WO2004018557A1

WO2004018557A1 - α-OLEFIN POLYMER COMPOSITIONS AND PROCESS FOR PRODUCTION THEREOF

Info

Publication number: WO2004018557A1
Application number: PCT/JP2003/010513
Authority: WO
Inventors: Rikuo Onishi; Yasuhisa Sugita; Ryoichi Tsunori; Tomio Tatsumi; Toshiya Abiko; Takenori Fujimura; Shinichi Yukimasa
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 2002-08-22
Filing date: 2003-08-20
Publication date: 2004-03-04
Also published as: TW200427754A

Abstract

An α-olefin polymer composition which is obtained by mixing (A) an α-olefin polymer, (B1) an organosilicon compound, and (C) a modified α-olefin polymer having a substituent reactive with a polar group and exhibiting a limiting viscosity of 0.7 dl/g or above or by bringing the components (A), (B1) and (C) into contact with each other; a modified polypropylene resin composition which is obtained by mixing (C2) a polypropylene resin having a polar group and (B) a silane coupling agent and which is specified in melt tension and MFR and has a p-xylene insolubles content of 1 wt% or below; and a process for the production of modified α-olefin polymer compositions, characterized by mixing a mixture consisting of (C6) a modified α-olefin polymer specified in limiting viscosity, Mw/Mn ratio and polar group content and (B) a silane coupling agent with (A) an α-olefin polymer having a limiting viscosity of 0.7 to 5.0 dl/g at an (A)/[(B) + (C)] weight ratio of 0/100 to 99/1.

Description

Technical Field Hyorefin polymer composition and method for producing the same

The present invention 1 relates to an α-olefin polymer having 2 to 20 carbon atoms, an organic silicon compound, and an α-modified with a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule. The present invention relates to an a-olefin polymer composition obtained by mixing (reacting) an -olefin polymer and a method for producing the same. The present invention 2 relates to an α-olefin polymer having 2 to 20 carbon atoms containing an organic silicon compound, and a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule. The present invention relates to an α-olefin polymer composition obtained by mixing (reacting) a modified hypoolefin polymer having 2 to 20 carbon atoms and a method for producing the same.

The present invention 3 relates to a modified polypropylene resin composition and a method for producing the same.

The present invention 4 relates to a method for producing a modified -olefin polymer composition. Background art

Conventionally, polyolefin melt tension has been improved with the aim of improving formability, but these have only been achieved through complex processes or the use of special equipment.

Methods for improving the melt tension of polyolefin include: (1) an electron beam crosslinking method of polypropylene (JP-A-62-121704, JP-A-2-695333, etc.), (2) Cross-linked polio using olefin-non-conjugated gen copolymer A method for forming a refin (Japanese Patent Application Laid-Open Nos. Hei 5-194659, Japanese Patent Application Laid-Open No. Hei 7-209628), and a method for coexisting ultra-high molecular weight polyethylene in polypropylene No. 200-017-224).

The method (1) requires special equipment for electron beam crosslinking, the method (2) requires the use of a special non-conjugated gen that is not industrially produced, and the method (3) requires a special spare. Neither can be said to be highly versatile in that a polymerization step is required.

In addition, the purpose of the present invention, namely, to improve the melt tension, is different from the purpose, and as a technique mainly for imparting chemical properties such as adhesiveness, paintability, hydrophilicity, etc. Several patents have been filed for the reaction of a silane coupling agent with a modified polyolefin, and for the reaction product thereof (Japanese Patent Application Laid-Open No. 59-184,272; Publication No. 0 149 49, Japanese Unexamined Patent Application Publication No. Hei 5-111264, Japanese Unexamined Patent Application Publication No. 2000-265365, etc.).

Among them, Japanese Patent Application Laid-Open No. Hei 1-150149 and Japanese Patent Laid-Open Publication No. Hei 5-112694 disclose a composition comprising a simple combination of a modified polyolefin and an alkoxyaminosilane. However, in the case of such a combination, there is a possibility that the gelation may partially proceed without increasing the melt tension.

Further, there is no disclosure of an unmodified monoolefin polymer component as the component (A). Japanese Patent Application Laid-Open No. 59-184,272 discloses a technique in which a modified polyolefin and a silane compound are blended, and further an unmodified polyolefin is blended. There is no description or suggestion about the modified α-olefin polymer.

Japanese Patent Application Laid-Open No. 2001-226655 discloses a reaction between a carboxylic acid-modified polymer, an amine compound having an alkoxysilyl group and a carbonyl compound. A one-pack type cross-linking composition in which a product is dissolved in an organic solvent and an ordinary thermoplastic resin is added is disclosed.

However, this composition is of the one-part type, which is different from the composition of the invention, which is usually solid.

Furthermore, Japanese Patent Application Laid-Open No. 2002-5188573 discloses a silane-cured thermoplastic elastomer obtained by reacting a rubber or a thermoplastic resin obtained by graphitizing or copolymerizing a carboxylic anhydride with an aminosilane. A toma composition is disclosed wherein the gel content is between 10 and 50% by weight.

This technique is fundamentally different from the α-olefin polymer compositions of the present invention where the preferred gel content is less than 1% by weight.

Further, the publication does not disclose or suggest a high-molecular-weight modified haloolefin polymer corresponding to the component (II).

Conventionally, various attempts have been made to further improve the properties of polyolefin.

For example, Japanese Unexamined Patent Application Publication Nos. Sho 59-184272, Hei 1-501946, Hei 4-34816, Hei 5-129494, and the like. And Japanese Patent Application Laid-Open No. 201-2265355 describe a silane cup made of an alkoxyaminosilane compound or the like for the purpose of improving the adhesive property, coatability, printability, hydrophilicity and other chemical properties of polyolefin. The reaction of a ring agent with a modified polyolefin and the reactants thereof are disclosed.

Of these, publications other than Japanese Patent Application Laid-Open No. 59-1884272 only disclose a yarn composition comprising a simple combination of a modified polyolefin and an alkoxyaminosilane compound. However, there is no mention of a combination of the silane compound with a polymer having properties capable of being highly dispersed.

In the case of such a simple combination, the melt tension of the composition is not expected to be improved, and the composition may gel. On the other hand, Japanese Patent Application Laid-Open No. 59-184432 discloses a composition in which a modified polyolefin and a silane compound are blended, and further a non-modified polyolefin is blended.

However, in Japanese Patent Application Laid-Open No. 59-184,272, there is no description that emphasizes that a silane compound is highly dispersed in unmodified polyolefin.

Furthermore, Japanese Patent Application Laid-Open Nos. Sho 59-184,722, JP-A-Heisei 501-4949, JP-A-Heisei 4-344,106, JP-A-Heisei 5-11 JP-A-26-94 and JP-A-2001-22653 are not aimed at improving the physical properties of polyolefins.

On the other hand, when the purpose is to improve the physical properties of polyolefin, there are no components obtained by the reaction between the silane coupling agent and the modified polyolefin, or the modified polyolefin contains a large amount of a modifying agent (for example, an acid). When the composition is used, the composition cannot be expected to improve the melt tension, and the composition may be partially gelled.

Generally, in order to improve the melt tension of a one-year-old olefin polymer such as polypropylene, it is essential to use complicated processes and special equipment.

Therefore, there has been a demand for improving the melt tension of _α- refined polymers such as polypropylene by combining extremely general-purpose equipment with practical raw materials.

The present inventions 1 and 2 have been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a hoolefin polymer composition which has no gelation, has an increased melt tension, and has greatly improved moldability, and a method for producing the same. It is.

The third object of the present invention is to provide a modified polypropylene resin composition having an excellent balance between melt tension and fluidity, and a method for producing the same. The present invention 4 is a modified one-year-old refining paper having an excellent balance between melt tension and fluidity. It is an object of the present invention to provide a method for producing a polymer composition. DISCLOSURE OF THE INVENTION ''

The present inventors have conducted intensive studies to achieve the above object, and as a result, using general-purpose equipment, an organic silicon compound and a compound containing an ethylenic double bond and a polar group in the same molecule Mixing (reaction) with an acid-modified α-olefin polymer, preferably a high molecular weight modified with a polar group derived from a polymer, to form a component capable of highly dispersing an organic silicon compound. It has been found that by performing the reaction in an α-olefin polymer having the following properties, the generation of gel is suppressed, the melt tension is increased, and an _α -olefin polymer composition having significantly improved moldability can be obtained. The invention has been completed.

Based on this finding, the present invention 1

1. (A) 'Intrinsic viscosity [] measured at 135 ° C in tetralin is in the range of 0.7 to 5 d 1 / g, and a monoolefin polymer having 2 to 20 carbon atoms 100 Parts by mass, (B 1) general formula (1)

X „S i Y _m (OR) ₄ — _{(n + m)} (1)

(Wherein, X is a polar group, preferably a substituent containing a group capable of reacting with a carboxylic acid or its anhydride, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n Represents an integer of 1 to 3, m represents an integer of 0 to 2, and (n + m) = 1 to 3.)

0.001 to 1 part by mass of an organic silicon compound represented by the formula: and (C 1) a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule, preferably an unsaturated carboxylic acid. 0.001 to 1% by mass of acid derived from acid and / or its anhydride, 13.5 ° (intrinsic viscosity measured in tetralin [??] force SO. Modified a-olefin polymer having 2 to 20 carbon atoms 0.1 _α -olefin polymer obtained by mixing (contacting) 0.1 to 30 parts by mass Body composition.

2. The olefin polymer composition according to 1 above, which satisfies the following ① to ③.

① The silicon compound derived from the organic silicon compound (B1) is 0.000

1 to 1 parts by mass,

② melt tension (MT) and melt flow rate (M l) force S, MT / 7 X (MI ) - to satisfy the ° · ^8> 1 relationship,

③ Less than 1 mass of insoluble components in paraxylene at 130 ° C

3. The α-olefin polymer composition according to the above 1, wherein X in the general formula (1) is one or more substituents selected from substituents including an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. .

4. The phosphoryl polymer composition according to the above 1, wherein the phosphoric polymer modified with the polar group of the component (C 1) further satisfies the following ① to ③.

(1) The polar group content and the molar ratio of the α-olefin polymer chain (ιδ ¹ value), 0.5: 1.0 to 3.0: 1.0

②Weight average molecular weight (Mw) Z number average molecular weight (Mn) is 2.5 or less

(3) Component with Mw of 10,000 or less is 0.5% by mass or less

5. The phosphoryl polymer composition according to the above 1, wherein the polar group derived from the compound containing the ethylenic double bond and the polar group in the component (C1) in the same molecule is maleic anhydride.

6. The α-olefin polymer composition according to the above 1, wherein the component (C1) is an acid-modified ct-olefin polymer obtained by using a propylene polymer or a 1-butene polymer.

7. The α-olefin polymer composition according to 1 above, wherein the component (成分) is a pyrene polymer or a 1-butene polymer having a mesopentad fraction [mmmm] of 97 mol% or more.

8. The average particle size of the (Α) component is 50-20 ° 0 μπι, and the bulk specific gravity is 0.2- 0. a 6 gZc ni ^3, α- Orefuin polymer composition according to the above 7.

9. The α-olefin polymer composition according to 1 above, wherein the component (B1) in which X in the general formula (1) is a substituent containing an amino group.

10. The method according to 1 above, wherein the component (B1) is dispersed in the component (II) under a temperature condition equal to or lower than the melting point of the component (II), and then the component (C1) is mixed (reacted). α-olefin polymer composition.

1 1. The method for producing an α-olefin polymer composition according to the above 1, wherein the component (II), the component (II) and the component (C1) are melt-kneaded or mixed in a solvent.

It is about.

In addition, the present inventors used a general-purpose facility and prepared an _α -olefin polymer in which an organic silicon compound was dispersed, and a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule. The reaction of an acid-modified α-olefin polymer, preferably having a high molecular weight, which has been modified by the method described above, suppresses the generation of gel, increases the melt tension, and significantly improves the moldability of the modified α-olefin polymer composition. It was found that a product was obtained, and the present invention was completed.

Based on this finding, the present invention 2

1. (Β 1) General formula (1)

X „S i Y _m (OR) ₄ — _{(n + m} ) (1)

0.001 to 1 part by mass of an organic silicon compound represented by the formula: (A) The intrinsic viscosity [] measured in tetralin at 135 ° C is in the range of 0.7 to 5 dl / g. 100 parts by mass of an α-olefin polymer having 2 to 20 carbon atoms, and (CI) A polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule, preferably an acid derived from an unsaturated carboxylic acid and / or an anhydride thereof, 0.001 to 1 mass ⁰ / ₀ Intrinsic viscosity measured in tetralin at 135 ° C [η] Force S 0.7 d 1 Modified by a polar group having 2 to 20 carbon atoms with a carbon content of 1 g or more, preferably acid The modified α-olefin polymer is obtained by mixing (contacting) 0.1 to 30 parts by mass, and has a melt tension (ΜΤ), melt flow rate 1, (Μ I) force S, MT / 7 X (MI) — Α-olefin polymer composition that satisfies the relationship of ⁰ · ⁸ > 1.

2. The phosphorefin polymer composition according to 1 above, wherein 130. Ο: —olefin polymer composition in which the amount of unnecessary components in paraxylene C is less than 1% by mass. '

3. The α-olefin polymer composition according to 1 above, wherein the -olefin polymer modified with the polar group of the component (C 1) further satisfies the following (1) to (3).

( ¹ ) The molar ratio ( ¹ value) between the polar group content and the <¾_olefin polymer chain, 0.5: 1.0 to 3.0: 1.0

(3) 0.5 mass of components with Mw of 10,000 or less. /. Less than

4. The haolefin polymer composition according to 1 above, wherein the compound containing the ethylenic double bond and the polar group of the component (C1) in the same molecule is maleic anhydride.

5. The α_, olefin polymer composition according to 1 above, wherein X in the general formula (1) is one or more substituents selected from substituents including an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. .

6. The α-olefin polymer composition according to the above 1, wherein the component (C1) is an acid-modified _α -olefin polymer obtained using a propylene polymer or a 1-butene polymer.

7. (Α) The component has a mesopentad fraction [mmmm] of 97 mol% or more. [0513] The α-olefin polymer composition according to the above-mentioned 1, which is a pyrene polymer or 1. an octene polymer.

8. The α; -olefin polymer composition according to the above 1, wherein X in the general formula (1) is a substituent containing an amino group.

9. (ii) The component is obtained by supplying the organic silicon compound represented by the general formula (1) to a drying step and a transferring step in the production of a propylene polymer or a 1-butene polymer, or a molding step of the polymer. 2. The α-refined polymer composition according to 1 above, which is obtained by:

10. The method for producing an α-olefin polymer composition according to 1 above, wherein the component (II) and the component (C1) are melt-kneaded or mixed in a solvent. It is about.

Furthermore, the present inventors have found that a composition obtained by mixing a polypropylene resin having a specific polar group, a silane coupling agent and an antioxidant exhibits a high melt tension, and completed the present invention. I came to.

Based on this finding, the present invention 3

1. Melt tension (Μ Τ) and melt rate (M l) obtained by mixing the following components (C 2) and (Β) are MT / 7 X (M l) — ° · ⁸ > A modified polypropylene resin composition that satisfies the relationship 1 and has a paraxylene-insoluble component amount (G value) of 1% by weight or less at 130 ° C.

. (C 2) 1 XI 0- 6 ~0 polarity base that - derived ethylenic double bond及Pi polar group to a compound containing in the same molecule 2 5 wt% comprising polypropylene resins: 1 0 0 parts by weight

(B) Silane coupling agent: 0.01 to 1 part by weight

2. In addition to the polypropylene resin (C2) and the silane coupling agent (B), a phosphorus-based and / or phenolic antioxidant (D) is further mixed by mixing 0.05 to 1 part by weight. 2. The modified polypropylene resin composition according to 1 above, wherein 3. The modified polypropylene resin composition according to the above 1, wherein the compound containing an ethylenic double bond and a polar group in the same molecule is maleic anhydride.

