JP2005171118A - Polypropylene resin composition and stretched film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polypropylene resin composition which is molded into a stretched film having a rigidity (Young's modulus), a heat-shrinking property and scratch resistance maintained at a conventional level and being excellent in a die deposition-preventing effect, a coloration-preventing effect at an end face, falling-off resistance, fusion sealing strength, transparency, blocking resistance and a hot slipping property, and to prepare a stretched film thereof. <P>SOLUTION: The polypropylene resin composition comprises a polypropylene polymer, fine powder silica having a whiteness of at least 80 obtained by a surface treatment with a surface-treating agent, of fine powder silica satisfying the following requirements (1)-(3), a phosphite compound represented by formula (I) and a benzofuranone compound: Requirement (1): The fine powder silica has a weight-average particle size of 2-10 μm measured by the laser counter method; Requirement (2): The fine powder silica has a BET specific surface area of 150-800 m<SP>2</SP>/g; and Requirement (3): The fine powder silica has a pore volume of 0.04-3 ml/g. The stretched film is composed of the polypropylene resin composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polypropylene resin composition and a stretched film made of the resin composition. More specifically, when molded into a stretched film, rigidity (Young's modulus), heat shrinkability, and scratch resistance are maintained at the conventional levels, and further, the effect of preventing the adhesion of the main body, the effect of preventing the end face from being colored, The present invention relates to a polypropylene-based resin composition excellent in drop-off property, fusing seal strength, transparency, blocking resistance, and hot slip property, and a stretched film made of the resin composition.

Stretched films made of polypropylene resins are widely used as various packaging materials because they are excellent in transparency and mechanical properties.
For example, in JP-A-7-228733, a polypropylene composition excellent in transparency, slipperiness and blocking resistance and a stretched film thereof have specific weight average particle diameter, BET specific surface area and pore volume. A polypropylene composition containing finely divided silica obtained by surface-treating partial silica in the range with a surface treatment agent and a stretched film thereof are described.

  JP-A-10-273494 discloses a resin composition containing polypropylene and phosphites as a method for improving the processing stability of a polypropylene resin.

  However, the polypropylene composition described in the above-mentioned publications and the like, and the effect of preventing the adhesion of the stretched film, coloration prevention effect on the end face, dropout resistance, fusing seal strength, transparency, blocking resistance, and hot slip resistance Further improvements have been desired.

JP 7-228733 A JP-A-10-273494

  The purpose of the present invention is to maintain rigidity (Young's modulus), heat shrinkage and scratch resistance when molded into a stretched film, and to prevent the adhesion of mains and coloration of the end face. Another object of the present invention is to provide a polypropylene-based resin composition excellent in drop-off resistance, fusing seal strength, transparency, blocking resistance, and hot slip properties, and a stretched film comprising the resin composition.

（式中、Ｒ¹、Ｒ²、Ｒ⁴及びＲ⁵はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、Ｒ³は水素原子又は炭素数１〜８のアルキル基を表す。Ｘは硫黄原子又は−ＣＨＲ⁶−（Ｒ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を示す。）で示される基を表し、ｎは０または１である。Ａは炭素数２〜８のアルキレン基又は＊−ＣＯ（Ｒ⁷）_m−（Ｒ⁷は炭素数１〜８のアルキレン基を、＊は酸素原子と結合する部位であることを示し、ｍは０または１である。）で示される基を表す。Ｙ又はＺのいずれか一方が、ヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子又は炭素数１〜８のアルキル基を表す。） As a result of intensive studies in view of such circumstances, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.
That is, the present invention
Surface treatment of finely divided silica satisfying the following requirements (B-1) to (B-3) with a surface treatment agent with respect to 100 parts by weight of the polypropylene polymer (A) and the polymer (A) 0.01 to 1 part by weight of finely divided silica (B) having a whiteness of 80 or more obtained, and 0.01 to 0.5 phosphites (C) represented by the following general formula (I) The present invention relates to a polypropylene resin composition containing parts by weight and 0.001 to 0.5 parts by weight of benzofuranones (Q), and a stretched film obtained using the resin composition.
Requirement (B-1): The weight average particle diameter measured by a laser counter method is 2 to 10 μm.
Requirement (B-2): The BET specific surface area is 150 to 800 m ² / g.
Requirement (B-3): The pore volume is 0.04 to 3 ml / g.

(Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a sulfur atom or —CHR ⁶ — (R ⁶ is a hydrogen atom, carbon Represents 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 is an alkylene group having 2 to 8 carbon atoms or * -CO. (R ⁷ ) _m — (R ⁷ represents an alkylene group having 1 to 8 carbon atoms, * represents a site bonded to an oxygen atom, and m is 0 or 1). Either Y or Z is a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or carbon The aralkyloxy group having 7 to 12 is represented, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

  According to the present invention, when formed into a stretched film, the rigidity (Young's modulus), heat shrinkability, and scratch resistance are maintained at the conventional levels. , A polypropylene resin composition excellent in drop-off resistance, fusing seal strength, transparency, blocking resistance, and hot slip properties, and a stretched film comprising the resin composition can be obtained.

