JP3416880B2 - Resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent transparency, flexibility and impact resistance. 2. Description of the Related Art As a method for improving the flexibility and impact resistance of a polypropylene resin, there have been proposed a method for improving the properties of crystalline polypropylene such as ethylene propylene copolymer rubber, ethylene butene copolymer rubber, low density polyethylene, and linear low density. A method of adding polyethylene or the like is generally known. However, it has been difficult for a composition having such a composition to simultaneously satisfy the transparency, flexibility, and impact resistance of a molded article. [0003] On the other hand, Japanese Patent Application Laid-Open No. 5-331328 discloses that a polypropylene-based resin is prepared by blending a specific propylene-based block copolymer containing a polybutene component, a polypropylene component and a propylene-ethylene copolymer component into polypropylene. Has improved its flexibility and impact resistance. [0004] However, the above-mentioned method is still insufficient in terms of transparency, and there is a problem that its use is restricted to applications requiring transparency. Therefore, the present invention provides a polypropylene resin composition having improved transparency without impairing the flexibility and impact resistance of the composition of the above-mentioned specific propylene-based block copolymer and polypropylene. Aim. The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned specific propylene-based block copolymer-polypropylene composition has been further improved. By blending specific polyethylene,
It has been found that a resin composition having excellent transparency while maintaining flexibility and impact resistance can be obtained, and the present invention has been completed. That is, the present invention provides (A) a polybutene component,
A block copolymer containing a polypropylene component and a propylene-ethylene random copolymer component, wherein the polybutene component is 0.01 to 5% by weight, the polypropylene component is 1 to 70% by weight, and the propylene-ethylene random copolymer component Is 25 to 99.99% by weight, and the propylene-ethylene random copolymer component contains 10 to 40 mol% of a monomer unit based on ethylene and 90 to 60 mol% of a monomer unit based on propylene, A propylene-based block copolymer (B) having a melt index of 0.5 to 50 g / 10 min and (C) a density of 0.86 to 0.94 g / cm ³ , ethylene and α having 3 to 10 carbon atoms -Consisting of a copolymer with an olefin, wherein (A) is 100 to 40% by weight based on the total amount of (A) and (B), (B) is 0 to 60% by weight
Wherein (C) is 1 to 100 parts by weight with respect to 100 parts by weight in total of (A) and (B). [0007] The propylene-based block copolymer (hereinafter simply referred to as "block copolymer") as the component (A) of the resin composition of the present invention comprises a polybutene component, a polypropylene component and a propylene-ethylene copolymer. Consists of coalescing components. If the polybutene component is replaced with another component, for example, a polyethylene component, the copolymer particles obtained by polymerization have poor solidification properties and high-temperature fluidity and cannot be the object of the present invention. The proportions of the polybutene component, the polypropylene component and the propylene-ethylene random copolymer component in the block copolymer used in the present invention are 0.01 to 5% by weight for the polybutene component and 1 to 70% for the polypropylene component. % By weight, and the propylene-ethylene random copolymer component is 25 to 99.99% by weight. In the present invention, the polybutene component is essential for improving the particle properties of the copolymer particles. In particular,
When the content of the polypropylene component is low, for example, 30
When the content is less than 10% by weight, the obtained copolymer particles tend to stick, but even in such a case, due to the presence of the polybutene component, the copolymer particles can have good fluidity. When the polybutene component is less than 0.01% by weight,
When the copolymer particles obtained by polymerization are left to accumulate, they are consolidated by the load, and the copolymer particles are further reduced to 50 to 50%.
