KR20120112076A - Propylene-based resin composition and film thereof - Google Patents

Abstract

PURPOSE: A propylene-based resin composition is provided to have excellent heat seal strength, impact resistance in low temperature, and blocking resistance, and to obtain a film hardly generating orange peel due to a heat treatment. CONSTITUTION: A propylene-based resin composition comprises 100.0 parts by weight of resin composition and 0.01-0.1 parts by weight of a specific acrylate-based compound and/or a specific phosphite-based compound. The resin composition comprises 70-90 weight% of propylene-based copolymer, and 30-10 weight% of ethylene-A-olefin-based copolymer if which density is 900-940 kg/m^3 and molecular weight distribution is 1-3. The propylene-based copolymer contains 50-90 weight% of a polymer component which has a main structural unit originated from propylene, and 50-10 weight% of an ethylene-propylene copolymer component of which structural unit content is 20-60 weight% originated from ethylene.

Description

Propylene resin composition and its film {PROPYLENE-BASED RESIN COMPOSITION AND FILM THEREOF}

The present invention relates to a propylene resin composition and a film thereof. More specifically, when it is a film, it is excellent in blocking resistance, impact resistance at low temperature, and heat-sealing strength, and when the package body which consists of this film is heat-treated, unevenness | corrugation is given to the surface of a package body (hereinafter "orange peel"). The propylene resin composition and its film which are hard to generate | occur | produce this may be described.

Since polypropylene films are excellent in heat resistance and rigidity, they are widely used in the fields of films, sheets, containers, and the like.

In recent years, the film used in the field for food packaging, for example, the film used for a retort food package, is required to have a film having heat resistance, rigidity, blocking resistance, heat seal strength, and a good appearance after heat treatment.

Patent Document 1 includes polypropylene-based resins selected from propylene homopolymers, random copolymers of propylene and ethylene, propylene-ethylene-butene-1 ternary copolymers, and block copolymers of propylene and ethylene. 75 mass% and a density of 0.860? Obtained by polymerizing ethylene and an? -Olefin with a single-site catalyst. 0.900 g / cm 3, intrinsic viscosity [η] 1.0? Ethylene-α-olefin copolymer 3 which is 1.8 (dl / g) 3? The resin composition for retort food packaging which consists of 25 mass% is described.

Moreover, in patent document 2, the propylene block copolymer 70? 95 weight% and the density is 890? 925 kg / m 3, and the amount of n-hexane extracted is 0.01? 2.6 wt% ethylene-α-olefin copolymer 5? Propylene-based resin composition containing 30% by weight (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 is an ethylene-α-olefin N-hexane extraction amount of the copolymer is based on 100% by weight of the total weight of the ethylene-α-olefin copolymer).

Japanese Laid-Open Patent Publication 2003-64228 Japanese Laid-Open Patent Publication 2006-161033

However, in the resin compositions described in Patent Documents 1 and 2, the blocking resistance, heat seal strength, poor appearance after heat treatment, and impact resistance at low temperature have not yet been satisfied, and further improvement has been required. 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 temperatures, and heat seal strength when used as a film, and in which orange peel due to heat treatment is less likely to occur. .

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that this invention could solve the said subject, and came to complete this invention.

That is, in this invention, the polymer component (component A) 50? Whose structural unit derived from propylene is a main structural unit. 90 weight% and content of the structural unit derived from ethylene is 20? Ethylene-propylene copolymer component (component B) which is 60 weight% 50? Propylene copolymer (polymer (I)) containing 10 weight% (however, the total weight of component A and component B shall be 100 weight%) 70? 90 wt%, and

Structural unit derived from ethylene, and carbon number 4? It has a structural unit derived from the 20-olefin, and its density is 900? 940-kg / m <3> and the ethylene-alpha-olefin type copolymer (polymer (II)) whose molecular weight distribution is 1 or more and less than 3 30? Resin composition consisting of 10% by weight (but the total weight of polymer (I) and polymer (II) is 100% by weight),

0.01 to the acrylate compound represented by the following formula (1) and / or the phosphite ester compound represented by following formula (2) with respect to 100 weight part of said resin compositions. It is a propylene resin composition containing 0.1 weight part.

(In formula, R <^1> and R <^2> is the same or different, respectively, and represents a C1-C8 alkyl group, a C6-C12 aryl group, or a C7-C18 aralkyl group, and R <^3> is a hydrogen atom or a carbon number An alkyl group of 1 to 3, R ⁴ represents a hydrogen atom or a methyl group)

(In formula, R <^5> , R <^6> , R <^8> and R <^9> are the same or different, respectively, and a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, An aralkyl group or phenyl group having 7 to 12 carbon atoms is represented, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8. X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom or a C 1? An alkyl group of 8 or a cycloalkyl group of 5 to 8 carbon atoms is represented, n is 0 or 1. A is an alkylene group of 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group (R ¹¹ is In the alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1. Each of Y and Z has a hydroxyl group and 1 to 8 carbon atoms. It represents an alkoxy group or a C7-12 aralkyloxy group, and the other represents a hydrogen atom or a C1-8 alkyl group. Put out)

Moreover, this invention is a polymer component (component A) 50? Whose structural unit derived from propylene is a main structural unit. 90 weight% and content of the structural unit derived from ethylene is 20? Ethylene-propylene copolymer component (component B) which is 60 weight% 50? Propylene copolymer (polymer (I)) containing 10 weight% (however, the total weight of component A and component B shall be 100 weight%) 45? 90 wt%,

Structural unit derived from ethylene, and carbon number 4? It has a structural unit derived from the 20-olefin, and its density is 900? 940-kg / m <3> and the ethylene-alpha-olefin type copolymer (polymer (II)) whose molecular weight distribution is 1 or more and less than 3 30? 10 weight% and the resin composition which consists of 25 weight% or less of a propylene ethylene random copolymer (polymer (III)) (However, the total weight of a polymer (I), a polymer (II), and a polymer (III) is 100 weight. %) And

0.01 to the acrylate compound represented by the formula (1) and / or the phosphite ester compound represented by the formula (2) to 100 parts by weight of the resin composition. It is a propylene resin composition containing 0.1 weight part.