  The polypropylene polymer (A) used in the present invention is a propylene homopolymer or a propylene random copolymer. When the propylene-based polymer (A) used in the present invention is a propylene-based random copolymer, the propylene-based random copolymer obtained by copolymerizing propylene and ethylene, having at least 4 to 20 carbon atoms with propylene Propylene random copolymer obtained by copolymerizing one kind of α-olefin, or propylene based obtained by copolymerizing propylene, ethylene and at least one kind of α-olefin having 4 to 20 carbon atoms A random copolymer is mentioned.

  Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-butene, Hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl- 1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl -1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene , 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like. 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are more preferable.

  Examples of the propylene random copolymer used as the propylene polymer (A) in the present invention include a propylene-ethylene random copolymer and a propylene-α-olefin random copolymer. Examples of the propylene-α-olefin random copolymer include propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, propylene-ethylene-1- Examples include butene random copolymer, propylene-ethylene-1-hexene random copolymer, propylene-ethylene-1-octene random copolymer, and the like, preferably propylene-ethylene random copolymer, propylene-1-butene random. A copolymer, a propylene-1-hexene random copolymer, a propylene-ethylene-1-butene random copolymer, and a propylene-ethylene-1-hexene random copolymer.

  When the propylene random copolymer used as the propylene polymer (A) in the present invention is a propylene-ethylene random copolymer, the ethylene content is preferably from the viewpoint of the rigidity of the obtained stretched film. It is 01-10 weight%, More preferably, it is 0.1-5 weight%, More preferably, it is 0.4-4 weight%.

  When the propylene random copolymer used as the propylene polymer (A) in the present invention is a propylene-α-olefin random copolymer, the α-olefin content is determined from the viewpoint of the rigidity of the obtained stretched film. Preferably it is 0.01-30 weight%, More preferably, it is 0.1-12 weight%, More preferably, it is 0.4-8 weight%.

  When the propylene random copolymer used as the propylene polymer (A) in the present invention is a propylene-ethylene-α-olefin random copolymer, the total content of ethylene and α-olefin is obtained by stretching. From a viewpoint of the rigidity of a film, Preferably it is 0.01-30 weight%, More preferably, it is 0.1-12 weight%, More preferably, it is 0.4-10 weight%.

  The intrinsic viscosity ([η], unit: dl / g) measured in 135 ° C. tetralin of the propylene polymer (A) used in the present invention is preferably from 1 to 5 from the viewpoint of stretchability or fluidity. It is 8 dl / g, More preferably, it is 1.5-3 dl / g.

  The melting point (Tm, unit: ° C) defined from the peak temperature of the melting curve measured by a differential scanning calorimeter (DSC) of the propylene-based polymer (A) used in the present invention is stretchability, rigidity, or From the viewpoint of stretch processability, the temperature is preferably 120 to 165 ° C, more preferably 125 to 164 ° C, and still more preferably 130 to 163 ° C.

  The amount of the cold xylene soluble part (CXS, unit: wt%) of the propylene-based polymer (A) used in the present invention is preferably 15 wt% or less from the viewpoint of the rigidity and antiblocking property of the obtained stretched film. Yes, more preferably 6% by weight or less.

As a manufacturing method of the propylene polymer (A) used by this invention, the method of manufacturing with a well-known polymerization method using a well-known polymerization catalyst is mentioned.
Known polymerization catalysts include, for example, a catalyst system comprising a solid catalyst component essentially containing magnesium, titanium and halogen, an organoaluminum compound, and a third component such as an electron-donating compound used as necessary. A catalyst system comprising a transition metal compound of group IV of the periodic table having a pentadienyl ring and an alkylaluminoxane, or an ionic complex by reacting with a transition metal compound of group IV of the periodic table having a cyclopentadienyl ring. Examples thereof include a catalyst system composed of a compound to be formed and an organoaluminum compound. Preferred is a catalyst system comprising a solid catalyst component essentially containing magnesium, titanium and halogen, an organoaluminum compound, and an electron donating compound. For example, JP-A-61-218606, JP-A-61-287904 JP-A-1-319508, JP-A-7-216017, and the like.

  Known polymerization methods include, for example, a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method using no solvent, a gas phase polymerization method, and the like, preferably a gas phase polymerization method. Furthermore, a method of combining the above-described polymerization methods and continuously performing them, for example, a liquid phase-gas phase polymerization method and the like can be mentioned.

The finely divided silica (B) used in the present invention has a whiteness of 80 or more obtained by surface-treating finely divided silica that satisfies the following requirements (B-1) to (B-3) with a surface treatment agent. Some fine silica.
Requirement (B-1): The weight average particle diameter measured by a laser counter method is 2 to 10 μm.
Requirement (B-2): The BET specific surface area is 150 to 800 m ² / g.
Requirement (B-3): The pore volume is 0.04 to 3 ml / g.

  The weight average particle diameter measured by the laser counter method is preferably 2 to 6 μm, more preferably 2 to 5 μm. When the weight average particle diameter exceeds 10 μm, a void having fine powder silica as a nucleus may be generated, and the transparency may be greatly lowered. Moreover, when it is less than 2 μm, the effect of improving the blocking resistance may be small.

The BET specific surface area is preferably 150 to 500 m ² / g, more preferably 200 to 400 m ² / g. When the BET specific surface area exceeds 800 m ² / g, the decrease in transparency may be large, and when it is less than 150 m ² / g, the effect of improving blocking resistance may be small.

