JP2012126836A - Propylene polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymer composition which is excellent in impact resistance.SOLUTION: The propylene polymer composition includes: a component (X); and 0.001 to 3 pts.wt of a component (Y) and 0.001 to 3 pts.wt of a component (Z), based on 100 pts.wt of the component (X). The component (X) is a propylene copolymer composed of: 30 to 95 wt.% of a polymer whose main structural unit is derived from propylene and which has a melting point of >155°C; and 5 to 70 wt.% of a copolymer composed of structural units derived from propylene and ethylene and/or 1-butene. The component (Y) is glucose, trehalose or the like. The component (Z) is a phosphite ester having a specific structure.

Description

  The present invention relates to a propylene polymer composition having excellent impact resistance.

Propylene polymers are widely used in the fields of packaging, containers, home appliances, automobile parts and the like.
Among them, a copolymer having a propylene homopolymer part and a propylene / ethylene copolymer part has both the rigidity of the propylene homopolymer part and the impact resistance of the propylene / ethylene copolymer part. It is used for film and automobile bumpers. In order to suppress decomposition, these copolymers generally contain an antioxidant.
For example, in Patent Documents 1 and 2, [tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane] is melt-kneaded into a block copolymer as an antioxidant. The technology is described.
Patent Document 3 describes a food packaging molded article comprising a resin composition containing polypropylene and phosphites.

JP-A-9-3295 JP-A-9-71695 JP 2002-302579 A

However, phenolic antioxidants, phosphorus antioxidants, and phosphites that are used for general purposes have not been sufficient in inhibiting the decomposition of the rubber component (propylene / ethylene copolymer portion). In recent years, it has been desired to use naturally occurring safe compounds because of increasing environmental problems.
An object of the present invention is to provide a propylene polymer composition that suppresses the decomposition of a rubber component and is excellent in impact resistance.

（式中、ｍは２以上の整数を表す。）

成分（Ｚ）：下記式（ＩＩＩ）で表される亜リン酸エステル

〔式中、Ｒ^１、Ｒ^２、Ｒ^４およびＲ^５は、それぞれ同一または相違なり、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のアラルキル基またはフェニル基を表し、Ｒ^３はそれぞれ同一または相違なり、水素原子または炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子または下記式（ＩＩＩ−１）

（式中、Ｒ^６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）で示される２価の基を表し、Ａは炭素数２〜８のアルキレン基または下記式（ＩＩＩ−２）

（式中、Ｒ^７は単結合または炭素数１〜８のアルキレン基を表し、＊は酸素原子に結合する部位を表す。）で示される２価の基を表し、Ｙ、Ｚはいずれか一方がヒドロキシル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子または炭素数１〜８のアルキル基を表す。〕 In order to solve the above-mentioned problems, the present inventors have intensively studied and found that the present invention can solve the above-mentioned problems, and have completed the present invention.
That is, the present invention relates to 0.001 to 3 parts by weight of the following component (Y) and 100 parts by weight of the following component (X) with respect to 100 parts by weight of the following component (X) and the following component (X). And a propylene polymer composition containing 0.001 to 3 parts by weight of the following component (Z).
Component (X): A structural unit derived from propylene is the main structural unit, and a polymer (component (A)) having a melting point exceeding 155 ° C. is 30 to 95% by weight, derived from propylene and derived from ethylene A propylene copolymer (provided that the component (A) and the component (B) are composed of 5 to 70% by weight of a structural unit and / or a copolymer derived from a structural unit derived from 1-butene (component (B)). And the total weight of 100% by weight.)
Component (Y): a compound represented by the following formula (I), a compound represented by the following formula (II), a sugar compound selected from the group consisting of glucose and trehalose

_{C n H 2n + 2 O n} (I)

(In the formula, n represents an integer of 4 to 12.)

(In the formula, m represents an integer of 2 or more.)

Component (Z): Phosphite ester represented by the following formula (III)

^{Wherein, R 1, R 2, R} 4 and ^{R 5} are the same or becomes different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 to 12 carbon atoms An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ is the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a sulfur atom. Or the following formula (III-1)

(Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents a group having 2 to 8 carbon atoms. An alkylene group or the following formula (III-2)

(Wherein R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, * represents a site bonded to an oxygen atom), and Y and Z are either one of them. Represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, 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. ]

  According to the present invention, a propylene polymer composition having excellent impact resistance can be obtained.

  The propylene copolymer (component (X)) used in the present invention is a main structural unit derived from propylene and has a melting point of more than 155 ° C. (component (A)) 30 to 95% by weight. And a copolymer (component (B)) composed of a structural unit derived from propylene and a structural unit derived from ethylene and / or a structural unit derived from 1-butene (provided that the component (The total weight of (A) and component (B) is 100% by weight.)