(In formula, R <^1> and R <^2> is the same or different, respectively, and represents a C1-C8 alkyl group, a C6-C12 aryl group, or a C7-C18 aralkyl group, and R <^3> is a hydrogen atom or a carbon number An alkyl group of 1 to 3, R ⁴ represents a hydrogen atom or a methyl group)

(In formula, R <^5> , R <^6> , R <^8> and R <^9> are the same or different, respectively, and a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, An aralkyl group or phenyl group having 7 to 12 carbon atoms is represented, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8. X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom or a C 1? An alkyl group of 8 or a cycloalkyl group of 5 to 8 carbon atoms is represented, n is 0 or 1. A is an alkylene group of 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group (R ¹¹ is In the alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1. Each of Y and Z has a hydroxyl group and 1 to 8 carbon atoms. It represents an alkoxy group or a C7-12 aralkyloxy group, and the other represents a hydrogen atom or a C1-8 alkyl group. Put out)

According to this invention, the film which is excellent in blocking resistance, impact resistance at low temperature, and heat-sealing strength, and hard to generate | occur | produce orange peel by heat processing can be obtained.

The propylene resin composition of this invention is a polymer component whose structural unit derived from propylene is a main structural unit (henceforth, it may describe as "component A"). 90 weight% and content of the structural unit derived from ethylene is 20? Ethylene-propylene copolymer component which is 60 weight% (Hereinafter, it may describe as "component B".) 50? Propylene copolymer containing 10 weight% (but the total weight of component A and component B shall be 100 weight%) (Hereinafter, it may describe as "polymer (I).)) 70? 90 weight percent, and

Structural unit derived from ethylene, and carbon number 4? It has a structural unit derived from the 20-olefin, and its density is 900? It is 940 kg / m <3> and the ethylene-alpha-olefin copolymer whose molecular weight distribution is 1 or more and less than 3 (Hereinafter, it may describe as "polymer (II).") 30? Resin composition consisting of 10% by weight (but the total weight of polymer (I) and polymer (II) is 100% by weight),

0.01 to the acrylate compound represented by the following formula (1) and / or the phosphite ester compound represented by following formula (2) with respect to 100 weight part of said resin compositions. 0.1 parts by weight.

(In formula, R <^1> and R <^2> is the same or different, respectively, and represents a C1-C8 alkyl group, a C6-C12 aryl group, or a C7-C18 aralkyl group, and R <^3> is a hydrogen atom or a carbon number An alkyl group of 1 to 3, R ⁴ represents a hydrogen atom or a methyl group)

(In formula, R <^5> , R <^6> , R <^8> and R <^9> are the same or different, respectively, and a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, An aralkyl group or phenyl group having 7 to 12 carbon atoms is represented, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8. X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom or a C 1? An alkyl group of 8 or a cycloalkyl group of 5 to 8 carbon atoms is represented, n is 0 or 1. A is an alkylene group of 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group (R ¹¹ is In the alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1. Each of Y and Z has a hydroxyl group and 1 to 8 carbon atoms. It represents an alkoxy group or a C7-12 aralkyloxy group, and the other represents a hydrogen atom or a C1-8 alkyl group. Put out)

The "main structural unit" in component A of polymer (I) used for this invention means the structural unit which occupies 90 weight% or more of the component A, and the structural unit derived from propylene is the main structure of component A Unit. As content of the structural unit derived from propylene in component A, Preferably it is 90? 100 weight%, More preferably, it is 95? 100 wt%.

As needed, component A is ethylene and / or C4-C? You may have a structural unit derived from the (alpha) -olefin of 12, and it is ethylene and / or C4-C? As content of the structural unit derived from the (alpha) -olefin of 12, Preferably it is 10 weight% or less, More preferably, it is 5 weight% or less. Carbon number 4? Examples of the α-olefin of 12 include 1-butene, 1-hexene, 1-octene, and the like, and preferably 1-butene.

The content of the structural unit derived from ethylene in the polymer (I) component B is 20? From the viewpoint of excellent blocking resistance and impact resistance at low temperature. 60 weight%, Preferably it is 25? 50 weight% (however, the total weight of component B shall be 100 weight%).

Moreover, component B has a structural unit derived from propylene other than the structural unit derived from ethylene, and as content of the structural unit derived from propylene, it is 80? 40 weight%, Preferably it is 75? 50 weight% (however, the total weight of content of the structural unit derived from ethylene and content of the structural unit derived from propylene shall be 100 weight%).

As content of the component A and the component B in a polymer (I), content of the component A is 50? From a viewpoint of excellent balance of heat sealability and blocking resistance. It is 90 weight%, and content of component B is 50? 10 weight%, Preferably, content of component A is 60? It is 85 weight%, and content of component B is 40? 15 weight%, More preferably, the content of component A is 65? It is 80 weight%, and content of component B is 35? It is 15 weight% (however, the total weight of component A and component B shall be 100 weight%).

The melt flow rate (230 ° C.) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K7210 of the polymer (I) is preferably 1.5? From the viewpoint of improving the processability and hygiene of the film. 10 g / 10 minutes, More preferably, it is 2? 5 g / 10 min.

As a manufacturing method of a polymer (I), the method of superposing | polymerizing propylene, ethylene, etc. which are raw materials using a Ziegler-Natta catalyst, a metallocene catalyst, etc. are mentioned.

As a polymerization method of the polymer (I), a catalyst is added to propylene or ethylene in an inert solvent such as hexane, heptane, toluene or xylene, to polymerize liquid propylene or ethylene, or to a gaseous propylene or ethylene. And the method of polymerizing propylene and ethylene in a gaseous state, or the method of combining them.

As a method for producing the polymer (I), preferably from the viewpoint of productivity, component A is prepared in the first step in the substantially absence of an inert solvent, and then polymerized with propylene and ethylene in the gas phase in the second step, It is a method of manufacturing component B.

As a method of adjusting the content of the structural unit derived from ethylene of component A and component B of polymer (I), a method of adding an appropriate amount of molecular weight regulators such as hydrogen gas or metal compound and ethylene in each step during polymerization And the method of adjusting the temperature, pressure, etc. at the time of superposition | polymerization are mentioned.

