JP2018065922A - Polypropylene-based resin composition, and laminate and biaxially oriented polypropylene film formed from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene-based resin composition used for a biaxially oriented polypropylene film, which is excellent in blocking resistance and dispersibility of an antiblocking agent, has less white spots, improves soiling by falling off of the antiblocking agent, and is free from fusion to a seal bar in a heat seal step at the time of bag making.SOLUTION: The polypropylene-based resin composition (A) contains a propylene-based polymer (a) having a melting point of 150°C or higher and a propylene-α-olefin resin composition (B), where the resin composition (B) is a composition obtained by blending a propylene-α-olefin copolymer (b) having a melting point of 110-140°C and a specific antiblocking agent, and a proportion of the resin component in the resin composition (B) is 50-100 pts.wt. of the copolymer (b) with respect to 100 pts.wt. of the resin component.SELECTED DRAWING: None

Description

  The present invention relates to a biaxially stretched polypropylene film having excellent anti-blocking properties and anti-blocking agent dispersibility and less white spots. More specifically, the anti-blocking agent is excellent in dispersibility. The present invention relates to a polypropylene-based resin composition used for a biaxially stretched polypropylene film, a laminate formed therefrom, and a biaxially stretched polypropylene film, in which white spots generated due to the above are extremely small and the stain due to the removal of the antiblocking agent can be improved.

In recent years, the required performance of biaxially oriented polypropylene films has been increasing, and there is a strong demand for films with high commercial properties and optical properties. Among these, the dispersibility of the antiblocking agent greatly affects the transparency, appearance, secondary processability, etc., and significantly affects the commercial value.
Anti-blocking is an indispensable performance at the time of film forming or secondary processing, and anti-blocking agents are usually used as suitable compounding agents for improving these performances. Sex greatly affects vitiligo. If the dispersibility of the anti-blocking agent is poor, appearance defects due to vitiligo occur, and the value as a product is lowered. Therefore, those with few vitiligo are essential. As an antiblocking agent, silicon dioxide, for example, synthetic silica, is often used because it is relatively soft and the film surface is not easily damaged by rubbing between films.

  However, when this anti-blocking agent is blended with a resin by a stirrer, the particles of the anti-blocking agent are easy to disintegrate, the particles become small, not only deteriorate the blocking resistance but also cause secondary aggregation. Therefore, there is a problem that a white spot-like appearance defect occurs and the product value is lowered.

As an attempt to solve such a problem, various techniques have been proposed (see, for example, Patent Documents 1 to 6).
Patent Document 1 discloses a polypropylene resin composition containing specific property synthetic silica in specific property polypropylene resin particles. However, when synthetic silica is used which is relatively hard with a pore volume of 0.7 ml / g or less, this is blended with a highly crystalline propylene polymer and used as a biaxially stretched film for the surface layer. Is difficult to support the anti-blocking agent due to the interfacial peeling between the propylene-based polymer and the anti-blocking agent generated in the stretching process, so that the anti-blocking agent falls off due to friction with the rolls, and the molding machine or product is contaminated. Therefore, it was not satisfactory.
Patent Document 2 discloses a stretched film obtained by blending a specific property of polypropylene resin particles with a silicon dioxide powder synthesized by a sedimentation method, followed by melt extrusion. However, other than the sedimentation method, a product that sufficiently satisfies the balance between dispersibility and detachability has not been obtained.
Further, Patent Document 3 discloses a polypropylene-based film obtained from a resin composition containing spherical synthetic silica and a propylene-based polymer whose average particle diameter, specific surface area, pore volume, and oil absorption amount are in a specific range. Although described, transparency, blocking resistance, dispersibility, appearance, moldability and the like were insufficient.
Furthermore, Patent Document 4 discloses prevention of the antiblocking agent from falling off by blending a specific propylene-based resin composition.
However, even if it is not necessarily in the range of Patent Document 4, the anti-blocking agent can be removed and is different from the present application.
Patent Document 5 discloses a stretched polypropylene film in which organic fine particles and an acid-modified polyolefin resin are blended and excellent in transparency, blocking resistance, appearance, and drop-off resistance.
It is effective to improve the drop-off property by blending an acid-modified polyolefin resin as in this document and improving the affinity with organic fine particles, but the anti-blocking agent is not necessarily within the scope of Patent Document 5. The drop-off property can be improved and is different from the present application.
Patent Document 6 discloses a method for producing a masterbatch in which a specific inorganic particle antiblocking agent is blended with an olefin polymer, but is outside the scope of the porephin polymer specifically described in the examples of this patent document. In the present invention, the present invention has found that an effect which is not supposed in this patent document is manifested, and is different from the present application.

JP 2001-072812 A JP 2008-144043 A JP 2008-208210 A Japanese Patent Laid-Open No. 2006-30767 JP 2001-72813 A JP 2006-96939 A

Conventionally, when a polypropylene homopolymer is laminated and a biaxially stretched polypropylene film is produced by blending a regular spherical silica or a highly spherical organic antiblocking agent into the layer, the interface between the antiblocking agent and the polypropylene peels off. However, when voids are generated, the anti-blocking agent may come off when it comes into contact with the roll in the subsequent process, and the roll or product may be contaminated. An organic anti-blocking agent with high sphericity cannot be blended.
Therefore, an object of the present invention relates to a biaxially stretched polypropylene film having excellent blocking resistance and dispersibility of an antiblocking agent and having less white spots, in order to meet the high performance required for the biaxially stretched polypropylene film. Since the antiblocking agent used in the present invention has excellent dispersibility, there are very few white spots caused by aggregation or poor dispersion, and there is no fusion to the seal bar in the heat sealing process during bag making. The present invention relates to a polypropylene resin composition used for an axially stretched polypropylene film, a laminate comprising the same, and a biaxially stretched polypropylene film.

In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, obtained a resin composition comprising a specific propylene copolymer and a specific antiblocking agent and a specific propylene polymer. When the polypropylene-based resin composition is used, the crystallinity of the resin component existing around the antiblocking agent particles is lowered, and the interfacial stress between the antiblocking agent and the resin component generated in the stretching process is reduced, and the interface It has been found that peeling is remarkably reduced and the occurrence of voids, which is a factor that causes the antiblocking agent to drop off, is extremely reduced, so that the dropping property is improved without necessarily requiring acid-modified polypropylene or surface treatment.
Furthermore, since the specific antiblocking agent is excellent in dispersibility, white spots are very little even when mixed with polypropylene particles having a relatively large particle size.
Generally, when blending antiblocking agent particles with polypropylene particles, it is important to make the mixed polypropylene particle diameter as small as possible and to make classification difficult in order to improve dispersibility.
When it is difficult, there are techniques to reduce the pore volume of the anti-blocking agent, hydrophilic treatment or hydrophobic treatment to the anti-blocking agent surface, blending acid-modified resin, etc., and obtaining dispersibility, etc. Used. However, since the antiblocking agent used in the present invention is excellent in dispersibility, a high concentration of the antiblocking agent can be blended while maintaining good dispersibility even when the polypropylene particles are relatively large. There are few.
Further, from the viewpoint of heat resistance, it is necessary that the heat resistance of the entire film is high in terms of heat applied during printing and fusion to a heat seal bar during bag making.
In particular, for the fusion to the heat seal bar, the melting point of the surface that contacts the heat seal bar is preferably high, and when heat sealing is performed in the bag making process, the polypropylene resin with respect to the surface that contacts the heat seal bar If the melting point is lower than the set temperature of the seal bar, the film melts and sticks, and the bag-making suitability is remarkably lowered.
Therefore, by adjusting the resin composition of the film within the scope of the present invention, the heat resistance is maintained while preventing the low melting point by suppressing the amount of the low crystal component to the limit, and the blocking resistance and the dispersibility are excellent. As a result, a biaxially stretched polypropylene film with reduced contamination due to falling off of the antiblocking agent and the like has been completed.
Based on these findings, a polypropylene resin composition of the present invention, a laminate comprising the same, and a biaxially stretched polypropylene film were provided, and the present invention was completed.

