TWI613243B - Propylene resin composition and film thereof - Google Patents

Abstract

An object of the present invention is to provide a propylene-based resin composition and a film thereof which are excellent in blocking resistance, impact resistance at low temperature, heat-sealing strength, and reducing occurrence of orange peel due to heat treatment when the film is formed.

The solution of the present invention is a propylene-based resin composition containing 50 to 90% by weight of a polymer component containing a structural unit derived from propylene as a main structural unit, and a content of 20 to 60% by weight from a structural unit derived from ethylene. Ethylene-propylene copolymer component of 50% to 10% by weight of propylene-based copolymer 70 to 90% by weight, and density of 900 to 940 kg / m ³ , and ethylene-α-olefin based on molecular weight distribution of 1 to 3 The resin composition made of 30 to 10% by weight of the copolymer contains 0.01 to 0.1 part by weight of a specific acrylate compound and / or a specific phosphite compound with respect to 100 parts by weight of the resin composition.

Description

Acrylic resin composition and film

The present invention relates to a propylene-based resin composition and a film thereof. In more detail, when it becomes a film, it is excellent in blocking resistance, impact resistance at low temperature, and heat-sealing strength, and when a package made of a film is heat-treated, unevenness is unlikely to occur on the surface of the package (the following also applies) Acrylic resin composition described as "orange peel") and its film.

Polypropylene films are widely used in the fields of films, sheets, and containers due to their excellent heat resistance and rigidity.

In recent years, films used in the field of food packaging, such as those used in retort food packaging, require films that have both heat resistance, rigidity, anti-blocking properties, heat seal strength, and good appearance after heat treatment.

Patent Document 1 describes a polypropylene resin 97 selected from free propylene homopolymers, random copolymers of propylene and ethylene, propylene-ethylene-butene-1 terpolymers, and block copolymers of propylene and ethylene. 75% by mass, and ethylene-α-olefin having a density of 0.860 to 0.900 g / cm ³ and a limiting viscosity [η] of 1.0 to 1.8 (dl / g) obtained by polymerizing ethylene and α-olefin with a single-site catalyst Resin composition for retort food packaging consisting of 3-25% by weight of copolymer.

Further, Patent Document 2 describes an ethylene-α-olefin copolymer containing 70 to 95% by weight of a propylene-based block copolymer, a density of 890 to 925 kg / m ³ , and an extraction amount of n-hexane of 0.01 to 2.6% by weight. 30% by weight of a propylene-based resin composition (However, the content of the propylene-based block copolymer and the ethylene-α-olefin copolymer is based on 100% by weight of the total weight of the propylene-based resin composition, and the ethylene-α-olefin is copolymerized. The n-hexane extraction amount of the product is based on 100% by weight of the total weight of the ethylene-α-olefin copolymer).

[Prior technical literature]

[Patent Literature]

[Patent Document 1] JP 2003-64228

[Patent Document 2] JP 2006-161033

However, in the resin compositions described in the above Patent Documents 1 and 2, the blocking resistance, heat seal strength, poor appearance after heat treatment, and impact resistance at low temperatures have not yet been satisfied, and further requirements are required. Improvement. An object of the present invention is to provide a propylene-based resin composition and a film thereof which are excellent in blocking resistance, impact resistance at low temperature, heat-sealing strength, and which are unlikely to cause orange peel due to heat treatment when they are formed into a film.

The inventors conducted an intensive review, and found that the present invention can solve the above problems, and finally completed the present invention.

(式中，R¹及R²各自相同或相異，表示碳數1~8的烷基、碳數6~12的芳基或碳數7~18的芳烷基，R³表示氫原子或碳數1~3的烷基，R⁴表示氫原子或甲基)；

(式中，R⁵、R⁶、R⁸及R⁹各自相同或相異，表示氫原子、碳數1~8的烷基、碳數5~8的環烷基、碳數6~12的烷 基環烷基、碳數7~12的芳烷基或苯基，R⁷表示氫原子或碳數1~8的烷基；X表示硫原子或-CHR¹⁰-基(R¹⁰表示氫原子、碳數1~8的烷基或碳數5~8的環烷基)，n為0或1；A表示碳數2~8的伸烷基或＊-CO(R¹¹)m-基(R¹¹表示碳數1~8的伸烷基，＊表示與氧原子的鍵結部位，m為0或1)；Y、Z中的任一者表示羥基、碳數1~8的烷氧基或碳數7~12的芳烷氧基，另一者表示氫原子或碳數1~8的烷基)。 That is, the present invention is a propylene-based resin composition containing 50 to 90% by weight of a polymer component (component A) containing a structural unit derived from propylene as a main structural unit, and a content of 20 from a structural unit derived from ethylene. ~ 60% by weight of ethylene-propylene copolymer component (component B) 50 ~ 10% by weight (however, the total weight of component A and component B is 100% by weight) propylene-based copolymer (polymer (I)) 70 ~ 90% by weight, and a structural unit derived from ethylene and a structural unit derived from α-olefins having 4 to 20 carbon atoms, a density of 900 to 940 kg / m ³ , and an ethylene-α- having a molecular weight distribution of 1 or more and less than 3 A resin composition made of 30 to 10% by weight of an olefin-based copolymer (polymer (II)) (however, the total weight of the polymer (I) and the polymer (II) is 100% by weight). With respect to 100 parts by weight of the resin composition, 0.01 to 0.1 parts by weight of the acrylate-based compound represented by the following formula (1) and / or the phosphite-based compound represented by the following formula (2);

(Wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ³ represents a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group);

(Wherein R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl having 7 to 12 carbons, R ⁷ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom , An alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), n is 0 or 1; A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group ( R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1); any one of Y and Z represents a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms Or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

