JP2019127580A - Polyolefin resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of simultaneously suppressing fish eyes, which is a defect in appearance, and imparting an excellent matte tone. SOLUTION: Each component of a specific polypropylene resin (a), a specific high-density polyethylene resin (b), a specific high-density polyethylene resin (c), and a specific low-density polyethylene resin (d) is blended. The respective compounding ratios are (a) / (b) / (c) / (d) = 35-65 / 15-25 / 15-25 / 5-15 (weight ratio; however, (b) ≧ (c). )> (D), and (a) + (b) + (c) + (d) = 100). [Selection diagram] Fig. 1

Description

  The present invention relates to a polyolefin resin composition, and more particularly to a resin composition suitable for a matte polypropylene film having both high haze and suppression of appearance defects.

Polypropylene resin is widely used as a film material, but in recent years, in order to satisfy the required characteristics of films according to each application, such as rigidity, transparency, surface shape, etc., accompanying the expansion of film application range, The polypropylene resin used as the raw material is also required to have high functionality and high balance.
One of them is a matte film having a surface shape which is roughened with a high haze value without an appearance defect called fish eye as much as possible. Applications include, for example, packaging materials with excellent design utilizing the appearance, and materials for non-adhesive surfaces of adhesive films utilizing the surface shape.
One means for obtaining such a film includes performing matte printing on the film surface or laminating a material having an appearance like Japanese paper. However, from the viewpoint of environmental protection and productivity improvement, weight reduction of the packaging material and simplification of the process are urgent issues, and the film appearance alone is not deteriorated without deteriorating the characteristics as the conventional packaging material. It is preferable to have.
In order to have a matte appearance with a single film, it is important to use a resin composition that can express high haze and roughness.
As an example of a method for obtaining such a resin composition, there is a method of blending inorganic fine particles such as silica, talc, and calcium carbonate with a polypropylene resin.
In addition, as a method not relying on inorganic particles, a method using a specific polypropylene resin composition, a so-called propylene-ethylene block copolymer (for example, see Patent Documents 1 and 2) or a high density relative to a polypropylene resin Methods of blending polyethylene and low density polyethylene (see, for example, Patent Documents 3, 4, and 5) have been proposed.
However, in any method, in order to obtain a high haze, an influence on physical properties such as an increase in fish eyes and film rigidity cannot be avoided. Therefore, in order to meet the demand for suppression of appearance defects from the market, which is becoming more severe year by year, the appearance of resin materials with high functionalization and high balance at an unprecedented high level has been desired.

JP 2011-184683 A JP 2011-252081 A JP 7-233291 A JP 2003-213069 A JP 2011-194588 A

  In the present invention, the surface is roughened due to the presence of irregular irregularities, and high haze makes it possible not only to obtain an excellent matte feeling but also to cause an appearance defect such as a fish eye, and to be external. An object of the present invention is to provide a resin composition suitable for a matte-polypropylene film, which is excellent in high resistance to film breakage due to factors.

The present inventors have intensively studied to obtain a polypropylene-based film having the above-mentioned properties. As a result, it has been found that the above object can be achieved with a polyolefin resin composition obtained by blending a specific polypropylene resin and a specific polyethylene resin, and based on these findings, the present invention is completed. It came.
The present invention is formed by blending a polypropylene resin (a), a high density polyethylene resin (b), a high density polyethylene resin (c), and a low density polyethylene resin (d), each set in a specific range. It is a main feature of the present invention to obtain a polyolefin resin composition (X).
That is, according to the first aspect of the present invention, the following components (a) to (d) are blended, and the blending ratio of each is (a) / (b) / (c) / (d) = 35 to 65/15 to 25/15 to 25/5 to 15 (weight ratio; provided that (b) ≧ (c)> (d) and (a) + (b) + (c) + (d A polyolefin resin composition (X) is provided, which is characterized in that
-Polypropylene resin (a): Melting | fusing point is 115-170 degreeC, and melt flow rate (MFR) (230 degreeC, 2.16 kg load) is 2.0-20.0 g / 10min.
High density polyethylene resin (b): density is 0.935 to 0.970 g / cm ³ , melt flow rate (MFR) (190 ° C., 2.16 kg load) is 0.1 to 1.0 g / 10 min Be.
High density polyethylene resin (c): density is 0.935 to 0.970 g / cm ³ , melt flow rate (MFR) (190 ° C., 2.16 kg load) is 0.01 g / min or more and 0.1 g / min Less than 10 minutes.
Low-density polyethylene resin (d): a density of less than 0.910 g / cm ³ or more 0.935 g / cm ^3, a melt flow rate (MFR) (190 ℃, 2.16kg load) from 0.05 to 0. 5g / 10 minutes.

  According to the second invention of the present invention, the polyolefin resin composition (X) according to the first invention and the polypropylene resin (Y) are blended, and the blending ratio of each is (X) / (Y ) = 15-53 / 85-47 (weight ratio; provided that (X) + (Y) = 100). A polypropylene resin composition is provided.

Further, according to the third invention of the present invention, a fish formed from the polypropylene resin composition according to the second invention, having a total haze of 50% or more at a thickness of 30 μm and having a long side of 0.2 mm or more the number of eye, single-layer film is provided, wherein the 5 or less at 1 m ² per.
Furthermore, according to the fourth invention of the present invention, there is provided a multilayer film comprising at least one layer formed of the polypropylene resin composition according to the second invention.