4. Polypropylene resin (C 2) The modified polypropylene resin composition according to the above 1, which is a mixture of the following (C 3) and (C 5) or the following (C 4) and (C 5).

(C 3) Unmodified polypropylene resin having a melt flow rate of 0.01 to: lOOg / 10 minutes and a melting point of 145 to 170 ° C: 100 parts by weight

(C 4) a melt flow rate of 0. 0 1~: 1 0 0 g / 1 0 minutes, ¹ ³ C-NMR Mesopenta' de fraction was determined by measuring the ([mmmm]) is 4 0-9 Unmodified polypropylene resin of 0 mol%: 100 parts by weight

(C5) Modified polypropylene resin containing 0.001 to 1% by weight of the polar group and having an intrinsic viscosity of 0.7 dl Zg or more at 135 ° C in tetralin: 0 1 to 30 parts by weight

5. The melting enthalpy of the unmodified polypropylene resin (C 4) measured by differential scanning calorimetry (DSC) is 100 J / g or less, and the mesopentad fraction determined by ¹³ C-NMR measurement 5. The modified polypropylene resin composition according to the above item 4, wherein ([mmmm] and [rrrr]) satisfy a relationship of [rrrr] / (11 [mmmm]) ≥ 20%.

6. The modified polypropylene resin composition according to the above item 5, wherein the molar ratio of the polar group to the polymer chain of the modified polypropylene resin (C5) is 0.8 to 2.

7. The modified polypropylene resin according to the above 1 or 2, wherein the silane coupling agent (B) is an organosilicon compound represented by the general formula (1).

X _n S i Y _m (OR) ₄ — _{(n + m)} (1)

Wherein X is a substituent containing a functional group capable of reacting with the polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n is 1-3, and m is 0- Indicates an integer of 2, and (n + m) = 1 to 3. ] 8. — The modified polypropylene resin composition according to the above 7, wherein in the general formula (1): is a substituent containing an amino group.

9. Silane coupling agent (Β) contains 10 to 100,000 ppm, phosphorus-based and ぴ Z or phenol-based antioxidants (D) F 500-: L0, OOO ppm As described above, the silane coupling agent (B), the phosphorus-based and Z- or phenol-based antioxidants (D), and the following polypropylene-based resin (C3) or (C4) are mixed, and 100 parts by weight of the mixture is obtained. A method for producing a modified polypropylene resin composition, comprising mixing 0.1 to 3 parts by weight of the following modified polypropylene resin (C5).

(C 3) Unmodified polypropylene resin having a melt flow rate of 0.01 to: L 00 g / 10 minutes and a melting point of 145 to 170 ° C

(C 4) a melt flow rate of 0. 0 1~: 1 0 0 g / 1 0 minutes, ¹ ³ C-Mesopenta' de fraction was determined by measuring the NMR ([mmmm]) is 4 0-90 Unmodified polypropylene resin in mole%

(C5) A modified polypropylene resin containing 0.001 to 1% by weight of the polar group, and having an intrinsic viscosity of 0.7 d1 Zg or more measured at 135 ° C in tetralin.

100. Phosphorus and / or phenolic antioxidant (D) and phosphorus and / or phenolic antioxidant (D) so that the phosphorus and / or phenolic antioxidant (D) is contained in the range of 500 to 100,000 ppm. The polypropylene-based resin (C 3) or (C 4) is mixed, and the silane coupling agent (B) is reacted with the following modified polypropylene-based resin (C 5). A method for producing a modified polypropylene resin composition comprising mixing 0.1 to 30 parts by weight of a reactant.

(C3) An unmodified polypropylene resin having a melt flow rate of 0.01 to 100 g / l 0 minutes and a melting point of 144 to 170 ° C.

(C 4) Melt flow rate is 0.01-100 g / 10 minutes, ¹ Unmodified polypropylene resin whose mesopentad fraction ([mmmm]) determined by ³ C-NMR measurement is 40 to 90 mol%

(C 5) the polar base 0.0 0 1-1 weight including ^{_{0/0, 1 3 5 °}} C, the modified polypropylene resin is an intrinsic viscosity measured in tetralin is 0. 7 d 1 / g or more

It is about.

In addition, the present inventors have found that when an α-olefin polymer is mixed with a mixture of a specific modified α-olefin polymer and a silane coupling agent, a composition exhibiting high melt tension can be efficiently obtained. This led to the completion of the present invention.

Based on this finding, the present invention 4

1. The following (C6) component and (Β) component are mixed, and the following (Α) component is added to the mixture ((Β) + (C6)), and (A) / C (Β) + (C6) ] A method for producing a modified α-olefin polymer composition comprising mixing (weight ratio) so as to be 0/100 to 99/1.

(C 6) Modified α-olefin polymer having 2 to 20 carbon atoms, satisfying the following (a) to (d): 100 parts by weight

(a) The content of a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule: 0.001 to 0.4% by weight.

(b) Intrinsic viscosity measured in tetralin at 135 ° C: 0.9 to 5.0 d 1 Z g

(c) Weight average molecular weight Z number average molecular weight (MwZMn): 3 or less

(d) Molar ratio of the polar group to the polymer: 0.1 to 3.0 (B) Silane coupling agent: 0.001 to 0.5 part by weight

(A) An intrinsic polymer having an intrinsic viscosity of 0.7 to 5.0 d 1 / g, measured in tetralin at 135 ° C, having 2 to 20 carbon atoms. 2. modified a- melt tension (MT) of Orefuin polymer composition and Merutofu port one rate (MI) i MT / 7 X (MI) - met ° · ^8> 1 relationship One or, 1 30 ° 2. The method for producing a modified a-olefin polymer composition according to the above 1, wherein the amount of paraxylene-insoluble component (G value) of C is 1% by weight or less.

3. The method for producing the modified a-olefin polymer composition according to 1 above, wherein the modified a-olefin polymer (C 6) and the silane coupling agent (B) are melt-mixed.

4. The method for producing the modified << _ olefin polymer composition according to the above item 3, wherein the molten mixture [(B) + (C 6)] and the a-olefin polymer (A) are melt-mixed.

5. Modified a-olefin polymer (C 6) Production of modified a-olefin polymer composition according to 1 above, which is a modified S, modified propylene (co) polymer or modified 1-butene (co) polymer Method.

6. The method for producing a modified a-olefin polymer composition according to the above item 1, wherein the compound containing an ethylenic double bond and a polar group in the same molecule is maleic anhydride.

7. Silane coupling agent (B) 1 The process for producing a modified a-olefin polymer composition according to the above 1 or 2, which is an organosilicon compound represented by the general formula (1).

X n S i Y m (OR) ₄ — _{(n + ra)} (1)

Wherein X is a substituent containing a functional group capable of reacting with the polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n is 1-3, and m is 0- 2 represents an integer, and (n + m) = 1 to 3. ]

8. The method for producing a modified a-olefin polymer composition according to the above 7, wherein X in the general formula (1) is a substituent containing an amino group.

It is about.

Summarizing the above, the present invention provides:

1. (A) Intrinsic viscosity measured in tetralin at 135 ° C [77] Force 0.7 ~ 100 parts by mass of a ct-olefin polymer having 2 to 20 carbon atoms in the range of 5 d 1 / g, (B 1) general formula (1)

X „S i Y _m (OR) ₄ _ _{(n + m)} (1)

(In the formula, X is a substituent containing a group capable of reacting with a polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n is 1-3, and m is 0-2. And (n + m) = 1 to 3.)

0.001 to 1 part by mass of an organosilicon compound represented by the formula: and 0.001 to 1 part by mass of (C 1) a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule を. Intrinsic viscosity measured at 135 ° C in tetralin at 135 ° C [77] Force 0.7 d 1 / g 0.1 to 30 parts by mass of modified haloolefin polymer having 2 to 20 carbon atoms A monoolefin polymer composition obtained by mixing (contacting).

2. (Β 1) General formula (1)

X „S i Y _ra (OR) ₄ — _{(n + m)} (1)

(In the formula, X is a substituent containing a group capable of reacting with a polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n is 1-3, and m is 0-2. And (n + m) = 1 to 3.

Containing 0.001 to 1 part by mass of an organosilicon compound represented by the following formula: (A) an intrinsic viscosity [] measured in tetralin at 135 ° C in the range of 0.7 to 5 dl Zg; 100 parts by mass of a monoolefin polymer having 2 to 20 carbon atoms and 0.01 to 1 parts by mass of a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule. %, And the intrinsic viscosity [η] measured in tetralin at 135 ° C is 0.7 dl Zg or more. It is to give, and melt Tsutomu Cho (MT) and melt flow rate (M l) is, MT / 7X (M l) non Orefin polymer composition of claim 1 which satisfies an ^0` ^8> 1 relationship . 3. —In the same molecule, X in the general formula (1) contains a substituent containing a group capable of reacting with a carboxylic acid or an anhydride thereof, and an ethylenic double bond and a polar group of the component (C 1). 3. The α-olefin polymer composition according to the above 1 or 2, wherein the polar group derived from the compound contains an acid derived from an unsaturated carboxylic acid and / or an anhydride thereof.

4. The phosphoryl polymer composition according to the above 1 or 2, which satisfies the following (1) to (3).

(1) 0.001 to 1 part by mass of a silicon compound derived from the organic silicon compound of the component (、 1),

② melt tension (ΜΤ) and melt flow rate (M l) is, MT / 7 X (MI) -. 0 8> to satisfy the first relation,

③ 1 Less than 1 mass of insoluble in paraxylene at 30 ° C

5. The α-olefin polymer according to the above 1 or 2, wherein X in the general formula (1) is one or more substituents selected from a substituent containing an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. Composition.

6. The α-olefin polymer composition according to 1 or 2, wherein the -olefin polymer modified with the polar group of the component (C1) further satisfies the following (1) to (3).

( ¹ ) The molar ratio of the polar group content to the α-olefin polymer chain (J31 value), 0.5: 1.0 to 3.0: 1.0

②Weight average molecular weight (Mw) / number average molecular weight (Mn) is 2.5 or less

(3) Component with Mw of 10,000 or less is 0.5% by mass or less

7. The olefin polymer composition according to the above 1 or 2, wherein the polar group derived from the compound containing the ethylenic double bond and the polar group in the component (C1) in the same molecule is maleic anhydride.

8. (C1) component obtained using propylene polymer or 1-butene polymer. 3. The α-olefin polymer composition according to the above 1 or 2, which is an acid-modified o; -olefin polymer.

9. (i) The hooprefin polymer composition according to the above (1) or (2), wherein the component is a pyrene polymer or a 1-butene polymer having a mesopentad fraction [mmmm] of 97 mol% or more.

10. The a-olefin polymer according to 9 above, wherein the component (A) has an average particle size of 50 to 200 m and a bulk specific gravity of 0.2 to 0.6 gZ cm ^3. Composition.

1 1. The haloolefin polymer composition according to the above 1 or 2, wherein X in the general formula (1) is a substituent (B 1) containing an amino group.

1 2. Under the temperature condition below the melting point of the component (A), the component (B1) is dispersed in the component (A), and then the component (C1) is mixed (reacted). The olefin polymer composition according to the above.

1 3. The preparation of a mixture of the component (A) and the component (B1) is carried out in a drying step and a transporting step in the production of a propylene polymer or a 1-butene polymer, or in a molding step of the polymer. 3. The one-year-old refined polymer composition according to 1 or 2 above, which supplies the components.

1 4. The method for producing a monoolefin polymer composition according to 1 or 2 above, wherein the component (A), the component (B1) and the component (C1) are melt-kneaded or mixed in a solvent. .

15. The a-olefin polymer according to the above 1 or 2, wherein the component (A) containing the component (B 1) and the component (C 1) are melt-kneaded or mixed in a solvent. A method for producing the composition.

1 6. The melt tension (MT) and menoleto flow rate (Ml) obtained by mixing the following components (C2) and (B) are MT / 7 X (Ml) — ⁰ · ⁸

> A modified polypropylene resin composition that satisfies the relationship of 1 and has a paraxylene-insoluble component amount (G value) of 1 ° C or less at 130 ° C. . (C 2) ethylenic double bond and 1 X 1 0- ⁶ ~0 polarity base that - derived polar group to a compound containing in the same molecule 2 5 wt% comprising polypropylene resins: 1 00 parts by weight

(B) Silane coupling agent: 0.001 to 1 part by weight

1 7. A mixture of the polypropylene resin (C 2) and the silane coupling agent (B), together with a phosphorus and / or phenolic antioxidant (D), is mixed with 0.5 to 1 part by weight. 16. The modified polypropylene resin composition according to 16 above, which is obtained.

18. The modified polypropylene resin composition according to the above 16 or 17, wherein the compound containing an ethylenic double bond and a polar group in the same molecule is maleic anhydride.

1 9. Polypropylene resin (C2), the modified polypropylene according to 16 or 17 above, which is a mixture of (C3) and (C5) below, or a mixture of (C4) and (C5) below -Based resin composition.

(C 3) Melt flow resin SO. 01 to: lO Og / 10 min, unmodified polypropylene resin having a melting point of 145 to 170 ° C .: 100 parts by weight

(C 4) a melt flow rate of 0.0 1: a I 0 0 g / 1 0 min, ¹ ³ C-NMR was measured to seek the meso pentad fraction ([mmmm]) is 4 0-9 0 Unmodified polypropylene resin in mole%: 100 parts by weight

(C5) Modified polypropylene resin containing 0.001 to 1% by weight of polar base and having an intrinsic viscosity of 0.7 d 1 / g or more at 135 ° C in tetralin: 0.1 ~ 30 parts by weight

20. The melting enthalpy of the unmodified polypropylene resin (C 4) measured by differential scanning calorimetry (DSC) is 100 J / g or less, and ¹³ C—N MR was measured. Mesopentad fraction ([mmmm] and [rrrr,] force S, [rrrr] / (1-[mmmm]) ≥ 20% 21. The modified polypropylene resin composition according to the above item 19.

21. The modified polypropylene resin composition according to the above 20, wherein the molar ratio of the polar group to the polymer chain of the modified polypropylene resin (C5) is 0.8 to 2.

2 2. Silane coupling agent (B) force S, (B 1) —The modified polypropylene resin according to the above 16 or 17, which is an organic silicon compound represented by the general formula (1).

X _n S i Y _m (OR) ₄ — ( _{11 + ra} ) (1)

23. The modified polypropylene resin composition according to the above item 22, wherein X in the general formula (1) is a substituent containing an amino group.

24 · Silane so that the silane coupling agent (B) is included in the range of 10 to 10,000 ppm and the phosphorus and / or phenolic antioxidant (D) in the range of 500 to L0, OOO p pm Coupling agent (B), phosphorus and / or phenolic antioxidant (D), and the following polypropylene resin (C3) or

(C4) is mixed, and 0.1 to 30 parts by weight of the following modified polypropylene resin (C5) is mixed with 100 parts by weight of the mixture to produce a modified polypropylene resin composition. Method.

(C 3) Unmodified polypropylene resin with a menoleto flow rate of 0.01 to: lOOg / 10 minutes and a melting point of 145 to 170 ° C

(C 4) Melt flow rate is from 0.01 to: 100 g / 10 minutes, ¹

Unmodified polypropylene resin whose mesopentad fraction ([mmmm]) determined by ³ C-NMR measurement is 40-90 mol%

(C 5) 0.01 to 1% by weight containing polar base, 135 ° C, tetralin Modified polypropylene resin with intrinsic viscosity of 0.7 d1 / g or more measured in water

2 5. Phosphorus and / or phenolic antioxidant so that the phosphorus and / or phenolic antioxidant (D) is contained at 500 to 10,000 ppm

(D) and the following polypropylene resin (C 3) or (C 4) are mixed, and the silane coupling agent (B) is reacted with the following modified polypropylene resin (C 5). A method for producing a modified polypropylene resin composition, comprising mixing 0.1 to 30 parts by weight of the reactant with 0 part by weight.

