyl) phosphite (Ciba Specialty Chemicals Co., Ltd .; Irgaphos 168) 0.1 parts by weight of hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd .; DHT-4A) as a neutralizing agent, and nitrogen-sealed with a super mixer and mixed for 3 minutes. Thereafter, using a single screw extruder with a screw system of 40 mmD, the hopper was melt-kneaded at 230 ° C. while being sealed with nitrogen, and granulated (pelletized). It put into this pellet air circulation type dryer, and dried at 80 degreeC for 2 hours.

(Production Example 2)
The same procedure as in Production Example 1 was conducted except that hydrogen was supplied at a rate of 32.4 L / hour in the first stage polymerization step of Production Example 1 to obtain 59.2 kg of a propylene-based copolymer (PP-2). It was. Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 3)
A stainless steel autoclave with a stirrer having an internal volume of 400 liters was sufficiently substituted with propylene gas at room temperature, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, under the condition of a temperature of 65 ° C., 86 g of diethylaluminum chloride, 17 liters of hydrogen (standard condition conversion), and 17 g of the catalyst A were added.
After the autoclave was heated to an internal temperature of 70 ° C., propylene was supplied at a rate of 19.9 kg / hour and hydrogen was supplied at a rate of 29.9 L / hour to initiate polymerization. After 190 minutes, the introduction of propylene and hydrogen was stopped. The pressure was 0.30 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 5.0 kg / cm ² G when the supply was stopped. Then, after residual polymerization was performed until the internal pressure decreased to 2.0 kg / cm ² G, unreacted gas was discharged to 0.4 kg / cm ² . During this time, the polymerization temperature was maintained in the range of 70 ± 1 ° C. (first stage polymerization step).
Then, after the autoclave was brought to an internal temperature of 65 ° C., only ethylene was supplied at a rate of 6.46 kg / hour to start two-stage polymerization. After 108 minutes, the introduction of propylene and ethylene was stopped. The pressure increased with time during the supply of propylene and ethylene, and increased to 0.4 kg / cm ² G when the supply was stopped. During this time, the polymerization temperature was maintained in the range of 65 ± 1 ° C. (second stage polymerization step).
The obtained slurry was transferred to the next tank with a stirrer, 5 liters of butanol was added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, and 100 liters of pure water in which 100 g of sodium hydroxide was dissolved. In addition, after treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry was treated with a centrifuge to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane, thereby obtaining 62.6 kg of a propylene copolymer (PP-3).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 4)
(I) Production of Ti-based solid catalyst B 20 l of dehydrated and deoxygenated n-heptane was introduced into a tank equipped with a stirrer with an internal volume of 50 l replaced with nitrogen, and then 10 mol of magnesium chloride and 20 mol of tetrabutoxy titanium The reaction was carried out at 95 ° C. for 2 hours, the temperature was lowered to 40 ° C., 12 liters of methylhydropolysiloxane (viscosity 20 centistokes) was introduced, and the reaction was continued for another 3 hours. The resulting solid component was washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank equipped with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Next, 5 liters of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30 ° C. for 30 minutes. The temperature was raised to 70 ° C. and reacted for 3 hours. Then, the reaction solution was taken out, The resulting solid component was washed with n-heptane.
Subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and 0.3 mol of phthalic acid chloride was mixed and introduced at 90 ° C. for 30 minutes. And reacted at 95 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of titanium tetrachloride was added at room temperature, and the temperature was raised to 100 ° C., followed by reaction for 2 hours. After completion of the reaction, washing with n-heptane was performed. Further, 0.6 liters of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90 ° C. for 1 hour, and sufficiently washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.
Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane and 0.27 mol of vinyltrimethylsilane were introduced into the tank equipped with a stirrer substituted with nitrogen. And contacted at 30 ° C. for 1 hour. Next, the mixture was cooled to 15 ° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 15 minutes under 15 ° C., and after the introduction, the temperature was raised to 30 ° C. and reacted for 2 hours. By washing with heptane, 390 g of a solid catalyst component (B) was obtained.
The obtained Ti-based solid catalyst B contained 1.22% by weight of titanium.
Furthermore, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes at 15 ° C., and then about 0.4 kg / kg of propylene was controlled so as not to exceed 20 ° C. Preliminarily polymerized by introducing for 1 hour. As a result, a polypropylene-containing Ti-based solid catalyst B in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.
(Ii) Polymerization Polymerization was performed using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected. First, in a first reactor, a polymerization temperature of 60 ° C., a propylene partial pressure of 20 kg / cm ² , and hydrogen as a molecular weight control agent are continuously fed so that the molar ratio of hydrogen / propylene is 0.020. Aluminum was supplied at a rate of 5.25 g / hour, and the Ti-based solid catalyst B was supplied so that the polymer polymerization rate was 12 kg / hour. The powder polymerized in the first reactor (crystalline propylene polymer) was continuously withdrawn so that the amount of powder held in the reactor was 40 kg, and continuously transferred to the second reactor (first stage polymerization). Process).
Propylene and ethylene are continuously fed so that the molar ratio of ethylene / propylene is 0.49 at a polymerization temperature of 80 ° C. and a pressure of 20 kg / cm ² , and hydrogen as a molecular weight control agent is further added. While continuously supplying a hydrogen / propylene molar ratio of 0.0001, ethyl alcohol was supplied as an active hydrogen compound so that the molar ratio was 2.1 times that of triethylaluminum. The powder polymerized in the second reactor is continuously withdrawn into the vessel so that the amount of powder held in the reactor is 50 kg, and the reaction is stopped by supplying moisture-containing nitrogen gas to produce a propylene copolymer. (PP-4) was obtained (second stage polymerization step).
(Iii) Granulation Granulation was performed in the same manner as in Production Example 1.