(式中，R¹及R²各自相同或相異，表示碳數1~8的烷基、碳數6~12的芳基或碳數7~18的芳烷基，R³表示氫原子或碳數1~3的烷基，R⁴表示氫原子或甲基)；

(式中，R⁵、R⁶、R⁸及R⁹各自相同或相異，表示氫原子、碳數1~8的烷基、碳數5~8的環烷基、碳數6~12的烷基環烷基、碳數7~12的芳烷基或苯基，R⁷表示氫原子或碳數1~8的烷基；X表示硫原子或-CHR¹⁰-基(R¹⁰表示氫原子、碳數1~8的烷基或碳數5~8的環烷基)，n為0或1；A表示碳數2~8的伸烷基或＊-CO(R¹¹)m-基(R¹¹表示碳數1~8的伸烷基，＊表示與氧原子的鍵結部位，m為0或1)；Y、Z中的任一者表示羥基、碳數1~8的烷氧基或碳數7~12的芳烷氧基，另一者表示氫原子或碳數1~8的烷基)。 In addition, the present invention is a propylene-based resin composition containing 50 to 90% by weight of a polymer component (component A) having a structural unit derived from propylene as a main structural unit, and a content of the structural unit derived from ethylene as 20 to 60% by weight of an ethylene-propylene copolymer component (component B) 50 to 10% by weight (however, the total weight of component A and component B is 100% by weight) propylene-based copolymer (polymer (I)) 45 to 90% by weight, a structural unit derived from ethylene and a structural unit derived from α-olefins having 4 to 20 carbon atoms, a density of 900 to 940 kg / m ³ , and an ethylene-α- with a molecular weight distribution of 1 or more and less than 3 Resin composition made of an olefin-based copolymer (polymer (II)) at 30 to 10% by weight and a propylene-ethylene random copolymer (polymer (III)) at 25% by weight or less (the polymer (I) ) And the total weight of the polymer (II) and the polymer (III) are 100% by weight) and the acrylate-based compound represented by the formula (1) and / or the formula is based on 100 parts by weight of the resin composition. (2) 0.01 to 0.1 parts by weight of a phosphite compound;

(Wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ³ represents a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group);

(Wherein R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl having 7 to 12 carbons, R ⁷ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom , An alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), n is 0 or 1; A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group ( R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1); any one of Y and Z represents a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms Or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

According to the present invention, it is possible to obtain a thin film having excellent anti-blocking properties, high impact resistance at low temperatures, heat-sealing strength, and less likely to cause orange peel due to heat treatment.

[Mode for Carrying Out the Invention]

(式中，R¹及R²各自相同或相異，表示碳數1~8的烷基、碳數6~12的芳基或碳數7~18的芳烷基，R³表示氫原子或碳數1~3的烷基，R⁴表示氫原子或甲基)；

(式中，R⁵、R⁶、R⁸及R⁹各自相同或相異，表示氫原子、碳數1~8的烷基、碳數5~8的環烷基、碳數6~12的烷基環烷基、碳數7~12的芳烷基或苯基，R⁷表示氫原子或碳數1~8的烷基；X表示硫原子或-CHR¹⁰-基(R¹⁰表示氫原子、碳數1~8的烷基或碳數5~8的環烷基)，n為0或1；A表示碳數2~8的伸烷基或＊-CO(R¹¹)m-基(R¹¹表示碳數1~8的伸烷基，＊表示與氧原子的鍵結部位，m為0或1)；Y、Z中的任一者表示羥基、碳數1~8的烷氧基或碳數7~12的芳烷氧基，另一者表示氫原子或碳數1~8的烷基)。 The propylene-based resin composition of the present invention contains a polymer component (hereinafter also referred to as "component A") containing 50 to 90% by weight of a polymer component containing a structural unit derived from propylene as a main structural unit and a content of the structural unit derived from ethylene 20 to 60% by weight of an ethylene-propylene copolymer component (hereinafter also referred to as "component B") 50 to 10% by weight (however, the total weight of component A and component B is 100% by weight) propylene copolymer ( Hereinafter, it is also referred to as "polymer (I)") 70 to 90% by weight, and has a structural unit derived from ethylene and a structural unit derived from α-olefins having 4 to 20 carbon atoms, a density of 900 to 940 kg / m ³ , and a molecular weight A resin composition made of 30 to 10% by weight of an ethylene-α-olefin copolymer (hereinafter also referred to as "polymer (II)) with a distribution of 1 or more and less than 3 (however, polymer (I) and The total weight of the polymer (II) is 100% by weight), and the acrylate-based compound represented by the following formula (1) and / or the following formula (2) are based on 100 parts by weight of the resin composition. 0.01 ~ 0.1 parts by weight of the phosphite compound shown;

(Wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ³ represents a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group);

(Wherein R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl having 7 to 12 carbons, R ⁷ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom , An alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), n is 0 or 1; A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group ( R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1); any one of Y and Z represents a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms Or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

The "major structural unit" in the component A of the polymer (I) used in the present invention "Bit" means a structural unit that accounts for more than 90% by weight of the component A, and the structural unit derived from propylene is the main structural unit of the component A. The content of the structural unit derived from propylene in the component A is preferably 90 to 100% by weight, and more preferably 95 to 100% by weight.

Component A may optionally have a structural unit derived from ethylene and / or α-olefin having 4 to 12 carbons, and the content of the structural unit derived from ethylene and / or α-olefin having 4 to 12 carbons is preferably 10% by weight Hereinafter, it is more preferably 5% by weight or less. Examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 1-hexene, and 1-octene, and 1-butene is preferred.

The content of the structural unit derived from ethylene in the polymer (I) component B is from 20 to 60% by weight, preferably from 25 to 50% by weight (from the viewpoint of excellent blocking resistance and impact resistance at low temperature ( However, the total weight of the component B is 100% by weight).

In addition, component B is a structural unit derived from propylene in addition to a structural unit derived from ethylene. The content of the structural unit derived from propylene is 80 to 40% by weight, preferably 75 to 50% by weight. The total weight of the unit content and the content of the structural unit derived from propylene is 100% by weight).

The content of the component A and the component B in the polymer (I) is from the viewpoint of an excellent balance between heat sealability and anti-blocking property, the content of the component A is 50 to 90% by weight, and the content of the component B is 50 to 10% by weight, preferably the content of component A is 60 to 85% by weight, the content of component B is 40 to 15% by weight, the content of better component A is 65 to 80% by weight, and the content of component B is 35 to 15% by weight (however, the total weight of component A and component B is 100% by weight).

The polymer (I) has a melt flow index (230 ° C) measured at a temperature of 230 ° C and a load of 21.18N in accordance with JIS K7210. From the viewpoint of good film processability and hygiene, it is preferably 1.5 to 10 g. / 10 minutes, more preferably 2 ~ 5g / 10 minutes.

Examples of the method for producing the polymer (I) include a method of polymerizing propylene, ethylene, or the like as a raw material using a Ziegler-Natta catalyst or a metallocene catalyst.