(C 3) Unmodified polypropylene resin with a menoleto flow rate of 0.01 to 100 g / l 0 min and a melting point of 144 to 170 ° C

(C 4) Menoleto flow rate 0.01 to: 100 g / 10 minutes, ¹

³ C-NMR was measured to seek the main Sopenta' de fraction ([mmmm]) is the unmodified polypropylene resin which is a 4 0-90 mole ^_0/0

(C5) Modified polypropylene resin containing 0.001 to 1% by weight of polar base and having an intrinsic viscosity of 0.7 d1 / g or more measured at 135 ° C in tetralin

2 6. The following component (C6) and component (B) are mixed, and the following component (A) is added to the mixture [(B) + (C6)], and the mixture is added to (A) / [(B) + (C 6)] (Weight ratio) A method for producing a modified a-olefin polymer composition, which comprises mixing to give a force S, OZl 00 to 99/1.

(a) The content of a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule: 0.001 to 0.4% by weight. / ₀

(b) Intrinsic viscosity measured in tetralin at 135 ° C: 0.9 to 5.0 d1 / g (c) Weight average molecular weight / number average molecular weight (MwZMn): 3 or less

(d) Molar ratio of the polar group to the polymer chain: 0.1 to 3.0 (B) Silane coupling agent: 0.001 to 0.5 part by weight

(A) α-olefin polymer having 2 to 20 carbon atoms having an intrinsic viscosity of 0.7 to 5.0 d 1 § measured in tetralin at 135 ° C 27. Modified a-olefin polymer melt tension (ΜΤ) and Merutofu the low rate of the composition (M l) is met MT / 7 X (M l) ^10. ^{8> the} one relationship, and 1 3 0. The amount of paraxylene-insoluble components (G value) in C is 1 weight. 26. The method for producing the modified α-olefin polymer composition according to the above item 26, wherein the ratio is not more than / ₀ .

28. The process for producing a modified α-olefin polymer composition according to the above item 26 or 27, wherein the modified α-olefin polymer (C 6) and the silane coupling agent (Β) are melt-mixed.

29. The method for producing a modified α-lefin polymer composition according to the above item 28, wherein the molten mixture [(Β) + (C 6)] and the α-olefin polymer (Α) are melt-mixed.

30. Modified haloolefin polymer (C6) Force The method for producing the modified α-olefin polymer composition according to the above item 26 or 27, which is a modified propylene (co) polymer or a modified 1-butene (co) polymer .

31. The process for producing a modified hypoolefin polymer composition according to the above item 26 or 27, wherein the compound containing an ethylenic double bond and a polar group in the same molecule is maleic anhydride.

3 2. Said silane coupling agent (Β) Force S, (B1) —Modified α-olefin polymer composition according to the above 26 or 27, which is an organic silicon compound represented by the general formula (1) Method of manufacturing a product.

X n S i Ym (OR) ₄ _ _{(n + m)} (1)

[Wherein, X is a substituent containing a functional group capable of reacting with the polar group, and Y is a hydrocarbon. A group, a hydrogen atom or a halogen atom, R represents a hydrocarbon group, 11 represents an integer of 1 to 3, m represents an integer of 0 to 2, and (n + m) = 1 to 3. ]

3 3. The method for producing a modified α-olefin polymer composition according to the above item 32, wherein X in the general formula (1) is a substituent containing an amino group.

It is about. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram showing the compositions of Examples 20 to 35, Comparative Examples 6 to 9, and Reference Examples 1 to 8 and the relationship between ΔI and Δ of the calculated values.

FIG. 2 shows Examples 36 to 44, Comparative Examples 10 to 13, Undenatured Ρ _; 3 is a diagram showing the compositions of Reference Examples 1 to 8 and the relationship between ΜI and ΜΤ of the calculated values. FIG. 3 shows the compositions of Examples 45 to 62, Comparative Examples 14 to: 18 and native Ρ Ρ _ 5 to 8, Reference Examples 1 to 8 and the relationship between 計算 I and の of the calculated values. FIG. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present inventions 1 and 2 will be described in detail.

Examples of the α-olefin polymer having 2 to 20 carbon atoms, which is the component (II) of the present invention 1 and 2, include a high-density polyethylene, a low-density polyethylene, a propylene polymer, a propylene-based copolymer, and a 1-butene polymer. Coalesce, 1-butene copolymer, higher haloolefin polymer having 5 to 20 carbon atoms, and the like. Preferred are a propylene polymer and a 1-butene polymer.

If the carbon number of the raw material monomer of the α-olefin polymer exceeds 20, it is difficult to produce a practical high-molecular-weight polymer, and the content of low-molecular-weight components that adversely affect physical properties (eg, stickiness) increases. There is a problem.

As the molecular weight of the α-olefin polymer, the intrinsic viscosity [] measured in tetralin at 135 ° C. is 0.7 to 5 d 1 / g, preferably 1.0 to 3. 10513

5 d 1 / g, more preferably 1.0 to 2.5 d l / g.

When the intrinsic viscosity [77] is less than 0.7 d 1 / g, mechanical properties such as flexural modulus, flexural strength, and Izod impact strength of the a-olefin polymer compositions of the present inventions 1 and 2 decrease. However, if it exceeds 5 d 1 / g, the moldability will decrease.

Further, the shape of the α-olefin polymer of the present invention 1 is preferably a powder shape or a flake shape.

By using an α-olefin polymer having such a shape, (Β

1) The component organosilicon compound can be easily and highly dispersed in the α-olefin polymer composition.

In particular, a powdery α-olefin polymer having a high surface area is preferred.

As the surface ^{area, 0. 0 1~ 5 m 2 /} g, preferably from 0 · 0 5~ ² m 2 Bruno g.

The particle size of the flake-shaped a-olefin polymer is from 200 to 2000 μm, preferably from 200 to 150 μm.

The average particle size of the powdery haeofin polymer is from 50 to 2000 μπι; preferably from 200 to 150 ^ m.

If the average particle size is less than 50 m, the supply of the haloolefin polymer during melt kneading becomes unstable due to clogging and the like, and if the average particle size exceeds 200 μm, the _α -olefin polymer There is a possibility that the dispersion of the organosilane compound therein cannot be sufficiently performed, and that the supply of the one-year-old refin polymer becomes unstable.

The bulk specific gravity is 0.2 to 0.6 g / cm ³ , and preferably 0.30 to 0.55 g / cm. It is.

When the bulk density is less than 0. 2 g / cm ^3, and decreases the supply amount of the non Orefuin polymer during melt-kneading, it tends to cause a reduction in productivity, when it exceeds 0. 6 g / cm ^3, Although there are no major problems, the production of such a high bulk specific gravity polymer requires special production conditions and increases costs. Leads to.

Α- Orefin polymer of the present invention 1 and 2, when the propylene polymer and 1 one heptene polymer, its Mesopentatsu de fraction [mmmm] is preferably not ⁹ 7 mol% or more.

When [mmmm] is less than 9 7 mole ^_0/0, flexural modulus, physical properties of heat distortion temperature and the like decreases.

Here, the mesopentad fraction [mmmm] refers to the ¹³ C— proposed by A. Zambelli, et al., In “Macromolecules, 6, 9, 25 (1973)”. It means the isotactic fraction in pentad units in a propylene polymer molecule measured by NMR spectrum.

In the case of 1-butene polymer, as in the case of propylene polymer, it means the isotactic fraction in pentad units in 1-butene polymer molecule measured by ¹³ C-NMR spectrum. I do.

A method for determining the assignment of peaks in the measurement of ¹³ C_NMR spectrum is described in “Macromolecules, 8, 6887 (1975)” by A. Zambe (11i) and others. ) ".

The general formula (1) which is the component (B1) of the present inventions 1 and 2

X „S i Y _m (OR) ₄ _ _{(n + m)} (1)

(In the formula, X is a substituent containing a group capable of reacting with the polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n is 1-3, and m is 0-2. And (n + m) = 1 to 3.

In the organic silicon compound represented by the formula, X is preferably at least one substituent selected from substituents including an amino group, a hydroxyl group, an epoxy group and an isocyanate group, and particularly preferably a substituent including an amino group.

R is preferably an alkyl group having 1 to 6 carbon atoms, and (n + m) is 1 to T / JP2003 / 010513

2 is preferred.

Specific examples of the organic silicon compound include, for example, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminobutyritol (methoxyethoxy) silane, 3-aminopropylmethyldiethoxysilane , 3-aminopropino reethoxymethoxysilane, 4-aminobutyltriethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, m-aminophenyltrimethoxysilane, p-aminophenyltrimethoxysilane, 31 (1-aminopropoxy) 1,3,3-dimethyl-1-propionyltrimethoxysilane, methyltris (2-aminoethoxy) silane, 2- (2-aminoethylthioethyl) ethoxymethylsilane, 3- [2 — (2-aminoethylamino) Mouth pill] trimethoxysilane, 3-cyclohexylaminopropyltrimethoxysilane, 3-benzylaminoprobitrimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 3-aminopropinoresi Sopropylethoxysilane, 3-aminopropyldimethylethoxysilane, 3- (N-arylamino) propyltrimethysilane, Ali: luminotrimethylsilane, N-3- (Empty pilloxy-2-hydroxy pill) I 3-Aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, bis [3- (trimethoxysilyl) propyethylenediamine, Ν-methylaminopropyltrimethoxysilane, Ν-phenylaminopropyltriamine Methoxysilane, 31 Methyl_2-aminoethylamino propyl trimethoxysilane hydrochloride, (3-trimethoxysilylpropyl) diethylenetriamine, Ν- (trimethoxysilylpropyl) isothioperonium chloride, Ν- (trimethoxysilinole) Propinolate Ν, Ν, Ν-tree η-butylammo-pam bromide, Ν-trimethoxysilylpropyl monoamine, Ν, Ν-tri η-butylammo Numium chloride, N-trimethoxysilylpropyl mono N, N, N-trimethinoleammonium chloride, 2-aminoaminoethylaminomethylbenzoyloxydimethinolesilane, (aminoethylaminoaminomethyl) Phenethyltrimethoxysilane, N- (2-aminoethyl) -1-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -13-aminopropyltrimethoxysilane, N- (6-aminohexyl) ami Nopropyltrimethoxysilane, 3- (m-aminophenoxy) provided trimethoxysilane, N- (3-metal oxy-2-hydroxypropyl) -1,3-aminopropyltriethoxysilane, N— (3-triethoxysilylpropyl) One 4—hydroxybutylamide, N— (3-triethoxysilylpropyl) dal Conamide, hydroxymethyltriethoxysilane, tri-t-butoxysilanol nonole, bis (2-hydroxyxeti — 3-aminopropylinoletriethoxysilane, Ν— (triethoxysilylpropyl) mono-polyethylene oxide urethane , 3,4-epoxybutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) methylethoxysilane, (3-glycol Sidoxypropyl) methyl dimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 3-isocyanoate propyl triethoxysilane, 3-thiocyanoate propyl Ethoxysilane, Ο— (vinyl mouth xicetil) 一 — (triethoxysilylpropyl) ゥ ethane, ureidopropyltriethoxysilane, dimethoxymethyl-3-piperazinopropyl silane, 3-piperazinopropyl trime Examples include toxicoxysilane and 2- (2-aminoethylthioethyl) triethoxysilane, among which 3-aminoalkyltrialkoxysilanes are preferable, and 3-aminopropyltriethoxysilane is particularly preferable. Masire, The addition amount of the organic silicon compound (B 1) of the present invention 1 is 0.001 to 10 parts by mass, preferably 0.1 to 100 parts by mass of the a-olefin polymer (A). It is 0.5 parts by mass.

If the addition amount is less than 0.01 part by mass, the melt tension of the _α -olefin polymer composition will not be improved, and if it exceeds 1 part by mass, the improvement in the melt tension commensurate with the cost increase will not be observed.

The content of the organic silicon compound of the present invention 2 is 0.001 to 1 part by mass, preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the α-olefin polymer.

If the content is less than 0.001 part by mass, the melt tension of the α-olefin polymer composition will not be improved, and if it is more than 1 part by mass, no improvement in the melt tension corresponding to the cost increase will be observed.

The α-olefin polymer of the component (Α) containing the organic silicon compound of the component (B 1) of the present invention 2 is, for example, an α-olefin polymer of the component (Α) and an organic cage compound of the component (Β1). It can be produced by melt-kneading elemental compounds.

Examples of the melt kneading method include (1) a method of passing a dry mixture of a monoolefin polymer and an organic silicon compound through an extruder, and (2) a method of adding an organic silicon compound to an α-olefin polymer of the extruder. .

The melt-kneading temperature is generally from 170 to 300 ° C, preferably from 180 to 250 ° C. The melt-kneading (residence) time is from 10 seconds to 120 seconds.

At the time of melt-kneading, it is preferable to keep it under an inert gas atmosphere.

In some cases, steam may be added or volatile components may be removed under reduced pressure. As the molding machine, a single screw extruder, a twin screw extruder, or the like is used.

As a twin-screw extruder, 20 mm φ Laboplastomill, 3 5πιηιψ ΤΕΜ (Toshiba Machine twin screw extruder).

Further, it is also possible to add an organic silicon compound to the powder or granules of the olefins discharged from the polymerization vessel and melt-knead them to produce the pellet-like component (A).

Thus, the component (A) can be efficiently produced.

Examples of the olefin polymer modified with a polar group having 2 to 20 carbon atoms of the component (C1) of the present invention 1 and 2 include, for example, high-density polyethylene, low-density polyethylene, propylene polymer, and propylene-based copolymer. And modified polymers of unsaturated carboxylic acids and / or anhydrides thereof, such as 1-butene polymers, 1-butene copolymers and higher haloolefin polymers having 5 to 20 carbon atoms.

As the α-olefin polymer, a propylene polymer and a 1-butene polymer are preferable.

If the carbon number of the raw material monomer of the α-olefin polymer exceeds 20, it becomes difficult to produce a practical high-molecular-weight polymer and adversely affect physical properties (eg, stickiness). The content of low-molecular-weight components increases. Problem arises.

As the molecular weight of the α-olefin polymer modified with a polar group, the intrinsic viscosity [η] measured in tetralin at 135 ° C. is 0.7 d 1 / g or more, preferably 0.7 to 5 d 1 / g, more preferably 0.8 to 3 deciliters Zg.

In the present invention 1, when the intrinsic viscosity [77] is less than 0.7 dl / g, a component effective for expressing the melt tension of the α-one-year-old olefin polymer composition is not efficiently generated. '

If the intrinsic viscosity [] exceeds 5 d 1 / g, miscibility with the component (A) with the _α -olefin polymer tends to be poor, and gel by-products are likely to occur.

In the present invention 2, if the intrinsic viscosity [] is less than 0.7 dl / g, a component effective for developing the melt tension of the α-olefin polymer composition is efficiently generated. If it exceeds 5 dl / g, miscibility with the a-olefin polymer of the component (A) containing the organic silicon compound of the component (B 1) tends to be poor, and the by-product of the gel tends to occur.

Here, the effective components for the development of the melt tension include the high molecular weight of α-olefin formed by the reaction of the polar group-modified monoolefin polymer with the organic silicon compound and the water crosslinking reaction which is considered to occur subsequently. Polymers and haloolefin polymers having a long-chain branched or star-shaped structure are conceivable.

The content of the polar group derived from the compound containing the ethylenic double bond and the polar group of the present invention 1 and 2 in the same molecule is 0.001 to 1% by mass, preferably 0.01% by mass. ~ 0.5 mass. / ₀ .

If the content is less than 0.001% by mass, the above-mentioned melt-tension-generating component is generated by the reaction with the organic silicon compound or the reaction with the organic silicon compound contained in the component (II). If the content exceeds 1% by mass, a three-dimensional network structure (gel component) tends to be produced as a by-product in addition to the melt tension developing component due to the reaction with the organic silicon compound.

The amount of the a-olefin polymer modified with a polar group is 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the α-olefin polymer. It is.