  The film obtained by blending the polyolefin resin composition (X) of the present invention has a rough surface due to the presence of irregular irregularities, and not only has an excellent matte feeling because of its high haze, It produces an exceptional effect that has not been seen in the past, such as excellent resistance to film breakage due to external factors, without causing appearance defects such as fish eyes.

1 is a SEM image of the unstretched monolayer film obtained in Example 2. FIG. FIG. 2 is a view of an SEM image of the unstretched single-layer film obtained in Comparative Example 13.

  The polyolefin resin composition (X) of the present invention is characterized by blending each component satisfying the requirements (a) to (d) at a specific ratio. Furthermore, the polypropylene resin composition of the present invention is characterized by blending the components (X) and (Y) at a specific ratio. Below, each component which comprises the polyolefin resin composition (X) of this invention and a polypropylene resin composition is demonstrated in detail.

[Structural component]
1. Polypropylene resin (a)
The polypropylene resin (a) used in the polyolefin resin composition (X) of the present invention is preferably a propylene homopolymer or a propylene-α-olefin random copolymer having an α-olefin content of less than 2% by weight, and more. Preferred is a propylene-α-olefin random copolymer. The α-olefin which is a copolymerization component with propylene may be one kind or a combination of two or more kinds. The α-olefin is preferably ethylene or an α-olefin having 4 to 20 carbon atoms, more preferably ethylene or an α-olefin having 4 to 10 carbon atoms, still more preferably ethylene or 1-butene. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl -1-pentene, 2-methyl-1-hexene and the like can be mentioned. Further, a blend of two or more of these polymers of a propylene homopolymer and a propylene-α-olefin random copolymer may be used. The blend may be either a melt blend obtained by melt-kneading these separately produced polymers, or a polymer blend obtained as a multistage polymer produced by a multistage polymerization method.

(1) Melting | fusing point of polypropylene resin (a) Melting | fusing point of polypropylene resin (a) needs to be 115-170 degreeC, Furthermore, it is preferable that it is 120-165 degreeC.
If the melting point is 115 ° C. or more, the melting point of the obtained polyolefin resin composition (X) does not decrease excessively, and a film having sufficient heat resistance can be obtained. In addition, when the melting point is 170 ° C. or lower, the polyolefin resin composition (X) can be prevented from becoming an unmelted material when using a blend with the polypropylene resin (Y).

(2) MFR of polypropylene resin (a)
The MFR (a) at 230 ° C. and a load of 2.16 kg of the polypropylene resin (a) needs to be 2.0 to 20.0 g / 10 minutes, and further 5.0 to 15.0 g / 10. It is preferable that it is a minute.
When the MFR (a) is 2.0 g / 10 min or more, the viscosity of the obtained polyolefin resin composition (X) does not decrease excessively, and the extrusion load in granulation or film forming can be reduced. Thus, excellent productivity can be secured. If the MFR (a) is 20.0 g / 10 min or less, the difference in viscosity with the resins (b), (c) and (d) to be blended does not become too large, and the fish It is possible to suppress the generation of a polymer gel which is the cause of eye.

  In addition, the acquisition method of these polypropylene resins (a) can use what was manufactured by the well-known polymerization method using the various well-known propylene polymerization catalysts besides using commercially available resin. The method for producing the polypropylene resin (a) is not particularly limited, and can be produced by any conventionally known polymerization method such as a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method, and the MFR is 2.0. If it exists in -20.0 g / 10min, it is also possible to manufacture using a multistage polymerization method.

2. High density polyethylene resin (b)
The high density polyethylene resin (b) used for the polyolefin resin composition (X) of the present invention is an ethylene homopolymer or an ethylene-α-olefin copolymer. The α-olefin which is a copolymerization component (subcomponent) with ethylene as the main component may be one type or a combination of two or more types. The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, more preferably an α-olefin having 3 to 10 carbon atoms, still more preferably propylene or 1-butene. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl -1-pentene, 2-methyl-1-hexene and the like can be mentioned. Furthermore, two or more kinds of blends of ethylene homopolymer and ethylene-α-olefin copolymer can be used.

(1) Density of High Density Polyethylene Resin (b) The density (b) of high density polyethylene resin (b) used for the polyolefin resin composition (X) of the present invention is 0.935 to 0.970 g / cm ³ And preferably 0.940 to 0.965 g / cm ³ .
When the density (b) is 0.935 g / cm ³ or more, a sufficient high haze expression effect can be imparted to the polyolefin resin composition (X). Further, if the density (b) is 0.970 g / cm ³ or less, the difference in density from the resins (a), (c), and (d) to be blended will not be too large, causing fish eyes. The generation of the polymer gel can be suppressed.
The density (b) can be adjusted mainly by the amount ratio of the α-olefin having 3 to 20 carbon atoms copolymerized with ethylene. Here, the density is a value measured by the method D (density reducing pipe) according to JIS K7112: 1999.

(2) MFR of high density polyethylene resin (b)
The MFR (b) of the high-density polyethylene resin (b) at 190 ° C. and a load of 2.16 kg needs to be 0.1 to 1.0 g / 10 minutes, and further 0.2 to 0.8 g. It is preferably 10 minutes.
If MFR (b) is 0.1 g / 10 min or more, the viscosity difference at the time of melting with each of the blended resins (a), (c) and (d) does not become too large, and the fisheye Generation of the polymer gel which is the cause can be suppressed. Moreover, if MFR (b) is 1.0 g / 10 minutes or less, the expression effect of roughening enough for polyolefin resin composition (X) can be provided.
In addition, commercially available resin can be utilized for the acquisition method of these high density polyethylene resin (b).