  The pore volume is preferably 0.8 to 2 ml / g, more preferably 0.9 to 1.5 ml / g. When the pore volume exceeds 3 ml / g, the effect of improving the blocking resistance may be small, and when it is less than 0.04 ml / g, the scratch resistance may be inferior.

  The finely divided silica (B) used in the present invention has a whiteness of 80 or more, preferably 90 or more, more preferably 95 or more. When the whiteness is less than 80, the end surface of the film roll may be colored.

Examples of the surface treatment agent used to obtain finely divided silica (B) used in the present invention include paraffin, fatty acid, polyhydric alcohol, silane coupling agent, and silicone oil. Preferred are methyl hydrogen polysiloxane or dimethyl polysiloxane which is a silicone oil, and n-decyltrimethoxysilane which is a silane coupling agent.
By using finely divided silica surface-treated with a surface treatment agent, the dispersibility of finely divided silica in polypropylene can be improved, and a stretched film having good transparency and blocking resistance can be obtained.

  Content of the fine powder silica (B) used for this invention is 0.01-1 weight part with respect to 100 weight part of polypropylene-type polymers (A), Preferably it is 0.05-0.5 weight part. More preferably, it is 0.1 to 0.3 parts by weight. When the content of fine silica (B) is less than 0.01 parts by weight, the hot slip property and blocking property of the stretched film may be insufficient. When the content exceeds 1 part by weight, the transparency of the stretched film is poor. There is enough.

The weight average particle diameter, BET specific surface area, pore volume and whiteness of finely divided silica (B) used in the present invention are measured by the following methods.
(1) Weight average particle diameter: determined by a laser counter method.
(2) BET specific surface area: Determined by the BET method by N ₂ adsorption under the saturation temperature of liquid N ₂ .
(3) Pore volume: Determined by the N ₂ adsorption method under the saturation temperature of liquid N ₂ .
(4) Whiteness: Determined according to JIS P 8123.

（式中、Ｒ¹、Ｒ²、Ｒ⁴及びＲ⁵はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、Ｒ³は水素原子又は炭素数１〜８のアルキル基を表す。Ｘは硫黄原子又は−ＣＨＲ⁶−（Ｒ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を示す。）で示される基を表し、ｎは０または１である。Ａは炭素数２〜８のアルキレン基又は＊−ＣＯ（Ｒ⁷）_m−（Ｒ⁷は炭素数１〜８のアルキレン基を、＊は酸素原子と結合する部位であることを示し、ｍは０または１である。）で示される基を表す。Ｙ又はＺのいずれか一方が、ヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子又は炭素数１〜８のアルキル基を表す。） The phosphites (C) used in the present invention are phosphites represented by the following general formula (I).

(Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a sulfur atom or —CHR ⁶ — (R ⁶ is a hydrogen atom, carbon Represents 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 is an alkylene group having 2 to 8 carbon atoms or * -CO. (R ⁷ ) _m — (R ⁷ represents an alkylene group having 1 to 8 carbon atoms, * represents a site bonded to an oxygen atom, and m is 0 or 1). Either Y or Z is a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or carbon The aralkyloxy group having 7 to 12 is represented, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

In the phosphites (C) represented by the general formula (I), the substituents R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carbon number. A 5-8 cycloalkyl group, a C6-C12 alkyl cycloalkyl group, a C7-C12 aralkyl group, or a phenyl group is represented.

  Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl. Group, t-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group, and the like. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like.

R ¹ , R ² and R ⁴ are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an alkylcycloalkyl group having 6 to 12 carbon atoms. Among these, R ¹ and R ⁴ are more preferably a t-alkyl group such as a t-butyl group, a t-pentyl group or a t-octyl group, a cyclohexyl group, or a 1-methylcyclohexyl group.

R ² is more preferably carbon such as 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, etc. It is an alkyl group having 1 to 5, more preferably a methyl group, a t-butyl group, or a t-pentyl group.

R ⁵ 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 a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or i-propyl. Group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-pentyl group and the like, and an alkyl group having 1 to 5 carbon atoms.

The substituent R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and examples of the alkyl group having 1 to 8 carbon atoms include the same alkyl groups as described above. Preferably they are a hydrogen atom or a C1-C5 alkyl group, More preferably, they are a hydrogen atom or a methyl group.

  Substituent X, when n is 0, represents that two groups having a phenoxy group skeleton are directly bonded, and when n is 1, a sulfur atom or an alkyl group having 1 to 8 carbon atoms. Or the methylene group which the C5-C8 cycloalkyl group may substitute may be represented. Here, examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms substituted on the methylene group include the same alkyl groups and cycloalkyl groups as described above. As the substituent X, preferably n is 0 and a group having two phenoxy group skeletons is directly bonded, or n is 1, and a methylene group, a methyl group, an ethyl group, or an n-propyl group. , I-propyl group, n-butyl group, i-butyl group, t-butyl group and the like are substituted methylene groups.

In addition, the substituent A is an alkylene group having 2 to 8 carbon atoms or * -CO (R ⁷ ) _m (R ⁷ is an alkylene group having 1 to 8 carbon atoms, and * is a site bonded to an oxygen atom. And m is 0 or 1.).