If the amount is less than 0.1 part by mass, the amount of the melt tension generating component is reduced, and it is difficult to achieve a sufficient effect. The amount of the three-dimensional network structure, which is considered to be a by-product of the process, increases, and molding defects, appearance defects, etc. tend to occur. In addition, the proportion of the high-refined polymer modified with the polar group in the composition is increased, and the cost is increased. The α-olefin polymer modified with the polar group of the component (C 1) according to the first and second aspects of the present invention preferably further satisfies the following (1) to (3).

( ¹ ) The molar ratio of the polar group content to the chain of the polyolefin polymer ( ¹ value) force ^s , 0. 5: 1.0 ~ 3.0: 1.0

If the value is less than .5, the melt tension cannot be sufficiently improved, and if it exceeds 3.0, the generation of a three-dimensional network structure increases, which may cause problems such as poor molding and poor appearance.

Here, 3 ¹ value is the number average molecular weight Mn [gel permeation chromatography to Nkuroma chromatograph (GP C) Method] chain number of the calculated α- Orefuin polymer from (mol / g) and the polar group content (mol / g) means that a compound containing one molecule of an ethylenic double bond and a polar group in one molecule per chain of _α -olefin polymer is added when this value is 1. Become.

If MwZMn exceeds 2.5, the homogeneity of the molecular weight of the polymer modified with a polar group is reduced (components having different molecular weights are mixed), and the melt tension generated by the reaction with the organic silicon compound is reduced. The improving component also becomes non-uniform, making it difficult to achieve a stable melt tension improving effect.

(3) 0.5 mass of components with Mw of 10,000 or less. /. Less than

If it exceeds 0.5% by mass, the amount of low molecular weight components in the composition increases, which causes surface roughness and stickiness.

Examples of the polar group derived from the compound containing an ethylenic double bond and a polar group in the same molecule used for modifying the -olefin polymer of the present invention 1 and 2 include a carboxylic acid group, a carboxylic anhydride group, and a carboxylic acid. Ester group, carboxylic acid halide group, carboxylic acid amide group, carboxylic acid imide group, carboxylic acid salt group, sulfonic acid group, sulfonic acid ester group, sulfonic acid chloride group, sulfonic acid amide group, sulfonic acid Examples include compounds containing a polar group such as a base, an epoxy group, an amino group, an oxazoline group, and the like.

Specific examples of these compounds include carboxylic acid anhydrides, esters, halides, amides, imides and salts. 3 Of these, unsaturated dicarboxylic acids or their anhydrides are preferred.

Specific examples of unsaturated mono- or dicarboxylic acids include acrylic acid, methacrylic acid, maleic acid, endo-bicyclo [2.2.1] 1-heptene-1,2,3-dicarboxylic acid (endic acid), fumaric acid , Tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid and the like.

Specific examples of unsaturated carboxylic acid derivatives include maleenyl chloride, maleimide, maleic anhydride, endic anhydride, methyl acrylate, acrylic amide, methyl methacrylate, glycidyl methacrylate, methacrylic amide, and anhydride. Examples include citraconic acid, itaconic anhydride, nadic anhydride, monomethyl maleate, dimethyl maleate, monomethyl fumarate, dimethyl fumarate and the like.

Among these unsaturated carboxylic acids or derivatives thereof, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred, and maleic anhydride is more preferred.

These may be used alone or in combination of two or more.

The amount of the compound containing an ethylenic double bond and a polar group in the same molecule is 0.1 to 10 parts by mass, preferably 0.2 to 100 parts by mass of the α-olefin polymer. ~ 2 parts by weight is good.

If the amount of the compound used is less than 0.1 part by mass, the addition amount of the compound containing an ethylenic double bond and a polar group in the same molecule is small, and the ¹ value may be less than 0.5. is there.

If the amount exceeds 10 parts by mass, a compound containing an unreacted ethylenic double bond and a polar group in the same molecule that causes odor, for example, unsaturated rubonic acid and / or anhydride thereof will be added. For the modification of the a-olefin polymer of the present invention 1 or 2 with a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule, a radical initiator is usually used.

Examples of the radical initiators of the present invention 1 and 2 include butylperoxide, a, α-bis (t-butylpentanoloxy) diisopropinolebenzene, benzoinolenolenoxide, dichlorenbenzoenolenolenoxide, and dicuminolate. Noleside, t-butyl peracetate, t-butyl pergetyl acetate, t-butyl phenol oleate sobutyrate, t-butyl butyl phenol, sec-octate, t-butyl phenol acrylate, cumyl lipenolate, t-butyl Butyl perbenzoate, t-butyltin perphenyl acetate, t-butyl cumyl phenol, di-t-butyl phenol, 1,1-g tert-butyl peroxy 1, 3, 3, 5-trimethinolecyclohexane, 1, 1 -G-t-tinoloxy oxycyclohexane, 2,2-g- t-butynoleperoxy) butane, lauroyl beloxide, 2,5-dimethyl-2,5-di (peroxybenate) hexine-1,3,3-bis (t-butynolenoleoxyisopropyl) Benzene, 1,4-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-1,3,2,5-dimethinole-1,5 —Di (t-butylperoxy) hexane, 2,4,4-Trimethinolepentinole 2 —Noydrodolenoleoxide, Diisopropionolebenzene hydroxide norexoxide, Cumenodiol droneoloxide, 4,4 -G-t-butylinoleoxyvaleric acid 1-n-butyl ester, G-t-butylperoxyhexahydrophtalate, G-t-butylinolenoxellare DOO, t one Buchiruperuokishi one 3, 3, 5-preparative Rimechinore to Kisoeto, t-heptyl Bae Honoré OXY isopropylidene Honoré Kabi sulfonates, illusion Nikkuashi' Doperuokishido and Bininoretorisu (t one-butyl per ingenuity Shi) silane. Preferred radical initiators include 2,5-dimethyl-1,2,5-di (t-butynolenoleoxy) hexine-13, dicaminolenoreoxide, hi, hibis (t-butylperoxy) diisopropylbenzene, 5-dimethinolee 2,5-di (t-butylperoxy) hexane;

The amount of the radical initiator to be used is 0.01 to 1 part by mass, preferably 0.05 to 0.25 part by mass, per 100 parts by mass of the olefin polymer.

When the amount is less than 0.01 part by mass, the amount of the polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule is small, and the α-olefin polymer modified with the polar group is used. Weight average molecular weight (Mw) / number average molecular weight (Mn) may exceed 2.5.

If it exceeds 1 part by mass, the intrinsic viscosity [] of the α-olefin polymer modified with a polar group becomes less than 0.7 d 1 Zg, and the amount of components having a molecular weight of 10,000 or less exceeds ◦ · 5 mass%. May be.

The method for producing the α-olefin polymer modified with the polar group of the present invention 1 and 2 includes, for example, α; -olefin polymer, a radical initiator, unsaturated carboxylic acid and Ζ or anhydride thereof. A method of blending and melt-kneading is exemplified. The α-olefin polymer modified with the polar group of the present invention 1 contains irganox 101 0 [tetrakis (methylene-3- (3,, 5 ′)-diene) as long as the effect of the present invention is not impaired. t-Ptinolate 1 '-(hydroxyphenyl) propionate) methane], irgafos 16 8 [tris (2,4-di-t-butyl: nyl) phosphite] and antioxidants as described below Conventional additives such as neutralizing agents such as calcium stearate and the like can be further added.

The melting and kneading temperature of the present inventions 1 and 2 is generally 170 to 300 ° C, preferably 180 to 250 ° C. 3 Melt kneading (residence) time is 10 seconds to 120 seconds.

Examples of the twin-screw extruder include a 20 mm φ laboplast mill, 35πιπιφΤΕΜ (Toshiba Machine twin-screw extruder) and the like.

It is preferred that the α-olefin polymer modified with the polar group melt-kneaded is then subjected to the following treatment (1), treatment (2), or treatment (2). By this treatment, the content of a polar group derived from a compound containing an unreacted ethylenic double bond and a polar group in the same molecule can be reduced.

(1) Contact treatment in a mixed solvent of dialkynole ketone such as acetone and methylethyl ketone and aliphatic or alicyclic hydrocarbon such as hexane, heptane and decalin.

(2) Contact treatment in a solvent such as methanol or other alkyl ketone, or acetone or methyl ketone such as ethynoleethynole ketone or a mixed solvent of alcohol and dialkyl ketone.

The one-year-old olefin polymer composition of the present invention 1 comprises 100 parts by mass of the monoolefin polymer of the component (Α), 0.001 to 1 part by mass of the organosilicon compound of the component (Β1), and (C 1) Hyolephine polymer modified with the polar group of the component 0: It can be obtained by contacting! To 30 parts by mass.

Further, it is preferable that the α-age olefin polymer composition of the present invention 1 further satisfies the following items (1) to (3).

① The silicon compound derived from the organic silicon compound of (Β 1) component is 0.0 0.01 to :! Mass%

(2) Melt tension (ΜΤ) and melt flow rate (M l) are MT / 7 X (MI). · Satisfies the relationship ⁸ > 1. Here, the following relational expression holds between MTc and melt tension (MT [unit: g]) obtained from the melt flow rate (Ml [unit: g / 10 minutes]).

MT c = 7 X (Ml) "° ⁸ (3)

MT / MT c> 1 (4)

In addition, MT c [unit: g] = 7 X (MI) _. · ⁸ means from equation (3) that the melt tension is 7 times the melt tension of the olefin polymer.

Therefore, according to equation (4), the MT value means the melt tension level at which various physical properties due to the improvement of the melt tension are sufficiently exhibited, and the moldability, mainly the drawdown property of blow molding and thermoforming, and the pinch-off property and the like. It also serves as an index for high-speed moldability during film formation.

(3) Less than 1% by mass of insoluble components in paraxylene at 30 ° C

The α-olefin polymer composition of the present invention 2 comprises 100 parts by mass of a component (II) of a haloolefin polymer containing an organic silicon compound as a component (B 1) and 100 parts by mass of a component (C 1). It is obtained by mixing (reacting) 0.1 to 30 parts by mass of a olefin polymer modified with a polar group, and has a melt tension (ΜΤ), a melt flow rate (Ml) force, MT / 7 x ( MI)-° · ⁸ > 1. ,

In the α-olefin polymer composition of the present invention 2, the amount of the component insoluble in paraxylene at 130 ° C. is preferably less than 1% by mass.

As an index of the gel component amount in the present inventions 1 and 2, the component amount (G value) insoluble in paraxylene at 130 ° C was adopted.

When the amount of this component is 1% by mass or more, the appearance of the molded article may be deteriorated. Methods for measuring the amount of components insoluble in paraxylene at 130 ° C include the methods described below.

Methods for obtaining the a-olefin polymer compositions of the present inventions 1 and 2 include a melt-kneading method, a reaction method in a solution, and the like. And a melt-kneading method.

The conditions for the melt-kneading method include, for example, the following conditions.

The melt-kneading temperature is from 80 to 350 ° C, preferably from 130 to 250 ° C.

The melting and kneading time is 1 second to 6 hours, preferably 30 seconds to 3 hours.

As the molding machine, a single screw extruder, a twin screw extruder, or the like is used.

Examples of the twin-screw extruder include a 20 mm φ laboratory blast mill, 35 mm <i> TEM (Toshiba Machine twin-screw extruder) and the like.

In the present invention 1, in the case of the melt-kneading method, it is preferable that the organic silicon compound as the component (B 1) is sufficiently dispersed in advance in the α-olefin polymer as the component (A).

The α-olefin polymer composition obtained by dispersing the component (B 1) into the component (II) under the temperature condition equal to or lower than the melting point of the component (II) and then reacting the component (C 1) is more preferable.

In the present invention 2, in the case of the melt-kneading method, an α-olefin polymer of the component (Α) containing the organic silicon compound of the component (B1) is produced in the first half of the extruder, and in the latter half thereof. It is also possible to knead the o-olefin polymer modified with the polar group of the component (C1).

Various antioxidants can be added to the α-olefin polymer compositions of the present inventions 1 and 2 as long as the effects of the present invention are not impaired. Examples of the antioxidants of the present inventions 1 and 2 include phenol-based, zeolite-based, and phosphorus-based antioxidants.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-1-ρ-talesol, butylated hydroxy-sonoré, 2,6-di-tert-butynole 4-ethylphenol, and stearyl-1β- (3,5-di- t-puchiru 4-h 10513 Monophenolic antioxidants, such as droxyphenyl) propionate, 2,2'-methylenebis (4-methynole-6-t-p-tinolephenenole), 2,2'-methylenebis (4-ethynole-one 6-t-ptinolef) Enolole), 4,4, -thiobis (3-methyl-6-t-butynolephenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1,1] -Dimethyl-2-[[β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] bisphenol such as pentadecane Antioxidants, 1,1,3-tris (2-methyl-14-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3 , 5—Gee T Nole) Benzene, tetrakis [methylene 1-3 (3,, 5, zyg -t-butinole 1, 4, -hydroxyphenyl) propionate] methane, bis [3,3,1bis-1 (4,-hydroxy) _ 3 '— t-butyl phenyl) butyric acid] glycolone ester, 1,3,5-tris (3,, 5'-di_t-butyl-4'-hydroxybenzyl) — sec-triazine-2 Polymer phenolic antioxidants such as 4,61- (1H, 3H, 5H) trione and tocopherol.

Examples of the zeotype antioxidants include dilauryl-1,3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-1,3,3′-thiodipropionate, and the like.

Phosphorus-based antioxidants include triphenyl phosphite, diphenylisodesinolephosphite, phenyleisoisodecinolephosphite, 4,4'-butylidene-bis (3-methyl-6-t- Butylpyruditridecyl) phosphite, cyclic neopentanetetraylbis (octadecyl phosphite), tris (noylphenyl) phosphite, tris (mono) 3 or dinoyurphenyl) phosphite, disodecylpentaerythritol diphosphite, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -19,10-dihydro-19-oxa 1 10—Phosphaphenanthrene 1 10—Oxide, 10 0—Dexyloxy 9, 10 0—Dihydro 9 9 Oxa 1 10—Phosphaphenanthrene, Tris (2,4—Di 1 t Butyl phosphite, cyclic neopentane tolyl bis (2,4-g-butynolephenyl) phosphite, cyclic neopentante tolyl bis (2,6-g-t-4-methylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl).

The compounding amount of the antioxidant is preferably in the range of 100 to 100,000 mass ppm with respect to the total amount of the components (A), (Bl) and (C1).

Preferably, it is 1000 to 5000 mass ppm.

If the amount is less than 100 mass parts per million, the MI and MT may not be stable. Even if the amount exceeds 10,000 mass parts per million, an effect commensurate with cost cannot be obtained.

As the antioxidant, it is preferable to mix both a phosphorus antioxidant and a phenolic antioxidant.

Conventional additives such as a neutralizing agent such as calcium stearate can be further added.

Next, each component of the composition of the present invention 3 will be described.

The polypropylene resin (C 2) is a compound containing a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule (hereinafter, referred to as a modifier). the amount ^_0/0, preferably, 2X1 0- ⁵ ~0. 1 ⁵ wt ^_0/0, more preferably, not particularly limited as long as it is 5x1 0- ⁵ '0 0 weight ^_0/0 containing polypropylene resin. The content of the polar base is 1 xl 0 - If less than ⁶ wt ^_0/0, Shirankappuri down the reaction does not proceed too much and grayed agent (B), the melt tension of the composition is difficult to increase. On the other hand, if the content exceeds 0.25% by weight, the composition gels, and conversely, the melt tension of the composition decreases, and the heat resistance and mechanical properties decrease.

The content of the polar group can be determined by forming a polypropylene resin (C 2) into a film and measuring the Fourier transform infrared absorption spectrum using the film.

The polypropylene resin is a propylene homopolymer, or a random copolymer, a block copolymer, a graft copolymer, or a mixture thereof of propylene and a one-year-old olefin (eg, ethylene, 1-butene, etc.).