That is, according to the first invention of the present invention, a polypropylene resin composition (A) containing a propylene polymer (a) having a melting point of 150 ° C. or higher and a propylene-α-olefin resin composition (B). The propylene-α-olefin resin composition (B) is a composition obtained by blending a propylene-α-olefin copolymer (b) having a melting point of 110 to 140 ° C. and an antiblocking agent, Anti-blocking agent is a regular spherical silica having an average particle diameter of 1.0 to 5.0 μm by laser diffraction method, a specific surface area of 1 to 300 m ² / g by BET method and a pore volume of less than 0.7 ml / g (c ) Or an organic anti-blocking agent (d) having an average particle diameter of 1.0 to 5.0 μm by laser diffraction, and the anti-blocking in the polypropylene-based resin composition (A) The content of the adhesive is 0.01 to 1 part by weight with respect to 100 parts by weight of the propylene polymer (a), and the proportion of the resin component in the polypropylene resin composition (A) is the propylene polymer. (A) The propylene-α-olefin copolymer (b) is 1 to 15 parts by weight with respect to 100 parts by weight, and the proportion of the resin component in the propylene-α-olefin resin composition (B) is the resin component. Propylene-α-olefin copolymer (b) is 50 to 100 parts by weight with respect to 100 parts by weight, and a polypropylene resin composition (A) is provided.
According to the second invention of the present invention, in the first invention, the propylene-α-olefin copolymer (b) has a melt flow rate (230 ° C., 2.16 kg load) of 1 to 20 g / 10. The polypropylene resin composition is a propylene-ethylene-random copolymer or propylene-ethylene-1-butene random copolymer having a melting point of 120 to 140 ° C.

  According to a third aspect of the present invention, there is provided a laminate comprising at least two layers (1) and (2) different from each other, wherein the layer (1) is the polypropylene according to the first or second aspect. And the layer (2) contains the propylene polymer (a), and the content of the regular spherical silica (c) or the organic antiblocking agent (d) is a propylene polymer. (A) The laminated body which is less than 0.01 weight part with respect to 100 weight part is provided.

  Moreover, according to 4th invention of this invention, the biaxially stretched polypropylene film which consists of a laminated body in 3rd invention is provided.

  Moreover, according to 5th invention of this invention, the food packaging film which consists of a biaxially-stretched polypropylene film in 4th invention is provided.

  According to the polypropylene resin composition of the present invention, it has excellent blocking resistance and dispersibility, reduces stains due to white spots and dropping off of the antiblocking agent, and is further fused to the seal bar in the heat sealing process during bag making. It is possible to obtain a biaxially stretched polypropylene film having no slag.

  Hereinafter, the polypropylene resin composition of the present invention, the laminate comprising the same, and the biaxially stretched polypropylene film will be described in detail for each item, but the present invention is not limited to the following description, Any modifications can be made without departing from the scope of the invention. In the present specification, when a numerical value or physical property value is inserted before and after using the expression “to”, it is used in the meaning including the numerical value or physical property value before and after that.

[1] Polypropylene resin composition (A), propylene-α-olefin resin composition (B)
The polypropylene resin composition of the present invention is a polypropylene resin composition (A) containing a propylene polymer (a) having a melting point of 150 ° C. or higher and a propylene-α-olefin resin composition (B). The propylene-α-olefin resin composition (B) is a composition comprising a propylene-α-olefin copolymer (b) having a melting point of 110 to 140 ° C. and an antiblocking agent, and the antiblocking agent. A regular spherical silica (c) or laser having an average particle diameter of 1.0 to 5.0 μm by laser diffraction method, a specific surface area of 1 to 300 m ² / g by BET method and a pore volume of less than 0.7 ml / g An organic anti-blocking agent (d) having an average particle diameter of 1.0 to 5.0 μm by a diffraction method, and anti-blocking in a polypropylene resin composition (A) The content of the adhesive is 0.01 to 1 part by weight with respect to 100 parts by weight of the propylene polymer (a), and the proportion of the resin component in the polypropylene resin composition (A) is the propylene polymer. (A) The propylene-α-olefin copolymer (b) is 1 to 15 parts by weight with respect to 100 parts by weight, and the proportion of the resin component in the propylene-α-olefin resin composition (B) is the resin component. The polypropylene resin composition (A) is characterized in that the propylene-α-olefin copolymer (b) is 50 to 100 parts by weight with respect to 100 parts by weight.

As described above, the propylene-α-olefin resin composition (B) is a composition comprising a propylene-α-olefin copolymer (b) having a melting point of 110 to 140 ° C. and an antiblocking agent, Anti-blocking agent is a regular spherical silica having an average particle diameter of 1.0 to 5.0 μm by laser diffraction method, a specific surface area of 1 to 300 m ² / g by BET method and a pore volume of less than 0.7 ml / g (c ) Or an organic antiblocking agent (d) having an average particle diameter of 1.0 to 5.0 μm by laser diffraction.

[1-1] Propylene polymer (a)
The propylene polymer (a) is a propylene homopolymer having a melting point of 150 ° C. or higher, or a copolymer of propylene and an α-olefin other than propylene (hereinafter referred to simply as “propylene-α-” in the present specification). It may be referred to as “olefin copolymer”). The propylene polymer (a) preferably has a melting point of 155 ° C or higher, more preferably 157 ° C or higher, and further preferably 160 ° C or higher. Particularly preferred propylene polymer (a) is a propylene homopolymer having a melting point of 160 ° C. or higher. When the melting point of the propylene-based polymer (a) is 150 ° C. or more, it is preferable in terms of heat resistance. As a result, when a film used for a suitable application in the present invention is formed, the melting to the heat seal bar is performed. The suitability for bag making is greatly improved without wearing.
On the other hand, the upper limit of the melting point of the propylene polymer (a) is not particularly limited, but it is usually 170 ° C. or lower as a manufacturable product. The melting point of the propylene polymer (a) can be appropriately controlled mainly by the type of propylene and α-olefin other than propylene used as raw materials, the copolymerization ratio, MFR, and the like. The “melting point” as used herein refers to a differential scanning calorimetry method (DSC method) in accordance with the method described in JIS K7122 (1987) “Method for measuring the transition heat of plastics”, that is, a differential scanning calorimeter (DSC). : Melting peak temperature measured by Differential Scanning Calorimeter).

  The propylene-α-olefin copolymer is preferably a copolymer having a C 2-8 α-olefin excluding propylene and propylene as a comonomer, more preferably 99% by weight or more, and still more preferably 99%. It is a random copolymer of propylene and α-olefin of 0.5% by weight or more, particularly preferably 99.65% by weight or more and less than 100% by weight. Here, it may be a mixture of random copolymers having different α-olefins. Moreover, the comonomer which is a C2-C8 alpha olefin except the propylene copolymerized with a propylene may be used 1 type, and may be used in combination of 2 or more type. As the propylene-α-olefin copolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, and the like are preferable.

  Examples of the α-olefin having 2 to 8 carbon atoms excluding propylene include ethylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene and 3-methyl-1-butene. 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3 -Dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, 1-octene and the like can be mentioned.

  The propylene-based polymer (a) preferably has an isotactic index (II) indicating the crystallinity of 95% or more, more preferably 96% or more. When the isotactic index (II) is 95% or more, heat resistance is high, and therefore, it is preferable in terms of heat applied during printing and fusion to a heat seal bar during bag making. Control of the crystallinity of the propylene polymer (a) can be adjusted by controlling the molecular weight distribution according to the copolymerization ratio of the raw materials and the catalyst used. In addition, the isotactic index (II) which shows the parameter | index of crystallinity is measured from the residual amount (weight%) at the time of extracting with boiling heptane for 6 hours with an improved Soxhlet extractor.

[1-2] Propylene-α-olefin copolymer (b)
The propylene-α-olefin copolymer (b) used in the present invention is a propylene-α-olefin copolymer having a melting point of 110 to 140 ° C. When the melting point is 140 ° C. or lower, the crystallinity of the propylene-α-olefin copolymer (b) is lowered, and the crystallinity of the resin component existing around the antiblocking agent particles is also lowered. It becomes difficult to prevent the antiblocking agent from falling off. On the other hand, when the melting point is 110 ° C. or higher, the production of the propylene-α-olefin copolymer becomes easy. The melting point of the propylene-α-olefin copolymer (b) is preferably 120 to 140 ° C, and more preferably 125 to 140 ° C.
Further, the heat of fusion is preferably 80 kJ / kg or less, more preferably 70 kJ / kg or less. As described above, the propylene-α-olefin copolymer (b) having a heat of fusion of 80 kJ / kg or less can maintain good drop-off resistance due to a decrease in crystallinity. Here, the melting point and the heat of fusion are values measured by a differential scanning calorimetry (DSC method) based on the method described in JIS K7122 (1987).

  The propylene-α-olefin copolymer is preferably a copolymer having a C 2-8 α-olefin excluding propylene and propylene as a comonomer, more preferably a propylene content of 85 to 97% by weight, still more preferably. A random copolymer of propylene and an α-olefin of 85 to 95% by weight, particularly preferably 85 to 90% by weight. When the propylene content of the propylene-α-olefin copolymer (b) is 97% by weight or less, the crystallinity of the propylene-α-olefin copolymer (b) is lowered and exists around the antiblocking agent particles. Since the crystallinity of the resin component is also reduced, voids are less likely to occur and the antiblocking agent is prevented from falling off. On the other hand, when the propylene content is 85% by weight or more, the production of the propylene-α-olefin copolymer is facilitated. Here, it may be a mixture of random copolymers having different α-olefins. Moreover, the comonomer which is a C2-C8 alpha olefin except the propylene copolymerized with a propylene may be used 1 type, and may be used in combination of 2 or more type. As the propylene-α-olefin copolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, and the like are preferable.