Here, examples of the alkylene group having 2 to 8 carbon atoms include an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group. And is preferably a propylene group. Further, * in the group represented by * -COR ^7- indicates that the carbonyl group is a site bonded to the oxygen atom of the phosphite group. Examples of the alkylene group having 1 to 8 carbon atoms in R ⁷ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and 2,2-dimethyl-1,3. -A propylene group etc. are mentioned. * —CO (R ⁷ ) _m — Preferably, m is 0, * —CO—, or m is 1, and R ⁷ is ethylene. * —CO (CH ₂ CH ₂ ) -.

  Either Y or Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy 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, as a C1-C8 alkyl group, the same alkyl group as the above is mentioned, for example, As a C1-C8 alkoxy group, an alkyl part is the said C1-C8, for example. The alkoxy group which is the same alkyl as an alkyl is mentioned. Moreover, as a C7-C12 aralkyloxy group, the aralkyloxy group whose aralkyl part is the same aralkyl as the said C7-C12 aralkyl is mentioned, for example.

The phosphites (C) used in the present invention are preferably the following compounds (compounds 1 to 13). The structures of Compounds 1 to 13 are shown in the following formulas (Chemical Formula 1) to (Chemical Formula 13).
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] Dioxaphosphepine

  Compound 2: 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g ] [1, 3, 2] Dioxaphosphocin

  Compound 3: 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3 , 2] Dioxaphosphepine

  Compound 4: 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d , G] [1,3,2] dioxaphosphocin

  Compound 5: 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin

  Compound 6: 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [ d, g] [1,3,2] dioxaphosphocin

  Compound 7: 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1 , 3,2] Dioxaphosphepine

  Compound 8: 2,10-dimethyl-4,8-di-t-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1, 3,2] dioxaphosphocin

  Compound 9: 2,4,8,10-tetra-t-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [ 1,3,2] dioxaphosphocin

  Compound 10: 2,10-dimethyl-4,8-di-t-butyl-6 [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin

  Compound 11: 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [ 1,3,2] dioxaphosphocin

  Compound 12: 2,10-diethyl-4,8-di-t-butyl-6 [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin

  Compound 13: 2,4,8,10-tetra-t-butyl-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d , F] [1,3,2] dioxaphosphine

  The content of the phosphites (C) used in the present invention is 0.01 to 0.5 parts by weight, preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the polypropylene polymer (A). The amount is 0.2 parts by weight, and more preferably 0.1 to 0.2 parts by weight. When the content of phosphites (C) is less than 0.01 parts by weight, the thermal stability of the polypropylene resin may be insufficient, and when it exceeds 0.5 parts by weight, the effect is saturated. And not economical.

  Examples of the benzofuranones (Q) used in the present invention include compounds represented by the following formula (Formula 14).

（式中、Ｒ⁸はフェニル基または、全炭素数が多くても１８個であって、１〜３個の炭素数１〜１２アルキル基、炭素数１〜１２のアルコキシ基、炭素数２〜１８のアルコキシカルボニル基または塩素原子で置換されたフェニル基を表す。Ｒ⁹は水素原子を表し、Ｒ¹¹は水素原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、アルキル部分に１〜１２個の炭素原子を持つフェニルアルキル基または塩素原子を表す。Ｒ¹⁰はＲ⁹またはＲ¹¹で表される基または原子を表す。Ｒ¹²は水素原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基または塩素原子を表す。）

(In the formula, R ⁸ is a phenyl group or a total of 18 carbon atoms at the most, and includes 1 to 3 carbon atoms having 1 to 12 alkyl groups, 1 to 12 carbon atoms alkoxy group, and 2 to 2 carbon atoms. 18 represents an alkoxycarbonyl group or a phenyl group substituted with a chlorine atom, R ⁹ represents a hydrogen atom, R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, an alkyl group. portion represents a phenyl alkyl group or a chlorine atom having 1 to 12 carbon atoms .R ¹⁰ is .R ¹² represents a group or atom represented by R ⁹ or R ¹¹ is a hydrogen atom, having 1 to 12 carbon atoms Represents an alkyl group, a cyclopentyl group, a cyclohexyl group or a chlorine atom.)

In the case where the substituent R ^{8 in the} above formula (Formula 14) is a phenyl group substituted by 1 to 3 alkyl groups having 1 to 12 carbon atoms, examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, and the like. Group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group Groups and the like.

In the case where the substituent R ⁸ of the above formula (Formula 14) is a phenyl group substituted with 1 to 3 carbon atoms of an alkoxy group, examples of the alkoxy group having 1 to 12 carbon atoms include, for example, a methoxy group Ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, 2-ethylhexoxy group, n -An octoxy group etc. are mentioned.

In the case where the substituent R ^{8 in the} above formula (Formula 14) is a phenyl group substituted with 1 to 3 C2-C18 alkoxycarbonyl groups, examples of the C2-C18 alkoxycarbonyl group include: Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group N-hexoxycarbonyl group, 2-ethylhexoxycarbonyl group, n-octoxycarbonyl group and the like.

The substituent R ^{8 in the} above formula (Formula 14) is preferably a phenyl group having a total carbon number of at most 18 and substituted with 1 to 3 alkyl groups having 1 to 12 carbon atoms. . Examples thereof include a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, and an octylphenyl group. More preferably, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group Group, a 3,6-dimethylphenyl group, and the like, and a 3,4-dimethylphenyl group is more preferable.

When the substituent R ^{11 in the} above formula (Formula 14) is an alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group and the like.