When the temperature is 70 ° C., the fluidity is extremely poor, which is not preferable. On the other hand, when the content of the polybutene component exceeds 5% by weight, the fluidity of the block copolymer is rather lowered, which is not preferable. The ratio of the polybutene component is preferably in the range of 0.04 to 3% by weight in consideration of better fluidity of the block copolymer particles. When the content of the polypropylene component is less than 1% by weight, the block copolymer particles tend to stick. On the other hand, if the proportion of the polypropylene component exceeds 70% by weight, the flexibility and impact resistance of the molded product are reduced, and the intended composition cannot be obtained. The polypropylene component is preferably in the range of 3 to 60% by weight in consideration of flexibility, mechanical strength, heat resistance, impact resistance and the like. Further, the content of the ethylene-propylene random copolymer component is 25 to 99.99% by weight. When the content of the above component is less than 25% by weight, the low-temperature impact resistance is poor, and 98.9 is obtained.
If it exceeds 9% by weight, the mechanical properties such as the strength and heat resistance of the molded product are inferior and are not preferred. The ethylene-propylene random copolymer component is preferably in the range of 40 to 97% by weight in consideration of low-temperature impact resistance, mechanical strength, and heat resistance. The content ratio of each of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component is as follows:
It is from 10 to 40 mol%, preferably from 15 to 35 mol%, of monomer units based on ethylene. The proportion of monomer units based on propylene is 90 to 60 mol%, preferably 85 to 65 mol%. When the content ratio of monomer units based on ethylene is 1
When the content is less than 0 mol% and the content ratio of the monomer unit based on propylene exceeds 90 mol%, the flexibility and impact resistance at low temperature of the obtained film are not sufficient, which is not preferable. On the other hand, when the content ratio of the monomer unit based on ethylene exceeds 40 mol% and the content ratio of the monomer unit based on propylene is less than 60 mol%, the transparency of the obtained resin composition becomes insufficient. Not preferred. Further, the block copolymer used in the present invention has a melt index of 0.5 to 50 g / 10 m.
in. Melt index is 0.5g / 10mi
When it is less than n, the moldability is poor, and 50 g / 10 mi
If n exceeds n, the effect of improving impact resistance is undesirably reduced. Considering the moldability of the obtained resin composition and the effect of improving impact resistance, the melt index is 1.
It is preferably in the range of 0 to 30 g / 10 min. The block copolymer used in the present invention comprises:
When the molecular weight distribution represented by the ratio of the weight average molecular weight to the number average molecular weight by gel permeation chromatography is from 1.5 to 3.5, moldability and bleeding of low molecular weight components can be prevented. Preferred for. The polybutene component in the block copolymer used in the present invention must have an isotacticity of 0.90 or more in order to prevent solidification of the block copolymer particles and improve fluidity at high temperatures. Preferably, there is. The isotacticity of poly 1-butene was measured by ¹³ C-NMR, and was measured by using Polymer Jr.
) Is the value of mm when the attribution is made based on Vol. 16 (1984) pp. 716-726. The block copolymer used in the present invention includes:
Polybutene component, polypropylene component, propylene-ethylene random copolymer component in one or more,
As long as the physical properties of the resin composition are not impaired, other α-olefins may be copolymerized and contained in a small amount, for example, in a range of 5 mol% or less. The block copolymer used in the present invention is composed of a so-called block copolymer in which at least two or more of a polybutene component, a polypropylene component and a propylene-ethylene random copolymer component are arranged in one molecular chain. It is conceivable that the molecular chain composed of each of the polybutene component, the polypropylene component and the propylene-ethylene random copolymer component is microscopically mixed to such an extent that mechanical mixing cannot attain. The block copolymer used in the present invention is obtained as a powder having excellent fluidity by polymerization. This is surprising considering that a conventional propylene-ethylene random copolymer having an ethylene content similar to that of the block copolymer used in the present invention can be obtained in a lump due to adhesion between particles. The block copolymer used in the present invention may be obtained by any method. The following is a particularly preferred example of the method. That is, the following components A and B, or C and / or D.A. Titanium compound B. Organoaluminum compound C.I. Electron donor D. In the presence of an iodine compound represented by the general formula (i) R-I (i) (where R is an iodine atom or an alkyl group having 1 to 7 carbon atoms or a phenyl group), propylene is added in an amount of 0.1 to 0.1. 500g polymer / g
Preliminary polymerization is performed so as to be in the range of the titanium compound to obtain a catalyst-containing prepolymer, and then the polymerization of propylene and ethylene through the polymerization of 1-butene and the polymerization of propylene in the presence of the catalyst-containing prepolymer. A method is preferred in which a random copolymerization of the mixture is sequentially performed to obtain a high-molecular-weight powdery substance, which is further decomposed with an organic peroxide. Such a manufacturing method is disclosed in Japanese Patent Application Laid-Open No. 5-33132.