  Examples of the α-olefin having 2 to 8 carbon atoms excluding propylene include ethylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene and 3-methyl-1-butene. 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3 -Dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, 1-octene and the like can be mentioned.

The propylene polymer (a) and the propylene-α-olefin copolymer (b) used in the present invention preferably have a melt flow rate (hereinafter also referred to as MFR) of 1 to 20 g / 10 min. 1-10 g / 10min is more preferable. A MFR of 1 g / 10 min or more and 20 g / 10 min or less is preferred in terms of extrudability and appearance.
The MFR was measured under the conditions of 230 ° C. and 2.16 kg load in accordance with ISO 1133: 1997. The unit is g / 10 minutes.
The MFR of the propylene-based polymer (a) and the propylene-α-olefin copolymer (b) is changed by changing the conditions of the polymerization temperature and the polymerization pressure, or by adding a chain transfer agent such as hydrogen during the polymerization, Easy to adjust.

The catalyst used for obtaining the propylene polymer (a) and the propylene-α-olefin copolymer (b) used in the polypropylene resin composition of the present invention is not particularly limited, and is a known catalyst. Can be used.
Ziegler-Natta catalysts are described in, for example, “Polypropylene Handbook” Edward P. Moore Jr. It is a catalyst system as outlined in Section 2.3.1 (pages 20-57) of the edited by Tetsuo Yasuda and Satoshi Sakuma, supervised by the Industrial Research Council (1998). For example, titanium trichloride and halogen Titanium trichloride catalyst composed of organoaluminum fluoride, solid catalyst component containing magnesium chloride, titanium halide and electron donating compound as essential components, magnesium supported catalyst composed of organoaluminum and organosilicon compounds, and solid catalyst component It refers to a catalyst in which an organoaluminum compound component is combined with an organosilicon treatment solid catalyst component formed by contacting organoaluminum and an organosilicon compound.
If it is a metallocene catalyst (for example, described in JP-A-5-295022), a Kaminsky catalyst using a metallocene compound can be used.

In addition, the polymerization process used to obtain the propylene polymer (a) and the propylene-α-olefin copolymer (b) used in the polypropylene resin composition of the present invention is not particularly limited, Known polymerization processes can be used. For example, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used. Further, either batch polymerization method or continuous polymerization method can be used, and if desired, a multi-stage continuous polymerization method such as two-stage or three-stage may be used. Moreover, it can manufacture also by melt-kneading mechanically 2 or more types of propylene-type polymers (a) or a propylene-alpha-olefin copolymer (b).
Furthermore, the propylene-α-olefin copolymer (b) used in the present invention is preferably a propylene-ethylene random copolymer and a propylene-ethylene-1-butene random copolymer, and these are in any ratio. It may be a mixture mixed in the above.

The proportion of the resin component in the polypropylene resin composition (A) of the present invention is 100 parts by weight of the propylene polymer (a) from the viewpoint of heat applied at the time of printing and fusibility to a heat seal bar at the time of bag making. On the other hand, a propylene-alpha-olefin copolymer (b) is 1-15 weight part, Preferably it is 1-12 weight part, More preferably, it is 1-10 weight part.
The proportion of the resin component in the propylene-α-olefin resin composition (B) used in the present invention is a propylene-α-olefin copolymer (100 parts by weight of the resin component from the viewpoint of the anti-blocking agent detachability). b) is 50 to 100 parts by weight, preferably 80 to 100 parts by weight, more preferably 90 to 100 parts by weight, still more preferably 95 to 100 parts by weight, and particularly preferably 100 parts by weight. Here, as a resin component other than the propylene-α-olefin copolymer (b) that can be used in a proportion of 50 parts by weight or less, polypropylene having a melting point higher than that of the propylene-α-olefin copolymer (b) is used. And at least one selected from propylene-α-olefin copolymers and propylene-based polymers (a) having a melting point of more than 140 ° C and less than 150 ° C.

[1-3] Anti-blocking agent The anti-blocking agent used in the present invention has an average particle diameter of 1.0 to 5.0 μm by a laser diffraction method, a specific surface area of 1 to 300 m ² / g and a pore volume by a BET method. Is an amorphous anti-blocking agent (d) having an average particle size of 1.0 to 5.0 μm by a regular spherical silica (c) having a particle size of less than 0.7 ml / g or a laser diffraction method.
The regular spherical silica (c) used in the present invention is regular spherical silicon dioxide. When the shape is spherical, the pore volume is smaller and the specific surface area is smaller than that of the irregular shape, so that the dispersibility is excellent and secondary aggregation is suppressed. As a result, in order to form a surface state having a uniform roughness, it is possible to improve the blocking resistance and suppress the occurrence of white spots due to aggregation.
The regular spherical silica (c) used in the present invention has an average particle size of 1.0 to 5.0 μm, preferably 1.0 to 4.0 μm, more preferably 1.5 to 3.5 μm. When it is 1.0 μm or more, the anti-blocking effect is excellent, and when it is 5.0 μm or less, the transparency is excellent.
The average particle diameter is a value measured by a laser diffraction method (based on ISO 13320 / JIS Z 8825-1).
Also, amorphous spherical silica (c) has a specific surface area of 1~300m ² / g, according to BET method is preferably 10~250m ² / g.
The regular spherical silica (c) used in the present invention has a pore volume of less than 0.7 ml / g, preferably 0.6 ml / g or less, while the lower limit is preferably 0.1 ml / g. It is.

  Further, the oil absorption amount of the regular spherical silica (c) is not particularly limited, but it can be said that the oil absorption amount has a correlation with the specific surface area and indicates the structure of the synthetic silica. For this reason, it is considered that the causal relationship is mainly high in the three-dimensional aggregate structure from the property of the amount of oil adsorbed. That is, if this value is large, it means that the synthetic silica alone tends to exist as an aggregate. Therefore, the regular spherical silica used in the present invention is preferably 1 to 150 ml / 100 g, more preferably 10 to 150 ml / 100 g. More preferred. It is preferable in terms of dispersibility that the oil absorption is 150 ml / 100 g or less.

When the average particle diameter of the regular spherical silica (c) is 5.0 μm or less, the unevenness of the surface of the obtained film is reduced, and thus the drop-off property is improved. On the other hand, when the average particle size is 1.0 μm or more, the slip property and blocking resistance of the film during winding are improved, which is preferable.
Further, when the specific spherical silica (c) has a specific surface area of 300 m ² / g or less, the silica is hard and is not easily disintegrated, so that secondary aggregation is difficult. As a result, the number of vitiligo is reduced and the appearance is improved.
Similarly, when the pore volume is less than 0.7 ml / g, silica is hard and difficult to disintegrate, and therefore, when mixed with the powdery propylene polymer (a), aggregation hardly occurs and vitiligo is reduced. Further, when the pore volume is less than 0.7 ml / g and within the range of 0.1 ml / g or more, secondary aggregation due to silica particle collapse is reduced, and thus the number of vitiligo is difficult to increase, and appearance This is preferable. Here, the measurement method of the pore volume is based on the mercury intrusion method or the N ₂ adsorption method.

The above-mentioned regular spherical silica (c) may be surface-treated with a surface treatment agent, and by being treated with the surface treatment agent, an effect of improving the detachability of the regular spherical silica (c) particles can be obtained. Examples of the surface treatment agent include paraffin, fatty acid, polyhydric alcohol, silane coupling agent, silicone oil, modified silicone oil, and citric acid. Among these, those treated with a silane coupling agent, silicone oil, modified silicone oil or citric acid are preferable, and in particular, in order to further enhance the effect of improving the detachability of silicon dioxide used as the regular spherical silica (c). For this, a surface treatment agent using a silane coupling agent or citric acid is preferable. The surface treatment agents listed above may be used alone or in combination of two or more.
Moreover, by using the regular spherical silica (c) surface-treated with the surface treatment agent, the dispersibility of the regular spherical silica (c) in the polypropylene resin can be improved, and the transparency and blocking resistance can be improved. A good biaxially stretched film can be obtained.

  The surface treatment method is not particularly limited, and various known methods can be used, but the surface treatment when using a silicone oil or a modified silicone oil or a silane coupling agent as the surface treatment agent. The method is exemplified below.

(1) In the case of silicone oil or modified silicone oil (1-1) A shaped spherical silica while stirring a solution of silicone oil or modified silicone oil (dissolved in toluene, xylene, petroleum ether, isopropyl alcohol, volatile silicone oil, etc.) Is added to impregnate the surface treatment agent, and then the solvent is removed and heat baking treatment is performed.
(1-2) While stirring the regular spherical silica using a mixer or blender, the silicone oil or the modified silicone oil or a solution thereof is sprayed while being stirred, followed by heat baking treatment.