When the substituent R ^{11 in the} above formula (Formula 14) is a phenylalkyl group having 1 to 12 carbon atoms in the alkyl moiety, for example, a phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl Group, phenylhexyl group, phenyloctyl group and the like.

The substituent R ^{11 in the} above formula (Formula 14) is preferably a hydrogen atom.
In addition, the substituent R ¹⁰ in the above formula (Formula 14) is preferably a group or an atom represented by R ¹¹ , more preferably an alkyl group having 1 to 12 carbon atoms, and further preferably t. -A butyl group.

When the substituent R ^{12 in the} above formula (Chemical Formula 14) is an alkyl group having 1 to 12 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group and the like. The substituent R ^{12 in the} above formula (Formula 14) is preferably a t-butyl group.

  As the benzofuranones (Q), the compound represented by the following formula (Chemical Formula 15) is particularly preferably 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one. It is.

  The benzofuranones (Q) used in the present invention can be appropriately selected from commercially available ones. For example, 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: HP136 (registered trademark)) Is mentioned.

  The content of the benzofuranones (Q) used in the present invention is a polypropylene polymer (from the viewpoints of prevention of adherence of mayani, coloration of the end face, fusing seal strength, and resistance to processing machine contamination (prevention of processing machine contamination). A) It is 0.001-0.5 weight part with respect to 100 weight part, Preferably it is 0.01-0.1 weight part.

The polypropylene-based resin composition of the present invention contains a phosphorus-based antioxidant from the viewpoints of prevention of adhesion of the main body, coloration of the end face, fusing seal strength, and resistance to processing machine contamination (prevention of processing machine contamination). Is preferred.
Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di Stearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, Tristearyl sorbitol triphosph Ite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4 -Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphites and their And the like. These phosphorus antioxidants may be used alone or in combination of at least two kinds.

  As the phosphorus-based antioxidant, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-) are preferable. t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphine Bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1, 3,2-oxaphosphorinane, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2 ′ -Diyl) phosphite.

  When the phosphorus-based antioxidant is added to the polypropylene resin composition of the present invention, the content of the phosphorus-based antioxidant is such that the adhesion of the mains, the coloration of the end face, the fusing seal strength, the resistance to processing machine contamination (processing) From the viewpoint of machine contamination prevention), it is usually 0.001 to 0.5 parts by weight, preferably 0.01 to 0.3 parts by weight, with respect to 100 parts by weight of the polypropylene polymer (A). .

  In addition, when the polypropylene-based resin composition of the present invention contains a phosphorus-based antioxidant, the total amount of the benzofuranones (Q) and the phosphorus-based antioxidant is set to From the viewpoint of coloring prevention, fusing seal strength, and resistance to processing machine contamination (prevention of processing machine contamination), it is usually 0.002 to 0.5 parts by weight with respect to 100 parts by weight of the polypropylene polymer (A). The amount is preferably 0.01 to 0.3 parts by weight.

  The polypropylene resin composition of the present invention may further contain other additives as necessary. Other additives include, for example, phenolic antioxidants, sulfur antioxidants, UV absorbers, light stabilizers, hydroxylamines, plasticizers, flame retardants, nucleating agents, metal deactivators, antistatic agents Agents, pigments, antiblocking agents, surfactants, processing aids, foaming agents, emulsifiers, brighteners, neutralizing agents such as calcium stearate, metal hydroxide compounds and hydrotalcite. These additives may be used alone or in combination of at least two kinds.

  In the case where the polypropylene-based resin composition of the present invention contains a phenol-based antioxidant, the polypropylene-based polymer is used from the viewpoints of prevention of adhesion of the surface, coloring of the end face, and resistance to processing machine contamination (prevention of processing machine contamination). (A) It is 0.2 parts weight or less normally with respect to 100 weight part, Preferably it is 0.02 weight part or less.

  In the case of containing a neutralizing agent in the polypropylene resin composition of the present invention, from the viewpoints of prevention of adhesion of the body, coloring of the end face, resistance to processing machine contamination (prevention of processing machine contamination), and prevention of mold corrosion. It is 0.001-0.2 weight part normally with respect to 100 weight part of polypropylene-type polymers (A), Preferably it is 0.01-0.1 weight part. The neutralizing agent is preferably calcium stearate.

  Examples of other resins other than the polypropylene polymer (A) contained in the polypropylene resin composition of the present invention as required include various olefin resins such as polyethylene and polybutene, ethylene and α-olefin. And copolymer elastomers. These may be produced with a heterogeneous catalyst or may be produced with a homogeneous catalyst such as a metallocene catalyst. Further, styrene-butadiene-styrene copolymer, styrene-based copolymer rubber hydrogenated with styrene-isoprene-styrene copolymer, other styrene-based copolymer rubber, and the like.

As a manufacturing method of the polypropylene resin composition of this invention, a well-known heat-melt-mixing method is mentioned, For example, the following method is mentioned.
(1) A method in which polypropylene, finely divided silica, phosphites and benzofuranones are directly blended into a mixing device such as a Henschel mixer and heated and melted and mixed (if necessary, phosphorus antioxidants, other additives and Other resins may be blended directly into a mixing device such as a Henschel mixer.)
(2) Fine powder silica, phosphites, benzofuranones, or a master batch of polypropylene containing at least two of these in a high concentration is mixed with polypropylene and heated and melt mixed (if necessary , Phosphorus antioxidants, other additives and other resins may be included in the masterbatch.)
(3) A method in which a meltable additive is melted, blended in an extruder or the like in a melted state, and melt-heated and mixed.