The ratio of component A and component B of polymer (I) can be controlled by the polymerization time at the time of manufacture of polymer (I), the size of a polymerization tank, the retention amount of a polymer in a polymerization tank, polymerization temperature, polymerization pressure, etc. As needed, you may dry at the temperature below the temperature which polypropylene melt | dissolves, in order to remove the residual solvent of polypropylene, the ultra low molecular weight oligomer etc. which by-produce at the time of manufacture. As a drying method, the method of Unexamined-Japanese-Patent No. 55-75410, Unexamined-Japanese-Patent No. 2565753, etc. are mentioned, for example.

Polymer (II) is a structural unit derived from ethylene, and carbon number 4? It has a structural unit derived from 20 alpha olefin. Carbon number 4? Examples of the α-olefin of 20 include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-hexadecene, 1-eicosene and 4-methyl- 1-pentene, 4-methyl-1-hexene, etc. are mentioned. Polymer (II) has 4? Two or more types of structural units derived from 20 alpha olefins may be included. Carbon number 4? As 20 alpha-olefin, Preferably it is 1-hexene from a viewpoint of improving heat-sealing strength.

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

Melt flow rate (190 degreeC) measured by the temperature of 190 degreeC and load 21.18 N according to JISK7210-1995 of polymer (II) becomes like this. 30 g / 10 minutes, More preferably, it is 0.5? 10 g / 10 min, more preferably 1? 5 g / 10 min. When the melt flow rate of the polymer (II) is 0.5 g / 10 min or more, orange peel is more difficult to occur, and when it is 30 g / 10 min or less, the heat seal strength is more excellent.

The molecular weight distribution of polymer (II) is 1 or more and less than 3, Preferably it is 1.5 or more and less than 2.5. When the molecular weight distribution is less than 3, the impact resistance at low temperature is excellent. Here, molecular weight distribution is ratio (Mw / Mn) with respect to the number average molecular weight (Mn) of the weight average molecular weight (Mw) measured by gel permeation chromatography (it may describe as "GPC" hereafter).

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

As a metallocene catalyst used for manufacture of an ethylene-alpha-olefin copolymer, it is a transition metal compound which has group which has cyclopentadiene type | mold anion skeleton, for example (it describes as a "metallocene system transition metal compound" hereafter). And the catalyst for olefin polymerization formed using) may be mentioned.

As the metallocene-based transition metal compound, for example, the formula ML _T X ' _{Q -T} (wherein M is a transition metal atom of Group 4 or lanthanoid series of the periodic table of the elements. L is cyclopentadiene A group having a type anion skeleton or a group containing a hetero atom, and at least one group having a cyclopentadiene type anion skeleton, a plurality of L may be crosslinked with each other. An atom or a hydrocarbon group having 1 to 20 carbon atoms, Q represents a valence of a transition metal atom, and T is an integer satisfying 0 <T ≦ Q).

As a metallocene transition metal compound represented by the said formula, For example, bis (1, 3-n- butylmethyl cyclopentadienyl) zirconium dichloride, bis (1, 3-n-propylmethyl cyclopentadienyl ) Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium di Chloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride Etc. can be mentioned.

It is preferable to use the said metallocene type transition metal compound in contact with an activation cocatalyst. As an activation cocatalyst, the activation cocatalyst formed by using together an alumoxane compound, an organoaluminum compound, and boron compounds, such as trityl borate and anninium borate, is mentioned. The metallocene-based transition metal compound may be used in combination with a particulate carrier including an inorganic carrier such as SiO ₂ , Al ₂ O ₃ , or an organic carrier such as a polymer such as ethylene or styrene.

The density of the polymer (II) is 900? As a method of setting it as 940 kg / m <3>, the method of adjusting the ratio which copolymerizes ethylene and (alpha) -olefin is mentioned.

The resin composition contained in the propylene resin composition of this invention contains a polymer (I) and a polymer (II). When a resin composition consists of a polymer (I) and a polymer (II), the resin composition is polymer (I) 70? 90 wt% and Polymer (II) 30? It consists of 10 weight%, and polymer (I) 75-? 90 wt% and Polymer (II) 25? It is preferable to consist of 10 weight% (however, the total weight of a polymer (I) and a polymer (II) shall be 100 weight%). If the polymer (I) is less than 70% by weight (that is, the polymer (II) exceeds 30% by weight), the heat sealability of the resulting film deteriorates, and if the polymer (I) exceeds 90% by weight (that is, If polymer (II) is less than 10 weight%), the unevenness | corrugation (orange peel) of the package surface by heat processing generate | occur | produces, and an external appearance worsens.

The resin composition contained in the propylene resin composition of the present invention may further include a propylene-ethylene random copolymer (polymer (III)) in addition to the polymer (I) and the polymer (II). When a resin composition consists of a polymer (I), a polymer (II), and a polymer (III), when the resin composition makes the total weight of a polymer (I), a polymer (II), and a polymer (III) 100 weight% , Polymer (I) 45? 90 weight%, polymer (II) 30? It is preferable that it consists of 10 weight% and 25 weight% or less of polymer (III), and the polymer (I) 50- 85 wt%, Polymer (II) 30? 10% by weight, polymer (III) 20? It is more preferable that it consists of 5 weight%, and a polymer (I) 50? 80 wt%, Polymer (II) 30? 10% by weight, polymer (III) 20? It is more preferable that it consists of 10 weight%. When the resin composition contains the polymer (III), the difference between the heat seal strength after heat treatment and the heat seal strength before heat treatment is small for the propylene resin composition containing the resin composition.

The polymer (III) is preferably a structural unit derived from ethylene. 7% by weight, more preferably 4? It contains 6 weight%. The polymer (III) is preferably a structural unit derived from propylene. 93% by weight, more preferably 96? It contains 94 weight%.

The acrylate compound used for this invention is represented by following formula (1).