3. High density polyethylene resin (c)
The high density polyethylene resin (c) used for the polyolefin resin composition (X) of the present invention is an ethylene homopolymer or an ethylene-α-olefin copolymer. The alpha-olefin which is a copolymerization component (subcomponent) with ethylene which is a main component may be 1 type, or 2 or more types of combinations. The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, more preferably an α-olefin having 3 to 10 carbon atoms, still more preferably propylene or 1-butene. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl -1-pentene, 2-methyl-1-hexene and the like can be mentioned. Furthermore, two or more kinds of blends of ethylene homopolymer and ethylene-α-olefin copolymer can be used.
(1) Density of high density polyethylene resin (c) The density (c) of the high density polyethylene resin (c) used for the polyolefin resin composition (X) of the present invention is 0.935 to 0.970 g / cm ³ . And preferably 0.940 to 0.965 g / cm ³ .
When the density (c) is 0.935 g / cm ³ or more, a sufficient high haze expression effect can be imparted to the polyolefin resin composition (X). In addition, if the density (c) is 0.970 g / cm ³ or less, the difference in density from the resins (a), (b), and (d) to be blended does not become too large, causing fish eyes. The generation of the polymer gel can be suppressed.
In addition, the density (c) can be adjusted mainly by a quantitative ratio with a C 3-20 α-olefin copolymerized with ethylene. Here, the density is a value measured by the D method (density striking tube) according to JIS K7112: 1999.

(2) MFR of high density polyethylene resin (c)
The MFR (c) of the high-density polyethylene resin (c) at 190 ° C. and a load of 2.16 kg needs to be 0.01 g / 10 min or more and less than 0.1 g / 10 min, and further 0.02 It is preferable that it is -0.09g / 10min.
When the MFR (c) is 0.01 g / 10 min or more, the difference in viscosity with the resins (a), (b), and (d) to be blended does not become too large. Generation of the polymer gel which is the cause can be suppressed. Moreover, if MFR (c) is less than 0.1 g / 10min, sufficient roughening expression effect can be imparted to the polyolefin resin composition (X).
In addition, the acquisition method of these high-density polyethylene resins (c) can utilize commercially available resin.

4. Low density polyethylene resin (d)
The low density polyethylene resin (d) used for the polyolefin resin composition (X) of the present invention is an ethylene homopolymer or ethylene-α-olefin copolymer of a high pressure method. The α-olefin which is a copolymerization component (subcomponent) with ethylene as the main component may be one type or a combination of two or more types. The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, more preferably an α-olefin having 3 to 10 carbon atoms, still more preferably propylene or 1-butene. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl -1-pentene, 2-methyl-1-hexene and the like can be mentioned. Furthermore, two or more kinds of blends of ethylene homopolymer and ethylene-α-olefin copolymer can be used.

(1) Density of low density polyethylene resin (d) The density (d) of the low density polyethylene resin (d) used in the polyolefin resin composition (X) of the present invention is 0.910 g / cm ³ or more and 0.935 g / cm. it is required to be less than ^3, and more preferably from 0.915~0.930g / cm ^3.
When the density (d) is 0.910 g / cm ³ or more, the density difference from the high-density polyethylene resins (b) and (c) does not become too large, and the density (d) is 0.935 g / cm 2. If it is less than ³ cm ³ , the density difference with the polypropylene resin (a) does not become too large, so the density difference with each of the blended resins (a), (b) and (c) is alleviated, It is possible to suppress the generation of a polymer gel which is the cause of eye.
The density (d) can be adjusted mainly by the amount ratio of the C 3-20 α-olefin copolymerized with ethylene. Here, the density is a value measured by the D method (density striking tube) according to JIS K7112: 1999.

(2) MFR of low density polyethylene resin (d)
The MFR (d) at a load of 190 ° C. and 2.16 kg of the low density polyethylene resin (d) needs to be 0.05 to 0.5 g / 10 min, and further 0.06 to 0.45 g It is preferably 10 minutes.
If MFR (d) is 0.05 g / 10 min or more, the viscosity difference at the time of melting with each of the blended resins (a), (b) and (c) does not become too large, and the fisheye Generation of the polymer gel which is the cause can be suppressed. Moreover, if MFR (d) is 0.5 g / 10 minutes or less, the expression effect of roughening enough for polyolefin resin composition (X) can be provided.
In addition, commercially available resin can be utilized for the acquisition method of these low density polyethylene resin (d).

5. Ratio of (a), (b), (c), (d) in Polyolefin Resin Composition (X) The polyolefin resin composition (X) of the present invention is a polypropylene resin (a), a high density polyethylene resin (b) ), High density polyethylene resin (c), and low density polyethylene resin (d), and the blending ratio of each is (a) / (b) / (c) / (d) = 35-65. / 15 to 25/15 to 25/5 to 15 (weight ratio; provided that (b) ≧ (c)> (d) and (a) + (b) + (c) + (d) = 100) It is preferable that it is 41-59 / 17 to 23 / 17-23 / 7-13.
By making the blending ratio of the polypropylene resin (a) 35% by weight or more, the molded product has sufficient heat resistance and strength, and furthermore, a blend of the polyolefin resin composition (X) and the polypropylene resin (Y). At times, compatibility of the polyolefin resin composition (X) with the polypropylene resin (Y) can be secured. Moreover, the expression effect of sufficient roughening can be provided to polyolefin resin composition (X) by the mixture ratio of polypropylene resin (a) being 65 weight% or less.
By setting the blending ratio of the high density polyethylene resin (b) to 15% by weight or more, it is possible to impart a sufficient surface roughening expression effect to the polyolefin resin composition (X). Moreover, generation | occurrence | production of the polymer gel which is a cause of a fisheye can be suppressed by the mixture ratio of high density polyethylene resin (b) being 25 weight% or less.
By making the blending ratio of the high-density polyethylene resin (c) 15% by weight or more, it is possible to impart a sufficient roughening effect to the polyolefin resin composition (X). Moreover, generation | occurrence | production of the polymer gel which is the cause of a fisheye can be suppressed by the compounding ratio of a high density polyethylene resin (c) being 25 weight% or less.
By setting the blending ratio of the low density polyethylene resin (d) to 5% by weight or more, it is possible to obtain a uniformly roughened surface in a molded article containing the polyolefin resin composition (X). Moreover, sufficient roughening expression effect can be provided to polyolefin resin composition (X) by the mixture ratio of low density polyethylene resin (d) being 15 weight% or less.