As a manufacturing method of the propylene copolymer (component (X)) used for 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 without a solvent, a gas phase polymerization method, and the like, preferably a gas phase polymerization method, These polymerization methods are combined and a method in which they are continuously performed, for example, a liquid phase-gas phase polymerization method and the like can be mentioned.

  As content of the component (A) and component (B) contained in the propylene copolymer (component (X)) used for this invention, content of a component (A) is 30 to 95 weight%, Preferably, it is 50 to 95% by weight, and more preferably 60 to 90% by weight. On the other hand, the content of the component (B) is 5 to 70% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight (provided that the component (A) and the component ( The total weight of B) is 100% by weight.) When the content of the component (A) is less than 30% by weight, the heat resistance may be inferior, and when it exceeds 95% by weight, the impact resistance may be inferior.

  The melting point of component (A) exceeds 155 ° C., preferably 158 ° C. or higher, and more preferably 160 ° C. or higher. When the melting point of component (A) is 155 ° C. or lower, the resulting propylene copolymer may have insufficient rigidity.

  The intrinsic viscosity of component (A) is preferably 1.0 to 3.5 dl / g, more preferably 1.5 to 3.0 dl / g, from the viewpoint of excellent workability.

  Component (A) has a structural unit derived from propylene as the main structural unit, and a structural unit other than the structural unit derived from propylene, for example, a structural unit derived from ethylene or a structural unit derived from 1-butene has a melting point. May be included in a range that does not fall below 155 ° C. The content of the structural unit derived from propylene is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and particularly preferably 100% by weight. (However, the weight of the component (A) is 100% by weight).

  Component (B) is a copolymer composed of a structural unit derived from propylene and a structural unit derived from ethylene, a copolymer composed of a structural unit derived from propylene and a structural unit derived from 1-butene, and propylene. Specific examples include a copolymer composed of a structural unit derived from, a structural unit derived from ethylene, and a structural unit derived from 1-butene.

  The content of the structural unit derived from ethylene and / or the structural unit derived from 1-butene contained in the component (B) is preferably 1 to 80 weight from the viewpoint of excellent balance between rigidity and impact resistance. %, More preferably 10 to 60% by weight, still more preferably 15 to 55% by weight (provided that the weight of component (B) is 100% by weight).

  The intrinsic viscosity of the component (B) is preferably 1.5 to 5.0 dl / g, more preferably 2.0 to 4.8 dl / g, from the viewpoint of excellent blocking resistance, impact resistance, and the like. Particularly preferred is 2.5 to 4.8 dl / g.

（式中、ｍは２以上の整数を表す。） The sugar compound (component (Y)) used in the present invention is selected from the group consisting of a compound represented by the following formula (I), a compound represented by the following formula (II), glucose and trehalose.

_{C n H 2n + 2 O n} (I)

(In the formula, n represents an integer of 4 to 12.)

(In the formula, m represents an integer of 2 or more.)

  In the formula (I), n is an integer of 4 to 12, preferably an integer of 5 to 8, and more preferably 6.

  Examples of the compound represented by the formula (I) include erythritol, threitol, arabinitol, xylitol, adonitol, allitol, iditol, galactitol, sorbitol, taritol, mannitol, boretitol, perseitol, octitol and the like.

The compound represented by the formula (I) may be an optically active substance such as D-form or L-form, or an optically inactive substance such as DL-form.
The compound represented by the formula (I) is preferably a sugar alcohol having n of 6, such as allitol, iditol, galactitol, sorbitol, taritol or mannitol represented by the Fisher projection formula as shown below, and sorbitol or mannitol is More preferred.

A commercially available product may be used as it is for the compound represented by the formula (I). The compound represented by the formula (I) may be an anhydride or a hydrate.

  Examples of the compound represented by the formula (II) include 1,2,3-cyclopropanetriol (1,2,3-cyclopropanetriol), 1,2,3,4-cyclobutanetetraol (1,2,3). , 4-cyclobutanetetraol), 1,2,3,4,5-cyclopentanepentaol (1,2,3,4,5-cyclopentanepentaol), 1,2,3,4,5,6-cyclohexanehexaol ( 1,2,3,4,5,6-cyclopentanehexaol), 1,2,3,4,5,6,7-cycloheptaneheptaol (1,2,3,4,5,6,7-cycloheptaneheptaol) 1,2,3,4,5,6,7,8-cyclooctaneoctanol (1,2,3,4,5,6,7,8-cyclooctaneoctaol) and the like.