(Production Example 5)
A stainless steel autoclave with a stirrer having an internal volume of 400 liters was sufficiently substituted with propylene gas at room temperature, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, 86 g of diethylaluminum chloride, 12 liters of hydrogen (standard condition conversion), and 18 g of the catalyst A were added under the condition of a temperature of 65 ° C.
After the autoclave was heated to an internal temperature of 70 ° C., propylene was supplied at a rate of 20.3 kg / hour and hydrogen was supplied at a rate of 12.2 L / hour to initiate polymerization. After 190 minutes, the introduction of propylene and hydrogen was stopped. The pressure was 0.30 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 4.9 kg / cm ² G when the supply was stopped. Thereafter, residual polymerization was performed until the pressure in the vessel decreased to 0.5 kg / cm ² G. During this time, the polymerization temperature was maintained in the range of 70 ± 1 ° C. (first stage polymerization step).
Next, after the autoclave was brought to an internal temperature of 65 ° C., propylene was supplied at a rate of 1.62 kg / hour and ethylene was supplied at a rate of 6.46 kg / hour to start two-stage polymerization. After 78 minutes, the introduction of propylene and ethylene was stopped. The pressure increased with time during the supply of propylene and ethylene, and increased to 0.8 kg / cm ² G when the supply was stopped. Thereafter, the unreacted gas in the vessel was released to 0.3 kg / cm ² . During this time, the polymerization temperature was maintained in the range of 65 ± 1 ° C. (second stage polymerization step).
The obtained slurry was transferred to the next tank with a stirrer, 5 liters of butanol was added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, and 100 liters of pure water in which 100 g of sodium hydroxide was dissolved. In addition, after treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry was treated with a centrifugal separator to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane to obtain 60.1 kg of a propylene copolymer (PP-5).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 6)
Polymerization was carried out using a continuous reaction apparatus consisting of a fluidized bed reactor having an internal volume of 230 liters. The reactor is continuously supplied with a polymerization temperature of 85 ° C., a propylene partial pressure of 22 kg / cm ² , and hydrogen as a molecular weight control agent is continuously supplied so that the molar ratio of hydrogen / propylene is 0.0021, and triethylaluminum is added. At 5.25 g / hour, the Ti-based solid catalyst B was fed so that the polymer polymerization rate was 20 kg / hour. The powder polymerized in the reactor is continuously withdrawn into the vessel so that the amount of powder retained in the reactor is 60 kg, and the reaction is stopped by supplying nitrogen gas containing moisture, and the propylene polymer (PP- 6) was obtained.
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 7)
A stainless steel autoclave with a stirrer having an internal volume of 400 liters was sufficiently substituted with propylene gas at room temperature, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, 86 g of diethylaluminum chloride, 10.5 ml of propionic acid, 33 liters of hydrogen (converted to the standard state), and 20 g of the catalyst A were added under the condition of a temperature of 65 ° C.
After raising the internal temperature of the autoclave to 70 ° C., propylene was supplied at a rate of 18.9 kg / hour and hydrogen was supplied at a rate of 58.5 L / hour to initiate polymerization. After 200 minutes, the introduction of propylene and hydrogen was stopped. The pressure was 0.31 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 5.1 kg / cm ² G when the supply was stopped. Then, after residual polymerization was performed until the internal pressure decreased to 2.0 kg / cm ² G, unreacted gas was released to 0.5 kg / cm ² . During this time, the polymerization temperature was maintained in the range of 70 ± 1 ° C. (first stage polymerization step).
Next, after the autoclave was brought to an internal temperature of 65 ° C., propylene was supplied at a rate of 1.62 kg / hour and ethylene was supplied at a rate of 6.46 kg / hour to start two-stage polymerization. After 84 minutes, the introduction of propylene and ethylene was stopped. The pressure increased with time during the supply of propylene and ethylene, and increased to 1.2 kg / cm ² G when the supply was stopped. During this time, the polymerization temperature was maintained in the range of 65 ± 1 ° C. (second stage polymerization step).
The obtained slurry was transferred to the next tank with a stirrer, 5 liters of butanol was added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, and 100 liters of pure water in which 100 g of sodium hydroxide was dissolved. In addition, after treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry was treated with a centrifugal separator to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane to obtain 61.2 kg of a propylene copolymer (PP-7).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 8)
The single-stage polymerization in Production Example 1 was carried out in the same manner as in Production Example 1 except that hydrogen was supplied at a rate of 6.1 L / hour to obtain 60.3 kg of a propylene-based copolymer (PP-8).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 9)