6. Polypropylene resin (Y)
The polypropylene resin (Y) used in the polypropylene resin composition of the present invention is a polypropylene resin that can be used by blending with the polyolefin resin composition (X) of the present invention, preferably a propylene homopolymer or an α-olefin. It is a propylene-alpha-olefin random copolymer whose content is less than 2% by weight, and more preferably a propylene homopolymer. The α-olefin which is a copolymerization component with propylene may be one kind or a combination of two or more kinds. The α-olefin is preferably ethylene or an α-olefin having 4 to 20 carbon atoms, more preferably ethylene or an α-olefin having 4 to 10 carbon atoms, still more preferably ethylene or 1-butene. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 2-methyl -1-pentene, 2-methyl-1-hexene and the like can be mentioned. Further, a blend of two or more of these polymers of a propylene homopolymer and a propylene-α-olefin random copolymer may be used.
The polypropylene resin (Y) may have the same composition as the polypropylene resin (a) in the polyolefin resin composition (X) or may have a different composition, but a propylene homopolymer is particularly preferable.

(1) Melting Point of Polypropylene Resin (Y) The melting point of the polypropylene resin (Y) is not particularly limited, but is preferably 115 to 170 ° C., and more preferably 120 to 165 ° C.
When the melting point is 115 ° C. or more, a film having sufficient heat resistance and rigidity can be obtained. In addition, if the melting point is 170 ° C. or lower, it is not necessary to excessively increase the melting temperature at the time of film extrusion molding, so it is possible to suppress the occurrence of resin degradation products and ensure excellent quality stability. Can do.

(2) MFR of polypropylene resin (Y)
The MFR (Y) at a temperature of 230 ° C. under a load of 2.16 kg of the polypropylene resin (Y) is not particularly limited, but is 2.0 to 20.0 g / 10 min as a range suitable for film extrusion. Is more preferable, and it is more preferably 5.0 to 15.0 g / 10 min.
If MFR (Y) is 2.0 g / 10 min or more, the extrusion load in film forming can be reduced, and excellent productivity can be ensured. Moreover, if MFR (Y) is 20.0 g / 10 minutes or less, the viscosity difference at the time of melting with the polyolefin resin composition (X) to be blended does not become too large, and the polymer gel which is the cause of the fish eye Can be suppressed.

  In addition, the acquisition method of these polypropylene resins (Y) can utilize what was manufactured by the well-known polymerization method using the various well-known propylene polymerization catalysts besides using commercially available resin. The production method of the polypropylene resin (Y) is not particularly limited and can be produced by any polymerization method such as a conventionally known slurry polymerization method, bulk polymerization method, gas phase polymerization method, and the MFR is 2.0. If it exists in -20.0 g / 10min, it is also possible to manufacture using a multistage polymerization method.

7). Proportions of (X) and (Y) in the polypropylene resin composition The polypropylene resin composition of the present invention comprises the polyolefin resin composition (X) of the present invention and a polypropylene resin (Y), It is necessary that the blending ratio of (X) / (Y) = 15 to 53/85 to 47 (weight ratio; provided that (X) + (Y) = 100), and further 20 to 48 / It is preferable that it is 80-52.
By setting the blend ratio of the polyolefin resin composition (X) to 15% by weight or more, a film having a high haze value and a high surface roughness can be obtained. Moreover, the film which has sufficient impact resistance can be obtained by the compounding ratio of polyolefin resin composition (X) being 53 weight% or less.

[Other ingredients]
8. Olefin-based copolymer elastomer The polyolefin resin composition (X) of the present invention is an olefin for the purpose of lowering the melting point, imparting flexibility, improving the impact resistance, or improving the compatibility with the polypropylene resin (Y). A copolymer elastomer can be blended.
The main monomer (main component) relating to the polymer in the olefin copolymer elastomer is preferably selected from any one of ethylene, propylene, and 1-butene, and more preferably ethylene or propylene. The comonomer (subcomponent) is preferably at least one kind different in structure from the main monomer selected from the group consisting of ethylene, propylene, α-olefins having 4 to 10 carbon atoms and alkadienes having 4 to 10 carbon atoms. It is desirable that the content of the comonomer is 10% by weight or more and less than 50% by weight. When the comonomer content is 10% by weight or more and less than 50% by weight, the flexibility is improved, the impact resistance is good, and the combined effect becomes remarkable.
As the comonomer, ethylene, propylene, 1-butene, 1-hexene or 1-octene is preferable, and propylene, 1-butene, 1-hexene or 1-octene is more preferable.
Preferred representative examples of the olefin copolymer elastomer include ethylene-propylene copolymer elastomer, ethylene-propylene-1-butene copolymer elastomer, ethylene-1-butene copolymer elastomer, ethylene-1-hexene copolymer Unitary elastomer, ethylene-1-octene copolymer elastomer, ethylene-propylene-butadiene copolymer, ethylene-propylene-isoprene copolymer elastomer, ethylene-ethylene-butylene-ethylene block copolymer elastomer, ethylene-propylene-butylene -Ethylene block copolymer elastomer, propylene 1-butene copolymer elastomer, etc. are mentioned. Blends of one or more of these olefin copolymer elastomers can also be used.