(In formula, R <^1> and R <^2> is the same or different, respectively, and represents a C1-C8 alkyl group, a C6-C12 aryl group, or a C7-C18 aralkyl group, and R <^3> is a hydrogen atom or a carbon number An alkyl group of 1 to 3, R ⁴ represents a hydrogen atom or a methyl group)

Carbon number ^{1 to} R ¹ and R ^2; As an alkyl group of 8, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, t-a push _{(-C (CH 3) 2 CH} 2 CH 3), and the like a 2-ethylhexyl group, cyclohexyl group, having 6? As an aryl group of 12, a phenyl group etc. are mentioned, for example, C7-C? As an aralkyl group of 18, a benzyl group etc. are mentioned, for example, Preferably it is C4-C? It is an alkyl group which has a tertiary carbon of 8, More preferably, it is a t-butyl group or t-amyl group, More preferably, it is a t-amyl group.

Carbon number in R ³ ? As an alkyl group of 3, a methyl group, an ethyl group, n-propyl group, isopropyl group, etc. are mentioned, for example, A preferable R <^3> is a hydrogen atom or a methyl group.

R ⁴ is preferably a hydrogen atom.

As an acrylate compound represented by the said Formula (1), it is 2, 4- di-t-butyl-6- [1- (3, 5- di- t- butyl- 2-hydroxyphenyl), for example. Ethyl] phenylacrylate, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenylacrylate, 2,4-di- t-butyl-6- (3,5-di-t-butyl-2-hydroxy-benzyl) phenylmethacrylate, 2,4-di-t-butyl-6- [1- (3,5-di -t-butyl-2-hydroxyphenyl) ethyl] phenyl methacrylate, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) Ethyl] phenyl methacrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylmethacrylate, 2-t-butyl-6- (3 -t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4- Ethylphenylmethacrylate, 2-t-amyl-6- (3-t-amyl-2-hydroxy-5-methylbenzyl) -4-methylphenylmethacrylate, 2-t-amyl-6- (3- t-amyl-2-hydroxy-5-meth Tilbenzyl) -4-methylphenyl acrylate and the like, and preferably 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) Ethyl] phenyl acrylate.

As a manufacturing method of the acrylate compound represented by said formula (1), the method etc. which are described in Unexamined-Japanese-Patent No. 2010-270310 are mentioned, for example.

The phosphite ester type compound used for this invention is represented by following formula (2).

(In formula, R <^5> , R <^6> , R <^8> and R <^9> are the same or different, respectively, and a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, An aralkyl group or phenyl group having 7 to 12 carbon atoms is represented, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8. X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom or a C 1? An alkyl group of 8 or a cycloalkyl group of 5 to 8 carbon atoms is represented, n is 0 or 1. A is an alkylene group of 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group (R ¹¹ is In the alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1. Each of Y and Z has a hydroxyl group and 1 to 8 carbon atoms. It represents an alkoxy group or a C7-12 aralkyloxy group, and the other represents a hydrogen atom or a C1-8 alkyl group. Put out)

Carbon number at R ⁵ , R ⁶ , R ⁸ and R ⁹ ? As the alkyl group of 8, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, i -Octyl group, t-octyl group, 2-ethylhexyl group, etc. are mentioned, C5? Examples of the cycloalkyl group of 8 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Examples of the alkylcycloalkyl group of 12 include 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group, and the like. As an aralkyl group of 12, a benzyl group, the (alpha)-methyl benzyl group, the (alpha), (alpha)-dimethylbenzyl group etc. are mentioned, for example.

As R ⁵ , R ⁶ , R ⁸ , Preferably it is C1-C? An alkyl group of 8, carbon number 5? Cycloalkyl groups of 8 or 6? It is an alkylcycloalkyl group of 12. Especially, as R <^5> , R <^8> , More preferably, they are t-alkyl groups, such as a t-butyl group, a t-pentyl group, and a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.

As R ⁶ , More preferably, it is C1-C. It is an alkyl group of 5, More preferably, they are a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, or t-pentyl group, Especially Preferably, they are a methyl group, t-butyl group, or t-pentyl group.

As R ⁹ , Preferably it is a hydrogen atom, C1-C? Alkyl groups of 8 or 5? It is a cycloalkyl group of 8, More preferably, it is C1-C? It is an alkyl group of 5, and is a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, or t-pentyl group.

Carbon number in R ⁷ ? As an alkyl group of 8, the same alkyl group as the above is mentioned, for example. Preferably it is a hydrogen atom or C1-C? It is an alkyl group of 5, More preferably, it is a hydrogen atom or a methyl group.

Moreover, when n is 0, the substituent X shows that the group which has two phenoxy group skeletons is couple | bonded directly, and when n is 1, a sulfur atom or C1-C? Alkyl groups of 8 or 5? The methylene group which may be substituted by the cycloalkyl group of 8 is shown. Here, the carbon number substituted with the methylene group is 1? An alkyl group of 8, carbon number 5? As a cycloalkyl group of 8, the alkyl group and cycloalkyl group similar to the above are mentioned, respectively. As the substituent X, preferably n is 0, and a group having two phenoxy group skeletons is directly bonded, or n is 1, a methylene group or a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-butyl group, i-butyl group, t-butyl group, etc. are substituted methylene groups.

In addition, substituent A is C2-C? An alkylene group of 8 or * -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 represents 0 or 1).

Where carbon number 2? As a representative example of the alkylene group of 8, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a 2, 2- dimethyl- 1, 3- propylene group, etc. are mentioned, for example. And preferably a propylene group. Also * -CO (R ¹¹⁾ groups in the m- * indicates that the group of parts that combine with the oxygen atoms of the phosphite group. Carbon number in R ¹¹ ? As a representative example of the alkylene group of 8, a methylene group, an ethylene group, a propylene group, a butylene group, pentamethylene group, hexamethylene group, an octamethylene group, 2, 2- dimethyl- 1, 3- propylene group etc. are mentioned, for example. Can be mentioned. The * -CO (R ¹¹ ) m-group is preferably a * -CO- group where m is 0, or a * -CO (CH ₂ CH ₂ )-group where m is 1 and R ¹¹ is ethylene.

Either one of Y and Z has a hydroxyl group and carbon number 1? 8 alkoxy groups or carbon atoms? 12 aralkyloxy group, and the other is a hydrogen atom or C1-C? The alkyl group of 8 is shown.