Polymerization was carried out using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected. First, in a first reactor, a polymerization temperature of 55 ° C., a propylene partial pressure of 18 kg / cm ² , and hydrogen as a molecular weight control agent are continuously fed so that the molar ratio of hydrogen / propylene is 0.022. Aluminum was supplied at a rate of 5.25 g / hour, and the Ti-based solid catalyst B was supplied so that the polymer polymerization rate was 10 kg / hour. The powder polymerized in the first reactor (crystalline propylene polymer) was continuously withdrawn so that the amount of powder held in the reactor was 35 kg, and continuously transferred to the second reactor (first stage polymerization). Process).
Propylene and ethylene are continuously supplied so that the molar ratio of ethylene / propylene is 3.0 at a polymerization temperature of 80 ° C. and a pressure of 20 kg / cm ² , and hydrogen as a molecular weight control agent is further added. While continuously supplying a hydrogen / propylene molar ratio of 0.40, ethyl alcohol was supplied as an active hydrogen compound so that the molar ratio was 1.4 times that of triethylaluminum. The powder polymerized in the second reactor is continuously withdrawn into the vessel so that the amount of powder held in the reactor is 50 kg, and the reaction is stopped by supplying moisture-containing nitrogen gas to produce a propylene copolymer. (PP-9) was obtained (second stage polymerization step).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 10)
Polymerization was carried out using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected. First, in the first reactor, a polymerization temperature of 85 ° C., a propylene partial pressure of 22 kg / cm ² , and hydrogen as a molecular weight control agent are continuously fed so that the molar ratio of hydrogen / propylene is 0.0022. Aluminum was supplied at a rate of 5.25 g / hour, and the Ti-based solid catalyst B was supplied at a polymer polymerization rate of 20 kg / hour. The powder polymerized in the first reactor (crystalline propylene polymer) was continuously withdrawn so that the amount of powder held in the reactor was 60 kg, and continuously transferred to the second reactor (first stage polymerization). Process).
Propylene and ethylene are continuously supplied so that the molar ratio of ethylene / propylene is 0.30 at a polymerization temperature of 80 ° C. and a pressure of 20 kg / cm ² , and hydrogen as a molecular weight control agent is further added. While continuously supplying a hydrogen / propylene molar ratio of 0.0005, ethyl alcohol was supplied as an active hydrogen compound so that the molar ratio was 2.2 times that of triethylaluminum. The powder polymerized in the second reactor is continuously withdrawn into the vessel so that the amount of powder held in the reactor is 40 kg, the reaction is stopped by supplying nitrogen gas containing moisture, and the propylene copolymer (PP-10) was obtained (second stage polymerization step).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(Production Example 11)
A stainless steel autoclave with a stirrer having an internal volume of 400 liters was sufficiently substituted with propylene gas at room temperature, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, under the condition of a temperature of 65 ° C., 86 g of diethylaluminum chloride, 8.3 liters of hydrogen (standard condition conversion), and 18 g of the catalyst A were added.
After the autoclave was heated to an internal temperature of 70 ° C., propylene was supplied at a rate of 18.4 kg / hour and hydrogen was supplied at a rate of 6.08 L / hour to initiate polymerization. After 230 minutes, the introduction of propylene and hydrogen was stopped. The pressure of the polymerization initiator at 0.23 kg / ^cm 2 G, increased over time in propylene feed was increased to 4.6 kg / cm ² G at a feed stop time. Then, after the pressure in the vessel is subjected to residual polymerization until drops to 2.0 kg / cm ² G, and releasing the unreacted gas to 0.3 kg / cm ^2. During this time, the polymerization temperature was maintained in the range of 70 ± 1 ° C. (first stage polymerization step).
Next, after the autoclave was brought to an internal temperature of 65 ° C., propylene was supplied at a rate of 1.04 kg / hour and ethylene was supplied at a rate of 4.15 kg / hour to start two-stage polymerization. After 53 minutes, the introduction of propylene and ethylene was stopped. The pressure increased with time during the supply of propylene and ethylene, and increased to 0.6 kg / cm ² G when the supply was stopped. During this time, the polymerization temperature was maintained in the range of 65 ± 1 ° C. (second stage polymerization step).
The obtained slurry was transferred to the next tank with a stirrer, 5 liters of butanol was added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, and 100 liters of pure water in which 100 g of sodium hydroxide was dissolved. In addition, after treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry was treated with a centrifuge to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane, thereby obtaining 62.0 kg of a propylene-based copolymer (PP-11).
Thereafter, granulation was performed in the same manner as in Production Example 1.