(1) Density of Olefin-Based Copolymer Elastomer The density of the olefin-based copolymer elastomer is preferably 0.860 g / cm ³ or more and less than 0.910 g / cm ³ , more preferably 0.865 to 0. It is in the range of 905 g / cm ³ . If the density is less than 0.910 g / cm ³ , the compatibility of the polyolefin resin composition (X) with the polypropylene resin (Y) can be further improved.
Here, the density is a value measured according to JIS K7112.

(2) MFR of olefin copolymer elastomer
The melt flow rate (MFR) of the olefin copolymer elastomer is preferably in the range of 0.5 to 10 g / 10 minutes. If the melt flow rate (MFR) of the olefin copolymer elastomer is 0.5 g / 10 min or more, the extrusion characteristics at the time of film forming will be good, and the possibility of affecting the productivity of the film will increase. ,preferable. When the melt flow rate (MFR) is 10 g / 10 min or less, stickiness and bleed out hardly occur, and the impact resistance is improved, which is preferable.
MFR here is a value measured at a heating temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210: 1999, Annex A, Table 1, Condition D, and its unit is g / 10 minutes.

(3) Blending Amount of Olefin-Based Copolymer Elastomer The blending amount of the olefin-based copolymer elastomer is preferably in the range of 3 to 20 parts by weight with respect to 100 parts by weight of the polyolefin resin composition (X). By suppressing the compounding amount to 20 parts by weight or less, the polyolefin resin composition (X) according to the present invention does not impair the roughening expression effect originally possessed, and in 3 parts by weight or more, it is compatible. The effects of blending including improvement (lowering the melting point, imparting flexibility, and improving impact resistance) can be expected.
In addition, a commercially available elastomer can be utilized for the acquisition method of these olefin type copolymer elastomers.

9. Other Components In the polyolefin resin composition (X) of the present invention, a propylene-ethylene block co-polymer having a different composition from the various components used for the polyolefin resin composition (X) of the present invention within a range not impairing the effects of the present invention. A polypropylene resin such as a polymer, a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, or a styrene elastomer may be appropriately blended.
Further, within the range not impairing the effects of the present invention, antioxidants, ultraviolet absorbers, neutralizers, nucleating agents, light stabilizers, antistatic agents, lubricants, antiblocking agents, odor adsorbents, antibacterial agents, Known additives such as pigments, inorganic and organic fillers, and various synthetic resins can be added as needed.

[Production Method of Polyolefin Resin Composition (X)]
The polyolefin resin composition (X) of the present invention comprises a polypropylene resin (a), a high density polyethylene resin (b), a high density polyethylene resin (c), a low density polyethylene resin (d), and, if necessary, the above-mentioned Add the additives of [Other components], resin of other components, elastomer, etc. to Henschel mixer (trade name), V blender, ribbon blender, ribbon blender, tumbler blender etc. and mix and homogenize, then single screw extruder, multiple It can be exemplified that it is obtained as a pelletized polyolefin resin composition (X) by a method of melt-kneading and pelletizing in a temperature range of 190 to 260 ° C. by a kneader such as a shaft extruder, a kneader or a Banbury mixer.

[Production Method of Polypropylene Resin Composition]
The polypropylene resin composition of the present invention is a resin composition obtained by blending the polyolefin resin composition (X) of the present invention and a polypropylene resin (Y). As an aspect of a preferred production method, (1) a polyolefin resin composition (X), polypropylene resin (Y), and if necessary, the additives of the above-mentioned [other components], resin of other components, elastomers, etc., Henschel mixer (trade name), V blender, ribbon blender, tumbler A method of melting and kneading and pelletizing in a temperature range of 190 to 260 ° C. with a kneader such as a single screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer after being introduced into a blender and mixed and homogenized. Blend method), (2) pellet-shaped polyolefin resin composition (X), pellet-shaped polypropylene resin (Y), and If necessary, add the above-mentioned [Other component] additives, other component resins, elastomers, etc. in pellet form to Henschel mixer (trade name), V blender, ribbon blender, tumbler blender etc. Method of mixing and homogenizing (dry blend method), (3) pellet-shaped polyolefin resin composition (X), pellet-shaped polypropylene resin (Y), and, if necessary, additives for the above-mentioned [other components] , Resin of the other components, elastomers, etc. in pellet form, put into Henschel mixer (trade name), V blender, ribbon blender, ribbon blender, tumbler blender etc. and mixed and homogenized (dry blend method), then film forming Method to feed the film into a film (melt blending method), (4) pellet-like polyolefin A resin composition (X), a pellet-shaped polypropylene resin (Y), and, if necessary, a plurality of hoppers in the form of pellets containing the above-mentioned [other components] additives, other component resins, elastomers, and the like. Alternatively, each predetermined amount is film-formed after being respectively charged into the plurality of hoppers or the main hopper and at least one side feed supply port of a film forming machine provided with a main hopper upstream and at least one side feed supply port downstream. It can be exemplified that it is obtained as a pellet-like or film-like polypropylene-based resin composition by a method of supplying to a machine to form a film (melt-blending method).