Where carbon number 1? As an alkyl group of 8, the alkyl group same as the above is mentioned, for example, C1-C? As an alkoxy group of 8, an alkyl part is the said C1-C ?, for example. The alkoxy group which is the same alkyl as the alkyl of 8 is mentioned. And carbon number 7? As an aralkyloxy group of 12, the aralkyl moiety is, for example, the above carbon number 7? And an aralkyloxy group which is the same aralkyl as 12 aralkyl.

As a phosphite ester type compound, Preferably it is the following compound 1.

Compound 1: 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [ 1,3,2] dioxaphosphine

As a manufacturing method of the phosphite ester compound represented by said Formula (2), the method etc. which are described in Unexamined-Japanese-Patent No. 10-273494 are mentioned, for example.

In this invention, it is preferable to use together the acrylate type compound represented by said Formula (1) and the phosphite ester type compound represented by said Formula (2), and it is 2, 4- di-t-amyl-6- [1 -(3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenylacrylate and 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4 It is more preferable to use hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine in combination.

When a resin composition consists of a polymer (I) and a polymer (II), the acrylate compound represented by the said Formula (1) contained in the propylene resin composition of this invention, and / or the phosphite ester type represented by said Formula (2) The content of the compound is 0.01? To 100 parts by weight of the resin composition. 0.1 parts by weight, preferably 0.03? 0.07 parts by weight.

When a resin composition consists of a polymer (I), a polymer (II), and a polymer (III), the acrylate type compound represented by said Formula (1) contained in the propylene resin composition of this invention, and / or said Formula (2) Content of the phosphite ester type compound represented by is 0.01? With respect to 100 weight part of the resin composition. 0.1 parts by weight, preferably 0.03? 0.07 parts by weight.

When the compounding quantity of the acrylate compound represented by said formula (1) and / or the phosphite ester compound represented by said formula (2) is less than 0.01 weight part, heat seal strength may be inadequate and it exceeds 0.1 weight part The effect of the present invention is saturated and only economical.

The propylene resin composition of this invention mixes a polymer (I), a polymer (II), the acrylate compound represented by the said Formula (1), the phosphite ester compound represented by the said Formula (2), and optionally a polymer (III). It can be obtained by melt kneading.

The melt kneading can be carried out using a conventionally known method and apparatus. For example, the method of melt-kneading after mixing each component which comprises a propylene resin composition using mixing apparatuses, such as a Henschel mixer, a ribbon blender, and a tumble mixer; Using a fixed-quantity feeder, a homogeneous mixture is obtained by continuously mixing each component constituting the propylene-based resin composition in a constant ratio, and then mixing the mixture into a single screw or two-axis or more extruder, Banbury mixer, roll kneader, or the like. The method of melt-kneading using this is mentioned.

As temperature of the said melt kneading, Preferably it is 180 degreeC? 350 degreeC, More preferably, it is 180 degreeC? 320 ° C.

You may add an additive and other resin to the propylene resin composition of this invention as needed. As an additive, antioxidant, a ultraviolet absorber, an antistatic agent, a lubricating agent, a nucleating agent, an adhesive, an antifog additive, an anti blocking agent, etc. are mentioned, for example. As other resin, the olefin resin, the elastomer which is a copolymer of ethylene and an alpha olefin, etc. are mentioned. These may be produced by heterogeneous catalysts or may be produced by homogeneous catalysts (for example, metallocene catalysts). Moreover, elastomers, such as styrene-type copolymer rubber which hydrogenated the styrene-butadiene-styrene copolymer and the styrene-isoprene-styrene copolymer, are mentioned.

The propylene resin composition of this invention is suitable as a material of a film. As a manufacturing method of a film, a well-known film manufacturing method is mentioned, For example, T die method, the tubular method, etc. are mentioned.

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

The film of the present invention has a thickness of 5? It is preferable that it is 500 micrometers, and is 30? It is more preferable that it is 150 micrometers.

As a use of the film of this invention, a packaging use etc. are mentioned, For example, packaging uses, such as food, a fiber, and sundries, are mentioned. Preferably it is a retort food packaging film.

The film of this invention may be surface-treated, such as a corona discharge treatment, a flame treatment, a plasma treatment, and an ozone treatment by the method employ | adopted industrially normally.

You may laminate | stack the film of this invention and another film.

As another film, a polypropylene biaxially stretched film, a stretched nylon film, a stretched polyterephthalate film, aluminum foil, etc. are mentioned, for example.

As a method of laminating | stacking the film of this invention and another film, a dry lamination method, an extrusion lamination method, etc. are mentioned, for example.

As a use of the film of this invention, Preferably it is a heavy goods packaging use.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated using an Example and a comparative example. In addition, the measured value of each item in an Example and a comparative example was measured by the following method.

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

Content (P _A ) of component A of polymer (I), and content (P _B ) of component B were calculated | required from the material resin at the time of manufacturing component A and component B.

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

IR spectral measurements of polymer (I) were carried out and according to the method for the block copolymer (ii) described on page 616 of the Polymer Analysis Handbook (published by Kinokuniya Bookstore, 1995) in ethylene of polymer (I) Content of the structural unit derived was calculated | required, and content of the structural unit derived from ethylene contained in component B was calculated | required by following formula (1).

E _B = E _T / P _B Equation (1)

(However, the content of the component B of E _T and E _B are, each represents the content of the structural unit derived from ethylene in the composition B in the polymer (I) and the polymer (I), P _B is the polymer (I) Indicates)

(3) Melt flow rate (MFR, unit: g / 10 min)

The melt flow rate of the polymer (I) was measured at a temperature of 230 ° C. and a load of 21.18 N according to JIS K7210. The melt flow rate of the polymer (II) was measured at a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995.

(4) Density (unit: kg / ㎥)

The density of polymer (II) was measured in accordance with the method prescribed | regulated by the A method in JISK7112-1980. In addition, the sample was subjected to annealing described in JIS K6760-1995.

(5) molecular weight distribution (Mw / Mn)

Using the gel permeation chromatography (GPC) method, the weight average molecular weight (Mw) and number average molecular weight (Mn) of polymer (II) were measured and Mw / Mn was calculated | required by the following conditions. The baseline on the chromatogram connects the point of the stable horizontal region with a shorter holding time than the sample elution peak is exhibited, and the point of the stable horizontal region with a sufficient holding time than the solvent elution peak is observed. Produced straight line.