Examples of the polymerization method of the polymer (I) include a method of polymerizing propylene or ethylene in an inert solvent such as hexane, heptane, toluene, xylene, and the like, a method of polymerizing liquid propylene or ethylene, and A method of adding a catalyst to propylene or ethylene to polymerize propylene or ethylene in a gas phase state, or a combination of these methods.

As a method for producing the polymer (I), from the viewpoint of productivity, it is preferable to produce component A in the first step in the absence of a substantially inert solvent, and then to dispose the component A in the gas phase in the second step. Method for polymerizing propylene and ethylene to produce component B.

As a method for adjusting the content of the structural unit derived from ethylene of component A and component B of the polymer (I), a method of adding an appropriate amount of a molecular weight modifier such as hydrogen or a metal compound and ethylene in each step during polymerization may be mentioned, Method for adjusting temperature, pressure, etc. during polymerization.

The ratio of the component A and the component B of the polymer (I) can be determined by the polymerization time, the size of the polymerization tank, the amount of polymer held in the polymerization tank, the polymerization temperature, and the polymerization pressure during the production of the polymer (I). Wait for control. As needed In order to remove the residual solvent of polypropylene or the ultra-low molecular weight oligomers by-produced during production, it can be dried at a temperature below the melting temperature of polypropylene. As a drying method, the method described in Unexamined-Japanese-Patent No. 55-75410, Japanese Patent Publication No. 2565553, etc. are mentioned, for example.

The polymer (II) has a structural unit derived from ethylene and a structural unit derived from an α-olefin having 4 to 20 carbon atoms. Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 1-heptene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -Hexadecene, 1-icosene, 4-methyl-1-heptene, 4-methyl-1-hexene, and the like. The polymer (II) may contain two or more kinds of structural units derived from α-olefins having 4 to 20 carbon atoms. The α-olefin having 4 to 20 carbon atoms is preferably 1-hexene from the viewpoint of improving heat seal strength.

The density of the polymer (II) is 900 to 940 kg / m ³ , and preferably 900 to 930 kg / m ³ . Since the density of the polymer (II) is 900 kg / m ³ or more, it is excellent in terms of rigidity, and because it is 930 kg / m ³ or less, it has excellent impact resistance at low temperatures.

The polymer (II) has a melt flow index (190 ° C) measured at a temperature of 190 ° C and a load of 21.18N in accordance with JIS K7210-1995, preferably 0.5 to 30 g / 10 minutes, and particularly preferably 0.5 to 10 g / 10. Minutes, more preferably 1 to 5 g / 10 minutes. When the melt flow index of the polymer (II) is 0.5 g / 10 minutes or more, orange peel is less likely to occur, and when it is 30 g / 10 minutes or less, heat seal strength is more excellent.

The molecular weight distribution of the polymer (II) is 1 or more and less than 3, and preferably 1.5 or more and less than 2.5. Since the molecular weight distribution is less than 3, it has excellent impact resistance at low temperatures. Here, the molecular weight distribution is determined by gel permeation chromatography ( The ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) measured in the following is also described as "GPC".

As a method of making the molecular weight distribution of the polymer (II) 1 or more and less than 3, for example, a method of copolymerizing ethylene with an α-olefin using a metallocene catalyst can be mentioned.

Examples of the metallocene catalyst used in the production of an ethylene-α-olefin copolymer include a transition metal compound using a group having a dicyclopentadiene type anion skeleton (hereinafter also referred to as "diocene metallocene transition" Catalysts for the polymerization of olefins formed from metal compounds ").

Examples of the metallocene-based transition metal compound include a formula ML _T X ′ _QT (where M is a transition metal atom of Group 4 of the periodic table or a lanthanum series. L is a dicyclopentadiene form An anion skeleton group or a group containing a hetero atom, at least one of which is a group having a dicyclopentadiene anion skeleton. A plurality of L may bridge each other. X ′ is a halogen atom, a hydrogen atom, or a carbon atom having 1 to 20 carbon atoms. Hydrocarbon group. Q represents the atomic valence of a transition metal atom, and T is a compound satisfying 0 <T ≦ Q integer).

Examples of the metallocene-based transition metal compound represented by the above formula include bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride and bis (1,3-n-propylmethyl) Cyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1 , 3-diethylcyclopentadienyl) zirconium dichloride, ethylene di (indenyl) zirconium dichloride, ethylene di (4-methyl-1-indenyl) zirconium dichloride, Ethyl bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride and the like.

The aforementioned metallocene-based transition metal compound is preferably used in contact with an activated promoter. Examples of the activation catalyst include an alumoxane compound or an activation catalyst formed by using an organoaluminum compound in combination with a boron compound such as triphenylmethyl borate or aniline borate. Further, the diocene metallocene-based transition metal compound may be used in combination with a granular carrier containing an inorganic carrier such as SiO ₂ and Al ₂ O ₃ and an organic carrier such as a polymer such as ethylene and styrene.

As a method of making the density of polymer (II) 900-940 kg / m <^3>, the method of adjusting the ratio of copolymerization of ethylene and an alpha-olefin is mentioned.

The resin composition system contained in the propylene resin composition of the present invention includes a polymer (I) and a polymer (II). When the resin composition is composed of the polymer (I) and the polymer (II), the resin composition is composed of 70 to 90% by weight of the polymer (I) and 30 to 10% by weight of the polymer (II). It is preferably composed of 75 to 90% by weight of the polymer (I) and 25 to 10% by weight of the polymer (II) (however, the total weight of the polymer (I) and the polymer (II) becomes 100% by weight) . When the polymer (I) is less than 70% by weight (that is, when the polymer (II) exceeds 30% by weight), the heat-sealability of the obtained film becomes poor, and when the polymer (I) exceeds 90% by weight (that is, the polymer ( II) When it is less than 10% by weight), unevenness (orange peel) occurs on the surface of the package due to heat treatment, and the appearance is deteriorated.