  In the heat-melt mixing method described above, the phosphorus-based antioxidant, other additives, and other resins that are added as necessary are finely divided silica, phosphites, benzofuranones, or at least two of these. It may be added at the same time as the seed, or may be added at another stage.

  Examples of the apparatus used for the heat melting and mixing include an extruder, a Banbury mixer, and a batch kneader. The heating / melting / mixing method is preferably performed in the presence of an inert gas (nitrogen, argon, etc.). The temperature of the heating / melting / mixing is usually less than 300 ° C., preferably 180 to 250 ° C. is there.

  Examples of the method for producing a stretched film comprising the polypropylene resin composition of the present invention and the stretching method include ordinary methods, such as (1) longitudinal uniaxial stretching method and (2) lateral uniaxial stretching. Examples thereof include (3) sequential biaxial stretching method, (4) simultaneous biaxial stretching method, and (5) tubular biaxial stretching method. These stretching methods will be described below.

(1) Longitudinal uniaxial stretching method After melting polypropylene with an extruder, it is extruded from a T-die and cooled and solidified into a sheet with a cooling roll. Next, the obtained sheet is preheated and stretched in a longitudinal direction with a series of heating rolls, and subjected to corona treatment or the like as necessary and wound.

(2) Lateral uniaxial stretching method After melting polypropylene with an extruder, it is extruded from a T-die and cooled and solidified into a sheet with a cooling roll. Next, both ends of the obtained sheet are gripped by two rows of chucks arranged in the flow direction, respectively, and the two rows of chucks are widened in a heating furnace composed of a preheating portion, a stretching portion, and a heat treatment portion. The film is stretched in the direction, and subjected to corona treatment or the like, if necessary, and wound up.

(3) Sequential biaxial stretching method After melting polypropylene with an extruder, it is extruded from a T-die and cooled and solidified into a sheet with a cooling roll. Next, the obtained sheet is preheated and stretched in the longitudinal direction by a series of heating rolls. Subsequently, both ends of the obtained longitudinally stretched sheet are respectively gripped by two rows of chucks arranged in the flow direction, and the above two rows of chuck intervals are set in a heating furnace including a preheating portion, a stretching portion, and a heat treatment portion. The film is stretched in the transverse direction by spreading, and subjected to corona treatment or the like as necessary, and wound up.
The melting temperature of polypropylene in the sequential biaxial stretching method is usually 230 to 290 ° C. The longitudinal stretching temperature is usually 130 to 150 ° C., and the longitudinal stretching ratio is usually 4 to 6 times. The transverse stretching temperature is usually 150 to 165 ° C., and the transverse stretching ratio is usually 8 to 10 times.

(4) Simultaneous biaxial stretching method After melting polypropylene with an extruder, it is extruded from a T-die and cooled and solidified into a sheet with a cooling roll. Subsequently, both ends of the obtained sheet are respectively gripped by two rows of chucks arranged in the flow direction, and the above two rows of chuck intervals and the individual pieces in the row are formed in a heating furnace including a preheating portion, a stretching portion, and a heat treatment portion. By extending the chuck interval, the film is stretched in the vertical and horizontal directions at the same time, and subjected to corona treatment or the like, if necessary, and wound.

(5) Tubular biaxial stretching method After melting polypropylene with an extruder, it is extruded from an annular die and cooled and solidified into a tube shape in a water tank. Next, the obtained tube is preheated in a heating furnace or a series of hot rolls, then passed through a low speed nip roll, and wound in a high speed nip roll to be stretched in the flow direction. At this time, the tube is expanded by the internal pressure of the air stored between the low-speed nip roll and the high-speed nip roll, thereby stretching in the width direction. The stretched film that has passed through the high-speed nip roll is heat-treated in a heating furnace or a series of hot rolls, and subjected to corona treatment or the like, if necessary, and wound.

The stretched film of the present invention may be a single layer film or a laminated film including at least one layer that is the stretched film of the present invention.
Other layers used for the laminated film are not particularly limited. Examples of the method for producing the laminated film include a normal coextrusion method.

  Applications of the stretched film of the present invention include food packaging films, non-food packaging films, heat shrink films and the like.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples. The physical property value or evaluation of each item in the examples was measured or evaluated by the following method.
In addition, the processing method and stretch processability evaluation of the stretched film used for the Example and the comparative example were performed in accordance with the following method.

(Description I) Film Processing A polypropylene resin composition was extruded at a resin temperature of 280 ° C. using a T-die sheet processing machine and solidified with a cooling roll at 15 ° C. to prepare a sheet having a thickness of 300 μm. Next, this sheet was stretched under the stretching conditions shown below using a tenter type sequential biaxial stretching apparatus to obtain a biaxially stretched film having a thickness of 12 μm.
Stretching machine: Mitsubishi Heavy Industries tenter type sequential biaxial stretching machine Longitudinal stretching temperature: 120 ° C
Longitudinal stretch ratio: 4 times Transverse preheating temperature: 130 ° C
Transverse stretching temperature: 125 ° C
Horizontal draw ratio: 4 times Film winding speed: 14.5 m / min

The physical properties of the propylene polymer, the polypropylene resin composition, and the stretched film used in Examples and Comparative Examples were measured according to the following methods.
(1) Intrinsic viscosity ([η], unit: dl / g)
Using an Ubbelohde viscometer, the temperature was measured at 135 ° C. using tetralin as a solvent.