(2) In the case of a silane coupling agent (2-1) After preparing a solution of the silane coupling agent in water, an organic solvent, etc., and stirring the solution, the shaped spherical silica was added to impregnate the surface treatment agent, Remove the solvent by filtration, squeezing, centrifuging, etc. and dry.
(2-2) Spray a solution of a silane coupling agent, its water, an organic solvent or the like while stirring the regular spherical silica using a mixer or blender and dry.
In addition, there is a method of coating a silica surface with a fatty acid metal salt or wax.

The amount of the silicone oil, modified silicone oil, or silane coupling agent that is a surface treatment agent for the regular spherical silica (c) depends on the degree of surface treatment and the specific surface area of the regular spherical silica, but cannot be generally determined. Surface treatment is actually performed at about 0.5 to 20 parts by weight with respect to 100 parts by weight of spherical silica, and the optimum amount can be determined.
In the case of using silicone oil and / or modified silicone oil, the baking treatment is usually about 200 to 350 ° C. for about 5 to 30 minutes in the case of dimethyl silicone oil, and usually about 120 for methyl hydrogen silicone oil. The reaction can be performed at a temperature of ˜150 ° C. for about 1 to 2 hours.

  The silicone oil and the modified silicone oil that can be used for the surface treatment are not particularly limited, and examples of the silicone oil (straight silicone oil) include dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane. The modified silicone oil includes those having an organic functional group in the side chain of dimethylpolysiloxane, those having a molecular chain terminal, or those having both side chain and terminal, for example, fluoroalkylpolysiloxane, Carbinol modified polysiloxane, polyether modified polysiloxane, amino modified polysiloxane, epoxy modified polysiloxane, carboxyl modified polysiloxane, methacryl modified polysiloxane, mercapto modified polysiloxane, phenol Modified polysiloxane, alkyl-modified polysiloxane, methylstyryl group-modified polysiloxane, fluorine-modified polysiloxane, and the like. Of these, methyl hydrogen polysiloxane, carbinol modified polysiloxane, amino modified polysiloxane, epoxy modified polysiloxane, carboxyl modified polysiloxane, methacryl modified polysiloxane or mercapto modified polysiloxane are preferably used.

  The silane coupling agent that can be used for the surface treatment is not particularly limited. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, methyltrimethoxysilane, γ -Methacryloxypropyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and the like. Among these, γ-methacryloxypropyltrimethoxysilane (organosilane) or 3-aminopropyltriethoxysilane (aminosilane) is preferable.

  The organic anti-blocking agent (d) used in the present invention has an average particle size by laser diffraction method of 1.0 to 5.0 μm, preferably 1.0 to 4.0 μm, more preferably 1.5 to 5.0 μm. 3.5 μm. When it is 1.0 μm or more, the anti-blocking effect is excellent, and when it is 5.0 μm or less, the transparency is excellent. Examples of the organic antiblocking agent include crosslinked polymethyl methacrylate fine particles, non-melting polysiloxane fine particles, polyamide fine particles, acrylic resin fine particles, and condensed fine particles having a triazine ring. Among these, it is preferable to use crosslinked polymethyl methacrylate fine particles.

The content of the antiblocking agent used in the present invention is selected in the range of 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the propylene polymer (a). . When the content is 0.01 parts by weight or more, the blocking resistance when a film is formed is excellent. Moreover, the transparency when it is set as a film as it is 1 weight part or less is excellent. Moreover, the ratio (blending amount) of the antiblocking agent in the propylene-α-olefin resin composition (B) used in the present invention is the resin component 100 in the resin composition (B) from the viewpoint of dispersibility of the antiblocking agent. Preferably it is 1-50 weight part with respect to a weight part, More preferably, it is 1-20 weight part, More preferably, it is 1-10 weight part, Most preferably, it is 1-5 weight part.
The antiblocking agent used by this invention can select and use an applicable product. A product corresponding to the regular spherical silica (c) can be obtained from, for example, Mizusawa Chemical Industry Co., Ltd., and a specific commercial product may include a trade name: Mizpearl series. A product corresponding to the organic antiblocking agent (d) can be obtained from, for example, Soken Chemical Co., Ltd., and specific commercial products include trade name: Chemisnow MX series.

[1-4] Other compounding agents In the polypropylene-based resin composition of the present invention, additives that are usually used for polypropylene-based resins are appropriately blended as necessary within a range that does not impair the object of the present invention. Can do. Examples of the additive include an antioxidant, an antistatic agent, a neutralizing agent, a stabilizer, and an inorganic filler.

[1-5] Preparation Method of Polypropylene Resin Composition (A) and Propylene-α-Olefin Resin Composition (B) As a preparation method of the polypropylene resin composition (A) of the present invention, a propylene polymer ( In the method of adding a predetermined amount of propylene-α-olefin copolymer (b) and regular spherical silica (c) or organic antiblocking agent (d) directly to the powder or pellet of a), the surroundings of the antiblocking agent particles It is impossible to lower the crystallinity of the resin component present in the resin and to prevent the antiblocking agent from falling off.
In order to produce the polypropylene resin composition (A) so as to exhibit the effects of the present invention, a propylene-α-olefin resin composition (B) described later, that is, a propylene-α-olefin copolymer (b) is prepared. Prepare in advance a composition (masterbatch) in which powders or pellets are blended with each predetermined amount of the shaped spherical silica (c) or the organic antiblocking agent (d) and further used as necessary. A method of adding the master batch to the powder or pellets of the propylene polymer (a) is necessary.

The polypropylene-based resin composition (A) of the present invention is mixed with a propylene-based polymer (a), a propylene-α-olefin resin composition (B), and a predetermined amount of additives used as necessary, and then melted. It is obtained by kneading.
A known method such as a tumbler mixer, a super mixer, a Henschel mixer (trade name), a screw blender, or a ribbon blender can be applied to the mixing. The melt kneading is not particularly limited as long as it is a method of melt kneading at a temperature equal to or higher than the melting point of the propylene-based polymer (a) using, for example, a melt extruder or a Banbury mixer.
The melt-kneading method can be easily carried out with either a single screw extruder or a twin screw extruder. However, in order to more effectively disperse the shaped spherical silica (c) or the organic antiblocking agent (d), A screw extruder is preferred.

The propylene-α-olefin resin composition (B) used in the present invention comprises a propylene-α-olefin copolymer (b), a shaped spherical silica (c) or an organic antiblocking agent (d), and further if necessary. It is obtained by melting and kneading after mixing predetermined amounts of additives used.
A known method such as a tumbler mixer, a super mixer, a Henschel mixer (trade name), a screw blender, or a ribbon blender can be applied to the mixing. The melt kneading is not particularly limited as long as it is a method of melt kneading at a temperature equal to or higher than the melting point of the propylene-α-olefin copolymer (b) using, for example, a melt extruder or a Banbury mixer.
The melt-kneading method can be easily carried out with either a single screw extruder or a twin screw extruder. However, in order to more effectively disperse the shaped spherical silica (c) or the organic antiblocking agent (d), A screw extruder is preferred.

As a preparation method of the propylene-α-olefin resin composition (B) used in the present invention, it can also be obtained by the following side feed method. That is, in a melt extruder equipped with a main hopper and a side feed supply port, a predetermined amount of propylene-α-olefin copolymer (b) powder or pellets is supplied from the main hopper, and the shaped spherical silica ( c) or a method in which a predetermined amount of the organic antiblocking agent (d) is supplied and melt kneaded at a temperature equal to or higher than the melting point of the propylene-α-olefin copolymer (b). The powder or pellet of the propylene-α-olefin copolymer (b) is a powder obtained by mixing the propylene-α-olefin copolymer (b) and a predetermined amount of additives to be used as necessary, or melt-kneaded after mixing. Pellets.
A known method such as a tumbler mixer, a super mixer, a Henschel mixer (trade name), a screw blender, or a ribbon blender can be applied to the mixing. The melt-kneading performed after mixing is not particularly limited as long as it is a method of melt-kneading at a temperature equal to or higher than the melting point of the propylene-α-olefin copolymer (b) using, for example, a melt extruder or a Banbury mixer.
The melt kneading method in the melt extruder provided with the main hopper and the side feed supply port can be easily carried out by either a single screw extruder or a twin screw extruder. However, the shaped spherical silica (c) or the organic antiblocking agent ( In order to carry out the dispersion of d) more effectively, a twin screw extruder is suitable.