No. 8 and the like, and the block copolymer in the present invention is preferably produced according to the method. In this case, in the polymerization of the propylene-ethylene random copolymer component, the monomer unit based on propylene in the copolymer component is 60 to 90 mol%, preferably 65 to 85 mol%, and the monomer unit based on ethylene is It is necessary to mix propylene and ethylene so that the monomer unit is in the range of 10 to 40 mol%, preferably 15 to 35 mol%. For this purpose, usually, the mixing ratio of propylene and ethylene is 3% in terms of the gaseous ethylene concentration.
１４14 mol%, and preferably 3.5-12 mol%. Next, the component (B) of the resin composition of the present invention is polypropylene. The polypropylene in the present invention is a homopolymer of propylene, 90 mol% or more of propylene and an α-olefin other than propylene, for example,
Ethylene, 1-butene, 1-pentene, 1-hexene,
A random copolymer of at least 10 mol% of one or more such as 1-heptene and 4-methyl-1-pentene can be suitably used. The component (C) of the resin composition of the present invention has a density of 0.86 to 0.94 g / cm ³ and is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. is there. Such a copolymer is generally called a linear low density polyethylene. Considering the transparency, flexibility and impact resistance of the resin composition of the present invention, the density of the copolymer as the component (C) is 0.89 to 0.935 g / cm ^3.
It is preferable that The ethylene component is 75 to 9
9 wt%, α-olefin having 3 to 10 carbon atoms is 25 to 1
% By weight of the copolymer.
As the olefin, 1-butene, 1-pentene, 1-
Hexene, 1-heptene, 1-octene, 4-methyl 1
-It is preferably pentene or the like. The above-mentioned (A) of the resin composition of the present invention,
The amount of the components (B) and (C) is 40 to 100% by weight, preferably 50 to 100% by weight, based on the total amount of the components (A) and (B). Similarly, the component (B) is 60 to 0% by weight, preferably 50 to 0% by weight in the total amount of (A) and (B).
(A) component is less than 40% by weight, and (B) component is 60% by weight.
If the content is more than 10% by weight, mechanical strength is improved, but flexibility and impact resistance are undesirably reduced. The component (C) is used in an amount of 1 to 100 parts by weight, preferably 2 to 80 parts by weight, based on 100 parts by weight of the total of (A) and (B). When the amount of the component (C) is less than 1 part by weight, the effect of improving transparency is not sufficient.
If the amount exceeds 0 parts by weight, the effect of the transparency is rather lowered, which is not preferable. The above resin composition is appropriately blended with other resins and known additives such as an antioxidant, a light stabilizer, an antistatic agent, a crystal nucleating agent and the like within a range not to impair the effect. be able to. The resin composition of the present invention has excellent flexibility,
Since it has impact resistance and transparency, it can be used in various fields that require flexibility and transparency.
For example, wrap film, shrink film, stitch film, sealant film, sizing film, adhesive tape, masking film, agricultural film, medical film, etc. for film applications, stationery sheet, bite sheet, desk mat, As a molded article such as an agricultural sheet, it can be suitably used for a decorative box, a decorative bag, a packaging box, a packaging bag, a food container, miscellaneous goods parts, a toy, and the like. EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The measuring method used in the following examples will be described. 1) The number average molecular weight (Mn), the weight average molecular weight (Mw), and the ratio of the molecular weight of 10,000 or less were measured by GPC (gel permeation chromatography).