(2) Melting point (Tm, unit: ° C)
Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co.), a propylene polymer or a polypropylene resin composition was preliminarily hot-press-molded (preheated at 230 ° C. for 5 minutes, then 50 kgf / cm ² over 3 minutes). The pressure is increased to a pressure and held for 2 minutes, and then cooled at 30 ° C. for 5 minutes at a pressure of 30 kgf / cm ² , 10 mg of a sample taken from the sheet is heat-treated at 220 ° C. for 5 minutes in a nitrogen atmosphere, Cool down to 150 ° C. at a temperature drop rate of 300 ° C./min and hold at 150 ° C. for 1 minute, further cool to 50 ° C. at a drop rate of 5 ° C./min and hold at 50 ° C. for 1 minute, and further from 50 ° C. to 180 ° C. The peak temperature showing the maximum intensity in the melting peak curve when heated at a heating rate of 5 ° C./min was determined as the melting point (Tm (° C.)).

(3) Xylene-soluble component amount (CXS, unit: wt%)
10 g of the propylene polymer was dissolved in 1000 ml of boiling xylene, then slowly cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, allowed to stand at 20 ° C. overnight, and the precipitated polymer was filtered. Separately, xylene was evaporated from the filtrate, dried under reduced pressure at 60 ° C. to recover a polymer soluble in xylene at 20 ° C., and CXS was calculated from the weight of the recovered polymer.

(4) Comonomer content (unit:% by weight)
(4-1) Ethylene content Determined by the IR spectrum method according to the method described in the paragraph “(i) Random copolymer” on page 256 of the Polymer Analysis Handbook (published by Asakura Shoten in 1985).
(4-2) 1-butene content Determined from the following formula by IR spectrum method.
1-butene content (% by weight) = 1.208 K ′
K ′: absorbance at 767 cm ⁻¹

(5) Melt flow rate (MFR, unit: g / 10 min)
It measured at 230 degreeC according to the method of the condition 14 (Condition Number 14) of JISK7210.

(6) Mayani Extrude a polypropylene resin composition from a T die with a lip opening of 1 mm and a width of 1 cm at a resin temperature of 280 ° C. at 10 kg / Hr using an extruder using a full flight type 40 mmφ single screw, 1 hour 30 The adhesion of the sealant to the die lip after the lapse of minutes was judged visually. Judgment is ○ (good) when there is almost no adherence, △ (somewhat inferior) when it adheres over a width of less than 1/2 of the die lip, and from the 1/2 of the die lip The case where it adhered across was made x (inferior).

(7) End face color of film The film obtained in the above description (I) was bundled so as to have a thickness of 2 cm, and the end face color was visually determined. Judgment made white (circle) (good), faint yellow (triangle | delta) (slightly inferior), and pale yellow made x (inferior).

(8) Fusing seal strength (unit: N)
From the film obtained in the above description (I), a test piece having a width of 25 mm was taken from the machine direction (MD), and after a fusing cut at 230 ° C. by an automatic hot tack tester manufactured by Teller, equipped with a fusing seal bar, Tensile stress-strain curves were taken with an automatic tensile tester at a tensile speed of 5 mm / min, and the breaking strength was measured.

(7) Haze (Unit:%)
It measured according to ASTM D1103 using the film obtained by the above-mentioned description (I).

(9) Blocking resistance (kg / 12cm ² )
From the film obtained in the above description (I), a 30 mm × 150 mm film test piece was collected, and the film was put together so that 40 mm overlapped in the longitudinal direction. Conditioning was performed at 60 ° C. for 3 hours. Thereafter, the sample was left in an atmosphere of 23 ° C. and 50% humidity for 30 minutes or more, and a shear tensile test was performed at a speed of 200 mm / min. Four sections of the same film were measured a total of four times, and the average of the data was calculated as the strength required for peeling the sample.

(8) Hot slip (sliding friction coefficient)
Using the film obtained in the above description (I), the film was measured according to ASTM-D1894-63 at a film temperature of 55 ° C. in a constant temperature room with a relative humidity of 65% RH.

(9) Scratch resistance The silicon sheet laminated | stacked on the flat plate was installed in the measurement stand, and the film for a measurement obtained by description (I) was fixed on this silicon sheet. Thereafter, another measurement film was placed on the fixed measurement film, a load of 2 kg was applied to the other measurement film, and this film was slid 10 times in one direction. The measurement film on the side fixed on the silicon sheet was visually observed for damage, and the result was determined according to the following criteria.
○: Not scratched.
X: A streak was clearly attached.

(10) Dropout resistance (dropout of antiblocking agent)
In the above description (I), film formation was continued for 30 minutes, and the powder adhering to the nip roll immediately before the winder (dropping off the antiblocking agent) was wiped off with a black cloth, and the amount of powder adhered was visually confirmed. . The result was determined according to the following criteria.
○: Almost no powder adhered, and the drop-off resistance was good.
(Triangle | delta): Some amount of powder was adhering and the fall-off resistance was bad.
X: The powder was greatly adhered and the drop-off resistance was poor.