Of these, propylene homopolymer is preferred.

The polar group of the polypropylene resin (C 2) may be a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule used for modifying the monoolefin polymer of the present inventions 1 and 2. The same can be mentioned.

The modifier used in the present invention 3 is not particularly limited, and examples thereof include the same modifiers as those of the present inventions 1 and 2.

Such a polypropylene resin (C 2) can be produced, for example, by melt-kneading a polar group-free polypropylene resin, a radical initiator, and the above-mentioned modifier.

At this time, the conditions such as the blending conditions and the reaction conditions can be appropriately adjusted so that the ratio of the polar group is lxlO ¹⁶ to 0.25% by weight.

Specific examples of the radical initiator of the present invention 3 include the same radical initiators as those of the present inventions 1 and 2.

In the present invention, as the polypropylene resin (C 2), a polypropylene resin not containing a polar base (an unmodified polypropylene resin) and a polar base are used. A mixture with a containing polypropylene resin (modified polypropylene resin) can also be used.

At this time, the ratio of the polar group in the modified polypropylene resin and the mixing ratio of these are appropriately determined so that the ratio of the polar group contained in the mixture finally becomes 1 × 10 ¹⁶ to 0.25% by weight. Can be adjusted.

When such a mixture is used as the polypropylene resin (C2), preferably, the following (C3) and (C5), or the mixture of the following (C4) and (C5) is used.

(C3) The melt flow rate is preferably from 0.01 to: 100 g / l 0 min, more preferably from 0.1 to 50 g / 10 min, even more preferably from 1 to 20 g / l. The melting point is preferably between 145 and 170. C, more preferably an unmodified polypropylene resin at 150-170 ° C

(C4) The methanol flow rate is preferably from 0.01 to: 100 g / 10 minutes, more preferably from 0.1 to 50 gZ10 minutes, and still more preferably from 1 to 20 g. / 1 0 minutes, ¹³ C-NMR was measured to seek the main Sopenta' de fraction ([mmmm]) force S, preferably, 40-9 0 mol%, more preferably, 60-8 0 mol ⁰ / ₀ unmodified polypropylene resin

The content of (C 5) polarity base is preferably 0.00 1-1 wt%, good Ri preferably 0. 0 1 to 0.5 wt ^{_{0/0, 1 3 5 °}} C, Tetorari Intrinsic viscosity measured in solution is preferably 0.7 dl, g or more, more preferably 0.7 to 5.0 dl / g, and still more preferably 0.8 to 3.0 dl / g. Modified polypropylene resin

The unmodified polypropylene resin (C4) used here is an unmodified soft polypropylene resin.

When such a mixture is used, the reaction between the modified polypropylene resin (C5) and the silane coupling agent (B) (the formation of a melt tension developing component) 2003/010513 reaction), and will be performed in the unmodified polypropylene resin (C3) or (C4).

As a result, the generation of gel which contributes to yarn breakage during the measurement of melt tension can be suppressed.

Further, a component effective for improving the melt tension can be uniformly distributed in the unmodified resin.

If the melt flow ratio of the unmodified polypropylene resins (C3) and (C4) is less than 0.01 g / 10 minutes, the moldability of the resin composition may be reduced.

On the other hand, if it exceeds 100 g / 10 minutes, the effect of improving workability by improving the melt tension may be reduced.

If the melting point is lower than 144 ° C, the heat resistance of the polypropylene resin may be impaired.

When Mesopentatsu de fraction is less than 4 0 mol ^_0/0, there is a possibility that the strength and heat resistance of the soft polypropylene榭fat is impaired.

On the other hand, when it exceeds 90 mol ^_0/0, there is a possibility that the flexibility of the soft polypropylene resin cracking a loss.

In the modified polypropylene resin (C5), the content of the polar group was 0.001% by weight. If the _{ratio is} less than / _0, there is a possibility that the effect of improving the melt tension is not so much exhibited.

On the other hand, 1 exceeds weight ^_0/0, past react only with a silane coupling agent (B) proceeds and gelation, there is a risk that melt tension decreases.

When the intrinsic viscosity is less than 0.7 d 1 / g, there is a possibility that a component having a property effective for the development of melt tension may not be efficiently generated, or that the melt tension of the obtained resin composition may lower the melt tension. There is.

On the other hand, if it exceeds 5.0 d 1 / g, the unmodified polypropylene resin (C PC orchid 003 fine 513

3) Poor mixing with (C 4) may cause gel by-products to occur easily.

The unmodified polypropylene resin (C5) has a melting enthalpy measured by a differential scanning calorimeter (DSC) of preferably lOOJZg or less, more preferably 90JZg or less. Above 100 jZg, flexibility may be impaired.

Also, the mesopentad fraction ([mmm m] and [rrrr]) force determined by measuring ¹³ C-NMR, preferably ([rrrr] Z 1— [mmm m]) ≥ 20% Fulfill.

This value is more preferably 20 to 30%.

If it is less than 20%, elastic recovery may be impaired.

The pentad fractions [mm mm] and [rrrr] are as shown in A. Zambelli 1 S, Macromolecules, Vol. 6, 9 proposed in 2 page 5 (1 9 7 3), respectively taste Thanked Mesopenta' de fraction and racemic pair Nta' de fraction in Penta' degrees polypropylene molecular chain as determined from ^{1 3} C one NMR spectrum .

A method for determining the assignment of peaks in the ¹³ C-NMR spectrum is described by A. Zambelli (A. Zambeli 11 i), et al., In Macromolecules, Vol. I went to the attribution proposed on page 87 (1975).

Modified polypropylene-based resin (C 5), the molar ratio of the polar base and polymer chains (i3 ² value) force, preferably, 0.5 a 5 to 3, more preferably, is at 0 · 8 to 2. ◦ .

If the molar ratio is less than 0.5, the polar base may be too small and the melting tension of the resin composition may not be improved. On the other hand, if it exceeds 2, the molecular chain may be cut too much and the intrinsic viscosity may decrease.

Note that / 3 ^binary, gel permeation chromatography Chillon chromatography (GP C) method with measurement boss was a number-average molecular weight (Mn) of the polymer chain number of the calculated modified polypropylene-based resin (C 5) and a (mol / g) It means the ratio to the polar group (mol Zg). If this value is 1, one molecule of the modifying agent is added per one polymer chain.

The amount of the modified polypropylene resin (C5) is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight of the unmodified polypropylene resin (C3) or (C4). , 1 to 20 parts by weight.

If the amount is less than 0.1 part by weight, the polar base in the polypropylene resin (C 3) may be too small.

On the other hand, if it exceeds 30 parts by weight, the polar base may become too large. Such unmodified polypropylene resins (C 3) and (C 4) can be appropriately polymerized by a known method.

The modified polypropylene resin (C5) can be produced by the same method as described above.

The silane coupling agent (B) of the present invention 3 is not particularly limited, but is preferably (B1) an organic silicon compound represented by the general formula (1).

X „S i Y _m (OR) ₄ — _{(n + m} ) (1)

[Wherein, X is a substituent containing a functional group capable of reacting with the polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, 11 is 1-3, m is 0- 2 represents an integer, and (n + m) = 1 to 3. ]

The details of the organosilicon compound represented by the general formula (1) are as described in the present inventions 1 and 2.

The blending amount of the silane coupling agent (B) is as follows. 2) 0.001 to 1 part by weight, preferably 0.1 to 0.5 part by weight, per 100 parts by weight.

If the amount is less than 0.001 part by weight, the effect of improving the melt tension is reduced.

On the other hand, if it exceeds 1 part by weight, the effect of improving the melt tension is not exhibited even if the amount is increased, so that the silane coupling agent (B) is not effectively used. It also increases the manufacturing cost.

Furthermore, it may gel, and conversely, the melt tension may decrease.

Examples of the antioxidant (D) of the present invention 3 include tris (2,4-di-t-butylphenyl) phosphite (Circa succinoreti ケ ilgafos 1668 (trade name) manufactured by Chemika Norez). (2,6-di-t-butyl-4-methino-refininole) Pentaerythri-tono-resin phosphite (made by Adeki-A-Igas Co., Ltd., PEP-36 (trade name)), 4,4,1-biphenyl phosphine Phosphorus antioxidants such as acid tetrakis (2,4-di-tert-butylphenyl) (manufactured by Clearant Japan, S ande Stab P—E.PQ (trade name)) and tetrakis (methylene _ 3 -— (3'5, 1-t, 1-hydroxyl-hydroxy-2-propionate) Propionate) Methane (manufactured by Ciba-Susio-Noretti Chemicals, Inc., Irganox 101 (trade name)), Tetrakis [methylene One 3— (3,5'-di-t-butyl-1-4'-hydroxyphenyl)] propionate (made by ADEKI ARGAS, MARK AO 60 (trade name)), n-otatadecyl-3 (4,4 Phenolic antioxidants such as hydroxy-3,5, di-t-butylphenol and propionate (manufactured by Chinoku Specialty Chemicals, Irganox 1076 (trade name)).

Other examples include the phenolic antioxidants and the phosphorus antioxidants of the present inventions 1 and 2. Of these, Irganox 110 and Irgafos 168 are preferred.

The phosphorus-based and phenol-based antioxidants may be used alone or in combination of two or more.

Further, these antioxidants may be used in combination.

The amount of the antioxidant (D) to be blended is 0.1 to 0.5 part by weight, preferably 0.1 to 0.5 part by weight, per 100 parts by weight of the polypropylene resin (C 2). .

If the amount is less than 0.05 part by weight, quality may be reduced during processing and storage of the polypropylene resin.

On the other hand, if it exceeds 1 part by weight, the cost may increase.

In the modified polypropylene resin composition of the third invention, the melt tension (MT) and the melt flow ratio (Ml) satisfy the relationship of MT / 7 X (Ml) "° · ⁸ > 1.

This ratio is preferably a value greater than 2.

A composition satisfying this relationship is superior to a conventional polypropylene-based resin in that it exhibits high fluidity while maintaining a high melt tension.

On the other hand, a composition that does not satisfy this relationship has insufficient melt tension, making it difficult to use in large blow molding, foam molding, and other applications and molding methods that are difficult to apply if the drawdown is too large. .

This relationship is based on the fact that the component generated by the reaction between the modified polypropylene resin (C4) and the silane coupling agent (Β) contributes to the improvement of ΜΤ (structure having a high molecular weight and a branched structure). It is established when it becomes.

That is, when the molecular weight of the modified polypropylene resin (C 4) is extremely small (for example, [77] is 0.19), the relationship of the formula can be satisfied because the molecular weight of the branched structure formed is low. No enhancement component is formed. Further, when the polarity base Z polymer chains of the modified polypropylene resin (C 4) (] 3 ² value) is significantly higher (e.g., but 1 2), the three-dimensional network structure does not stop in the formation of branched structures It is believed that the reaction proceeds until formation. The network structure thus formed is merely a gel component, and does not work as an improving component.

Another factor that holds the relationship of the equation is that ΜΤthe improving component is uniformly dispersed in the resin.

For this purpose, it is important that the modified polypropylene resin (C4) be uniformly dispersed (sufficiently compatible) in the unmodified polypropylene resin (C2, C3).

That is, when the molecular weight of the modified polypropylene resin (C 4) is significantly different from the molecular weight of the unmodified polypropylene resin (C 2, C 3) or when the polarity of the modified polypropylene resin (C 4) is extremely high. (e.g., if the amount of the acid is 4 by weight. / ₀ and significantly higher), the phase for solubility is significantly decreased, uniform dispersion of the in ΜΤ improve Ingredient unmodified polypropylene resin (C 2, C 3) Is obstructed, and the relation of the expression cannot be satisfied.

In other words, (1) by selecting a modified polypropylene resin (C4) that is effective for forming a structure that can contribute to improvement, and (2) by selecting manufacturing conditions that allow the generated (4) improving component to be uniformly dispersed in the resin. , ΜΤ value can be adjusted freely.

By such adjustment of 高, a high quality product that satisfies the relationship of the expression can be obtained.

The modified polypropylene resin composition of the present invention 3 has a paraxylene-insoluble component amount (G value) at 130 ° C. of 1% by weight or less.

It is preferably at most 0.7% by weight, particularly preferably at most 0.5% by weight. G value is the amount of gelled component with ultra-high molecular weight, and G value is 1 weight. /. If it exceeds, the appearance may be poor when the composition is molded.

G value 1 weight ⁰ /. If it exceeds, reduce Blend amount and the amount of acid-modified polypropylene (C 4), reducing the amount of the silane coupling agent (B), also of the modified polypropylene (C 4); 8 ^binary By reducing the value, the G value can be reduced to 1% by weight or less.

The composition of the present invention 3 may contain, if necessary, a nucleating agent, an antioxidant, an ultraviolet absorber, an external lubricant, a plasticizer, an antistatic agent, a coloring agent, a flame retardant, a flame retardant auxiliary, and other additives. Alternatively, a thermoplastic resin or the like can be appropriately compounded.

Examples of the nucleating agent include aluminum di (pt-butylbutylate) and other metal salts of carboxylic acids, methylenebis (2,4-di-t-butylphenol) acid phosphate sodium and others Metal salts of phosphoric acid, talc, phthalocyanine derivatives and the like.

Examples of the plasticizer include polyethylene glycol, polyamide oligomer, ethylene bisstearamide, estenolate phthalonate, polystyrene oligomer, polyethylene wax, mineralolae inole, and silicone oil.

Examples of the flame retardant include brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether.

Examples of the flame retardant aid include antimony trioxide and other antimony compounds.

These additives and thermoplastic resins may be used alone or in a combination of two or more.

Next, a method for producing the composition of the present invention 3 will be described.

The composition of the present invention can be produced by mixing the following (C 2) and (B) or the following (C 2), (B) and (D). (C 2) 1 × 10 ⁶ to 0.25 weight of a polar group derived from a compound containing an ethylenic double bond and a polar group in the same molecule. / ₀ including polypropylene resin: 100 parts by weight

(B) Silane coupling agent: 0.01 to 1 part by weight

(D) Phosphorus-based and Z- or phenol-based antioxidants: 0.05 to 1 part by weight. Suitable amounts of each component are as described above.

Here, as a method of mixing the components, a melt kneading method, a solution mixing method, and the like can be cited, but the melt kneading method is preferable in consideration of economic efficiency.

When the melt-kneading method is used, it is preferable to disperse the silane coupling agent (B) in the polypropylene resin (C 2) in advance. The mixing of the components is preferably performed at 80 to 350 ° C, more preferably 130 to 250 ° C, preferably for 1 second to 6 hours, more preferably 30 seconds to 3 hours.

The polypropylene resin (C2) can be produced by mixing the following (C2) and (C4) or the following (C4) and (C5).

(C 2) Melt flow rate is 0.0 1 ~ :! OO gZl O content, unmodified polypropylene resin having a melting point of 145 to 170 ° C: 100 parts by weight (C 3) Menoleto flow rate from 0.01 to: 100 g / 1 0 minutes, ¹ ³ C-NMR was measured to seek the main Sopentaddo fraction ([mmmm]) is 4 0 90 mol% unmodified polypropylene resin: 1 0 0 parts by weight

(C4) a modified polypropylene resin containing 0.001-1% by weight of the polar group and having an intrinsic viscosity of 0.7 d 1 / g or more measured at 135 ° C. in tetralin; : 0.1 to 30 parts by weight

The composition of the present invention 3 is preferably produced by the following method.

Silane coupling agent (B) 100 to 100,000 ppm, preferably 100 to 500 ppm, phosphorus-based and phenol- or phenol-based antioxidants (D) Force S500-: 100,000 ppm, preferably 100-500 ppm, as included, silane coupling agent (B), phosphorus-based and / or phenol Mix antioxidant (D) and polypropylene resin (C 2) or (C 3).

Thereafter, 0.1 to 30 parts by weight of the modified polypropylene resin (C4) is mixed with 100 parts by weight of the mixture.