Preferred are 1,2,3,4,5,6-cyclohexanehexol such as myo-inositol, epi-inositol, allo-inositol, muco-inositol, neo-inositol, chiro-inositol, scyllo-inositol, The represented myo-inositol or scyllo-inositol is more preferred.

  As the compound represented by the formula (II), a commercially available product may be used as it is. The compound represented by the formula (II) may be an anhydride or a hydrate.

  Commercially available glucose can be used as it is for the glucose used in the present invention. Glucose may be anhydrous or hydrated. Glucose may be α-form or β-form. The glucose may be D-form or L-form.

  As the trehalose used in the present invention, a commercially available product can be used as it is regardless of the presence or absence of crystal water.

  Content of the sugar compound (component (Y)) used for this invention is 0.001-3 weight part with respect to 100 weight part of component (X), Preferably, it is 0.001-2 weight part. Yes, and more preferably 0.005 to 1 part by weight.

  Moreover, the sugar compound (component (Y)) used for this invention may use 1 type individually or in combination of 2 or more types. When used in combination, the total amount is 0.001 to 3 parts by weight, preferably 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight per 100 parts by weight of component (X). Part.

  The sugar compound (component (Y)) used in the present invention is preferably mannitol, inositol, sorbitol, glucose or trehalose.

〔式中、Ｒ^１、Ｒ^２、Ｒ^４およびＲ^５は、それぞれ同一または相違なり、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のアラルキル基またはフェニル基を表し、Ｒ^３はそれぞれ同一または相違なり、水素原子または炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子または下記式（ＩＩＩ−１）

（式中、Ｒ^６は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）で示される２価の基を表し、Ａは炭素数２〜８のアルキレン基または下記式（ＩＩＩ−２）

（式中、Ｒ^７は単結合または炭素数１〜８のアルキレン基を表し、＊は酸素原子に結合する部位を表す。）で示される２価の基を表し、Ｙ、Ｚはいずれか一方がヒドロキシル基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子または炭素数１〜８のアルキル基を表す。〕 The phosphite ester (component (Z)) used in the present invention is represented by the following formula (III).

^{Wherein, R 1, R 2, R} 4 and ^{R 5} are the same or becomes different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 to 12 carbon atoms An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ is the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a sulfur atom. Or the following formula (III-1)

(Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents a group having 2 to 8 carbon atoms. An alkylene group or the following formula (III-2)

(Wherein R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, * represents a site bonded to an oxygen atom), and Y and Z are either one of them. Represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, 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. ]

  Content of the phosphorous acid ester (component (Z)) used for this invention is 0.001-3 weight part with respect to 100 weight part of component (X), Preferably, it is 0.005-2 weight Part, more preferably 0.01 to 1 part by weight.

In the formula (III), examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ , R ² , R ⁴ and R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples include n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group.

  Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, and 1-methyl-4-i-propylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, and an α, α-dimethylbenzyl group.

R ¹ , R ² and R ⁴ are the same or different and are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkylcycloalkyl group having 6 to 12 carbon atoms. . R ¹ and R ⁴ are the same or different and 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 independently 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 preferably a C 1-5 alkyl group, more preferably a methyl group, a t-butyl group or a t-pentyl group. R ⁵ is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, etc. 5 is preferably an alkyl group or a hydrogen atom, more preferably a methyl group or a hydrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³ include 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, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- An alkyl group having 1 to 5 carbon atoms such as a butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group or a hydrogen atom is preferable, and a methyl group or a hydrogen atom is more preferable.

X represents a single bond, a sulfur atom or a divalent group represented by the formula (III-1). Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁶ in the formula (III-1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , Sec-butyl group, t-butyl group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group. , A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. R ⁶ is preferably a C 1-5 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group, or a hydrogen atom. X is preferably a single bond or a divalent group represented by the formula (III-1), and more preferably a single bond.

A represents an alkylene group having 2 to 8 carbon atoms or a divalent group represented by the above formula (III-2), preferably an alkylene group having 2 to 8 carbon atoms. Group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like, and propylene group is more preferable. The divalent group represented by the formula (III-2) is bonded to the oxygen atom and the benzene nucleus, but * indicates that it is bonded to the oxygen atom. Examples of the alkylene group having 1 to 8 carbon atoms represented by R ⁷ include methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1, A 3-propylene group etc. are mentioned. Such R ⁷ is preferably a single bond or an ethylene group.