The resin composition contained in the propylene-based resin composition of the present invention may contain a propylene-ethylene random copolymer (polymer (III)) in addition to the polymer (I) and the polymer (II). When the resin composition is composed of polymer (I), polymer (II), and polymer (III), the total weight of polymer (I), polymer (II), and polymer (III) is 100 weights At%, the resin composition is preferably composed of 45 to 90% by weight of polymer (I), 30 to 10% by weight of polymer (II), and 25% by weight or less of polymer (III), and more preferably, polymerized Object (I) 50 ~ 85 wt%, polymer (II) 30 to 10 wt%, polymer (III) 20 to 5 wt%, particularly preferably polymer (I) 50 to 80 wt%, polymer (II) 30 to It is composed of 10% by weight and 20 to 10% by weight of polymer (III). When the resin composition contains the polymer (III), the difference between the heat-sealing strength of the propylene-based resin composition containing the resin composition after heat treatment and the heat-sealing strength before heat treatment becomes small.

The polymer (11) preferably contains 3 to 7 wt% of a structural unit derived from ethylene, and more preferably contains 4 to 6 wt%. The polymer (III) preferably contains 97 to 93% by weight of a structural unit derived from propylene, and more preferably 96 to 94% by weight.

The acrylate-based compound used in the present invention is represented by the following formula (1).

(式中，R¹及R²各自相同或相異，表示碳數1~8的烷基、碳數6~12的芳基或碳數7~18的芳烷基，R³表示氫原子或碳數1~3的烷基，R⁴表示氫原子或甲基)。

(Wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ³ represents a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group).

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third Butyl, n-pentyl, third pentyl (-C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl, cyclohexyl, etc. Examples of the aryl group having 6 to 12 carbon atoms include benzene Examples of the aralkyl group having 7 to 18 carbon atoms include benzyl and the like, and an alkyl group having a tertiary carbon having 4 to 8 carbon atoms is preferred, and a third butyl group or a third pentyl group is particularly preferred. And more preferably a third pentyl group.

Examples of the alkyl group having 1 to 3 carbon atoms in R ₃ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Preferred R ₃ is a hydrogen atom or a methyl group.

R _{4 is} preferably a hydrogen atom.

Examples of the acrylate-based compound represented by the formula (1) include 2,4-di-third-butyl-6- [1- (3,5-di-third-butyl-2-hydroxyphenyl) Ethyl] phenylacrylate, 2,4-di-tertiarypentyl-6- [1- (3,5-di-tertiarypentyl-2-hydroxyphenyl) ethyl] phenylacrylate, 2, 4-Di-third-butyl-6- (3,5-di-third-butyl-2-hydroxybenzyl) phenyl methacrylate, 2,4-di-third-butyl-6- [1- ( 3,5-di-tert-butyl-2-hydroxyphenyl) ethyl] phenyl methacrylate, 2,4-di-tert-pentyl-6- [1- (3,5-di-tert-pentyl 2-hydroxyphenyl) ethyl] phenyl methacrylate, 2-third butyl-6- (3-third butyl-2-hydroxy-5-methylbenzyl) -4-methyl Phenyl methacrylate, 2-third butyl-6- (3-third butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2-third Butyl-6- (3-third butyl-2-hydroxy-5-methylbenzyl) -4-ethylphenyl methacrylate, 2-third pentyl-6- (3-third Amyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2-third pentyl-6- (3-third pentyl-2-hydroxy-5-methyl Benzyl) -4-methylphenyl acrylate, etc., preferably 2,4-di-third Amyl-6- [1- (3,5-di-third-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate.

Examples of a method for producing the acrylic compound represented by the formula (1) include a method described in Japanese Patent Application Laid-Open No. 2010-270310.

The phosphite compound used in the present invention is represented by the following formula (2).

(式中，R⁵、R⁶、R⁸及R⁹各自相同或相異，表示氫原子、碳數1~8的烷基、碳數5~8的環烷基、碳數6~12的烷基環烷基、碳數7~12的芳烷基或苯基，R⁷表示氫原子或碳數1~8的烷基；X表示硫原子或-CHR¹⁰-基(R¹⁰表示氫原子、碳數1~8的烷基或碳數5~8的環烷基)，n為0或1；A表示碳數2~8的伸烷基或＊-CO(R¹¹)m-基(R¹¹表示碳數1~8的伸烷基，＊表示與氧原子的鍵結部位，m為0或1)；Y、Z中的任一者表示羥基、碳數1~8的烷氧基或碳數7~12的芳烷氧基，另一者表示氫原子或碳數1~8的烷基)。

(Wherein R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl having 7 to 12 carbons, R ⁷ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom , An alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), n is 0 or 1; A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group ( R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1); any one of Y and Z represents a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms Or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁵ , R ⁶ , R ^8, and R ⁹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and Dibutyl, third butyl, third pentyl, isooctyl, third octyl, 2-ethylhexyl and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include cyclopentyl and cyclopentyl. Hexyl, cycloheptyl, cyclooctyl, etc. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl, 1-methylcyclohexyl, and 1-methyl-4- Isopropylcyclohexyl and the like, and examples of the aralkyl group having 7 to 12 carbon atoms include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, and the like.

R ⁵ , R ⁶ , and R ^{8 are} preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl cycloalkyl group having 6 to 12 carbon atoms. Among them, R ⁵ and R ^{8 are more} preferably a tertiary alkyl group such as a third butyl group, a third pentyl group, a third octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.

R ^{6 is} preferably an alkyl group having 1 to 5 carbon atoms, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third butyl. Or third pentyl, particularly preferably methyl, third butyl or third pentyl.

R ^{9 is} preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and is a hydrogen atom, methyl group, or ethyl group. , N-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, or third pentyl.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁷ include the same alkyl groups as described above. A hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom or a methyl group is more preferred.

Moreover, when n is 0, the substituent X represents two groups having a phenoxy skeleton directly bonded, and when n is 1, it represents a sulfur atom or an alkyl group or carbon number having 1 to 8 carbon atoms. 5 to 8 cycloalkyl substituted methylene. Here, examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms substituted with a methylene group include the same alkyl groups and cycloalkyl groups as described above. As the substituent X, n is preferably 0, and two groups having a phenoxy skeleton are directly bonded, or n is 1, and is methylene or methyl, ethyl, n-propyl, isopropyl, or n Methylene substituted with butyl, isobutyl, third butyl, and the like.

In addition, the substituent A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m- group (R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, and * represents a bonding site with an oxygen atom, m is 0 or 1).