Device: WAters Manufacture WAters150C

Separation column: TOSOH TSK-GEL GMH6-HT

Measuring temperature: 140 ℃

Carrier: Orthodichlorobenzene

Flow rate: 1.0 mL / min

Injection volume: 500 μL

Detector: parallax refraction

Molecular Weight Standards: Standard Polystyrene

(6) Heat Seal Strength (Unit: Width N / 15 mm)

The film was sealed under the following conditions using the heat sealer by Toyo Tester Industry Co., Ltd. The seal piece was cut out to width 15mm, and it measured using the Orientek-made tensilon at a peeling angle of 90 degrees.

Seal Bar: Flat Double Sided Heating

Seal temperature: 200 ℃

Seal pressure: 1.0 kg / ㎠

Seal time: 1.0 sec

(7) Blocking resistance (Unit: N / 12 ㎠)

Using a 150 mm x 30 mm film (collected so that the film forming direction and the long side direction coincide), the films were overlapped, and a load of 500 g was applied at a range of 40 mm x 30 mm at 80 ° C. Condition adjustment was performed for 24 hours. Thereafter, the film was left to stand for 30 minutes or more in an atmosphere of 23 ° C. and 50% humidity, and peeled at a rate of 200 mm / min using a Toyo Seiko tensile tester, and the strength required for peeling the sample was measured. It was.

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

At -15 ° C, impact strength of the film was measured using a Toyo Periodical Film Impact Tester, and using a hemispherical impact head having a diameter of 15 mm.

(9) orange peel rating

The retort process was performed for 30 minutes on 120 degreeC conditions using the ALP made compact retort sterilizer, and the uneven state (orange peel) of the surface layer of the packaging bag after retort process was visually determined by the four-step method based on the following references | standards.

There is slightly orange peel, but is hardly seen.

2? Some orange peel is observed, but there is no effect on practical use at all.

Orange peel is observed, but can endure practical use.

Orange peel is observed considerably and cannot endure practical use.

The acrylate compound and the phosphite ester compound which were used by the Example and the comparative example were as follows.

[Acrylic Compound]

Sumiiser by Sumitomo Chemical Co., Ltd., which is 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate [registered trademark] GS Was used. Hereinafter, it is called "compound C."

Phosphoric Acid Ester Compound

2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] Sumiiser [registered trademark] GP manufactured by Sumitomo Chemical Co., Ltd., which is dioxaphosphine, was used. Hereinafter, it is called "compound D."

The polymer used by the Example and the comparative example was as follows.

Propylene Copolymer (1)

A propylene homopolymer component (component A) was obtained by polymerizing propylene in the gas phase in the first step using a Ziegler-Natta catalyst, followed by copolymerizing propylene and ethylene in the gas phase in the second step to produce a copolymer component of propylene and ethylene. (Component B) was obtained. As for the obtained copolymer, content of the structural unit derived from ethylene contained in 78 weight% of components A, 22 weight% of component B, and component B was 31 weight%.

0.01 parts by weight of calcium hydroxide, 100 parts by weight of the copolymer powder, Irganox manufactured by BASF Corporation 1010 (hereinafter referred to as "Compound A") 0.2 parts by weight, Irganox manufactured by BASF Corporation 168 ( (Hereinafter referred to as "Compound B") 0.05 part by weight, appropriate amount of 2,5-dimethyl-2,5di (tertiarybutylperoxy) hexane as a micron white [trademark] 5000S manufactured by Hayashi Chemical Co., Ltd. and a melt flow rate regulator After mixing in a Henschel mixer, the mixture was melt extruded to obtain pellets. The melt flow rate measured at 230 degreeC of the obtained pellet was 3 g / 10min. Hereinafter, the pellet may be called "PP1".

[Propylene copolymer (2)]

A propylene homopolymer component (component A) was obtained by polymerizing propylene in the gas phase in the first step using a Ziegler-Natta catalyst, followed by copolymerizing propylene and ethylene in the gas phase in the second step to produce a copolymer component of propylene and ethylene. (Component B) was obtained. As for the obtained copolymer, content of the structural unit derived from ethylene contained in 77 weight% of component A, 23 weight% of component B, and component B was 30 weight%.

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 a suitable amount of 2,5-dimethyl-2,5di (tertiarybutylperoxy) hexane as a melt flow rate regulator in 100 parts by weight of the copolymer powder. After mixing with a Henschel mixer, the mixture was melt-extruded to obtain pellets. The melt flow rate measured at 230 degreeC of the obtained pellet was 2.5 g / 10min. Hereinafter, the pellet may be called "PP2."

[Propylene-ethylene random copolymer (1)]

As the propylene-ethylene random copolymer, Noren [registered trademark] S131 manufactured by Sumitomo Chemical Co., Ltd. was used. This copolymer contained 5.6 weight% of structural units derived from ethylene. Hereinafter, the copolymer may be called "PP3".

[Propylene-ethylene random copolymer (2)]

As the propylene-ethylene random copolymer, Noren (registered trademark) WF577PG11 manufactured by Sumitomo Chemical Co., Ltd. was used. This copolymer contained 4.0 weight% of structural units derived from ethylene. Hereinafter, the copolymer may be called "PP4."

[Ethylene-α-olefin Copolymer (1)]

Sumikasen (registered trademark) EFV401 manufactured by Sumitomo Chemical Co., Ltd., an ethylene-hexene-1 copolymer, was used. Melt flow rate measured at 190 ° C was 3.8 g / 10 min, density was 902 kg / m 3 and molecular weight distribution (Mw / Mn) was 2.1. Hereinafter, the copolymer may be called "PE1".

[Ethylene-α-olefin Copolymer (2)]

Sumikasen [registered trademark] EFV402 manufactured by Sumitomo Chemical Co., Ltd., an ethylene-hexene-1 copolymer, was used. Melt flow rate measured at 190 ° C was 3.8 g / 10 min, density was 913 kg / m 3 and molecular weight distribution (Mw / Mn) was 2.0. Hereinafter, the copolymer may be called "PE2".