  One of Y and Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or carbon. The alkyl group of number 1-8 is shown. 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 and 2-ethylhexyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, t -Pentyloxy group, i-octyloxy group, t-octyloxy group, 2-ethylhexyloxy group may be mentioned. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group.

Among the compounds represented by the formula (III), R ¹ and R ⁴ are a t-alkyl group, cyclohexyl or 1-methylcyclohexyl group, R ² is an alkyl group having 1 to 5 carbon atoms, and R ⁵ Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, X is a single bond, and A is an alkylene group having 2 to 8 carbon atoms. Preferably there is.

  The compounds represented by the formula (III) may be used alone or in combination of two or more.

  Examples of such a compound represented by the formula (III) include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t. -Butyl dibenz [d, f] [1,3,2] dioxaphosphine [commercially available from Sumitomo Chemical Co., Ltd. as "Sumilyzer (registered trademark) GP". 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] dioxaphosphocine, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 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, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12H Dibenzo [d, g] [1,3,2] dioxaphosphocine, 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, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di -T-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- (3,5-di-t-butyl-4- Roxybenzoyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 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] dioxaphosphocine, 2,4,8,10-tetra-t -Butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 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, 2,4,8,10-tetra-t-butyl Ru-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1, 3,2] Dioxaphosphepine is preferred.

  Such a compound represented by the formula (III) can be produced, for example, by the method described in JP-A-10-273494.

  The intrinsic viscosity ([η] CXS (dL / g)) of the 20 ° C. xylene soluble part of the propylene polymer composition of the present invention is preferably 1.0 to 4.0 dl / g, more preferably, 1.5-3.5 dl / g.

  In addition, the intrinsic viscosity ([η] CXIS (dL / g)) of the 20 ° C. xylene insoluble part of the propylene polymer composition of the present invention is preferably 1.0 to 3.0 dl / g, more preferably 1.5 to 2.5 dl / g.

  The melt flow rate of the propylene polymer composition of the present invention is preferably 0.5 to 10 g / 10 min, and more preferably 1.0 to 5.0 g / 10 min.

  In this invention, you may add additives other than a sugar compound (component (Y)) and phosphorous acid ester (component (Z)) to a propylene polymer composition as needed. Examples of the additive include metal soaps, ultraviolet absorbers, antistatic agents, lubricants, nucleating agents, antifogging agents, and antiblocking agents.

  The propylene polymer composition of the present invention can use a known method and apparatus in order to obtain a homogeneous mixture. For example, propylene copolymer (component (X)) powder and various additives are mixed in advance using a mixing device such as a Henschel mixer, ribbon blender, tumble mixer, etc. For example, a method of continuously supplying a propylene copolymer (component (X)) and various additives is preferably used.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The measuring methods of physical properties used in Examples and Comparative Examples are shown below.

(1) Intrinsic viscosity ([η], unit: dL / g)
The measurement was performed in 135 ° C. tetralin using an Ubbelohde viscometer.
(2) 20 ° C. xylene soluble part (CXS) and insoluble part (CXIS) (unit: wt%)
200 mL of xylene was added to 1 g of the polymer, and the mixture was boiled and completely dissolved, then the temperature was lowered, and the condition was adjusted at 20 ° C. for 1 hour or longer. Then, it isolate | separated into the soluble part and the insoluble part using the filter paper. The solvent was removed from the filtrate to dryness to obtain a soluble part (CXS) sample, and the insoluble part (CXIS) remaining on the filter paper and the weight of each were measured.
(3) [η] CXS, [η] CXIS
The intrinsic viscosities of CXS and CXIS were [η] CXS and [η] CXIS, respectively.
(4) Comonomer (ethylene) content (unit: wt%)
The ethylene content in the propylene polymer was determined by the method described on pages 616 to 619 of the Polymer Analysis Handbook (1995, published by Kinokuniya Shoten). The ethylene content in (Component B1) was determined by calculation using the content of (Component B).
(5) Melt flow rate (MFR, unit: g / 10 min)
According to JIS K7210, the measurement was performed at a temperature of 230 ° C. and a load of 21.18 N.

[Example 1]
[Production of propylene polymer (1)]
The catalyst was adjusted and polymerized according to Reference Example 2 of JP 2010-53342 A to obtain a continuous polymer of propylene homopolymer (A1) and propylene / ethylene copolymer (B1). The contents of (A1) and (B1) are 84% by weight and 16% by weight, the ethylene content in (B1) is 38% by weight, [η] of the component (A1) is 2.2 dl / g, ( [Η] of component B1) was 3.6 dl / g.