[Film forming method]
The polypropylene resin composition containing the polyolefin resin composition (X) of the present invention is obtained as a film by a known melt extrusion film forming method.
For example, film formation such as an unstretched film by T-die cast method generally performed industrially, a uniaxially stretched film or biaxial stretched film in which heat stretching is performed after casting, or an inflation method in which cooling is performed in water or an air atmosphere Production of the film is possible by the method.
The film produced in this manner can be used as a single layer film or a multilayer (lamination) film.
In producing a film formed from the polypropylene resin composition of the present invention, polypropylene resin (a), high density polyethylene resin (b), high density polyethylene resin (c), low density polyethylene resin (d), and necessary According to the above, the additive of the above-mentioned [other component], resin of the other component, resin, elastomer and the like are mixed and homogenized, and then pelletized into polyolefin resin composition (X) in the form of pellets melt-kneaded by a kneader. It is preferable to supply the pellet-form polypropylene resin composition formed by mix | blending a polypropylene resin (Y) to a film molding machine, and to set it as a film.
Moreover, when manufacturing a multilayer film, when a multilayer film is provided with the layer obtained from resin compositions other than the polypropylene resin composition of this invention, as a material of this layer, polyolefin resin composition (X) of this invention is used. A propylene-ethylene block copolymer or a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, or a styrene-based elastomer having a different composition from the various components used in It can be used.

Next, the single layer film and the multilayer film of the present invention will be described in detail. The film of the present invention is a film obtained by melt extrusion film forming of a polypropylene resin composition containing the above-mentioned polyolefin resin composition (X) of the present invention as described in the above-mentioned film forming method, In the case of a multilayer film, at least one layer constituting the multilayer film is obtained using the above-described polypropylene resin composition of the present invention. According to the film of the present invention, by using the above-described polypropylene resin composition of the present invention, the film has a rough surface due to the presence of irregular irregularities, and has an excellent matte feeling due to high haze. A film having the same can be provided. In addition, when the film of this invention is a multilayer film and the layer obtained using the polypropylene-type resin composition containing the polyolefin resin composition (X) of this invention mentioned above is other than surface layer, the unevenness | corrugation of the surface is Although the size of the film can not be reduced, in this case as well, a deep, high haze, matte film can be obtained.
Specifically, the single-layer film of the present invention is obtained by melt extrusion film formation of a polypropylene resin composition containing the above-mentioned polyolefin resin composition (X) of the present invention, and the total haze at a thickness of 30 μm is 50% It is preferable that the number of fish eyes having a long side of 0.2 mm or more, more specifically appearance defects with a polymer gel as a core, is 5 or less per 1 m ² . The multilayer film of the present invention is preferably obtained by melt extrusion film formation using at least one layer of the above-described polypropylene resin composition of the present invention.
The thickness of the film is not particularly limited, but is preferably 5 to 200 μm, and more preferably 10 to 100 μm.
The surface of the film can be subjected to corona or plasma discharge treatment, flame treatment, ozone treatment, etc. in order to improve wettability of the surface.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is limited to a following example and is not interpreted.
[Method of measuring physical properties]
The detailed description of the present invention and the measurement of physical properties and analytical values of each item in the examples are according to the following methods.
(1) Melting point (unit: ° C)
Using a differential scanning calorimeter (DSC), once the temperature was raised to 200 ° C. and the thermal history was erased, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature rising rate was again 10 ° C./min. The temperature of the endothermic peak top at the time of measurement was taken as the melting point.
(2) MFR (unit: g / 10 minutes)
The MFR of the polypropylene resin was measured under the following conditions according to JIS K7210: 1999, Annex A, Table 1, Condition M.
Test temperature: 230 ° C Nominal load: 2.16kg
Die shape: 2.095mm in diameter, 8.000mm in length
The MFR of the polyethylene resin was measured under the following conditions in accordance with Annex A Table 1 and Condition D of JIS K7210: 1999.
Test temperature: 190 ° C Nominal load: 2.16kg
Die shape: 2.095mm in diameter, 8.000mm in length
(3) Haze of film (unit:%)
After adjusting the film under an atmosphere of 23 ° C. and 50% RH for 24 hours or more, haze (HAZE) was measured according to JIS-K7136, and this was defined as “total haze (%)”. The larger the value obtained, the more opaque it is.
(4) Film rigidity (unit: MPa)
The tensile modulus of elasticity of the film was measured under the following conditions, and the obtained value was used as a measure of stiffness. The method of calculating the tensile modulus of elasticity was in accordance with JIS K7127. In addition, it sampled so that a sample long side might become MD (flow direction at the time of film extrusion molding).
Sample length: 150 mm Sample width: 15 mm
Chuck distance: 100 mm Crosshead speed: 1 mm / min