[2] Laminate The laminate of the present invention is a laminate composed of at least two layers (1) and (2), and the layer (1) comprises the polypropylene resin composition of the present invention. The layer (2) contains the propylene polymer (a), and the regular spherical silica (c) or the organic antiblocking agent (d) with respect to 100 parts by weight of the propylene polymer (a). The content is less than 0.01 parts by weight, preferably 0 parts by weight.

[2-1] Layer (1)
A layer (1) is a layer which consists of a polypropylene resin composition of this invention. As will be described later, the biaxially stretched polypropylene film obtained from the laminate of the present invention obtained by forming a film is useful as a food packaging film. In this case, the layer (1) is used as a non-printing surface. It is preferable to be used. By using the polypropylene resin composition of the present invention for the layer (1), as shown in the examples, it is excellent in blocking resistance and dispersibility, and a good film is obtained against white spots and shedding. Can do.

[2-2] Layer (2)
The layer (2) is a layer containing the propylene polymer (a). When the biaxially oriented polypropylene film obtained from the laminate of the present invention obtained by film formation is used as a food packaging film, it is preferably a laminate comprising at least three layers. In this case, the layer (2) Becomes the core layer. Hereinafter, when the expression “core layer” is used, it is an explanation assuming a laminate including at least three layers.
The core layer usually does not contain an antiblocking agent or is preferably used in a small amount even if it is used. In the laminate of the present invention, the layer (2) contains 100 parts by weight of the propylene polymer (a). On the other hand, the content of the antiblocking agent is less than 0.01 parts by weight. In the resin composition used for the layer (2), the lower limit of the content of the antiblocking agent is 0.
The layer (2) is not particularly limited as long as it is a layer containing the propylene polymer (a). However, the layer (2) only needs to have good adhesion when laminated with the layer (1), so that the propylene polymer (a ) Is preferably 50% by weight or more, more preferably 70% by weight or more, based on 100% by weight of the total components contained in the layer (2). In the laminate of the present invention, the same kind of propylene polymer (a) may be used for the layer (1) and the layer (2), or different ones may be used. However, it is a laminate that a combination of the propylene-based polymer (a) used in each of the layer (1) and the layer (2) having similar physical properties such as melting point, MFR, crystallinity, etc. is used. From the viewpoint of adhesion between the layers.

When the layer (2) is a core layer, the layer (2) preferably contains an antistatic agent. In the resin composition used for the layer (2), any conventionally known antistatic agent can be used. Examples thereof include cationic, anionic and nonionic (glycerin, amine, amide). An antistatic agent such as These antistatic agents may be used alone or in combination of two or more.
In the layer (2), the antistatic agent is preferably 0.1 parts by weight or more, more preferably 0.1 parts by weight or more and 8 parts by weight with respect to 100 parts by weight of the propylene polymer (a). It is as follows. By being 0.1 parts by weight or more, the antistatic effect in the layer (2) becomes good, and the upper limit is usually 10 parts by weight from the viewpoint of adhesion between the layer (1) and the layer (2).

[2-3] Other layers The laminate of the present invention has other layers such as a laminate layer, an anchor coat layer, a sealant layer, and a printed layer in addition to the layers (1) and (2). Also good. In particular, when the laminate of the present invention is used for a food packaging film or the like, the printed layer is laminated on the side opposite to the layer (1) with the layer (2) in between for use in a food packaging film or the like. Is preferred.

[3] Biaxially stretched polypropylene film The biaxially stretched polypropylene film of the present invention comprises the laminate of the present invention obtained by film formation as described above. Therefore, the biaxially stretched polypropylene film of the present invention is a multilayer film composed of two or more layers. The layer (1) which is a layer made of the polypropylene resin composition of the present invention is a non-printing surface, and the layer in contact with the non-printing surface is a layer containing the propylene polymer (a) of layer (2), specifically Specifically, the above-described core layer is preferable.

  In the biaxially stretched polypropylene film of the present invention, the total thickness is preferably 5 to 60 μm, more preferably 15 to 40 μm. The biaxially stretched polypropylene film of the present invention is widely used for packaging applications such as food packaging, fiber packaging, and miscellaneous goods packaging.

  A surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.) was used as a film surface of a biaxially stretched polypropylene film obtained from a polypropylene resin composition containing the regular spherical silica (c) or the organic antiblocking agent (d) according to the present invention. In accordance with JIS B 0651 (2001) “Geometric characteristics of products (GPS) —Surface properties: Contour curve method—Characteristics of stylus surface roughness measuring machine” with SURFCOM 1500DX) or an equivalent device. The measured ten-point average roughness value (SRRz) is preferably in the range of 1.0 to 2.3 from the viewpoint of the balance of scratch resistance, dropout resistance, and blocking resistance. In particular, when the 10-point average roughness value is in the range of 1.0 to 2.3, the smaller the value, the better the drop-off property, while the 10-point average roughness value is 1.0 to 2. In the range of 3, the larger the value, the better the anti-blocking property.

[3-1] Stretching method of biaxially stretched polypropylene film The biaxially stretched polypropylene film of the present invention can be produced by a simultaneous or sequential biaxial stretching method or an inflation method. Among these, the sequential biaxial stretching method shown below is preferable.
The polypropylene resin composition of the present invention described above is melt-molded with a T-die to produce a raw fabric sheet, and then longitudinally stretched using a difference in roll peripheral speed. Specifically, the raw sheet is passed between two rolls having different rotation speeds at a temperature of usually 90 to 150 ° C., preferably 100 to 140 ° C., and usually 3 to 3 in the rotation direction (longitudinal direction) of the roll. Stretch 7 times, preferably 4-6 times. Next, the longitudinally stretched film is usually stretched 6 to 12 times, preferably 7 to 10 times in a tenter oven.

  Subsequently, it is desirable to heat set this biaxially oriented polypropylene film usually at a temperature of 130 to 180 ° C. Furthermore, for the purpose of improving the printability and promoting the expression of the effect of the antistatic agent, a heat treatment by corona discharge treatment or corona treatment and heating of a winder roll is preferably 80 to 130 ° C., more preferably 90 to 120. C., more preferably 100 to 110.degree.

[3-2] Use of biaxially stretched polypropylene film The biaxially stretched film of the present invention is widely used for packaging applications such as food packaging, fiber packaging, and miscellaneous goods packaging. The use is preferably performed on the opposite side of the food packaging film that is printed on the surface. In the case of the opposite side where the food packaging film is not printed, it is required to give product value such as dropout during production, blocking during secondary processing and final product, transparency and appearance, Since the biaxially stretched polypropylene film of the present invention is excellent in these properties, it can be suitably used. When the biaxially stretched polypropylene film of the present invention is used as a food packaging film, the layer (1) made of the above-described polypropylene resin composition of the present invention is used as an opposite side (non-printing surface) layer on which printing is not performed. It is preferable to use it because it can improve the product value and impart performance such as high quality maintenance.

The present invention will be described more specifically with reference to the following examples. However, the following examples are examples of embodiments of the present invention, and the present invention is not limited to the following examples. . Further, various production conditions and evaluation result values in the following examples have meanings as preferred values of the upper limit or the lower limit in the embodiment of the present invention, and the preferred range is the value of the above upper limit or lower limit. And a range defined by a combination of values of the following examples or values of the examples.
The physical properties of Examples and Comparative Examples were measured by the following methods.

[Polypropylene resin properties]
1. MFR:
Using a melt indexer L244 manufactured by Takara Thermistor, measurement was performed under the conditions of 230 ° C. and 2.16 kg load in accordance with ISO 1133: 1997. The unit is g / 10 minutes.
2. Melting point:
It was measured by a differential scanning calorimetry method (DSC method) based on the method described in JIS K7122 (1987) “Method for measuring the transition heat of plastic”. The unit is ° C.
Specifically, using a trade name Q2000 type differential thermal scanning calorimeter (DSC) manufactured by TA Instruments Inc., a sample of 5.0 mg was taken, and the temperature was once increased to 200 ° C. to erase the thermal history. Thereafter, the endothermic peak top temperature when the temperature was lowered to −10 ° C. at a temperature lowering rate of 10 ° C./min and again raised to 200 ° C. at a temperature rising rate of 10 ° C./min was taken as the melting point. In addition, when several peaks were observed, the highest peak temperature was made into melting | fusing point.
3. GPC (Q value)
The polypropylene resin in the present invention has a ratio [Mw / Mn (hereinafter referred to as Q value)] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained by gel permeation chromatography (GPC). It is preferably 5 to 5.5.
The Q value is an index representing the spread of the molecular weight distribution, and the larger the value, the wider the molecular weight distribution. Therefore, from the viewpoint of moldability, the Q value is preferably 2.5 or more, more preferably 2.6 or more, and further preferably 2.7 or more. On the other hand, from the viewpoint of cleanliness due to the amount of the low molecular weight component, the Q value is preferably 5.5 or less, more preferably 5.2 or less.
The Q value is a physical property value affected by the uniformity of the active site of the catalyst. Since a catalyst containing a single metallocene complex has a relatively uniform active site, a catalyst containing a single metallocene complex is used. In many cases, the resulting propylene polymer has a Q value of about 2 to 2.5.
The specific measurement method of GPC is as follows.
Apparatus: GPC manufactured by Waters (ALC / GPC 150C)
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: Showa Denko AD806M / S (3 in series)
-Mobile phase solvent: orthodichlorobenzene (ODCB)
・ Measurement temperature: 140 ℃
・ Flow rate: 1.0 ml / min
・ Injection volume: 0.2ml
Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
Conversion from the retention capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve prepared in advance by standard polystyrene (PS). The standard polystyrenes used are all the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000 A solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL To create a calibration curve. The calibration curve uses a cubic equation obtained by approximation by the least square method.
In addition, the following numerical value is used for the viscosity formula [η] = K × M ^α used for conversion to molecular weight.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78
4). Comonomer composition
^The comonomer content was measured by ¹³ C-NMR method. That is, the measurement was performed at 130 ° C. using a GSX-400 FT-NMR manufactured by JEOL Ltd., and the number of integration was 6000 times. The resulting peak is Appl. Polym. Sci. 80, 2001, 1880-1890. The comonomer (ethylene, 1-butene) content was calculated according to