[Pelination of propylene polymer (1)]
For 100 parts by weight of the propylene polymer (1) powder, 0.03 part by weight of mannitol, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4, 0.05 parts by weight of 8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine “Sumilyzer (registered trademark) GP” (manufactured by Sumitomo Chemical Co., Ltd.) Using a 40 mmφ single screw extruder manufactured by Tanabe Plastics Machine Co., Ltd., melt kneading was performed at 250 ° C., and the strand extruded from the die was cut to obtain pellets. [Η] of the obtained pellet was 2.33 dl / g, [η] CXS was 2.95 dl / g, [η] CXIS was 2.23 dl / g, and the CXS content was 10% by weight.

[Example 2]
The propylene polymer (1) was pelletized by the same method as in Example 1 except that mannitol used in Example 1 was changed to inositol. [Η] of the obtained pellet was 2.30 dl / g, [η] CXS was 2.87 dl / g, [η] CXIS was 2.18 dl / g, and the CXS content was 10% by weight.

[Example 3]
The propylene polymer (1) was pelletized by the same method as in Example 1 except that mannitol used in Example 1 was changed to sorbitol. [Η] of the obtained pellet was 2.32 dl / g, [η] CXS was 2.90 dl / g, [η] CXIS was 2.25 dl / g, and the CXS content was 10% by weight.

[Example 4]
The propylene polymer (1) was pelletized by the same method as in Example 1 except that mannitol used in Example 1 was changed to D-glucose (manufactured by Wako Pure Chemical Industries, Ltd.). [Η] of the obtained pellet was 2.33 dl / g, [η] CXS was 2.90 dl / g, [η] CXIS was 2.25 dl / g, and the CXS content was 10% by weight.

[Example 5]
The propylene polymer (1) was pelletized in the same manner as in Example 1 except that mannitol used in Example 1 was changed to trehalose (manufactured by Tokyo Chemical Industry Co., Ltd.). [Η] of the obtained pellet was 2.31 dl / g, [η] CXS was 2.86 dl / g, [η] CXIS was 2.22 dl / g, and the CXS content was 10% by weight.

[Comparative Example 1]
The propylene polymer (1) was pelletized by the same method as in Example 1 except that the Sumilizer GP was used alone. [Η] of the obtained pellet was 2.24 dl / g, [η] CXS was 2.54 dl / g, [η] CXIS was 2.18 dl / g, and the CXS content was 10% by weight.

[Comparative Example 2]
The propylene polymer (1) was pelletized by the same method as in Example 1 except that mannitol used in Example 1 was changed to Irganox 1010 (manufactured by Ciba Specialty Chemicals). [Η] of the obtained pellet was 2.30 dl / g, [η] CXS was 2.80 dl / g, [η] CXIS was 2.23 dl / g, and the CXS content was 10% by weight.

  The pellets of Comparative Example 1 in which the Sumilizer GP was used alone and Comparative Example 2 in which the Sumilizer GP and Irg1010 were used together had lower [η] CXS compared to the Examples. It is estimated that the impact resistance is inferior.

  The propylene polymer composition of the present invention is excellent in impact resistance and can be used for packaging films, automotive materials and the like. Since natural saccharides are used in particular, it is preferable for food packaging.

Claims (1)

With respect to 100 parts by weight of the following component (X) and the following component (X), 0.001 to 3 parts by weight of the following component (Y), and 100 parts by weight of the following component (X), the following component (Z) A propylene polymer composition containing 0.001 to 3 parts by weight.
Component (X): A structural unit derived from propylene is the main structural unit, and a polymer (component (A)) having a melting point exceeding 155 ° C. is 30 to 95% by weight, derived from propylene and derived from ethylene A propylene copolymer (provided that the component (A) and the component (B) are composed of 5 to 70% by weight of a structural unit and / or a copolymer derived from a structural unit derived from 1-butene (component (B)). And the total weight of 100% by weight.)
Component (Y): a compound represented by the following formula (I), a compound represented by the following formula (II), a sugar compound selected from the group consisting of glucose and trehalose

_{C n H 2n + 2 O n} (I)

(In the formula, n represents an integer of 4 to 12.)

(In the formula, m represents an integer of 2 or more.)

Component (Z): Phosphite ester represented by the following formula (III)

^{Wherein, R 1, R 2, R} 4 and ^{R 5} are the same or becomes different, a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 to 12 carbon atoms An alkylcycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group, R ³ is the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X is a single bond or a sulfur atom. Or the following formula (III-1)

(Wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents a group having 2 to 8 carbon atoms. An alkylene group or the following formula (III-2)

(Wherein R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, * represents a site bonded to an oxygen atom), and Y and Z are either one of them. Represents a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, 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. ]