[Ethylene-α-olefin Copolymer (3)]

Sumikasen (registered trademark) EFV405 manufactured by Sumitomo Chemical Co., Ltd., an ethylene-hexene-1 copolymer, was used. Melt flow rate measured at 190 ° C was 3.8 g / 10 min, density was 924 kg / m 3 and molecular weight distribution (Mw / Mn) was 2.2. Hereinafter, the copolymer may be called "PE3".

[Ethylene-α-olefin Copolymer (4)]

Sumikasen [registered trademark] EFV203 manufactured by Sumitomo Chemical Co., Ltd., an ethylene-hexene-1 copolymer, was used. Melt flow rate measured at 190 ° C was 2.0 g / 10 min, density was 913 kg / m 3 and molecular weight distribution (Mw / Mn) was 2.0. Hereinafter, the copolymer may be called "PE4".

[Ethylene-α-olefin Copolymer (5)]

Sumikasen [registered trademark] EFV205 manufactured by Sumitomo Chemical Co., Ltd., an ethylene-hexene-1 copolymer, was used. Melt flow rate measured at 190 ° C was 2.0 g / 10 min, density was 922 kg / m 3 and molecular weight distribution (Mw / Mn) was 2.1. Hereinafter, the copolymer may be called "PE5".

[Ethylene-α-olefin Copolymer (6)]

Sumikasen [registered trademark] LFS150 manufactured by Sumitomo Chemical Co., Ltd., an ethylene-butene-1 copolymer, was used. Melt flow rate measured at 190 ° C was 1.1 g / 10 min, density was 922 kg / m 3 and molecular weight distribution (Mw / Mn) was 3.4. Hereinafter, the copolymer may be called "PE6".

[Ethylene-α-olefin Copolymer (7)]

Tafmer [registered trademark] P0680 manufactured by Mitsui Chemicals, Inc., an ethylene-propylene copolymer, was used. Melt flow rate measured at 190 ° C was 0.4 g / 10 min, density was 885 kg / m 3 and molecular weight distribution (Mw / Mn) was 1.9. Hereinafter, the copolymer may be called "PE7."

Example 1

A mixture obtained by pellet blending 85% by weight of the propylene copolymer (1) and 15% by weight of the ethylene-α-olefin copolymer (1) was obtained. To 100 parts by weight of this mixture, a mixture in which 0.05 parts by weight of compound C and 0.05 parts by weight of compound D was added was melt kneaded using a 90 mmφ extruder equipped with a metal filter having a filtration accuracy of 40 μm, and two 65 mmφ extruders. It introduce | transduced into the feed block type T die | dye (die width 1250mm, lip opening degree 1.5mm), and melt-extrusion was performed at die temperature 240 degreeC.

The extruded molten film was cooled and solidified by a chill roll having a cooling temperature of 40 ° C. rotating at 50 m / min to obtain an unstretched film having a thickness of 70 μm. The blocking property of the film was measured using this unstretched film.

Subsequently, the obtained unstretched film, the aluminum foil of thickness 7 micrometers, and the polyethylene terephthalate film of thickness 12 micrometers were laminated | stacked by the dry lamination method. The heat seal strength of this laminate was measured.

Moreover, the laminated body was heat-processed for 30 minutes at 120 degreeC in the thermostat, and the heat-sealing strength of the heat-treated laminated body was also measured.

Moreover, the packaging bag of 15 cm x 18 cm was manufactured using the laminated body so that an unstretched film might become inside of the bag. Otoka Food Co., Ltd. "Bon Curry Gold [trademark] Spicy", a commercial retort food, was placed in the packaging bag. Unstretched films were heat-sealed. Orange peel evaluation was performed using this packaging bag. The results are shown in Table 2.

[Example 2]

Except for obtaining a mixture obtained by pellet blending 80% by weight of the propylene copolymer (1) and 20% by weight of the ethylene-α-olefin copolymer (1), by the same method as in Example 1, an unstretched film, a laminate and a packaging bag Got. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 3]

As an ethylene-alpha-olefin copolymer, the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1 except having used 15 weight% of ethylene-alpha-olefin copolymers (2). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

Example 4

As an ethylene-alpha-olefin copolymer, the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1 except having used 15 weight% of ethylene-alpha-olefin copolymers (3). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 5]

As an ethylene-alpha-olefin copolymer, the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1 except having used 15 weight% of ethylene-alpha-olefin copolymers (4). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 6]

As an ethylene-alpha-olefin copolymer, the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1 except having used 15 weight% of ethylene-alpha-olefin copolymers (5). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 7]

A mixture obtained by pellet blending 85% by weight of the propylene copolymer (1) and 15% by weight of the ethylene-α-olefin copolymer (1) was obtained. 0.05 weight part of compound C was added with respect to 100 weight part of this mixture, and the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 8]

A mixture obtained by pellet blending 85% by weight of the propylene copolymer (1) and 15% by weight of the ethylene-α-olefin copolymer (1) was obtained. 0.05 weight% of compound D was added with respect to 100 weight part of this mixture, and the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 9]

As a propylene copolymer, the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1 except having used 85 weight% of propylene copolymers (2). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 10]

The same procedure as in Example 1 was carried out except that a mixture of pellet blended of propylene copolymer (1) with 72% by weight, ethylene-α-olefin copolymer (3) with 20% by weight and propylene-ethylene random copolymer (1) with 8% by weight was used. By the method, the unstretched film, the laminated body, and the packaging bag were obtained. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 11]

The same procedure as in Example 1 was carried out except that a mixture of 64 wt% propylene copolymer (1), 20 wt% ethylene-α-olefin copolymer (3) and 16 wt% propylene-ethylene random copolymer (1) was used. By the method, the unstretched film, the laminated body, and the packaging bag were obtained. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Example 12]

The same procedure as in Example 1 was carried out except that a mixture of pellet blended 64% by weight of propylene copolymer (1), 20% by weight of ethylene-α-olefin copolymer (3) and 16% by weight of propylene-ethylene random copolymer (2) was used. By the method, the unstretched film, the laminated body, and the packaging bag were obtained. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

Comparative Example 1

The unstretched film which consists of 100 weight% of propylene copolymers (1) was manufactured by the method similar to Example 1. Moreover, the laminated body and the packaging bag were obtained using this unstretched film. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

Comparative Example 2

The mixture which pellet-blended 85 weight% of a propylene copolymer (1) and 15 weight% of an ethylene-alpha-olefin copolymer (1) was melt-kneaded by the method similar to Example 1, and the unstretched film was obtained. Moreover, the laminated body and the packaging bag were obtained using this unstretched film. The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Comparative Example 3]

As an ethylene-alpha-olefin copolymer, the unstretched film, laminated body, and packaging bag were obtained by the method similar to Example 1 except having used 15 weight% of ethylene-alpha-olefin copolymers (6). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

[Comparative Example 4]

As an ethylene-alpha-olefin copolymer, the unstretched film, the laminated body, and the packaging bag were obtained by the method similar to Example 1 except having used 15 weight% of ethylene-alpha-olefin copolymers (7). The blocking property of an unstretched film and the heat-sealing strength of a laminated body were measured, and the orange peel evaluation of the packaging bag was performed.