Alternatively, a phosphorus-based and / or phenol-based antioxidant (D) is contained so that the phosphorus-based and / or phenol-based antioxidant (D) is contained in an amount of 500 to 100,000 ppm, preferably 1,000 to 5,000 ppm. D) is mixed with a polypropylene resin (C 2) or (C 3).

On the other hand, the silane coupling agent (B) is reacted with the modified polypropylene resin (C4).

Thereafter, 0.1 to 30 parts by weight of the reactant is mixed with 100 parts by weight of the mixture.

Since the composition of the present invention 3 has a high melt tension, it is possible to greatly improve the moldability of the polypropylene resin.

The composition of the present invention can be molded by sheet molding, film molding, thermoforming, foam molding, blow molding, or other molding methods. This is effective when performing professional molding or foam sheet molding, which was difficult to mold.

Such a composition of the present invention is very versatile because it can be easily produced with existing production equipment.

In addition, the need for relatively expensive silane compounds is reduced, which is economical in terms of manufacturing costs.

The molded article of the composition of the present invention can be used for various general-purpose trays, interior materials for automobiles, and the like. Hereinafter, a method for producing the modified o-olefin polymer composition of the present invention 4 will be described.

In the production method of the present invention 4, 100 parts by weight of a modified α-olefin polymer having 2 to 20 carbon atoms (C 6), and 0.0 ◦ 1 to 0.5 parts by weight of a silane coupling agent (Β), Preferably, 0.01 to 0.05 part by weight is mixed, and the mixture [(Β) + (C 6)] is mixed with an _α -olefin polymer having 2 to 20 carbon atoms (Α). Are mixed so that (A) Ζ [(Β) + (C 6)] (weight ratio), 0 to 100 to 99/1, preferably 0 to 100 to 95/5 .

When the amount of the silane coupling agent (Β) is less than 0.001 part by weight, the composition does not exhibit a desired melt tension.

On the other hand, when the amount exceeds 0.5 parts by weight, the silane coupling agent (Β) is not effectively used, and the production cost is increased.

(Α) / [(Β) + (C 6)] 1 If the ratio is outside the above range, the composition will not exhibit the desired melt tension.

In the production method of the present invention, the mixing method of each component is not particularly limited, and includes, for example, a melt mixing method and a solution mixing method. However, the melt mixing method is preferable in view of economy.

Therefore, in the present invention, the modified a-olefin polymer (C 6) and the silane coupling agent (B) are preferably melt-mixed.

Preferably, the modified monoolefin polymer (C 6) and the silane coupling agent (B) are melt-mixed, and the melt mixture [(B) + (C 6)] and _α -olefin polymer ( Α) is melt-mixed.

The mixing temperature of the modified hypoolefin polymer (C 6) and the silane coupling agent IJ (Β) is preferably 160 to 300 ° C., more preferably 200 to 250 ° C., and the mixing time Is preferably 1 second to 10 minutes, more preferably 30 seconds to 4 minutes. 03010513

If the temperature is lower than 160 ° C or less than 1 second, these reactions may not be completed.

On the other hand, when the temperature exceeds 300 ° C. or 10 minutes, the deterioration of the modified monoolefin polymer (C 6) and the gelation of the mixture [(B) + (C 6)] tend to progress. The mixing conditions of the mixture [(B) + (C 6)] and the α-olefin polymer (Α) are not particularly limited, but preferably the same temperature and time as described above.

Next, each component used in the production method of the present invention 4 will be described.

The modified α-olefin polymer (C 6) is an α-olefin polymer having 2 to 20 carbon atoms modified by a compound containing an ethylenic double bond and a polar group in the same molecule (hereinafter referred to as a “modifier”). It is united.

Modified α- Orefuin polymer (C 6) is containing chromatic of the polar base from denaturant, 0.0 0 1 to 0.4 wt ^_0/0, preferably 0.0 1 to 0.4 weight ^_0/0, more preferably 0.0 3 to 0.3 wt%.

When the content of the polar group is less than 0.001% by weight, the composition does not exhibit a desired melting tension.

On the other hand, if it exceeds 0.4% by weight, the composition gels and the G value is 1% by weight. / ₀ will be exceeded.

The content of the polar group can be determined by forming a modified α-olefin polymer (C 6) into a film and measuring the Fourier transform infrared absorption spectrum using the film.

Examples of the polar group of the modified _α -olefin polymer (C 6) of the present invention 4 include the same polar groups as those of the present invention 1 and 2.

The modifier used in the present invention 4 is not particularly limited, and examples thereof include the same modifiers as those used in the present invention 1 and 2.

The modified _α- olefin polymer (C 6) of the present invention 4 was prepared at 135 ° C. Intrinsic viscosity ([77]) measured in a solution, 0.9 to 5.0 d 1 Zg, preferably: 9 to 3.5 dl Zg, more preferably 1.0 to 2 5 d 1 / g.

If [ ₇₇ ] is less than 0.9 dlZg, the composition will not exhibit the desired melt tension.

On the other hand, if it exceeds 5.0 d 1 _g, the moldability of the composition will decrease.

Also, the composition gels and the G value exceeds 1% by weight.

The modified olefin polymer (C 6) has a weight average molecular weight and a number average molecular weight (Mw / Mn) of 3 or less, preferably 2.5 or less.

When NwZMn exceeds 3.0, the uniformity of (C 6) is reduced, and the composition does not exhibit a desired melt tension.

Note that Mw and Mn can be measured by gel permeation chromatography (GPC).

The modified α-refined polymer (C 6) has a molar ratio (β ³ value) between the polar group and the polymer chain of 0.1 to 3.0, preferably 0.5 to 3.0. Preferably, it is 0.5 to 2.0.

/ 3 When ³ value is less than 0.1, that the composition is such not to express the desired melt tension. On the other hand, if it exceeds 3.0, the composition gels and the G value exceeds 1% by weight.

Incidentally,] 3 ³ value means a ratio of the calculated from Μη measured by GP C method (C 6) polymer strand number (mol Zg) and a polar base (mol / g), the value is 1 In this case, one molecule of the modifying agent is added per one polymer chain. Such a modified olefin polymer (C 6) can be produced, for example, by melt-kneading a one-year-old olefin polymer having 2 to 30 carbon atoms, a radical initiator and the above-mentioned modifier.

At this time, the conditions such as the blending conditions and the reaction conditions are determined based on the polar base content of (C 6), [77], MwZMn and | 3 ³ values can and Tekisen adjusted child to be within the above range.

The (Α) α-olefin polymer having 2 to 20 carbon atoms of the present invention 4 includes, for example, ethylene (co) polymer, propylene (co) polymer, 1-butene

(Co) polymer, higher olefin (co) polymer, etc., alone or in combination of two or more.

Of these, a propylene (co) polymer or 1-butene (co) polymer is preferred. These polymers can be appropriately polymerized by a known method.

Examples of the radical initiator of the present invention 4 include the same radical initiators as those of the present inventions 1 to 3.

The preferred modified olefin polymer (C 6) used in the present invention 4 is a maleic anhydride-modified propylene (co) polymer and a maleic anhydride-modified 1-butene (co) polymer.

The silane coupling agent (Β) of the present invention 4 is not particularly limited, but is preferably (Β1) an organic silicon compound represented by the general formula (1).

X n S i Ym (OR) ₄ — _{(n + m)} (1)

[Wherein, X is a substituent containing a functional group capable of reacting with the polar group, Y is a hydrocarbon group, a hydrogen atom or a halogen atom, R is a hydrocarbon group, n is 1-3, and m is 〇- 2 represents an integer, and (n + m) = 1 to 3. ]

In the production method according to the fourth aspect of the present invention, the modified propylene polymer (C 6) and the silane coupling agent (B) are mixed under the above-mentioned conditions to obtain a mixture which is a component effective for the development of a melting tension. [(B) + (C6)] can be obtained efficiently. The detailed mechanism by which the mixture [(B) + (C6)] is produced is unknown, but is presumed as follows.

That is, when the modified α-olefin polymer (C 6) and the silane coupling agent (Β) are mixed, a polar group derived from the modifying agent graphed on the hyolephine polymer reacts with the polar group (Β). Reacts with the site (for example, X in the general formula (1)) to form a structure in which (C) is grafted with (Β), and further, the structure is derived from (Β) in this structure. It is presumed that the site (for example, ΔR in the general formula (1)) condenses to form a mixture [(B) + (C 6)].

The mixture [(B) + (C 6)] is presumed to be a branched, cross-linked or ultra-high molecular weight α-olefin polymer centered on a silicon atom.

At this time, if the jS ³ value of (C 6) is large, or if there is an excess of (B), the mixture [(B) + (C 6)] is likely to gel. Specifically, when the maleic anhydride-modified propylene polymer (C6) and 3-aminopropyl trimethoxysilane (B) are mixed, the carboxylic anhydride derived from maleic anhydride grafted on the propylene polymer is used. Material,

The graft structure is formed by the reaction with the amino group of (B), and the methoxy group derived from (B) of this structure is condensed to form a mixture [(B) + (C 6)]. It is estimated to generate.

The a-olefin polymer (A) of the present invention 4 is an a-olefin polymer having 2 to 20 carbon atoms, and the [η] force ^s measured at 135 ° C in tetralin is 0.7. 5.5.0 d 1 / g, preferably 0.9-3.5 d 1 / g, more preferably 1.0-2.5 d I Zg.

When [77] is less than 0.7 d 1 / g, the physical properties such as the mechanical strength of the composition are reduced.

On the other hand, if it exceeds 5.0 d 1 / g, the moldability of the composition will decrease. As the α-olefin polymer (Α), those similar to the raw materials for producing the modified α-olefin polymer (C 6) can be used.

Preferred are a propylene (co) polymer and a 1-butene (co) polymer.

These polymers can be appropriately polymerized by a known method.

In the production method of the present invention 4, preferably, a phosphorus-based and / or phenol-based antioxidant is further mixed with the modified α-olefin polymer (C 6) and the silane coupling agent (Β).

Specific examples of such an antioxidant of the present invention 4 include the same phosphorus antioxidants and phenolic antioxidants as those of the present inventions 1 to 3. In the production method of the present invention 4, if necessary, an antioxidant, a nucleating agent, an antioxidant, an ultraviolet absorber, an external lubricant, a plasticizer, an antistatic agent, a coloring agent, a flame retardant, a flame retardant auxiliary, and the like , Or a thermoplastic resin or the like can be appropriately mixed. Specific examples of the nucleating agent, plasticizer, flame retardant and flame retardant auxiliary of the present invention 4 include the same nucleating agent, plasticizer, flame retardant and flame retardant auxiliary as those of the present invention 3. These additives and thermoplastic resins may be used alone or in a combination of two or more.

The modified α-refined polymer composition obtained by the production method of the present invention 4 preferably has a melt tension (Μ), a melt flow rate (Ml), and MT / I (MI) —. · Satisfies the relationship ⁸ > 1.

This ratio is more preferably a value greater than 2.

A composition satisfying this relationship is superior to a conventional α-olefin polymer composition in that it exhibits good fluidity while maintaining a high melt tension.

On the other hand, a composition that does not satisfy this relationship does not sufficiently improve the moldability by improving the melt tension, so it is used for large blow molding and foam molding, and other applications and molding methods that are difficult to apply if the drawdown is too large. Difficult to use for Become.

The modified α-refined polymer composition obtained by the production method of the present invention is 130. The amount of paraxylene-insoluble component (G value) of C is preferably 1% by weight or less, more preferably 0.5% by weight or less.

The G value is the amount of the gelled component with an ultrahigh molecular weight. If the G value exceeds 1% by weight, the physical properties of the composition are reduced due to the occurrence of multiple gels.

Since the modified α-olefin polymer composition obtained by the production method of the present invention has a high melt tension, it is possible to greatly improve the moldability of the α-olefin polymer.

This composition can be molded by sheet molding, film molding, thermoforming, foam molding, blow molding, or other molding methods. This is effective when performing blow molding and sheet molding, which was difficult.

The molded article of this composition can be used for various general-purpose trays, interior materials for automobiles, and the like.

The production method of the present invention can be easily carried out with an existing production apparatus, and is not limited to a modified polyolefin polymer, and produces a composition using another modified thermoplastic resin (for example, polycarbonate or the like). It is very versatile because it can be applied to any situation.

In addition, the required amount of the relatively expensive silane coupling agent can be reduced, which is economical in terms of manufacturing cost.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

The physical properties of the present invention were measured according to the following methods.

[Physical property measurement method]

(1) Molecular weight distribution M w / M n is determined by gel permeation chromatography It was calculated from the Mw and Mn of propylene polymer conversion measured by the following equipment and conditions by the (GPC) method.

Components with Mw of 10,000 or less were also measured by this GPC method.

G P C measuring device

Column: TOSOGMHHR— H (S) HT

Detector: RI detector for liquid chromatogram WATERS 1 50C measurement conditions

Solvent: 1, 2, 4-trichlorobenzene

Temperature: 14.5 ° C

Flow rate: 1.0ml

Sample concentration: 2.2 mg / ml

Injection volume: 1 60 microliter

Calibration curve: Univ e s a l C ali i b r a t i o n

Analysis program: HT—GPC (Ver. 1.0)

(2) The mesopentad fraction ([mmmm] and [rrrr]) of the polymer was measured using the following apparatus and conditions.

JEOL Ltd. J NM—EX 400 ^13C— NMR system Method Proton complete decoupling method

220 mg / 3 milliliter

Solvent: 90: 1 0 (volume ratio) of 1, 2, 4-trichlorobenzene and heavy benzene

Temperature: 130 ° C

Panores width: 4 5 °

Pulse repetition time: 4 seconds

Totalization: 1 000 times

(3) Measurement of acid content of acid-modified α-olefin polymer It was calculated by forming a film of the acid-modified α-olefin polymer and measuring the Fourier transform infrared absorption spectrum using the film.

(4) Melt flow rate (ΜI [unit: g / 10 min])

The measurement was performed at a measurement temperature of 230 ° C and a load of 2.16 kg according to JIS-K7210.

In the case of the propylene polymer composition, an orifice having a length of 8 mm and a diameter of 2.095 mm was used.

(5) Measuring method of 'melt tension' (MT [unit: g])

The measurement was performed using a Capillograph 1C manufactured by Toyo Seiki Co., Ltd. at a measurement temperature of 230 ° C and a take-up speed of 3.lm / min.

(6) 1 Method for measuring the amount of paraxylene insolubles (G value) at 30 ° C

To a 1 liter round bottom flask, add 1 g of the polymer composition of the sample, 250 mg of BHT (2,6-g-t-butyl-p-cresono-le), and 500 milliliters of para-xylene. Stirred.

The obtained para-xylene solution was quickly filtered through a 400-mesh stainless steel wire gauze, and then the wire gauze was vacuum-dried at 90 ° C for 4 hours, weighed, and the mass of the components that did not pass through the wire gauze was determined. 1 The amount of paraxylene insoluble part at 30 ° C was determined.

(7) Intrinsic viscosity: 135 ° (: Measured in tetralin.

(8) Average particle size of polymer powder

The particles were classified using sieves having different meshes, and the particle size at 50% by mass was defined as the average particle size.

(9) Bulk specific gravity of polymer powder: Measured in accordance with JIS K6911.

(1 0) β 0 ² and beta ³ value was measured by the method described above. ' (11) Melting enthalpy (ΔΗ): Measured with a differential scanning calorimeter (DSC).

Example 1

① Synthesis of (A) component [propylene polymer]

(1) Preparation of solid catalyst component

After replacing a 0.5-liter, three-necked flask equipped with a stirrer with nitrogen gas, 60 milliliters of dehydrated octane and 16 g of ethoxymagnesium were added.

After heating to 40 ° C, 2.4 milliliters of silicon tetrachloride was added, and the mixture was stirred for 2 minutes, and then 1.6 milliliters of dibutyl phthalate was added.

The temperature of the solution was raised to 80 ° C., followed by 77 milliliters of titanium tetrachloride dropwise added thereto, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a contact operation.