Here, as a representative example of an alkylene group having 2 to 8 carbon atoms, for example, ethylidene group, propylidene group, butylidene group, pentamethylene group, hexamethylene group, octamethylene group, and 2, 2-dimethyl-1,3-propane and the like are preferred, and propane is preferred. The * in the * -CO (R ¹¹ ) m- group represents a moiety in which a carbonyl group is bonded to an oxygen atom of a phosphite group. Typical examples of the alkylene group having 1 to 8 carbon atoms in R ¹¹ include methylene, ethylene, propyl, butylene, pentamethylene, hexamethylene, and octaethylene. Methyl, 2,2-dimethyl-1,3-propane, and the like. The * -CO (R ¹¹ ) m- group is preferably a * -CO- group in which m is 0 or m is 1, and R ¹¹ is a * -CO (CH ₂ CH ₂ )-group in ethylene.

Either Y or Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Here, examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above, and examples of the alkoxy group having 1 to 8 carbon atoms include those having an alkyl portion and the above 1 to 8 carbon atoms. The alkoxy group having the same alkyl group as the alkoxy group having 7 to 12 carbon atoms includes, for example, an aryl group having the same aralkyl group as that of the aralkyl group having 7 to 12 carbon atoms. Alkoxy.

磷環庚烷。 As a phosphite compound, the following compound 1 is preferable. Compound 1: 2,4,8,10-tetratert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d , f] [1,3,2]

Phosphloheptane.

Examples of a method for producing a phosphite compound represented by the formula (2) include a method described in Japanese Patent Application Laid-Open No. 10-273494.

磷環庚烷。 In the present invention, it is preferred to use an acrylate compound represented by the above formula (1) and a phosphite compound represented by the above formula (2) in combination, and more preferably to use 2,4-di-tertiarypentyl-6 -[1- (3,5-Di-third-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate and 2,4,8,10-tetra-tert-butyl-6- [3- (3 -Methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] di

Phosphloheptane.

When the resin composition is composed of the polymer (I) and the polymer (II), the acrylate-based compound represented by the above formula (1) and / or the above formula ( The content of the phosphite compound shown in 2) is 0.01 to 0.1 parts by weight, and preferably 0.03 to 0.07 parts by weight, based on 100 parts by weight of the resin composition.

When the resin composition is composed of the polymer (I), the polymer (II), and the polymer (III), the acrylate-based compound represented by the above formula (1) contained in the propylene-based resin composition of the present invention The content of the phosphite compound represented by the above formula (2) is 0.01 to 0.1 part by weight, and preferably 0.03 to 0.07 part by weight with respect to 100 parts by weight of the resin composition.

When the acrylate compound represented by the above formula (1) and / or the above formula (2) When the compounding amount of the phosphite-based compound shown is less than 0.01 part by weight, the heat-sealing strength is insufficient, and when it exceeds 0.1 part by weight, the effect of the present invention is saturated, which is uneconomical.

The propylene-based resin composition of the present invention can be a polymer (I), a polymer (II), an acrylate-based compound represented by the formula (1), a phosphite-based compound represented by the formula (2), An arbitrary polymer (III) is obtained by mixing and melt-kneading.

The above-mentioned melt-kneading system can be performed using a known method and apparatus. For example, a method using a mixing device such as a Hanschel mixer, a belt mixer, a barrel mixer, and the like to mix the components constituting the propylene-based resin composition and then melt-kneading them can be used. After each component of the propylene resin composition is continuously mixed at a certain ratio to obtain a homogeneous mixture, a uniaxial or biaxial or more extruder, Banbury mixer, roll mixer, etc. are used. The method of melt-kneading the mixture.

The temperature of the above-mentioned melt-kneading is preferably 180 ° C to 350 ° C, and more preferably 180 ° C to 320 ° C.

Additives or other resins may be added to the propylene-based resin composition of the present invention as necessary. Examples of the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a slip agent, a nucleating agent, an adhesive, an anti-fogging agent, and an anti-blocking agent. Examples of the other resin include an olefin-based resin, an elastomer of a copolymer of ethylene and an α-olefin, and the like. These systems can be manufactured by heterogeneous catalysts, and can also be manufactured by homogeneous catalysts (such as metallocene catalysts). Further, a styrene-based copolymer rubber in which a styrene-butadiene-styrene copolymer or a styrene-isoprene-styrene copolymer has been hydrogenated can be cited. And other elastomers.

The propylene-based resin composition of the present invention is suitable as a material for a film. Examples of the method for producing a thin film include well-known methods for producing a thin film, and examples thereof include a T-die method and a tube method.

As a manufacturing method of an unstretched film, a T die method is preferable.

The thickness of the film system of the present invention is preferably 5 to 500 μm, and more preferably 30 to 150 μm.

Examples of applications of the film of the present invention include packaging applications, and examples include packaging applications for foods, fibers, and miscellaneous goods. Films for retort food packaging are preferred.

In the film of the present invention, a surface treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, an ozone treatment, or the like can be applied by a method generally used in industry.

The film of the present invention may be laminated with another film.

Examples of other films include polypropylene biaxially stretched film, stretched nylon film, stretched polyethylene terephthalate film, and aluminum foil.

Examples of a method for laminating the film of the present invention and other films include a dry layer method and an extruded layer method.

As the application of the film of the present invention, it is preferably used for packaging heavy goods.

[Example]

Hereinafter, this invention is demonstrated using an Example and a comparative example. The measured values of the items in the examples and comparative examples were measured by the following methods.

(1) Content of component A and component B of the polymer (I) (unit: weight%)

Since the material balance when producing component A and component B, to obtain the content of (P _A) of the component A polymer (I), the content of (P _B) of the B component.

(2) The content of the structural unit derived from ethylene contained in the ethylene-propylene copolymer component (component B) of the polymer (I) (unit: weight%)

The IR spectrum of the polymer (I) was measured, and the polymer (I) was obtained according to the method of (ii) block copolymer described in page 616 of the Polymer Analysis Handbook (1995, issued by Kii Kokuya Bookstore). The content of the structural unit derived from ethylene is determined by the following formula (1).

E _B = E _T / P _B Formula (1) (However, E _T and E _B each represent the content of the structural unit derived from ethylene in the polymer (I) and the component B in the polymer (I), and P _B represents Content of component B in the polymer (I)).

(3) Melt flow index (MFR, unit: g / 10 minutes)

The polymer (l) melt flow index was measured at a temperature of 230 ° C and a load of 21.18N in accordance with JIS K7210. The melt flow index of the polymer (11) is measured at a temperature of 190 ° C and a load of 21.18N by a method specified in JIS K7210-1995.