In the comparative example 1 which does not contain an ethylene-alpha-olefin type copolymer from the result of Table 2, orange peel evaluation is bad, and in the comparative example 2 which does not contain an acrylate type compound and a phosphite ester type compound, heat-seal strength is In Comparative Example 3 using an ethylene-α-olefin-based copolymer in which the molecular weight distribution does not satisfy the requirements of the present invention, the impact resistance is poor, and the ethylene-α-olefin-based air whose density does not satisfy the requirements of the present invention. In the comparative example 4 using coalescence, it turned out that blocking resistance is inferior.

Claims (6)

Polymer component (component A) 50 whose structural unit derived from propylene is a main structural unit. 90 weight% and content of the structural unit derived from ethylene is 20? Ethylene-propylene copolymer component (component B) which is 60 weight% 50? Propylene copolymer (polymer (I)) containing 10 weight% (however, the total weight of component A and component B shall be 100 weight%) 70? 90 weight percent, and
Structural unit derived from ethylene, and carbon number 4? It contains the structural unit derived from the 20-olefin, and has a density of 900? 940-kg / m <3> and the ethylene-alpha-olefin type copolymer (polymer (II)) whose molecular weight distribution is 1 or more and less than 3 30? Resin composition consisting of 10% by weight (but the total weight of polymer (I) and polymer (II) is 100% by weight),
0.01 to the acrylate compound represented by the following formula (1) / or the phosphite ester compound represented by the following formula (2) with respect to 100 weight part of said resin compositions. Propylene-based resin composition containing 0.1 parts by weight.

(In formula, R <^1> and R <^2> is the same or different, respectively, and represents a C1-C8 alkyl group, a C6-C12 aryl group, or a C7-C18 aralkyl group, and R <^3> is a hydrogen atom or a carbon number An alkyl group of 1 to 3, R ⁴ represents a hydrogen atom or a methyl group)

(In formula, R <^5> , R <^6> , R <^8> and R <^9> are the same or different, respectively, and a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, An aralkyl group or phenyl group having 7 to 12 carbon atoms is represented, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8. X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom or a C 1? An alkyl group of 8 or a cycloalkyl group of 5 to 8 carbon atoms is represented, n is 0 or 1. A is an alkylene group of 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group (R ¹¹ is In the alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1. Each of Y and Z has a hydroxyl group and 1 to 8 carbon atoms. It represents an alkoxy group or a C7-12 aralkyloxy group, and the other represents a hydrogen atom or a C1-8 alkyl group. Put out) Polymer component (component A) 50 whose structural unit derived from propylene is a main structural unit. 90 weight% and content of the structural unit derived from ethylene is 20? Ethylene-propylene copolymer component (component B) which is 60 weight% 50? Propylene copolymer (polymer (I)) containing 10 weight% (however, the total weight of component A and component B shall be 100 weight%) 45? 90 wt%,
Structural unit derived from ethylene, and carbon number 4? It contains the structural unit derived from the 20-olefin, and has a density of 900? 940-kg / m <3> and the ethylene-alpha-olefin type copolymer (polymer (II)) whose molecular weight distribution is 1 or more and less than 3 30? 10 wt%, and
A propylene-ethylene random copolymer (polymer (III)) consisting of 25% by weight or less of a resin composition (with the total weight of polymer (I), polymer (II) and polymer (III) being 100% by weight),
0.01 to the acrylate compound represented by the formula (1) and / or the phosphite ester compound represented by the formula (2) to 100 parts by weight of the resin composition. Propylene-based resin composition containing 0.1 parts by weight.

(In formula, R <^1> and R <^2> is the same or different, respectively, and represents a C1-C8 alkyl group, a C6-C12 aryl group, or a C7-C18 aralkyl group, and R <^3> is a hydrogen atom or a carbon number An alkyl group of 1 to 3, R ⁴ represents a hydrogen atom or a methyl group)

(In formula, R <^5> , R <^6> , R <^8> and R <^9> are the same or different, respectively, and a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C6-C12 alkylcycloalkyl group, An aralkyl group or phenyl group having 7 to 12 carbon atoms is represented, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 8. X represents a sulfur atom or a -CHR ¹⁰ -group (R ¹⁰ represents a hydrogen atom or a C 1? An alkyl group of 8 or a cycloalkyl group of 5 to 8 carbon atoms is represented, n is 0 or 1. A is an alkylene group of 2 to 8 carbon atoms or a * -CO (R ¹¹ ) m-group (R ¹¹ is In the alkylene group having 1 to 8 carbon atoms, * represents a bonding site with an oxygen atom, and m is 0 or 1. Each of Y and Z has a hydroxyl group and 1 to 8 carbon atoms. It represents an alkoxy group or a C7-12 aralkyloxy group, and the other represents a hydrogen atom or a C1-8 alkyl group. Put out) The method of claim 2,
3 to 3 structural units of polymer (III) derived from ethylene; Propylene-based resin composition containing 7% by weight. The method according to claim 1 or 2,
The acrylate compound represented by the formula (1) is 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate Propylene-based resin composition. The method according to claim 1 or 2,
Phosphoric acid ester compound represented by formula (2) is 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy ] Dibenzo [d, f] [1,3,2] dioxaphosphine The propylene resin composition. The film which consists of a propylene resin composition of Claim 1 or 2.