Thereafter, the stirring was stopped to settle the solid, and the supernatant was extracted.

100 milliliters of dehydrated octane was added, the temperature was raised to 125 with stirring, and the temperature was maintained for 1 minute. After stirring was stopped, the solid was settled and the supernatant was extracted.

This washing operation was repeated seven times.

Further, 122 milliliters of titanium tetrachloride was added, and the mixture was stirred at an internal temperature of 125 ° C for 2 hours to perform a second contact operation.

Thereafter, the above washing with dehydrated octane at 125 ° C. was repeated six times to obtain a solid catalyst component.

(2) Prepolymerization

After replacing a 0.5-liter three-necked flask with a stirrer with a nitrogen gas, 400 ml of dehydrated heptane, 25 millimoles of triisobutylamine-dimethyl, 25 millimoles of dicyclopentinoresime 2.5 mmol of toxicoxysilane and 4 g of the above solid catalyst component were added. At room temperature, propylene was introduced with stirring.

One hour later, stirring was stopped, and as a result, a prepolymerized catalyst component in which 4 g of propylene was polymerized per 1 g of the solid catalyst was obtained.

(3) Polymerization of propylene

A stainless steel autoclave with an internal volume of 10 liters with a stirrer was thoroughly dried, replaced with nitrogen, and dehydrated with 6 liters of heptane, 12.5 millimoles of triethylamine, 12.5 millimoles of dicyclopentyldimethoxysilane 0.3 milliliters Remol was added.

Here, after replacing nitrogen in the system with propylene, 0.098 MPa of hydrogen was charged, and then propylene was introduced with stirring.

After the inside of the system was stabilized to an internal temperature of 80 ° C and a total pressure of 0.785 MPa, 50 ml of a heptane slurry containing 0.025 mmol of the above prepolymerized catalyst component in terms of Ti atoms was added, and propylene was added. The polymerization was carried out at 80 ° C. for 3 hours while continuously supplying.

After the polymerization was completed, 50 milliliters of methanol was added, the temperature was lowered, and the pressure was released. The entire contents were transferred to a filtration tank equipped with a filter, heated to 85 ° C, and separated into solid and liquid. Further, the solid portion was washed twice with 6 liters of heptane at 85 ° C and dried under vacuum to obtain 2.5 kg of a propylene polymer (A).

The catalytic activity per 1 g of the solid catalyst was 33.1 kg / g-cat. · 3 hr in 3 hours of polymerization.

The characteristics of this propylene polymer are shown below.

a. Intrinsic viscosity: 1.70 d 1 / g

b ¹³ C NMR mesopentad fraction [mmmm]: 98.0 mo 1

c Average particle size of polymer powder: 1 200 μm

d Bulk specific gravity of polymer powder: 0.38 g / cm ³ ② Synthesis of (CI) component [maleic anhydride-modified propylene polymer]

The propylene polymer used as the raw material of the component (C 1) was synthesized in the same manner as in the above (3) propylene polymerization in the synthesis of the component (A) except that hydrogen was not added.

The intrinsic viscosity [77] of the obtained propylene polymer was 7.65 (11 _§ ).

To 2 kg of the above propylene polymer, 6 g of maleic anhydride and perhexyne 25B / 40 (manufactured by NOF CORPORATION, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne) 3 g of an inert solid (40% dilution) was dry blended and melt-blended with a 20-millimeter twin-screw extruder.

Acetone (0.5 kg) and heptane (0.7 kg) were added to the obtained pellet-like sample (1 kg), and the mixture was heated and stirred at 85 ° C. for 2 hours (implemented in a pressure vessel). After the same operation, the pellets were collected with a wire mesh, and then immersed in 1.5 kg of acetone for 15 hours.

Thereafter, the pellets were collected with a wire mesh, air-dried, and vacuum-dried at 80 ° C for 6 hours and at 130 ° C for 6 hours.

The characteristics of the maleic anhydride-modified propylene polymer are shown below.

a. Maleic anhydride content: 0.098% by mass

b. Intrinsic viscosity [η]: 1.43 d 1 / g

c. ¹ value: 0.99

d. Mw / Mn: 2.03

e. Mw less than 10,000: 0.2% by mass

③ Preparation of propylene polymer composition

As the component (A), 380 g of the above-mentioned propylene polymer powder, and as the component (B1), 0.995 g of 3-aminopropyltriethoxysilane (APTES), and ilganox 1010 were added. 0.24 g, ilgafoss 1 6 8 Was added and 0.5 g of calcium stearate was added, and 0.2 g of calcium stearate was added.

Next, as the component (C1), 20 g of the maleic anhydride-modified propylene polymer was added, mixed, and then melt-blended at 230 ° C. using a twin-screw extruder. Table 1 shows the physical property values of the obtained propylene polymer composition.

The value of MTc is a calculated value obtained from Equation (3).

The value of MTZMTC of the obtained propylene polymer composition was as high as 2.0.

Examples 2 to 5

A propylene polymer composition was prepared in the same manner as in Example 1 except that the amount of the component (C 1) was changed.

Table 1 shows the results.

The value of MT / MTc of the obtained propylene polymer composition showed a high value of 1.5 to 2.7.

Examples 6 to 8

In the synthesis of the component (A) in Example 1 (3), in the propylene polymerization, a propylene polymer composition was prepared in the same manner as in Example 1 except that the component (A) having a different intrinsic viscosity was used under different hydrogen conditions. Was prepared.

The bulk specific gravity of the polymer powder ranged from 0.36 to 0.39 g / cm ³ .

Table 1 shows the results.

The value of MT / MTc of the obtained propylene polymer and composition was as high as 1.6 to 2.7.

Example 9

In the synthesis of component (A) in Example 1 (3) In the propylene polymerization, titanium trichloride and getyl aluminum The same procedure as in Example 1 was repeated except that the following components were used and the component (A) was synthesized under the conditions of (2) prepolymerization and (3) propylene polymerization. Was prepared.

Table 1 shows the results.

The value of MT / MTc of the obtained propylene polymer composition was as high as 2.1.

(2) Prepolymerization

After replacing a 2.0-liter three-necked flask equipped with a stirrer with nitrogen gas, dehydrated heptane 1.5 liters, getyl aluminum chloride (DEAC) 31.5 g And 4.5 g of Solvay catalyst (titanium trichloride).

At room temperature, propylene was introduced with stirring, and stopped 80 minutes later. As a result, a prepolymerized catalyst in which 0.8 g of propylene was polymerized per 1 g of the solid catalyst was obtained.

(3) Polymerization of propylene

A stainless steel autoclave with an internal volume of 10 liters equipped with a stirrer was sufficiently dried, and after purging with nitrogen, 6 liters of dehydrated heptane was added, and nitrogen in the system was replaced with propylene.

Thereafter, hydrogen was introduced at 0.05 MPa, and propylene was introduced with stirring.

After the system was stabilized to an internal temperature of 60 ° C and a total pressure of 0.73 MPa, a heptane slurry containing 0.6 _g containing the above prepolymerized catalyst component as a solid catalyst was added, and propylene was continuously added. The polymerization was carried out at 60 ° C. for 4 hours while feeding the mixture. 2.4 kg of propylene polymer was obtained and the activity was 4. O kg / g-cat. · 4 hr. '

The characteristics of the obtained propylene polymer are shown below. a. Intrinsic viscosity [77]: 1.79 d 1 / g

. b Mesopenta' de fraction by ^{13 C NMR [mmmm]: 93.} 3 mo 1 0 / o,

c. Average particle size of polymer powder: 300 ^ m

d. Bulk specific gravity of polymer powder: 0.5 1 gZ cm ³

Comparative Example 1

A propylene polymer composition was prepared in the same manner as in Example 1, except that the component (B1) was not used.

Table 1 shows the results.

The value of MTZMTc of the obtained propylene polymer composition was as low as 0.6.

Comparative Example 2

A propylene polymer composition was prepared in the same manner as in Example 1 except that the component (C 1) was not used.

Table 1 shows the results.

The value of MTZMTc of the obtained propylene polymer composition was as extremely low as 0.5.

Example 10: L 4

(C 1) A propylene polymer was prepared in the same manner as in Example 1 except that the component (C 1) having a different intrinsic viscosity and a different maleic anhydride content was obtained by changing the amount of peroxide used during the synthesis of the component. A coalescing composition was prepared.

Table 1 shows the results.

The value of MTZMTc of the obtained propylene polymer composition showed a high value of 1.7 to 3.2.

Comparative Example 3

(A) Propylene was prepared in the same manner as in Example 14 except that no component was used. A polymer composition was prepared.

The resulting propylene polymer composition had many gels and could not be measured for MI and MT.

Comparative Example 4

Example 1 was repeated except that the component (C1) of Example 1 was replaced with a commercially available modified propylene polymer (manufactured by Sanyo Chemical Co., Umex 1010) having a low intrinsic viscosity and a high maleic anhydride content. Similarly, a propylene polymer composition was prepared.

Table 1 shows the results.

The value of MTZMTc of the obtained propylene polymer composition was as low as 0.4.

Comparative Example 5

The procedure was performed in the same manner as in Example 1, except that a commercially available modified propylene polymer (manufactured by Toyo Kasei Co., Ltd., Toyo Tack H 1 000 P) having a low intrinsic viscosity and a high maleic anhydride content was used instead of the component (C 1) in Example 1. A propylene polymer composition was prepared in the same manner as in Example 1.

Table 1 shows the results.

Examples 15 to 18

A propylene polymer composition was prepared in the same manner as in Example 1 except that the amount of the component (B1) was changed.

Table 1 shows the results.

The value of MT / MTc of the obtained propylene polymer composition showed a high value of 2.7 to 3.0.

Example 19 10513 A propylene polymer composition was prepared in the same manner as in Example 1 except that 3-aminopropyl trimethoxysilane (APTMS) was used instead of APTES.

Table 1 shows the results.

The value of MT / MTc of the obtained propylene polymer composition was 1.2.

In each example, the component (A), the component (B1) and the component (C1) were simultaneously blended and melted and kneaded, but the components (A) and (B1) were sufficiently blended. Thereafter, the same results as in the case of blending and melt-kneading the component (C 1) were obtained.

Example 20

① (B1) Contain components (A) Synthesis of components

To 600 g of the same propylene polymer as the component (A) of Example 1, 1.8 g of 3-aminopropyltriethoxysilane (APTES) as an organosilicon compound (B 1) and 10 g of Irganox 0.24 g of tetrakis (tetrakis (methylene-3- (3,, 5'-di-tert-butyl-14'-hydroxy-pheno-nore) methane)) and ilgafos 168 [tris (2 , 4-di-t-butylphenyl) phosphite] and 0.2 g of calcium stearate, and mixed well.

This powdery mixture was melt-mixed at 230 ° C. using a 20-millimeter twin screw extruder to obtain a propylene polymer pellet containing 300,000 ppm of APTES.

② Synthesis of (C 1) component

It was synthesized in the same manner as the component (C 1) of Example 1.

③ Preparation of propylene polymer composition

Including 400 g of the above-mentioned (B 1) component-containing (A) component pellet, 20105 g of 3010513 component pellets were mixed and melt-blended at 230 ° C using a 20 mm twin screw extruder.

Table 2 shows the physical property values of the obtained propylene polymer composition.

The value of MTc is a calculated value obtained from Equation (3).

The values of MI and MT of the obtained propylene polymer composition were 5.1 g / 10 minutes and 4.2 g, respectively.

This MT value was 2.2 times the MTc value obtained by the relational expression (3) between Ml and MT.

That, MT of obtained propylene polymer composition, as shown in FIG. 1, MT / 7X (Ml) - showed ⁸ = 1 higher melt tension than the (calculated) - °.

Example 21-24

A propylene polymer composition was prepared in the same manner as in Example 20, except that the content of the organic silicon compound in the component (A) was changed by changing the blending amount of ATES. Table 2 shows the results.

The ratio of M I ZMT values of the obtained propylene polymer composition showed a high value of 2.9 to 3.8.

Examples 25 to 27

In the synthesis of component (A) in Example 20 (3), in the polymerization of propylene, propylene was used in the same manner as in Example 20 except that propylene polymer components having different intrinsic viscosities synthesized under different hydrogen conditions were used. A polymer composition was prepared.

Table 2 shows the results.

The ratio of M I / MT of the obtained propylene polymer composition showed a high value of 1.8 to 3.0.

Comparative Example 6

Propylene was prepared in the same manner as in Example 20 except that no organic silicon compound was added. A ren polymer composition was prepared.

Table 2 shows the results.

The ratio of the values of M I ZMT of the obtained propylene polymer composition was 0.6, an extremely low value.

Comparative example Ί

A propylene polymer composition was prepared in the same manner as in Example 20, except that the component (C 1) was not used.

Table 2 shows the results.

The ratio of the values of M I / MT of the obtained propylene polymer composition showed an extremely low value of 0.5.

Example 2 8 to 3 2

A propylene polymer composition was prepared in the same manner as in Example 20, except that the maleic anhydride content of the component (C 1) was changed.

Table 2 shows the results.

The ratio of M I / MT values of the obtained propylene polymer composition was as high as 1.9 to 3.7.

Examples 33 to 35

A propylene polymer composition was prepared in the same manner as in Example 20, except that the amount of the component (C 1) was changed.

Table 2 shows the results.

The ratio of M I ZMT values of the obtained propylene polymer composition showed a high value of 1.7 to 3.0.

Comparative Example 8

Propylene was used in the same manner as in Example 20 except that a commercially available modified propylene polymer having a low intrinsic viscosity and a high content of maleic anhydride (Umettas 110, manufactured by Sanyo Chemical Co., Ltd.) was used as the component (C 1). A polymer composition was prepared. Table 2 shows the results.

The ratio of M I ZMT values of the obtained propylene polymer composition was extremely low, 0.4.

Comparative Example 9

As in Example 20, except that a commercially available modified propylene polymer (manufactured by Toyo Kasei Co., Ltd., Toyo Tack H 1 000 P) having a low intrinsic viscosity and a high maleic anhydride content was used as the component (C 1). A propylene polymer composition was prepared. Table 2 shows the results.

The ratio of M I / MT values of the obtained propylene polymer composition showed an extremely low value of 0.3.

Reference Examples 1 to 8

Examples 1 to 8 (same as Examples 20 to 27) Table 3 shows the measurement results of the MI and MT of the propylene polymer.

The Ml ZMT c ratio showed an extremely low value of 0.3 to 0.5.

CD

Table 2

o

APTES: 3-aminopropyltriethoxysilane

Table 3 Physical properties of propylene polymer (reference values)

Production Example 1

[Synthesis of maleic anhydride-modified propylene polymer]

(1) Preparation of solid catalyst component

After replacing a 0.5-liter three-necked flask with a stirrer with a nitrogen gas, 60 ml of dehydrated octane and 16 g of magnesium ethoxy were added.

This was heated to 40 ° C, 2.4 milliliters of silicon tetrachloride was added, and the mixture was stirred for 20 minutes, and then 1.6 milliliters of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., followed by dropwise addition of 77 milliliters of titanium tetrachloride, followed by stirring at an internal temperature of 125 ° C. for 2 hours to perform a contact operation.

Add 100 milliliters of dehydrated octane and stir to 125 ° C After the temperature was raised and maintained for 1 minute, the stirring was stopped to allow the solid to settle, and the supernatant was extracted.

This washing operation was repeated seven times.

Thereafter, 122 milliliters of titanium tetrachloride was further added, and the mixture was stirred at an internal temperature of 125 for 2 hours, and a second contact operation was performed.

(2) Preparation of pre-polymerization catalyst component

After replacing a 0.5-liter three-necked flask with a stirrer with a nitrogen gas, dehydrated heptane 400 milliliters, triisobutyl aluminum dimethyl 25 millimoles, dicyclopentyl dimethoxysilane 2 · 5 millimoles and 4 g of the solid catalyst component prepared in the above (1) were added.

To this, propylene was introduced at room temperature with stirring.