Waters GPC-150C was used at 35 ° C. using o-dichlorobenzene as a solvent. The column used is TSK gel GMH6-HT manufactured by Tosoh, and has a gel size of 10 to 15 μm. Calibration curves used as standard samples had weight average molecular weights of 950, 2900, 10,000, 50,000 and 49.000.
It was made using 80,000, 2.7 million and 6.75 million polystyrene. 2) A method for measuring the proportions of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component and a method for measuring the proportion of the polybutene component ¹³ C-NMR spectrum chart Was calculated.
That is, the respective proportions of the monomer units based on ethylene and the monomer units based on propylene in the propylene-ethylene random copolymer component are described first in Polymer, Vol. 29, 1988, p. 1848. The peak assignment is determined by the method and then the monomer units based on ethylene and the monomer units based on propylene are determined by the method described in Macromolecules, Vol. 10 (1977), page 773. Were calculated. Then
Based on propylene, the weight and ratio of the polybutene component were calculated from the integrated intensity ratio of the peak attributed to methyl carbon in the monomer unit and the peak attributed to methyl carbon in the polybutene component. 3) Measurement of isotacticity of poly 1-butene The measurement was carried out by ¹³ C-NMR, and the results were reported in Polymer Journal (Polymer J.) Vol. 16 (1984) 71.
The measurement was performed based on pages 6 to 726. 4) Melt index (MI) Measured according to JIS K7210. 5) Flexural modulus Measured according to JIS K7203. 6) Izod impact value (notched, 23
° C) It measured according to JISK7110. 7) Haze value Haze value was measured according to JIS K6714. Preparation Examples 1-1 to 1-3 (Preliminary polymerization) A 1-liter glass autoclave reactor equipped with a stirrer was sufficiently replaced with nitrogen gas, and 400 l of heptane was charged. Reactor temperature 20
C. and kept at 0.degree.
18 mmol, 22.7 mmol of ethyl iodide, 18.5 mmol of diethylaluminum chloride, and titanium trichloride (“TOS-17”, Marubeni Solvay Chemical)
After adding 2.7 mmol, propylene was continuously introduced into the reactor for 30 minutes so as to become 3 g per 1 g of titanium trichloride. The temperature during this period was kept at 20 ° C. After stopping the supply of propylene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene was washed four times with purified heptane. As a result of analysis, 1 g of titanium trichloride
2.9 g of propylene was polymerized per unit. (Main Polymerization) Step 1: A 1-liter stainless steel autoclave reactor equipped with a 1-butene polymerization stirrer was sufficiently replaced with nitrogen gas, and 40 ml of heptane was charged. Keep the temperature inside the reactor at 20 ° C,
18.15 mmol of diethylaluminum chloride,
Diethylene glycol dimethyl ether 0.18mmo
l, 22.7 mmol of ethyl iodide, and titanium-containing polypropylene obtained by pre-polymerization as titanium trichloride.
After adding 2.7 mmol, 1-butene was continuously introduced into the reactor for 2 hours so that the amount became 15 g per 1 g of titanium trichloride. The temperature during this period was kept at 20 ° C. 1
-After stopping the supply of butene, the inside of the reactor was replaced with nitrogen gas to obtain a titanium-containing poly 1-butene polymer. As a result of the analysis, 14 g of 1-butene was polymerized per 1 g of titanium trichloride. Step 2: Polymerization of Propylene and Copolymerization of Propylene-Ethylene To a 2-liter autoclave having been subjected to N ₂ substitution, 1 liter of liquid propylene and 0.70 mmol of diethylaluminum chloride were added, and the internal temperature of the autoclave was raised to 70 ° C. The temperature rose. 0.087 mmol of titanium-containing poly 1-butene polymer was added as titanium trichloride, and propylene was polymerized at 70 ° C for 60 minutes. No hydrogen was used during this time. Next, the internal temperature of the autoclave was rapidly reduced to 55.