(9) Young's modulus (unit: kg / cm ² )
A test piece having a width of 20 mm was taken from the film obtained in the above description (I) in the machine direction (MD) and the transverse direction (TD), and SS was tested with a tensile tester at a chuck interval of 60 mm and a tensile speed of 5 mm / min. A curve was taken and the initial elastic modulus was measured.

(10) Heat shrinkage rate (unit:%)
A film test piece of 30 cm in the MD direction and 20 cm in the TD direction was taken from the film obtained in the above description (I), and two parallel lines with an interval of 10 cm were written in each of the MD direction and the TD direction. After leaving it still in a 120 degreeC oven for 5 minutes, it took out and it cooled at room temperature for 30 minutes, Then, the length of the rating line of the test piece was measured. The heat shrinkage was determined by the following formula.
Heat shrinkage rate = 100 × {(10−evaluation length after heating (cm)) / 10}

Example 1
Propylene polymer A-1 (propylene-ethylene-butene copolymer, ethylene content 2.5% by weight, butene content 7.3% by weight, intrinsic viscosity 1.97 dl / g, melting point 131 ° C., xylene-soluble component The amount of calcium stearate 0.05 parts by weight, the following phosphite compound (1) 0.15% by weight, the following benzofuranones (1) 0.02% by weight with respect to 100 parts by weight The following surface-treated silica (1) 0.2% by weight was mixed with a Henschel mixer, and granulated and pelletized at 220 ° C. with a 65 mmφ extruder. The MFR of the pellet was 2.9 g / 10 minutes. A film was prepared from the resulting granulated pellets according to the above description I. The physical properties of the obtained film are shown in Tables 1 and 2. Table 1 shows the results of the Mayani test performed using the obtained granulated pellets.

Comparative Example 1
In Example 1, the following phosphorous ester compound (1) and the following benzofuranones (1) were not used, but instead the following phosphorous antioxidant (1) 0.1% by weight and the following phenolic antioxidant The same procedure as in Example 1 was conducted except that 0.05% by weight of the agent (1) was added. The MFR of the pellet was 2.9 g / 10 minutes. Using the obtained pellets, a film was prepared in the same manner as in Example 1, and the physical properties of the film were evaluated. Further, a meanani test was conducted in the same manner as in Example 1 using the obtained granulated pellets. The results are shown in Tables 1 and 2.

Stabilizers used in Examples and Comparative Examples are shown below.
Phosphite compound (1)
Compound name: 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3 , 2] Dioxaphosphepine (CAS No. 203255-81-6, trade name: Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.))

Benzofuranones (1)
Compound name: 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (trade name: HP136 (manufactured by Ciba Specialty Chemicals))

Phosphorous antioxidant (1)
Compound name: Tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgafos 168 (Ciba Specialty Chemicals))

Phenolic antioxidants (1)
Compound name: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010 (manufactured by Ciba Specialty Chemicals))

Surface-treated silica (1)
For 95 parts by weight of differential silica having a weight average particle diameter measured by a laser counter of 3.0 μm, a BET specific surface area of 321 m ² / g, and a pore volume measured by the N ₂ adsorption method of 1.25 ml / g. Then, 5 parts by weight of silicon oil was added and mixed uniformly to obtain finely divided silica subjected to surface treatment. The whiteness of the obtained finely powdered silica subjected to the surface treatment was 97.

  The polypropylene-based resin composition used in Example 1 is excellent in the effect of preventing the adhesion of the scabbard and the effect of preventing the coloring of the end face, and the stretched film has a dropout resistance, a fusing seal strength, a transparency (haze), and a blocking resistance. It can be seen that it is excellent in hot slip property and also excellent in rigidity (Young's modulus), heat shrinkage rate and scratch resistance.

  On the other hand, the polypropylene resin composition used in Comparative Example 1 that does not contain phosphites and benzofurans, which are requirements of the present invention, is not effective in preventing the adhesion of the main body and the effect of preventing the coloring of the end face. It can be seen that the stretched film has insufficient drop resistance and transparency (haze).

Claims (3)

Surface treatment of finely divided silica satisfying the following requirements (B-1) to (B-3) with a surface treatment agent with respect to 100 parts by weight of the polypropylene polymer (A) and the polymer (A) 0.01 to 1 part by weight of finely divided silica (B) having a whiteness of 80 or more obtained, and 0.01 to 0.5 phosphites (C) represented by the following general formula (I) A polypropylene resin composition containing parts by weight and 0.001 to 0.5 parts by weight of benzofuranones (Q).
Requirement (B-1): The weight average particle diameter measured by a laser counter method is 2 to 10 μm.
Requirement (B-2): The BET specific surface area is 150 to 800 m ² / g.
Requirement (B-3): The pore volume is 0.04 to 3 ml / g.

(Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. Group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, X is a sulfur atom or —CHR ⁶ — (R ⁶ is a hydrogen atom, carbon Represents 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 is an alkylene group having 2 to 8 carbon atoms or * -CO. (R ⁷ ) _m — (R ⁷ represents an alkylene group having 1 to 8 carbon atoms, * represents a site bonded to an oxygen atom, and m is 0 or 1). Either Y or Z is a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or carbon The aralkyloxy group having 7 to 12 is represented, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.   The polypropylene resin composition according to claim 1, wherein the benzofuranones (Q) are 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one.   A stretched film comprising the polypropylene resin composition according to claim 1.