(4) Density (unit: kg / m ³ )

The density of the polymer (11) is measured in accordance with the method prescribed by the A method in JIS K7112-1980. In addition, JIS K6760-1995 was applied to the samples. Recorded annealing.

(5) Molecular weight distribution (Mw / Mn)

The gel permeation chromatography (GPC) method was used to measure the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer (II) under the following conditions to obtain Mw / Mn. The baseline on the chromatogram is a point that connects a stable horizontal region that is sufficiently shorter than the sample dissolution peak that has a retention time, and a stable horizontal region that is longer than that when the solvent dissolution peak is observed. Straight line.

Installation: WAters150C by WAters

Separation column: T-OSOH TSK-GEL GMH6-HT

Measurement temperature: 140 ° C

Carrier: o-dichlorobenzene

Flow: 1.0mL / min

Injection volume: 500 μL

Detector: Differential Refraction

Molecular weight reference material: standard polystyrene

(6) Heat seal strength (unit: N / 15mm width)

The film was sealed under the following conditions using a Toyo TESTER Industrial Sealer. The sealing sheet was cut to a width of 15 mm, and the peeling angle was 90 °, and measurement was performed using Tensilon manufactured by ORIENTEC.

Seal rod: heating on both sides of the plane

Sealing temperature: 200 ° C

Sealing pressure: 1.0kg / cm ²

Sealing time: 1.0sec

(7) Anti-blocking property (unit: N / 12cm ² )

A 150 mm × 30 mm film (collected in such a manner that the film-forming direction and the long-side direction are consistent) was used, and the films were overlapped with each other. A load of 500 g was applied to a range of 40 mm × 30 mm, and the state was adjusted at 80 ° C. for 24 hours. Then, the film was left in an environment of 23 ° C. and a humidity of 50% for 30 minutes or more, and was peeled at a speed of 200 mm / minute using a Toyo Seiki tensile tester, and the strength required for peeling of the sample was measured.

(8) Shock resistance (unit: kJ / m)

The impact strength of the film was measured at -15 ° C using a Toyo Seiki film impact tester and a hemispherical punch with a diameter of 15 mm.

(9) Orange peel evaluation

A small retort sterilizer made by ALP was used to perform retort treatment at 120 ° C for 30 minutes, and the convex and concave state of the surface layer (orange peel) of the retort-treated packaging bag was visually determined by a 4-level method based on the following standard. .

1. ． ． Although orange peel occurs slightly, it is almost invisible.

2. ． ． Although several orange peels were observed, there was no practical impact at all.

3． ． ． Although orange peel was observed, it was resistant to practical use.

4． ． ． A considerable amount of orange peel was observed, which was unbearable and practical.

The acrylate-based compounds and phosphite-based compounds used in the examples and comparative examples are as follows.

[Acrylic compound]

Using 2,4-di-tertiarypentyl-6- [1- (3,5-di-tertiarypentyl-2-hydroxyphenyl ) Ethyl] phenyl acrylate Sumilizer [registered trademark] GS manufactured by Sumitomo Chemical Co., Ltd. This is hereinafter referred to as "Compound C".

[Phosphite compound]

磷環庚烷之住友化學株式會社製的Sumilizer[註冊商標]GP。以下稱為「化合物D」。 2,4,8,10-tetratert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] Two

Sumilizer [registered trademark] GP manufactured by Sumitomo Chemical Co., Ltd. This is hereinafter referred to as "Compound D".

The polymers used in the examples and comparative examples are as follows.

[Propylene copolymer (1)]

Using a Ziegler-Natta catalyst, in the first step, propylene is polymerized in the gas phase to obtain a propylene homopolymer component (component A). Then in the second step, propylene and ethylene are co-polymerized in the gas phase. Polymerization yielded a copolymer component (component B) of propylene and ethylene. The content of the obtained copolymer-based component A was 78% by weight, the content of component B was 22% by weight, and the content of the structural unit derived from ethylene contained in component B was 31% by weight.

In 100 parts by weight of the copolymer powder described above, 0.01 parts by weight of calcium hydroxide, 0.2 parts by weight of Irganox [registered trademark] 1010 (hereinafter referred to as "compound A") manufactured by BASF Corporation were mixed by a Hanschel mixer, and BASF Corporation was used. 0.05 parts by weight of Irganox [registered trademark] 168 (hereinafter referred to as "compound B"), Micron White [registered trademark] 5000S manufactured by Hayashi Kasei Corporation, and 2,5-dimethyl-2 as a melt flow index adjuster After an appropriate amount of 5,5-di (tert-butylperoxy) hexane, the mixture was melted and extruded to obtain pellets. The melt flow index of the obtained pellets measured at 230 ° C was 3 g / 10 minutes. Hereinafter, this pellet is also referred to as "PP1".

[Propylene copolymer (2)]

Using a Ziegler-Natta catalyst, in the first step, propylene is polymerized in the gas phase to obtain a propylene homopolymer component (component A). Then in the second step, propylene and ethylene are co-polymerized in the gas phase. Polymerization yielded a copolymer component (component B) of propylene and ethylene. The content of the obtained copolymer-based component A was 77% by weight, the content of Component B was 23% by weight, and the content of the structural unit derived from ethylene contained in Component B was 30% by weight.

In 100 parts by weight of the copolymer powder described above, 0.01 parts by weight of calcium hydroxide, 0.03 parts by weight of compound C, 0.075 parts by weight of compound D, and 2,5-as a melt flow index adjuster were mixed by a Hanschel mixer. After an appropriate amount of dimethyl-2,5-bis (third butylperoxy) hexane was obtained, the mixture was melt-extruded to obtain pellets. The melt flow index of the obtained pellets measured at 230 ° C was 2.5 g / 10 minutes. Hereinafter, this pellet is also referred to as "PP2".

[Propylene-ethylene random copolymer (1)]

As the propylene-ethylene random copolymer, Noblen [registered trademark] S131 manufactured by Sumitomo Chemical Co., Ltd. was used. The copolymer contained 5.6% by weight of structural units derived from ethylene. Hereinafter, this copolymer is also referred to as "PP3".

[Propylene-ethylene random copolymer (2)]

The propylene-ethylene random copolymer is produced by Sumitomo Chemical Co., Ltd. Noblen [registered trademark] WF577PG11. The copolymer contained 4.0% by weight of structural units derived from ethylene. Hereinafter, this copolymer is also referred to as "PP4".