[Anti-blocking agent properties]
1. Average particle diameter: measured using a laser diffraction particle size distribution measuring apparatus.
2. BET specific surface area; calculated from nitrogen adsorption measurement using an automatic gas adsorption amount measuring device.
3. Pore volume: Calculated from nitrogen adsorption measurement using an automatic gas adsorption amount measuring device.
4). Oil absorption: measured according to JIS K5101.

[Film evaluation method]
1. Evaluation of fusion to the seal bar Evaluation of fusion to the seal bar is as follows.
・ Equipment: “TP-701-B HEAT SEAL TESTER” manufactured by Tester Sangyo Co., Ltd.
・ Seal temperature: 155 ℃
Seal pressure: 2 kg / cm ² (0.20 MPa)
・ Sealing time: 1 sec
・ Seal bar: 1cm x 20cm
Two films described in the examples and comparative examples were overlapped and inserted into the seal bar, and whether or not they were fused to the seal bar when sealed under the above-mentioned conditions was evaluated.
A: No adhesion to the seal bar is observed.
○: Fusing to the seal bar is hardly observed. ×: Fusing to the seal bar.
2. Hayes:
Using a Nippon Denshoku turbidimeter (NDH2000), it was measured according to ASTM D-1003. The smaller the haze value, the better the transparency.

3. Blocking strength (N / 10 cm ² ):
The measurement was performed according to the method described in ASTM D-1893. Films were adjusted to a size of 30 cm (width) × 20 cm (length), and these films were stacked on the corona-treated surface and non-treated surface, and a gear oven at 40 ° C. under a load of 15 kg / cm ² (1.47 MPa) ( After leaving for 7 days in Tabei Espec / Tabai Gear Oven: GPH-100), a test piece cut to ² cm (width) x 15 cm (long) and an overlapping area of 10 cm ² is used as a tensile tester (Toyo Seiki Seisakusho) The peel strength was measured with a tensile speed of 500 mm / min. The smaller the peel strength value, the better the blocking resistance.

4). Stacking blocking:
A sample of a biaxially stretched polypropylene film is subjected to corona discharge treatment on both sides, and the resulting film is adjusted to a size of 20 cm (width) × 20 cm (length). The product was allowed to stand for 5 days in a state where a load of 50 kg was applied in a gear oven adjusted to 1 (product of Tabai Espec Co., Ltd./Tabai Gear Oven: GPH-100).
The film peeled state when both ends of the obtained film were loosened by hand three times was subjected to sensory evaluation, and blocking resistance was evaluated in the following five stages, and a value of ◯ or higher was evaluated as good.
Good blocking resistance: ◎ → ○ → △ → × → XX: Poor blocking resistance ◎: The films are already peeled even if they are not loosened by hand.
○: After loosening by hand, the film becomes peeled.
Δ: After loosening by hand, 50% or more of the film is in a peeled state.
X: After loosening by hand, 50% or more of the film is in a close contact state in a plate shape.
XX: After loosening by hand, the film is in close contact with the plate, and there is no peeled part.

5). Anti-blocking agent shedding test:
In the winding process of the biaxially stretched polypropylene film, a black mount was attached to a guide roll that was fixed so as not to rotate, and then the biaxially stretched polypropylene film was held for 5 minutes while being slid on the surface of the mount. Thereafter, the whiteness of the white powder portion of the anti-blocking agent attached to the black mount was visually evaluated in five stages, and the o or better was evaluated as good.
Good detachability: ◎ → ○ → △ → × → XX: Poor detachability ◎: Almost no white part.
○: Some white portions are present.
Δ: A thin white portion is present throughout.
X: There is clearly a white portion on the whole.
XX: The whole has a dark white part.

6). Ten-point average roughness value (SRRz):
The film surface was measured with a surface roughness meter (SURFCOM 1500DX) manufactured by Tokyo Seimitsu Co., Ltd. In the present invention, the measurement was performed in accordance with JIS B 0651 (2001) “Product Geometric Characteristic Specification (GPS) —Surface Property: Contour Curve Method—Characteristic Surface Roughness Measuring Machine Characteristic”. Measurement conditions of the measuring instrument are: stylus tip curvature radius: 5 μm, cutoff wavelength: 0.05 mm, cutoff type: 2CR (phase compensation), measurement speed: 0.3 mm, measurement direction: MD direction of film, measurement range : 2 mm ² . The MD direction, which is the measurement direction, refers to the film feed direction when extrusion molding, that is, the direction parallel to the longitudinal direction of the film.
The ten-point average roughness value is defined in JIS B 0601 (2001) “Product Geometrical Specification (GPS) —Surface Properties: Contour Curve Method—Terminology, Definition, and Surface Property Parameters”. When the 10-point average roughness value was in the range of 1.0 to 2.3, it was evaluated that the balance between the dropout property and the blocking resistance was good.

7). Maximum height (SRt)
The measurement was performed in the same manner as the ten-point average roughness value. The maximum height is defined in JIS B0601 (2001) “Product Geometric Specification (GPS) —Surface Properties: Contour Curve Method—Terms, Definitions, and Surface Properties Parameters”. The smaller the value, the better the scratch resistance and drop-off property.

8). Center plane average (SRa)
The film surface was measured with a surface roughness meter (SURFCOM 1500DX) manufactured by Tokyo Seimitsu Co., Ltd. In the present invention, the measurement was performed in accordance with JIS B 0651 (2001) “Product Geometric Characteristic Specification (GPS) —Surface Property: Contour Curve Method—Characteristic Surface Roughness Measuring Machine Characteristic”. Measurement conditions of the measuring instrument are: stylus tip curvature radius: 5 μm, cutoff wavelength: 0.05 mm, cutoff type: 2CR (phase compensation), measurement speed: 0.3 mm, measurement direction: MD direction of film, measurement range : 2 mm ² . The MD direction, which is the measurement direction, refers to the film feed direction when extrusion molding, that is, the direction parallel to the longitudinal direction of the film.
The average value of the center plane is defined by JIS B 0601 (2001) “Product Geometric Characteristic Specifications (GPS) —Surface Properties: Contour Curve Method—Terms, Definitions, and Surface Property Parameters”. When the center plane average value was in the range of 0.01 to 0.03, it was evaluated that the balance between the drop-off property and the blocking resistance was good.
9. Surface protrusion:
The film surface was measured under the same conditions as the ten-point average roughness value, and the number per 2 mm ^{2 of} protrusions of 0.1 μm or more was measured. When the number of surface protrusions of 0.1 μm or more was 200 or more, the blocking resistance was evaluated as good.

10. Vitiligo count:
Ten films were visually evaluated. A 30 cm × 21 cm frame was arbitrarily formed on the film, and the number of vitiligo in the frame was counted. The smaller the number of vitiligo, the better the appearance.