(5) Fish eye of film (unit: piece / m ² )
Using a film having a thickness of 30 μm and a size of MD 300 mm × TD (vertical direction at the time of film extrusion) 200 mm, fish eyes having a long side of 0.2 mm or more were visually counted. The same operation was carried out on 10 sheets of film, and after the average number of fisheye per sheet was determined, the number of fisheye per 1 m ^{2 of} area was calculated.
(6) Impact resistance of film (unit: kJ / m)
After measuring the amount of work (J) required for penetrating fracture at an ambient temperature of 23 ° C., using a device conforming to JIS P8134, hitting the fixed film specimen with a 25.4 mm hemispherical metal penetration part The surface roughness of the film determined by dividing by the thickness of the film test piece (7) After adjusting the film for 24 hours or more in an atmosphere of 23 ° C. and 50% RH, the film is in accordance with JIS B-0601. About the contact surface with the cooling roll immediately after the die at the time of molding, the central surface average value (Ra) at a cutoff of 0.25 mm was measured and used as an index of the film surface roughness. The larger the obtained value, the larger the unevenness of the film surface.
This value is preferably 0.35 or more, and more preferably 0.37 or more in order to obtain a matte tone having a large and rough surface and sufficiently rough surface. Also, in order to suppress unintended unevenness transfer during film winding and air entrainment, this value is preferably 0.50 or less, and more preferably 0.48 or less.

[Resin used]
The various resin used for the Example and the comparative example is described below.
[Polypropylene resin (a)]
a-1: Made by Japan Polypropylene Corp., trade name Wintec (registered trademark), grade name WFX4M
Propylene-ethylene random copolymer by metallocene catalyst Melting point 125 ° C., MFR (230 ° C., 2.16 kg load) = 7 g / 10 min a-2: manufactured by Nippon Polypro Co., Ltd., trade name Novatec (registered trademark) PP, grade Name FX4G
Propylene-ethylene-1-butene random copolymer by Ziegler-Natta catalyst Melting point 126 ° C., MFR (230 ° C., 2.16 kg load) = 5 g / 10 minutes a-3: Nippon Polypro Co., Ltd., trade name Novatec ( Registered trademark) PP, grade name EG7F
Propylene-ethylene random copolymer with Ziegler-Natta catalyst Melting point: 143 ° C., MFR (230 ° C., 2.16 kg load) = 1.3 g / 10 min a-4: Nihon Polypro Co., Ltd., trade name Wintech (registered) Trademark name, grade name WMG03
Metallocene-catalyzed propylene-ethylene random copolymer Melting point 142 ° C., MFR (230 ° C., 2.16 kg load) = 30 g / 10 min a-5: manufactured by Nippon Polypro Co., Ltd., trade name Novatec (registered trademark) PP, grade Name BC3HF
Propylene-ethylene block copolymer by Ziegler-Natta catalyst Melting point 162 ° C., MFR (230 ° C., 2.16 kg load) = 8.5 g / 10 min a-6: Product name Novatec (registered trademark) manufactured by Nippon Polypro Co., Ltd. ) PP, grade name FB3B
Propylene homopolymer with Ziegler-Natta catalyst Melting point: 161 ° C, MFR (230 ° C, 2.16 kg load) = 7.5 g / 10 min

[High density polyethylene resin (b)]
b-1: Nippon Polyethylene Co., Ltd. product name Novatec (registered trademark) HD, grade name HB530
Density 0.962 g / cm ³ , MFR (190 ° C., 2.16 kg load) = 0.3 g / 10 min b-2: manufactured by Nippon Polyethylene Co., Ltd., trade name Novatec (registered trademark) HD, grade name HF560
Density 0.963 g / cm ³ , MFR (190 ° C, 2.16 kg load) = 7 g / 10 min

[High density polyethylene resin (c)]
c-1: Nippon Polyethylene Co., Ltd., trade name Novatec (registered trademark) HD, grade name HF313
Density 0.950 g / cm ³ , MFR (190 ° C., 2.16 kg load) = 0.05 g / 10 min

[Low density polyethylene resin (d)]
d-1: Nippon Polyethylene Co., Ltd. product name Novatec (registered trademark) LD, grade name LF128
Density 0.922 g / cm ³ , MFR (190 ° C., 2.16 kg load) = 0.25 g / 10 min d-2: Nippon Polyethylene Co., Ltd., trade name Novatec (registered trademark) LD, grade name LF443
Density 0.924 g / cm ³ , MFR (190 ° C, 2.16 kg load) = 1.5 g / 10 min

[Polypropylene resin (Y)]
Y-1: Japan Polypropylene Corporation, trade name Novatec (registered trademark) PP, grade name FA3KM
Propylene homopolymer with Ziegler-Natta catalyst Melting point: 163 ° C., MFR (230 ° C., 2.16 kg load) = 10 g / 10 min Y-2: Same as polypropylene resin (a-1) Y-3: Polypropylene resin (a- Same as 4)

Examples 1 to 8 and Comparative Examples 1 to 13
[Pelletization of polyolefin resin composition (X)]
Each of the above-mentioned polypropylene resin (a), high density polyethylene resin (b), high density polyethylene resin (c), and low density polyethylene resin (d) pellets was mixed in a tumbler at the ratios shown in Table 1. After homogenization, the mixture was melt-kneaded at 230 ° C. using a 35 mm diameter twin-screw extruder according to the following melt-kneading conditions to obtain pellets of the polyolefin resin composition (X).

[Molding method of single-layer matte polypropylene film]
Pellet-like polypropylene resin composition obtained by mixing and homogenizing each pellet of the obtained polyolefin resin composition (X) and the above-mentioned polypropylene resin (Y) in a tumbler in the ratio shown in Table 1 Was put into a hopper of a T-die molding machine, and an unstretched film was obtained with a T-die molding machine according to the following film molding conditions. Physical properties of each of the obtained films of Examples 1 to 8 and Comparative Examples 1 to 12 were measured according to the above-mentioned measurement method. Table 1 describes the evaluation results.
Moreover, after mixing each resin of resin (a)-(d) and polypropylene resin (Y) with a tumbler according to the ratio shown in Table 1 and equalizing each, according to the following melt-kneading conditions Using pellets melt-kneaded at 230 ° C. with an axial extruder, an unstretched film was obtained with a T-die molding machine according to the following film molding conditions. This is Comparative Example 13.