° C and simultaneously with 0.50 mmol of ethyl aluminum sesquiethoxide and 0.0% of methyl methacrylate.
A mixed solution of 14 mmol was added, ethylene was supplied, and the concentration of ethylene gas in the gas phase was adjusted to 7 mol%.
Propylene and ethylene were copolymerized at 55 ° C. for 120 minutes. During this time, the ethylene gas concentration was maintained at 7 mol% while confirming the concentration by gas chromatography. No hydrogen was used during this time. After completion of the polymerization, unreacted monomers were purged to obtain a particulate polymer. No adhesion to the polymerization tank or the stirring blade was observed at all. The yield is 140 g,
The polymerization ratio of all the polymers was 7,370 g-polymer / g-titanium trichloride. Also, as a result of the above-mentioned polymerization of propylene alone, titanium trichloride was added at 70 ° C. for 60 minutes.
Per gram, 1030 g of propylene had been polymerized.
As a result, the polybutene component in the block copolymer was 0.1.
It turns out that 19 wt% and the polypropylene component are 14 wt%. The results are shown in Table 1. Next, 1,3-bis- (t-butylperoxyisopropyl) benzene as an organic peroxide was added to 30 kg of the obtained polymer at a ratio shown in Table 2, and an antioxidant was added. After adding 0.1 phr and mixing with a Henschel mixer for 1 minute, the mixture was mixed with a φ65 mm single screw extruder.
The mixture was melt-kneaded at 0 ° C. to obtain pellets. Production Examples 2 and 3 In the polymerization of 1-butene in Production Example 1, the polymerization amount of 1-butene was set to 3 g and 50 g per 1 g of titanium trichloride, and the copolymerization of propylene and ethylene was carried out at an ethylene gas concentration of 1 g. The same operation as in Production Example 1 was performed except that the amounts were 3.5 mol% and 8 mol%, respectively. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1. Production Example 4 Production of propylene in Production Example 1 was carried out except that the polymerization of propylene was conducted at 60 ° C. for 10 minutes and the copolymerization of propylene and ethylene was carried out so that the ethylene gas concentration became 12 mol%. The same operation as in Example 1 was performed. In a separate polymerization experiment, the polymerization rate of propylene at this time was 240 g-PP / g.
-TiCl. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1. Production Example 5 In the polymerization of propylene in Production Example 1, polymerization of propylene was performed at 70 ° C. for 5 hours, and copolymerization of propylene and ethylene was carried out so that the ethylene gas concentration became 13 mol%.
The same operation as in Production Example 1 was performed except that the operation was performed at 5 ° C. for 120 minutes. In a separate polymerization experiment, the polymerization rate of propylene at this time was 5100 g-PP / g-TiCl. The results are shown in Table 1. Furthermore, it melt-kneaded with the amount of organic peroxide shown in Table 2 in the same manner as in Production Example 1. Comparative Production Example 1 The same operation as in Production Example 1 was carried out except that the polymerization of 1-butene was not carried out in the main polymerization of Production Example 1. Table 1 shows the results
It was shown to. Further, the mixture was melt-kneaded with the organic peroxide in the amount shown in Table 2 in the same manner as in Production Example 1. Comparative Production Example 2 The same operation as in Production Example 1 was carried out except that the polymerization of 1-butene was changed to 600 g per 1 g of titanium trichloride in the main polymerization of Production Example 1. The results are shown in Table 1. Production Example 1
In the same manner as described above, the mixture was melt-kneaded with the organic peroxide in the amount shown in Table 2. Comparative Production Examples 3 and 4 In the polymerization of propylene of Production Example 1, propylene and ethylene were copolymerized except that the ethylene gas concentration was 20 mol% and 2 mol%, respectively. The same operation was performed. The results are shown in Table 1. Further, the mixture was melt-kneaded with the organic peroxide in the amount shown in Table 2 in the same manner as in Production Example 1. [Table 1] [Table 2] Examples 1 and 2 The pellets of the block copolymer obtained in Production Examples 1-1 and 1-2 and polyethylene having a butene content of 2.5 mol% (density 0.92 g / cm ³ , 1) was mixed in the ratio shown in Table 3, and the cylinder temperature was adjusted to 23 with a 50-ton injection molding machine.