(2) Ethylene polymer (B)
The following (PE-1) to (PE-5) were used as the ethylene polymer.
(PE-1): HB439R manufactured by Nippon Polyethylene Co., Ltd. (MFR = 0.7 g / 10 min, density = 0.960 g / cm ³ )
(PE-2): Nippon Polyethylene HJ580 (MFR = 12 g / 10 min, density = 0.960 g / cm ³ )
(PE-3): Nippon Polyethylene HJ490 (MFR = 20 g / 10 min, density = 0.958 g / cm ³ )
(PE-4): Nippon Polyethylene HB233R (MFR = 0.3 g / 10 min, density = 0.946 g / cm ³ )
(PE-5): Nippon Polyethylene HF313 (MFR = 0.05 g / 10 min, density = 0.950 g / cm ³ )

Example 1
(PP-1) obtained in Production Example 1 was used as the propylene-based block copolymer (A), and (PE-1) was used as the ethylene-based polymer (B).
8 kg of a pellet-shaped propylene-based block copolymer (PP-1) and 2 kg of an ethylene-based polymer (PE-1) were mixed for 5 min with a tumbler mixer, and the resulting mixture was fed from an extruder with a diameter of 40 mmφ to a resin temperature of 240 It was melt-extruded into a sheet shape having a width of 400 mm at 0 ° C. Next, the molten sheet was guided to a polishing roll (polishing temperature: upper 50 ° C., middle 80 ° C., lower 50 ° C.) and solidified by cooling to produce a sheet having a thickness of 1.0 mm and a width of 350 mm.
Next, a low-gloss container was molded by placing a container molding die with a drawing ratio of 1.26 (depth: 120 mm, caliber: 95 mmφ) in a compressed air molding machine RDM50K (manufactured by Erich). The moldability was good, and the resulting container had a gloss value of 4% and good scratch resistance. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss. The results are shown in Table 3.