(Melting and kneading conditions)
Kneader: 35 mm diameter co-directional twin-screw kneader manufactured by Toshiba Machine Co. Kneading temperature: 230 ° C.
Screw rotational speed: 250 rpm Feeder rotational speed: 50 rpm
(Film forming conditions)
T-die molding machine: 35 mm diameter single-axis molding machine manufactured by Plako Corporation Extrusion temperature: 240 ° C
Die width: 330mm Lip opening: 0.8mm
Cooling roll temperature: 30 ° C. Take-up speed: 18.0 to 20.0 m / min Film thickness: 30 μm

[Discussion of Results of Examples and Comparative Examples]
As apparent from Table 1, the film using the polyolefin resin composition (X) and the polypropylene resin (Y) according to the present invention as raw materials has a rough surface, high haze and appearance defects. It is possible to obtain a film which has a reduced fish eye and excellent impact resistance (Examples 1 to 8).
On the other hand, at least one of (1) polypropylene resin (a), high density polyethylene resin (b), high density polyethylene resin (c), and low density polyethylene resin (d) satisfies any of the requirements described above When it is a polypropylene resin composition which mix | blended not the polyolefin resin composition (X) (comparative examples 1-10), (2) Blending ratio (weight ratio) of polyolefin resin composition (X) and polypropylene resin (Y) When the polypropylene resin composition deviates from the specific range described above (Comparative Examples 11 to 12), or (3) the polyolefin resin composition (X) manufactured in advance is not blended with the polypropylene resin (Y), Specifically, each of the resins (a) to (d) is mixed with the polypropylene resin (Y) without melt-kneading once or more and then melt-kneaded. In the case of a pelletized polypropylene-based resin composition (comparative example 13), it is possible that the film obtained has a high haze, surface roughness, low fish eye and impact resistance characteristics in a well-balanced manner. Not possible (Comparative Examples 1 to 13).
In addition, in Comparative Examples 1, 2, 6, 10, and 13, since a large number of fish eyes were present in the film, evaluation of physical properties other than fish eyes was not performed.
In addition, when the MD cross section of each film obtained was observed with a 2000 times magnification using an SEM (scanning electron microscope), as shown in the figure, the SEM image of the film of Example 2 (FIG. 1) In this case, it was possible to observe a domain having an elliptical shape and a size in the range of about 1 to 5 μm on a long side. On the other hand, in the SEM image (FIG. 2) of the film of Comparative Example 13, the shape was strain, and irregular domains of about 0.5 μm to 5 μm including a large number of small pieces were observed. In Comparative Example 13, since the size and shape of the domain can not be controlled, it is difficult to suppress the generation of an undesirable large domain causing the fisheye.
From the above results, in each example of the present invention, each performance of the rough surface film is significantly superior to each comparative example by pushing in a well-balanced manner, and the rationality and significance of the constitution of the present invention It can be said that the superiority over the prior art is clearly stated.

  The film blended with the polyolefin resin composition of the present invention has a rough surface and high haze, and does not cause appearance defects such as fish eyes, against film breakage due to external factors. It is excellent because of its high resistance. Also from the result of the SEM observation, it can be confirmed that the domain shape is precisely controlled. Taking advantage of these characteristics, for example, it can be used in various film fields such as improvement of the releasability from the roll by imparting surface irregularities to the non-adhesive surface of the pressure-sensitive adhesive film, and design improvement by imparting matte impression to the packaging film.

Claims (4)

Each component of the following (a) to (d) is blended, and the blending ratio of each is (a) / (b) / (c) / (d) = 35 to 65/15 to 25/15 to 25 / 5 to 15 (weight ratio; provided that (b) ≧ (c)> (d) and (a) + (b) + (c) + (d) = 100) Composition (X).
-Polypropylene resin (a): Melting point is 115-170 degreeC, Melt flow rate (MFR) (230 degreeC, 2.16 kg load) is 2.0-20.0 g / 10 minutes.
High density polyethylene resin (b): density is 0.935 to 0.970 g / cm ³ , melt flow rate (MFR) (190 ° C., 2.16 kg load) is 0.1 to 1.0 g / 10 min .
High density polyethylene resin (c): density is 0.935 to 0.970 g / cm ³ , melt flow rate (MFR) (190 ° C., 2.16 kg load) is 0.01 g / 10 min or more 0.1 g Less than 10 minutes.
Low-density polyethylene resin (d): a density of less than 0.910 g / cm ³ or more 0.935 g / cm ^3, a melt flow rate (MFR) (190 ℃, 2.16kg load) from 0.05 to 0. 5 g / 10 minutes.   The polyolefin resin composition (X) according to claim 1 and a polypropylene resin (Y) are blended, and each blending ratio is (X) / (Y) = 15 to 53/85 to 47 (weight ratio; However, (X) + (Y) = 100) The polypropylene resin composition characterized by the above-mentioned. It is formed from the polypropylene resin composition according to claim 2, the total haze at a thickness of 30 μm is 50% or more, and the number of fish eyes having a long side of 0.2 mm or more is 5 or less per 1 m ^2. A single layer film characterized by being   A multilayer film comprising at least one layer formed of the polypropylene resin composition according to claim 2.