[Materials used]
[1] Polypropylene resin Various polypropylene resins described in Table 1 were used.
[2] Anti-blocking agent The following are used as the regular spherical silica (c), and the characteristics are shown in Tables 2-3.
1. Product name “Mizpearl K-150” manufactured by Mizusawa Chemical Co., Ltd. (average particle size 1.6 μm, BET specific surface area 149 m ² / g, pore volume 0.2 ml / g, oil absorption 55 ml / 100 g)
2. Product name “Mizpearl K-300” manufactured by Mizusawa Chemical Co., Ltd. (average particle size 2.8 μm, BET specific surface area 146 m ² / g, pore volume 0.5 ml / g, oil absorption 131 ml / 100 g)
3. Product name “Mizpearl K-500” manufactured by Mizusawa Chemical Industry Co., Ltd. (average particle size 4.9 μm, BET specific surface area 186 m ² / g, pore volume 0.4 ml / g, oil absorption 76 ml / 100 g)
The following are used as organic antiblocking agents, and the characteristics are shown in Tables 2-3.
1. Product name “Chemisnow MX-180TA” (average particle size 1.8 μm), manufactured by Soken Chemical Co., Ltd.
The following are used as amorphous silica (B), and the characteristics are shown in Table 3.
B-1: “Silicia 550” manufactured by Fuji Silysia Chemical Co., Ltd. (average particle size 3.7 μm, BET specific surface area 500 m ² / g, bulk density 0.31 g / cm ³ , pore volume 0.8 ml / g, oil absorption (Amount 140ml / 100g)

[Example 1]
As a method for obtaining the polypropylene resin composition (A), first, for the propylene polymer (a), the propylene polymer (a) shown in Table 1 obtained by using a Ziegler catalyst, that is, propylene homopolymer. As an antioxidant, 0.05 parts by weight of BASF's Irganox (registered trademark: Irganox) 1010 and BASF's Irgafos (registered trademark Irgafox) 168 are used as a neutralizing agent with respect to 100 parts by weight of the combined powder particles. After mixing 0.05 parts by weight of calcium stearate and mixing with a Henschel mixer (trade name), it is granulated by melt extrusion at a resin temperature of 230 ° C. using a 30 mmφ twin screw extruder (PCM30 manufactured by Ikegai Co., Ltd.). A resin composition (a) was obtained.
The propylene polymer (a) in the obtained polypropylene resin composition (a) is a homopolymer of polypropylene (PP) having an isotactic index (II) indicating crystallinity of 98%, and MFR (MFR (measuring temperature 230 ° C., 2.16 kg load (21.18 N)) in accordance with ISO 1133: 1997) was measured at 3 g / 10 min by a DSC apparatus RDC220U manufactured by SII at an elevating temperature speed of 10 ° C./min. The melting point was 165 ° C.
Next, for the propylene-α-olefin resin composition (B), the propylene-α-olefin copolymer (b) -1 described in Table 1, that is, propylene-ethylene-1-butene random copolymer powder particles 100 parts by weight are 0.05 parts by weight of BASF Irganox (registered trademark: Irganox) 1010 and BASF Irgafos (registered trademark Irgafox) 168, respectively, and 0.1% calcium stearate as a neutralizing agent. 05 parts by weight, 1.8 parts by weight of regular spherical silica (c) having an average particle diameter of 1.6 μm shown in Table 2 as silicon dioxide, and mixing with a Henschel mixer (trade name), followed by 30-mmφ biaxial extrusion Propylene-α-ole which was granulated by melt extrusion at a resin temperature of 230 ° C. using a machine (PCM30 manufactured by Ikegai Co., Ltd.) Fin resin composition (B) -1 was obtained.
Thereafter, propylene-α-olefin copolymer (b) -1 is in a proportion of 10 parts by weight with respect to 100 parts by weight of propylene-based polymer (a) in polypropylene-based resin composition (a). -The alpha-olefin resin composition (B) -1 is mix | blended, it mixes with an auto blender (Brand name, the automatic weight measurement color mixing machine made from Tamaki Co., Ltd.), and a polypropylene resin composition (A) -1 is mixed. Obtained.
[Example 2]
Propylene- using the spherical particles (c) having an average particle diameter of 2.8 μm shown in Table 2 as silicon dioxide and the powder particles of the propylene-α-olefin copolymer (b) -1 shown in Table 1 A polypropylene resin composition (A) -2 was obtained in the same manner as in Example 1, except that the α-olefin resin composition (B) -2 was used.
[Example 3]
A regular spherical silica (c) having an average particle diameter of 2.8 μm shown in Table 2 was used as silicon dioxide, and the propylene-α-olefin copolymer (b) -2 shown in Table 1 or propylene-ethylene-1-butene was used. A polypropylene resin composition (A) -3 was obtained in the same manner as in Example 1, except that the propylene-α-olefin resin composition (B) -3 using powder particles of random copolymer was used.
[Example 4]
As the silicon dioxide, the regular spherical silica (c) having an average particle diameter of 2.8 μm shown in Table 2 was used, and the propylene-α-olefin copolymer (b) -3 shown in Table 1 or propylene-ethylene-1-butene was used. A polypropylene resin composition (A) -4 was obtained in the same manner as in Example 1, except that the propylene-α-olefin resin composition (B) -4 using powder particles of random copolymer was used.
[Example 5]
Propylene-α-olefin copolymer (b) -4 described in Table 1, that is, propylene-ethylene random copolymer, using regular spherical silica (c) having an average particle size of 2.8 μm shown in Table 2 as silicon dioxide A polypropylene resin composition (A) -5 was obtained in the same manner as in Example 1, except that the propylene-α-olefin resin composition (B) -5 was used.
[Example 6]
Propylene- using the spherical particles (c) having an average particle size of 4.9 μm shown in Table 2 as silicon dioxide and the powder particles of propylene-α-olefin copolymer (b) -1 shown in Table 1 A polypropylene resin composition (A) -6 was obtained in the same manner as in Example 1, except that the α-olefin resin composition (B) -6 was used.
[Example 7]
An organic anti-blocking agent (d) having an average particle size of 1.8 μm shown in Table 2 as polymethyl methacrylate (PMMA) is used as the propylene-α-olefin copolymer (b) -1 powder in Table 1. Propylene resin composition (B) -7 blended with 3.6 parts by weight with respect to 100 parts by weight of the particles, and then with respect to 100 parts by weight of propylene polymer (a) in polypropylene resin composition (a). Except for blending propylene-α-olefin resin composition (B) -7 so that the proportion of α-olefin copolymer (b) -1 is 7 parts by weight, it is the same as the method of Example 1. A polypropylene resin composition (A) -7 was obtained.
[Example 8]
An organic anti-blocking agent (d) having an average particle size of 1.8 μm shown in Table 2 as polymethyl methacrylate (PMMA) is used as the propylene-α-olefin copolymer (b) -1 powder in Table 1. Propylene resin composition (B) -8 blended with 3.6 parts by weight with respect to 100 parts by weight of the particles, and then with respect to 100 parts by weight of propylene polymer (a) in polypropylene resin composition (a). Except that the propylene-α-olefin resin composition (B) -8 was blended so that the proportion of the α-olefin copolymer (b) -1 was 8 parts by weight, it was the same as the method of Example 1. A polypropylene resin composition (A) -8 was obtained.