(Example 2)
Evaluation and molding were performed in the same manner as in Example 1 except that the blend ratio of the propylene-based block copolymer (PP-1) and the ethylene-based polymer (PE-1) in Example 1 was changed. The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

(Example 3)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene-based block copolymer (PP-2) of Production Example 2 was used. The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

Example 4
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene-based block copolymer (PP-3) of Production Example 3 was used. The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

(Example 5)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene-based block copolymer (PP-4) of Production Example 4 was used. The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

(Example 6)
Evaluation and molding were performed in the same manner as in Example 1 except that (PE-2) was used instead of the ethylene-based polymer (PE-1) in Example 1. The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

(Example 7)
Evaluation and molding were performed in the same manner as in Example 1 except that the molding die of Example 1 was changed to a drawing ratio of 1.05 (depth: 100 mm, aperture: 95 mmφ). The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

(Example 8)
Evaluation and molding were performed in the same manner as in Example 1 except that the molding die of Example 1 was changed to a drawing ratio of 1.42 (depth: 135 mm, aperture: 95 mmφ). The results are shown in Table 3. It can be seen that the thermoformed container having the configuration of the present invention is a deep-drawn container excellent in low gloss.

( Reference Example 1 )
Evaluation and molding were carried out in the same manner as in Example 1 except that the propylene block copolymer (PP-5) of Production Example 5 was used. The results are shown in Table 3. Reference Example 1 is a ratio MFR (A) / MFR (A1) of MFR (A) of the propylene-based block copolymer (A) and MFR (A1) of the propylene homopolymer component (A1) obtained in the first step. However, since it exceeded the range of the present invention, the low glossiness of the thermoformed container was inferior.

(Comparative Example 1)
Evaluation and molding were performed in the same manner as in Example 1 except that only the propylene-based block copolymer (PP-1) of Example 1 was used. The results are shown in Table 4. Comparative Example 1 was inferior in the low gloss of the thermoformed container because the blending ratio of the ethylene polymer was below the range of the present invention.

(Comparative Example 2)
Evaluation and molding were performed in the same manner as in Example 1 except that the blend ratio of the propylene-based block copolymer (PP-1) and the ethylene-based polymer (PE-1) in Example 1 was changed. The results are shown in Table 4. In Comparative Example 2, since the blending ratio of the ethylene polymer exceeded the range of the present invention, the low glossiness of the thermoformed container was inferior.

(Comparative Example 3)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene polymer (PP-6) of Production Example 6 was used. The results are shown in Table 4. In Comparative Example 3, since the composition of the propylene block copolymer exceeded the range of the present invention, the low glossiness of the thermoformed container was inferior.

(Comparative Example 4)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene-based block copolymer (PP-7) of Production Example 7 was used. The results are shown in Table 4. In Comparative Example 4, since the MFR of the propylene-based block copolymer exceeded the range of the present invention, the low glossiness of the thermoformed container was inferior.

(Comparative Example 5)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene block copolymer (PP-8) of Production Example 8 was used. The results are shown in Table 4. In Comparative Example 5, since the MFR of the propylene-based block copolymer exceeded the range of the present invention, the corner shape of the thermoformed container was sweet and the moldability was poor.

(Comparative Example 6)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene-based block copolymer (PP-9) of Production Example 9 was used. The results are shown in Table 4. In Comparative Example 6, since the ratio of the propylene homopolymer (A1) of the propylene-based block copolymer exceeded the range of the present invention, the scratch resistance was inferior.

(Comparative Example 7)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene-based block copolymer (PP-10) of Production Example 10 was used. The results are shown in Table 4. In Comparative Example 7, since the ethylene content E (A2) of the propylene-ethylene random copolymer component (A2) in the propylene-based block copolymer exceeds the range of the present invention, the low glossiness of the thermoformed container is inferior. It was a thing.