[Ethylene-α-olefin copolymer (1)]

Sumikathene [registered trademark] EFV401 manufactured by Sumitomo Chemical Co., Ltd. using an ethylene-hexene-1 copolymer. The melt flow index measured at 190 ° C was 3.8 g / 10 minutes, the density was 902 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 2.1. Hereinafter, this copolymer is also referred to as "PE1".

[Ethylene-α-olefin copolymer (2)]

Sumikathene [registered trademark] EFV402 manufactured by Sumitomo Chemical Co., Ltd. using an ethylene-hexene-1 copolymer. The melt flow index measured at 190 ° C was 3.8 g / 10 minutes, the density was 913 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 2.0. Hereinafter, this copolymer is also referred to as "PE2".

[Ethylene-α-olefin copolymer (3)]

Sumikathene [registered trademark] EFV405 manufactured by Sumitomo Chemical Co., Ltd. using an ethylene-hexene-1 copolymer. The melt flow index measured at 190 ° C was 3.8 g / 10 minutes, the density was 924 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 2.2. Hereinafter, this copolymer is also referred to as "PE3".

[Ethylene-α-olefin copolymer (4)]

Sumikathene [registered trademark] EFV203 manufactured by Sumitomo Chemical Co., Ltd. using an ethylene-hexene-1 copolymer. The melt flow index measured at 190 ° C was 2.0 g / 10 minutes, the density was 913 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 2.0. Hereinafter, this copolymer is also referred to as "PE4".

[Ethylene-α-olefin copolymer (5)]

Sumikathene [registered trademark] EFV205 manufactured by Sumitomo Chemical Co., Ltd. using an ethylene-hexene-1 copolymer. The melt flow index measured at 190 ° C was 2.0 g / 10 minutes, the density was 922 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 2.1. Hereinafter, this copolymer is also referred to as "PE5".

[Ethylene-α-olefin copolymer (6)]

Sumikathene [registered trademark] LFS150 manufactured by Sumitomo Chemical Co., Ltd. using an ethylene-butene-1 copolymer. The melt flow index measured at 190 ° C was 1.1 g / 10 minutes, the density was 922 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 3.4. Hereinafter, this copolymer is also referred to as "PE6".

[Ethylene-α-olefin copolymer (7)]

Tafmer [registered trademark] PO680 manufactured by Mitsui Chemicals Co., Ltd. of ethylene-propylene copolymer was used. The melt flow index measured at 190 ° C was 0.4 g / 10 minutes, the density was 885 kg / m ³ , and the molecular weight distribution (Mw / Mn) was 1.9. Hereinafter, this copolymer is also referred to as "PE7".

[Example 1]

85% by weight of propylene copolymer (1) and ethylene-α-olefin copolymer (1) 15 The mixture was obtained by blending the pellets by weight. A mixture of 100 parts by weight of compound C and 0.05 parts by weight of compound C and 0.05 parts by weight of compound D was melt-kneaded using a 90 mm Φ extruder having a metal filter with a filtering accuracy of 40 μm and two 65 mm Φ extruder. A T-die of feed block type (die width 1250 mm, lip opening 1.5 mm) was introduced, and melt extrusion was performed at a die temperature of 240 ° C.

The extruded molten film was cooled and solidified by a cooling roller having a cooling temperature of 40 ° C. rotated at 50 m / minute to obtain an unstretched film having a thickness of 70 μm. This non-stretched film was used to measure the blocking properties of the film.

Next, the obtained unstretched film, an aluminum foil having a thickness of 7 μm, and a polyethylene terephthalate film having a thickness of 12 μm were laminated by a dry lamination method. The heat seal strength of this laminate was measured.

In addition, this laminate was subjected to a heat treatment at 120 ° C. for 30 minutes in a constant temperature bath, and the heat-sealed strength of the heat-treated laminate was also measured.

Furthermore, a 15 cm × 18 cm packaging bag was produced using a laminate so that the unstretched film became the inside of the bag. "Bon Curry Gold [registered trademark] spicy flavor" made by Otsuka Food Co., Ltd., which is a commercially available retort food, was added to the packaging bag. The unstretched films were heat-sealed to each other. Using this packaging bag, orange peel evaluation was performed. Table 2 shows the results.

[Example 2]

An unstretched film was obtained in the same manner as in Example 1 except that 80% by weight of the propylene copolymer (1) and 20% by weight of the ethylene-α-olefin copolymer (1) were pelletized to obtain a mixture. Laminates and bags. Measurement The adhesiveness of the unstretched film and the heat-sealing strength of the laminate were determined, and the orange peel of the packaging bag was evaluated.

[Example 3]

An unstretched film, a laminate, and a packaging bag were obtained in the same manner as in Example 1 except that 15% by weight of the ethylene-α-olefin copolymer (2) was used as the ethylene-α-olefin copolymer. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 4]

An unstretched film, a laminate, and a packaging bag were obtained in the same manner as in Example 1 except that 15% by weight of the ethylene-α-olefin copolymer (3) was used as the ethylene-α-olefin copolymer. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 5]

An unstretched film, a laminate, and a packaging bag were obtained in the same manner as in Example 1, except that 15% by weight of the ethylene-α-olefin copolymer (4) was used as the ethylene-α-olefin copolymer. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 6]

Except that as the ethylene-α-olefin copolymer, 15% by weight of the ethylene-α-olefin copolymer (5) was used, the same method as in Example 1 was used to obtain an Stretch films, laminates and bags. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 7]

85% by weight of the propylene copolymer (1) and 15% by weight of the ethylene-α-olefin copolymer (1) were pelletized to obtain a mixture. With respect to 100 parts by weight of the mixture, 0.05 part by weight of compound C was added, and an unstretched film, a laminate, and a packaging bag were obtained by the same method as in Example 1. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 8]

85% by weight of the propylene copolymer (1) and 15% by weight of the ethylene-α-olefin copolymer (1) were pelletized to obtain a mixture. 100 parts by weight of the mixture was added with 0.05% by weight of Compound D, and an unstretched film, a laminate, and a packaging bag were obtained by the same method as in Example 1. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 9]

An unstretched film, a laminate, and a packaging bag were obtained in the same manner as in Example 1, except that 85% by weight of the propylene copolymer (2) was used as the propylene copolymer. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 10]