[Comparative Example 1]
Antiblocking agent master batch (hereinafter referred to as 1.8 parts by weight) of amorphous silica having an average particle diameter of 3.7 μm shown in Table 3 as silicon dioxide with respect to 100 parts by weight of the powder particles of the propylene polymer (a) MB (a) -1 was prepared, and then propylene-based polymer in MB (a) -1 with respect to 100 parts by weight of propylene-based polymer (a) in polypropylene-based resin composition (a). A polypropylene resin composition (A) -9 was obtained in the same manner as in the method of Example 1 except that MB (a) -1 was blended so that the polymer (a) would be 10 parts by weight.
[Comparative Example 2]
MB (a) in which 1.8 parts by weight of regular spherical silica (c) having an average particle diameter of 2.8 μm shown in Table 3 as silicon dioxide is blended with 100 parts by weight of powder particles of propylene-based polymer (a) -2 is prepared, and then 10 parts by weight of the propylene polymer (a) in MB (a) -2 with respect to 100 parts by weight of the propylene polymer (a) in the polypropylene resin composition (a). A polypropylene resin composition (A) -10 was obtained in the same manner as in the method of Example 1 except that MB (a) -2 was blended in such a ratio.
[Comparative Example 3]
Powder particles of propylene-α-olefin copolymer (b) -1 or propylene-ethylene-1-butene random copolymer shown in Table 1 having a melting point of 126 ° C instead of polypropylene resin composition (a) Example 1 except that the polypropylene-based resin composition (b) -1 using a propylene-α-olefin resin composition (B) -2 obtained in the same manner as in the method of Example 2 was blended. A polypropylene resin composition (A) -11 was obtained in the same manner as in the method.
[Comparative Example 4]
As described in Table 1, the regular spherical silica (c) having an average particle diameter of 2.8 μm shown in Table 3 is used as silicon dioxide, and the melting point is 142 ° C. instead of the propylene-α-olefin copolymer (b) -1. A polypropylene resin composition in the same manner as in Example 1 except that MB (B) -9 using propylene-α-olefin copolymer (b ′), ie, propylene-ethylene random copolymer powder particles, was used. Product (A) -12 was obtained.
[Comparative Example 5]
The organic anti-blocking agent (d) having an average particle diameter of 1.8 μm shown in Table 3 as polymethyl methacrylate (PMMA) is 1.8% by weight with respect to 100 parts by weight of the powder particles of the propylene-based polymer (a). MB (a) -3 was prepared, and then, 100 parts by weight of the propylene polymer (a) in the polypropylene resin composition (a), with respect to the propylene polymer in MB (a) -3 ( A polypropylene resin composition (A) -13 was obtained in the same manner as in Example 1, except that MB (a) -3 was blended so that a) was 10 parts by weight.
[Comparative Example 6]
An organic antiblocking agent (d) having an average particle diameter of 1.8 μm shown in Table 3 as polymethyl methacrylate (PMMA), 83 parts by weight of propylene polymer (a) powder particles, and propylene-α-olefin MB (a) -4 was prepared by blending 1.8 parts by weight with respect to 100 parts by weight of powder particles in total of 17 parts by weight of powder particles of copolymer (b) -1, and then a polypropylene resin composition (a The total amount of propylene polymer (a) and propylene-α-olefin copolymer (b) -1 in MB (a) -4 is 10 with respect to 100 parts by weight of propylene polymer (a) in A polypropylene resin composition (A) -14 was obtained in the same manner as in Example 1 except that MB (a) -4 was blended so as to be a part by weight.
[Comparative Example 7]
An organic antiblocking agent (d) having an average particle diameter of 1.8 μm shown in Table 3 as polymethyl methacrylate (PMMA), 67 parts by weight of propylene polymer (a) powder particles, and propylene-α-olefin MB (a) -5 was prepared by blending 1.8 parts by weight with respect to 100 parts by weight of powder particles in total of 33 parts by weight of powder particles of copolymer (b) -1, and then a polypropylene resin composition (a The total amount of propylene polymer (a) and propylene-α-olefin copolymer (b) -1 in MB (a) -5 is 10 with respect to 100 parts by weight of propylene polymer (a) in A polypropylene resin composition (A) -15 was obtained in the same manner as in Example 1 except that MB (a) -5 was blended so as to be a part by weight.
[Comparative Example 8]
Instead of blending the propylene-α-olefin resin composition (B) prepared in advance with the propylene-based polymer (a), it is shown in Table 3 as silicon dioxide with respect to 100 parts by weight of the propylene-based polymer (a) powder particles. 0.18 parts by weight of regular spherical silica (c) having an average particle size of 2.8 μm shown in FIG. 1, 10 parts by weight of powder particles of propylene-α-olefin copolymer (b) -1, and BASF as an antioxidant Irganox (registered trademark: Irganox) 1010 manufactured by BASF and Irgafos (registered trademark Irgafox) 168 manufactured by BASF, respectively, and 0.05 part by weight of calcium stearate as a neutralizing agent were directly blended, In the same manner as in Example 1, a polypropylene resin composition (A) -16 was obtained.

Next, the polypropylene resin compositions (A) of Examples 1 to 8 and Comparative Examples 1 to 8 are used as the surface layer (corresponding to the layer (1)) raw material and as the intermediate layer (corresponding to the layer (2)) raw material. , PP-1 (Novatech (registered trademark) PP FL203D manufactured by Nippon Polypro Co., Ltd. (propylene polymer, MFR 3.0 g / 10 min, melting point 162 ° C.)), each melt extruded at a resin temperature of 250 ° C., 30 The sheet was quenched with a cooling roll at 0 ° C. to prepare a two-kind / three-layer raw sheet.
The sheet was stretched 5 times in the longitudinal direction using a longitudinal stretching machine adjusted to a roll temperature of 120 ° C. and 10 times in the lateral direction using a lateral stretching machine adjusted to a furnace temperature of 160 ° C., and the thickness was 20 μm (the surface layer was 1.5 μm) of biaxially stretched polypropylene film was obtained. At this time, the corona discharge treatment was performed so that the wetting index by the wetting reagent on one side was 40 dyne / cm.
Table 2 shows the physical properties of the obtained biaxially stretched polypropylene film.

As is clear from Tables 1 to 3, the biaxially stretched polypropylene film using the silicon dioxide or organic antiblocking agent used in Examples 1 to 8, ie, the shaped spherical silica (c) or organic according to the present invention. The biaxially stretched polypropylene film using the anti-blocking agent (d) was excellent in blocking resistance and dispersibility, had few white spots, and a good film was obtained with respect to the anti-blocking agent falling off.
On the other hand, the film of Comparative Examples 1-8 was not able to obtain the film excellent in various physical property balance.
That is, Comparative Example 1 was an antiblocking agent outside the scope of the present invention, and the dispersibility was poor.
The anti-blocking agent of Comparative Example 2 is the same as that of Example 2, but the propylene-α-olefin copolymer (b) is not blended with the propylene-based polymer (a), so that it falls off. Sex is getting worse.
Comparative Example 3 uses a regular spherical anti-blocking agent, does not use the propylene polymer (a), and is blended with the propylene-α-olefin copolymer (b). Although the property is good, since the melting point of the base polypropylene is low and the heat resistance is low, the fusion property to the seal bar is deteriorated.
Comparative Example 4 uses a regular spherical antiblocking agent, and since the melting point of the propylene-α-olefin copolymer (b) is higher than the claims, the crystallinity of the resin component existing around the antiblocking agent can be lowered. The drop-off property has deteriorated.
Comparative Example 5 is an organic anti-blocking agent, which, like Comparative Examples 1 and 2, also contains a propylene-α-olefin copolymer (b) with respect to the propylene polymer (a). Because it is not, drop-off property is getting worse.
In Comparative Examples 6 and 7, the organic antiblocking agent (d) was blended with the mixture of the propylene polymer (a) and the propylene-α-olefin copolymer (b). Since the proportion of the propylene-α-olefin copolymer (b) in the resin component in the propylene-α-olefin resin composition (B) is not satisfied, the crystallinity of the resin component existing around the antiblocking agent can be lowered. Because it is not, drop-off property is getting worse.
In Comparative Example 8, 0.18 parts by weight of directly shaped spherical silica (c) and 10 parts by weight of propylene-α-olefin copolymer (b) -1 with respect to 100 parts by weight of propylene-based polymer (a). However, it is not a blended method using propylene-α-olefin copolymer (b) in advance, so the crystallinity of the resin component existing around the antiblocking agent can be lowered. The drop-off property has deteriorated.

  The polypropylene resin composition of the present invention, a laminate comprising the polypropylene resin composition, and a biaxially stretched polypropylene film have a good balance of various physical properties such as blocking resistance, dispersibility, transparency, and detachability. For example, food packaging, fiber packaging, etc. It is widely used for packaging applications such as miscellaneous goods packaging, and can be suitably used particularly for food packaging film applications.

Claims (5)

A polypropylene resin composition (A) containing a propylene polymer (a) having a melting point of 150 ° C. or higher and a propylene-α-olefin resin composition (B), wherein the propylene-α-olefin resin composition ( B) is a composition obtained by blending a propylene-α-olefin copolymer (b) having a melting point of 110 to 140 ° C. and an antiblocking agent, and the antiblocking agent has an average particle diameter by laser diffraction method. 1.0-5.0 μm, a regular spherical silica (c) having a specific surface area of 1-300 m ² / g by BET method and a pore volume of less than 0.7 ml / g, or an average particle size of 1.0 by laser diffraction method It is an organic antiblocking agent (d) of ˜5.0 μm, and the content of the antiblocking agent in the polypropylene resin composition (A) is a propylene polymer ( ) 0.01 to 1 part by weight with respect to 100 parts by weight, and the proportion of the resin component in the polypropylene resin composition (A) is propylene-α with respect to 100 parts by weight of the propylene polymer (a). -The olefin copolymer (b) is 1 to 15 parts by weight, and the proportion of the resin component in the propylene-α-olefin resin composition (B) is 100 parts by weight of the resin component. A polypropylene resin composition (A), wherein the polymer (b) is 50 to 100 parts by weight.   The propylene-α-olefin copolymer (b) has a melt flow rate (230 ° C., 2.16 kg load) of 1 to 20 g / 10 min and a melting point of 120 to 140 ° C. The polypropylene resin composition according to claim 1, which is a polymer or a propylene-ethylene-1-butene random copolymer.   It is a laminate comprising at least two different layers (1) and (2), wherein the layer (1) is made of the polypropylene resin composition according to claim 1 or 2, and the layer (2) is The propylene-based polymer (a) is contained, and the content of the regular spherical silica (c) or the organic anti-blocking agent (d) is 0.01 with respect to 100 parts by weight of the propylene-based polymer (a). A laminate that is less than parts by weight.   A biaxially stretched polypropylene film comprising the laminate according to claim 3.   A food packaging film comprising the biaxially stretched polypropylene film according to claim 4.