(Comparative Example 8)
Evaluation and molding were performed in the same manner as in Example 1 except that the propylene block copolymer (PP-11) of Production Example 11 was used. The results are shown in Table 4. In Comparative Example 8, since the polymerization ratio of the propylene-ethylene random copolymer component (A2) in the propylene-based block copolymer exceeded the range of the present invention, the low glossiness of the thermoformed container was inferior. .

(Comparative Example 9)
Evaluation and molding were performed in the same manner as in Example 1 except that (PE-3) was used instead of (PE-1) in Example 1. The results are shown in Table 4. In Comparative Example 9, since the MFR of the ethylene polymer exceeded the range of the present invention, the low glossiness of the thermoformed container was inferior.

(Comparative Example 10)
Evaluation and molding were performed in the same manner as in Example 1 except that (PE-4) was used instead of (PE-1) in Example 1. The results are shown in Table 4. Comparative Example 10 was inferior in the low glossiness of the thermoformed container because the density of the ethylene polymer was below the range of the present invention.

(Comparative Example 11)
Evaluation and molding were performed in the same manner as in Example 1 except that (PE-1) (PE-5) in Example 1 was used instead of (PE-5). The results are shown in Table 4. In Comparative Example 11, since the density of the ethylene polymer was not more than the range of the present invention, the thermoforming container was flawed and the moldability was poor.

(Comparative Example 12)
Evaluation and molding were performed in the same manner as in Example 1 except that the molding die of Example 1 was changed to a drawing ratio of 0.68 (depth: 65 mm, aperture: 95 mmφ). The results are shown in Table 4. Comparative Example 12 was inferior in the low glossiness of the thermoformed container because the squeezing ratio of the container was below the range of the present invention.

  The low gloss container of the present invention is excellent in moldability, scratch resistance and low gloss even in a deep-drawn thermoformed container. Therefore, it is particularly useful for premium products that require a high-class feeling.

Claims (2)

50 to 90% by weight of a propylene-based block copolymer (A) satisfying the following conditions (i) to ( iii ) at least, and a melt flow rate (MFR; 2.16 kg 190 ° C.) of 0.1 to 15 g / 10 min and a ratio of depth / caliber obtained by thermoforming a sheet formed from a resin composition containing 50 to 10% by weight of an ethylene polymer (B) having a density of 0.950 g / cm ³ or more Is a low-gloss container with a gloss value of 10% or less.
(I) The propylene homopolymer component (A1) is 40 to 90% by weight in the first step, and the propylene-ethylene random copolymer component (A2) containing 35 to 100% by weight of ethylene in the second step is 60 to 10%. (Ii) Melt flow rate (MFR; 2.16 kg 230 ° C.) is in the range of 0.5 to 5 g / 10 min.
(Iii) The ratio MFR (A) / MFR (A1) of MFR (A) of the propylene block copolymer (A) and MFR (A1) of the propylene homopolymer component (A1) obtained in the first step is 3 .0 or more 50 to 90% by weight of a propylene-based block copolymer (A) having at least an outer surface layer satisfying the following conditions (i) to (iii), and a melt flow rate (MFR; 2.16 kg 190 ° C.) of 0.1 to 5 g / 10 minutes and a depth obtained by plug-assisted pressure forming of a sheet formed from a resin composition containing 50 to 10% by weight of an ethylene polymer (B) having a density of 0.950 g / cm ³ or more / Low gloss container with a caliber ratio of 1.15 times or more and a gloss value of 5% or less .
(I) The propylene homopolymer component (A1) is 40 to 90% by weight in the first step, and the propylene-ethylene random copolymer component (A2) containing 35 to 75% by weight of ethylene in the second step is 60 to 10%. The ethylene content obtained by sequential polymerization by weight% exceeds 10% by weight.
(Ii) Melt flow rate (MFR; 2.16 kg, 230 ° C.) is in the range of 0.5 to 3.0 g / 10 min. (Iii) MFR (A) of propylene-based block copolymer (A) and The ratio MFR (A) / MFR (A1) of the MFR (A1) of the propylene homopolymer component (A1) obtained in one step is 3.0 or more.