Except that 72% by weight of the propylene copolymer (1), 20% by weight of the ethylene-α-olefin copolymer (3), and 8% by weight of the propylene-ethylene random copolymer (1) were blended in pellets to obtain a mixture, By the same method as in Example 1, an unstretched film, a laminate, and a packaging bag were obtained. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 11]

64% by weight of the propylene copolymer (1), 20% by weight of the ethylene-α-olefin copolymer (3), and 16% by weight of the propylene-ethylene random copolymer (1) were blended in pellets to obtain a mixture. By the same method as in Example 1, an unstretched film, a laminate, and a packaging bag were obtained. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Example 12]

Except that 64% by weight of the propylene copolymer (1), 20% by weight of the ethylene-α-olefin copolymer (3), and 16% by weight of the propylene-ethylene random copolymer (2) were blended in pellets to obtain a mixture, By the same method as in Example 1, an unstretched film, a laminate, and a packaging bag were obtained. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Comparative Example 1]

An unstretched film made of 100% by weight of the propylene copolymer (1) was produced by the same method as in Example 1. Furthermore, using this unstretched film, a laminate and a packaging bag were obtained. Measuring the adhesion and layer of unstretched film The heat-sealing strength of the combination was evaluated for orange peel of the packaging bag.

[Comparative Example 2]

In the same manner as in Example 1, a mixture of 85% by weight of the propylene copolymer (1) and 15% by weight of the ethylene-α-olefin copolymer (1) was melt-kneaded to obtain an unstretched film. . Furthermore, using this unstretched film, a laminate and a packaging bag were obtained. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Comparative Example 3]

An unstretched film, a laminate, and a packaging bag were obtained in the same manner as in Example 1 except that 15% by weight of the ethylene-α-olefin copolymer (6) was used as the ethylene-α-olefin copolymer. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

[Comparative Example 4]

An unstretched film, a laminate, and a packaging bag were obtained in the same manner as in Example 1 except that 15% by weight of the ethylene-α-olefin copolymer (7) was used as the ethylene-α-olefin copolymer. The blocking property of the unstretched film and the heat-sealing strength of the laminate were measured, and the orange peel of the packaging bag was evaluated.

As can be seen from the results in Table 2, in Comparative Example 1 not containing an ethylene-α-olefin copolymer, the orange peel was poorly evaluated, and in Comparative Example 2 not containing an acrylate-based compound and a phosphite-based compound, heat sealing was performed. Inferior in strength, in Comparative Example 3 where an ethylene-α-olefin copolymer having a molecular weight distribution that did not satisfy the requirements of the present invention was poor in impact resistance, and was used in an ethylene-α-olefin copolymer that did not satisfy the requirements of the present invention. In Comparative Example 4, the antiblocking property was poor.

Claims (6)

A propylene-based resin composition containing 50 to 90% by weight of a polymer component (component A) containing a structural unit derived from propylene as a main structural unit and 20 to 60% by weight of a structural unit derived from ethylene. Ethylene-propylene copolymer component (component B) 50 to 10% by weight (but the total weight of component A and component B is 100% by weight) 70 to 90% by weight of a propylene-based copolymer (polymer (I)), And an ethylene-α-olefin copolymer having a structural unit derived from ethylene and a structural unit derived from α-olefins having 4 to 20 carbon atoms, with a density of 900 to 940 kg / m ³ and a molecular weight distribution of 1 or more and less than 3. Polymer (II)) 30 to 10% by weight of the resin composition (however, the total weight of the polymer (I) and the polymer (II) is 100% by weight), and 100% by weight relative to the aforementioned resin composition In terms of parts, 0.01 to 0.1 parts by weight of the acrylate compound represented by the following formula (1) and / or the phosphite compound represented by the following formula (2);

(Wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ³ represents a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group);

(Wherein R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl having 7 to 12 carbons, R ⁷ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom , An alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), n is 0 or 1; A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group ( R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1); any one of Y and Z represents a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms Or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). A propylene-based resin composition containing a polymer component (component A) having a structural unit derived from propylene as a main structural unit at 50 to 90% by weight, and a content of 20 to 60% by weight with a structural unit derived from ethylene. Ethylene-propylene copolymer component (component B) 50 to 10% by weight (but the total weight of component A and component B is 100% by weight) propylene copolymer (polymer (I)) 45 to 90% by weight, An ethylene-α-olefin copolymer (polymerization) having a structural unit derived from ethylene and a structural unit derived from α-olefins having 4 to 20 carbon atoms, with a density of 900 to 940 kg / m ³ and a molecular weight distribution of 1 or more and less than 3. (II)) 30 to 10% by weight and a propylene-ethylene random copolymer (polymer (III)) 25% by weight or less of the resin composition (except polymer (I) and polymer (II) ) And the total weight of the polymer (III) is 100% by weight), and the acrylate-based compound represented by the formula (1) and / or the compound represented by the formula (2) with respect to 100 parts by weight of the resin composition 0.01 ~ 0.1 parts by weight of phosphite compound;

(Wherein R ¹ and R ² are the same or different, and represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, and R ³ represents a hydrogen atom or An alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group);

(Wherein R ⁵ , R ⁶ , R ⁸ and R ⁹ are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon group having 6 to 12 carbon atoms. Alkylcycloalkyl, aralkyl or phenyl having 7 to 12 carbons, R ⁷ represents a hydrogen atom or an alkyl having 1 to 8 carbons; X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom , An alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), n is 0 or 1; A represents an alkylene group having 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group ( R ¹¹ represents an alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1); any one of Y and Z represents a hydroxyl group and an alkoxy group having 1 to 8 carbon atoms Or an aralkoxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). For example, the propylene-based resin composition in the second item of the patent application, wherein the polymer (III) contains 3 to 7% by weight of a structural unit derived from ethylene. For example, the propylene-based resin composition according to item 1 or 2 of the application scope, wherein the acrylate-based compound represented by the formula (1) is 2,4-di-third-pentyl-6- [1- (3,5-di Third pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate. For example, the propylene-based resin composition according to item 1 or 2 of the patent application scope, wherein the phosphite-based compound represented by the formula (2) is 2,4,8,10-tetratert-butyl-6- [3- ( 3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] di

Phosphloheptane. A film is composed of an acrylic resin composition such as the scope of claims 1 or 2.