Under a condition of 0 ° C. and a mold temperature of 40 ° C., a bending test piece, an Izod impact test piece and a 1 mmt haze measuring plate were prepared. The measurement was performed after leaving these test pieces to stand at room temperature for 48 hours. The results are shown in Table 3. Example 3 The pellets of the block copolymer obtained in Production Example 1-2, the propylene homopolymer (* A in the table) and the polyethylene used in Example 1 were mixed in the proportions shown in Table 3, Example 1
The test was performed in the same manner as described above. The results are shown in Table 3. Examples 4 to 9 Table 3 shows the pellets of the block copolymer obtained in Production Examples 1-2, 1-3, 2, and 3 and the polyethylene used in Example 1.
And the test was performed in the same manner as in Example 1. The results are shown in Table 3. Example 10 A pellet of the block copolymer obtained in Production Example 3 and polyethylene having an octene content of 2.56 mol% (density 0.9
08 g / cm ³ , * 2 in the table) were mixed at the ratio shown in Table 3, and a test was conducted in the same manner as in Example 1. Table 3 shows the results
It was shown to. Examples 11 to 13 Pellets of the block copolymer obtained in Production Example 3 and random polypropylene having an ethylene content of 3 mol% (* in the table)
B) and the polyethylene used in Example 10 were mixed at the ratio shown in Table 3, and a test was performed in the same manner as in Example 1. The results are shown in Table 3. Examples 14 and 15 The pellets of the block copolymer obtained in Production Examples 4 and 5 and the polyethylene used in Example 1 were mixed at the ratio shown in Table 3 and tested in the same manner as in Example 1. Was done. The results are shown in Table 3. Comparative Example 1 Pellets of the block copolymer obtained in Production Example 1-2 were tested in the same manner as in Example 1. The results are shown in Table 3. Comparative Example 2 Pellets of the block copolymer obtained in Production Example 3 and random polypropylene having an ethylene content of 3 mol% (* in the table)
B) and the polyethylene used in Example 1 were mixed at the ratio shown in Table 3, and a test was performed in the same manner as in Example 1.
The results are shown in Table 3. Comparative Example 3 The pellets of the block copolymer obtained in Production Example 3 were tested in the same manner as in Example 1. The results are shown in Table 3. Comparative Example 4 The pellets of the block copolymer obtained in Production Example 3 and the polyethylene used in Example 1 were mixed at the ratio shown in Table 3,
A test was performed in the same manner as in Example 1. The results are shown in Table 3. Comparative Examples 5 to 8 The pellets of the block copolymer obtained in Comparative Production Examples 1 to 4 and the polyethylene used in Example 1 were mixed in the proportions shown in Table 3, and were mixed in the same manner as in Example 1. The test was performed. The results are shown in Table 3. [Table 3] [Table 4]

Claims (1)

(57) [Claim 1] (A) A block copolymer containing a polybutene component, a polypropylene component, and a propylene-ethylene random copolymer component, wherein the polybutene component is 0.01 to 5%. % By weight, 1 to 70% by weight of a polypropylene component, and 2% of a propylene-ethylene random copolymer component.
5 to 98.9% by weight, and the propylene-ethylene random copolymer component contains 10 to 40 mol% of a monomer unit based on ethylene and 9
0-60 mol%, melt index 0.5-5
0 g / 10 min propylene block copolymer (B) polypropylene and (C) a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms having a density of 0.86 to 0.94 g / cm ³ (A) is 100 to 40% by weight, and (B) is 0 to 60% by weight in the total amount of (A) and (B).
Wherein (C) is 1 to 100 parts by weight with respect to 100 parts by weight in total of (A) and (B).