One hour later, the stirring was stopped, and as a result, a prepolymerized catalyst component in which 4 g of propylene was polymerized per 1 g of the solid catalyst component was obtained.

(3) Synthesis of propylene polymer

A stainless steel autoclave with an internal volume of 10 liters equipped with a stirrer was sufficiently dried, purged with nitrogen, and then added with 6 liters of dehydrated heptane, 12.5 millimoles of triethylamine, and 2.5 millimoles of dicyclopentyldimethoxysilane. Was.

After replacing nitrogen in the system with propylene, propylene was introduced with stirring.

After the inside of the system became stable at an internal temperature of 80 ° C and a total pressure of 0.8 MPa, 50 milliliters of a heptane slurry containing 0.08 mmol of the prepolymerized catalyst component prepared in (2) above in terms of Ti atoms was converted. And polymerization was carried out at 80 ° C. for 3 hours while continuously supplying propylene. After the completion of the polymerization, 50 milliliters of methanol was added, and the temperature was reduced and the pressure was released. The entire content was transferred to a filtration tank equipped with a filter, and the temperature was raised to 85 ° C to perform solid-liquid separation.

Further, the solid portion was washed twice with 6 liters of heptane at 85 ° C. and dried under vacuum to obtain 2.5 kg of a propylene polymer.

The catalytic activity per 1 g of the solid catalyst component was 9.8 kg / g-cat. · 3 hr in 3 hours of polymerization.

This polymer exhibited the following properties.

Intrinsic viscosity []: 7.65 d 1 / g

Mw / Mn: 3.99 (Mn: 370,000)

Ingredient with Mw of 1,000,000 or more: 41% by weight

Mesopentad fraction by ¹³ C-NMR [mmmm]: 96.3 mo 1%

(4) Synthesis of maleic anhydride-modified propylene polymer (acid-modified PP-1) To 2 kg of the propylene polymer synthesized in (3) above, 6 g of maleic anhydride (transforming agent, MAH) and perhexine were added. 25 B / 40 (2,5-dimethyl-1,2,5-di (t-butylperoxy) hexine-1 / inorganic carrier (40/60 (wt / wt))) (trade name, radical initiator, chemical agent) And 2 g of PH (manufactured by Akzo Corporation), dry-blended, and melt-kneaded with a 20-millimeter twin-screw extruder.

To 1 kg of the obtained pellet-like sample, 0.5 kg of acetone and 0.7 kg of heptane were added, and the mixture was heated and stirred at 85 ° C for 2 hours.

The heating and stirring were performed in a pressure vessel.

After the operation was completed, the pellet was collected with a wire mesh and immersed in 1.5 kg of acetone for 15 hours.

Then, collect the pellets with a wire mesh, air-dry, and then at 80 ° C for 6 hours. After vacuum drying at 0 ° C for 6 hours, a maleic anhydride-modified propylene polymer (acid-modifiable PP-1) was obtained.

This polymer exhibited the following properties.

Maleic anhydride content (modification rate): 0.095% by weight

Intrinsic viscosity [η]: 1.35 d 1 / g

Polar base / polymer chain derived from anhydrous maleic phosphate (molar ratio) [; 3 ^ternary]: 1.0

Example 3 6

MI: 7.3 g / l 0 min, MT: 0.7 g, Tm: 16 1 ° C Polypropylene powder (Homopolypropylene, H700, manufactured by Idemitsu Petrochemical Co., Ltd.) (Native PP — L): 380 g, 3 —Aminopropyltriethoxysilane (APTES): 0.3 g, irganox 110 10 (trade name, phenolic antioxidant, CHIPA Specialty Chemicals) ): 0.24 g, irgafos 1668 (trade name, phosphorus antioxidant, manufactured by Ciba Specialty Chemicals): 0.56 g, calcium stearate: 0.2 g, Production Example 1 20 g of maleic anhydride-modified propylene polymer (acid-modified PP-1) synthesized in (4) was added, and thoroughly blended.

The powder blend was melt-kneaded at 230 ° C. using a 20 mm twin screw extruder to produce a polymer composition.

Table 4 shows the measurement results of various physical properties.

Example 3 7

Ml: 4.2 g / l 0 min, MT: 0.6 g, Tm 161 ° C polypropylene powder (homopolypropylene, H400, manufactured by Idemitsu Petrochemical Co., Ltd.) (Native PP — 2): 360 g, APTES 1.0 g, irganox 10 10: 0.24 g, inoregafos 16680.56 g, calcium stearate: 0.2 g, acid-modified PP -1: Add 40 g and add I rendered.

This powder blend was melt-kneaded at 230 ° C. using a 20 mm twin-screw extruder to produce a polymer composition.

Table 4 shows the measurement results of various physical properties.

Example 3 8

MI: 1.8 g / l 0 min, MT: 1.8 g, Tm: 160 ° C Polypropylene powder (Homopolypropylene, F200GP, manufactured by Idemitsu Petrochemical Co., Ltd.) (Native PP — 3) _: 380 g, APTE S: 1. O g, irganox 10 10: 0.24 g, irgafos 16 8: 0.56 g, calcium stearate: 0.2 g, 20 g of acid-modified PP-1 was added and the mixture was sufficiently blended.

Table 4 shows the measurement results of various physical properties.

Example 3 9

In the same manner as in Production Example 1 (4) except that MAH was changed to 8 g and ^ [to 0.8 g in Production Example 1 (4), a maleic anhydride-modified propylene polymer (modification ratio: 0. 05 7 wt%, intrinsic viscosity: 1.79 d 1 / g, polar group Z polymer chain: 0.84) (acid-modified PP-2) was synthesized.

A polymer composition was obtained in the same manner as in Example 36 except that acid-modified PP_2 was used instead of acid-modified PP-1.

Table 4 shows the measurement results of various physical properties.

Example 5

In Production Example 1 (4) ′, maleic anhydride-modified propylene polymer (modification rate: 0) was prepared in the same manner as in Production Example 1 (4) except that the amount of MAH was changed to 24 g and the amount of PH was changed to 16 g. 43 wt%, intrinsic viscosity: 0.75 d 1 / g, polar base / Polymer chain: 1.778) (acid-modified PP-3) was synthesized.

A polymer composition was obtained in the same manner as in Example 36 except that acid-modified PP-3 was used instead of acid-modified PP-1.

Table 4 shows the measurement results of various physical properties.

Comparative Example 10

A polymer composition was obtained in the same manner as in Example 36, except that APTES was not used.

Table 4 shows the measurement results of various physical properties.

Comparative Example 1 1

In Example 36, maleic anhydride having a modification rate of 4.2 wt%, an intrinsic viscosity of 0.19 d 1 Z g, a polar group Z polymer chain: 2.10 instead of the acid-modified PP-1 was used. A polymer composition was obtained in the same manner as in Example 36, except that a modified propylene polymer (Yumettasu 110 (trade name) manufactured by Sanyo Chemical Industries, Ltd.) (acid-modified PP-4) was used.

Table 4 shows the measurement results of various physical properties.

Comparative Example 1 2

In Example 36, maleic anhydride having a modification rate of 4.1 wt%, an intrinsic viscosity of 0.56 d1 Zg, and a polar group / polymer chain of 12.0 instead of the acid-modified PP-1 A polymer composition was obtained in the same manner as in Example 36, except that a modified propylene polymer (manufactured by Toyo Kasei Co., Ltd., Toyo Tac 100 P (trade name)) (acid-modified PP-5) was used.

Table 4 shows the measurement results of various physical properties.

Example 4 1

To 800 g of the native PP-1 used in Example 36, 2.0 g of APTES, 0.40 g of irganox, 0.148 g of irganox, 168: 1.12 g of irgafos, calcium stearate: 0.4 g was added and thoroughly blended. This powder blend was melt-kneaded at 230 ° C using a 20 mm twin-screw extruder to produce a polypropylene pellet containing 2,500 ppm of APTES and 2,000 ppm of antioxidant. .

380 g of this pellet and 20 g of the acid-modified PP-1 pellet were mixed and melt-kneaded at 230 ° C. using a 20 mm twin-screw extruder to produce a polymer composition.

Table 4 shows the measurement results of various physical properties.

Example 4 2

A polymer composition was produced in the same manner as in Example 41 except that the amount of APTES used in Example 41 was changed to 1 g.

Table 4 shows the measurement results of various physical properties.

Example 4 3

In Example 41, a polymer composition was produced in the same manner as in Example 41, except that the acid-modified PP_2 used in Example 39 was used instead of the acid-modified PP-1.

Table 4 shows the measurement results of various physical properties.

Comparative Example 1 3

A polymer composition was produced in the same manner as in Example 41 except that the acid-modified PP-1 was not used.

Table 4 shows the measurement results of various physical properties.

Example 44

Propylene polymer synthesized in Production Example 1 (3): 800 g, maleic anhydride: 0.8 g, perhexin 25 B / 40: 0.32 g, irganox 10 10: 0.48 g, irgafos 1668: 1.12 g, calcium stearate: 0.4 g were added, and the mixture was melt-kneaded at 230 ° C using a 2 Omm twin screw extruder. The resulting maleic anhydride-modified propylene polymer (modification _{rate: 0. 04 9 wt ° / 0} , [77]: 1. 9 6 d 1 / g, the polar base / polymer chain (0 ³ value): 0.7 1. Addition of 1.0 g of APTES to 400 g of pelletized sample of acid-modified (4ΡP-6) to obtain a reaction product of acid-modified PP-6 and APTES Next, Irganox 1010: 0.24 g, Irgafos 1668: 0.5 g: 0.2 g of calcium stearate, Ml: 7.3 gZl 0 min, Tm: 161 380 g of polypropylene (unmodified PP-4) at 20 ° C. and 20 g of the above-mentioned reaction product were melt-kneaded at 230 ° C. using a twin-screw extruder to produce a polymer composition.

Table 4 shows the measurement results of various physical properties.

In addition, all of the homopolypropylene resins (mmmm) polymerized using the Ziegler-Natta catalyst in Reference Examples 1 to 8 (see Table 3) were 96 to 96.5 mol%.

Example 36-44, Comparative Examples 10-13, Unmodified P P— :! ~ 3 and Reference Examples

FIG. 2 shows the relationship between M I and MT of the compositions 1 to 8.

In the figure, the calculated value is MT / 7X (M l). · Represents ⁸ = 1.

From this figure, it can be seen that the compositions of the examples have higher melt tension, show better fluidity, and are more practical than the compositions of the comparative examples.

Table 4

to

* 1: The amount is based on 100 parts by weight of unmodified polypropylene (G3). * 2: The amount is based on 100 parts by weight of the propylene polymer (C2). (D) Ilganox 1010 + Ilgafoss 168

Production Example 2

[Synthesis of unmodified propylene polymer]

(1) Preparation of solid catalyst component

After replacing a 0.5-liter, three-necked flask with a stirrer with nitrogen gas, 20 ml of dehydrated heptane, 4 g of diethoxymagnesium, and 1.6 g of dibutyl phthalate were added. While maintaining the system at 90 ° C., 4 milliliters of titanium tetrachloride was added dropwise with stirring.

Further, 111 milliliters of titanium tetrachloride was dropped and the temperature was raised to 110 ° C.

To the obtained solid phase, 115 milliliters of titanium tetrachloride was added, and the mixture was further reacted at 110 ° C for 2 hours.

After completion of the reaction, the product was washed several times with 100 milliliters of purified heptane to obtain a solid catalyst component.

(2) Preparation of pre-polymerization catalyst component

After replacing a 0.5-liter three-necked flask equipped with a stirrer with nitrogen gas, 300 ml of dehydrated heptane and 10 g of the solid catalyst component prepared in the above (1) were added. added.

After the inside of the system was brought to 15 ° C, 4.2 mmol of triethylaluminum and 1.1 mmol of cyclohexylmethyldimethoxysilane (CHMDS) were added, and propylene was introduced with stirring.

After 2 hours, the stirring was stopped, and as a result, a prepolymerized catalyst component in which 2 g of propylene was polymerized per 1 g of the solid catalyst component was obtained.

(3) Synthesis of propylene polymer

A 10 liter stainless steel autoclave with a stirrer was thoroughly dried and purged with nitrogen, then 2 kg of propylene, 6 mmol of triethylaluminum, 2.4 mmol of CHMDS, and 1-aryl-1-3 , 4—Dimethoxy 0.48 millimoles of benzene (ADMB) was added, and the temperature was raised to 65 ° C.

Next, 0.12 g of the prepolymerized catalyst component prepared in the above (2) was charged,

Polymerization was performed at 70 ° C for 3 hours. As a result, 1 35 ° C, intrinsic viscosity was measured in tetralin [eta] force ^s 5. 2

960 g of a 6 d 1 Zg propylene polymer was obtained.

By repeating this polymerization reaction, a propylene polymer as a raw material of the unmodified propylene polymer was synthesized.

(4) Synthesis of unmodified propylene polymer

To 100 parts by weight of the propylene polymer synthesized in the above (3), irganox 101: 0.06 parts by weight, irgafos 168: 0.14 parts by weight, calcium stearate: 0.05 parts by weight, Parhexin 25 B / 40: 0.035 parts by weight was added and thoroughly blended.

This powder blend was melt-kneaded at 180 ° C using a 20 mm twin-screw extruder to produce an unmodified propylene polymer (unmodified PP-5) pellet.

Table 5 shows the physical properties of the obtained polymer pellet.

Production Example 3

[Synthesis of maleic anhydride-modified propylene polymer]

To 100 parts by weight of the propylene polymer synthesized in Production Example 2 (3), 0.3 parts by weight of maleic anhydride and 0.1 part by weight of perhexine 25B / 40 were added and thoroughly blended.

This powder blend was melt-kneaded at 180 ° C using a 20 mm twin screw extruder.

The heating and stirring were performed in a pressure vessel. After the operation was completed, the pellet was collected and immersed in 1.5 kg of acetone for 15 hours.

Thereafter, the pellet was collected, air-dried, and vacuum-dried at 90 ° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer (acid-modified PP-7).

Table 5 shows the physical properties of this polymer.

Production Example 4-[Synthesis of unmodified propylene polymer]

In Production Example 2 (4), except that the amount of perhexin 25 B / 40 was changed to 0.15 parts by weight, the unmodified propylene polymer was prepared in the same manner as in Production Example 2 (4). Unmodified PP-6) was synthesized.

Table 5 shows the physical properties of this polymer.

Production Example 5

[Synthesis of unmodified propylene polymer]

(1) Synthesis of propylene polymer

In Production Example 2 (3), 1,070 g of a propylene polymer was synthesized in the same manner as in Production Example 2 (3) except that the amount of CHMDS used was changed to 0.48 mmol.

(2) Synthesis of unmodified propylene polymer

In Production Example 2 (4), except that the propylene polymer synthesized in (1) above was used instead of the propylene polymer synthesized in Production Example 2 (3), To synthesize an unmodified propylene polymer (unmodified PP-7).

Table 5 shows the physical properties of this polymer.

Production Example 6

[Synthesis of maleic anhydride-modified propylene polymer]

In Production Example 3, the propylene polymer synthesized in Production Example 2 (3) was used instead. In addition, except that the propylene polymer synthesized in Production Example 5 (1) was used, a maleic anhydride-modified propylene polymer (acid-modified PP

8) was synthesized.

Table 5 shows the physical properties of this polymer.

Production Example 7

[Synthesis of unmodified propylene polymer]

(1) Synthesis of propylene polymer

In Production Example 2 (3), propylene was used in the same manner as in Production Example 2 (3) except that the amount of CHMD S was changed to 0.48 mmol and the amount of ADMB was changed to 1.44 mmol. 849 g of a polymer was synthesized.

(2) Synthesis of unmodified propylene polymer

In Production Example 2 (4), except that the propylene polymer synthesized in (1) above was used instead of the propylene polymer synthesized in Production Example 2 (3), To synthesize an unmodified propylene polymer (unmodified PP-8).

Table 5 shows the physical properties of this polymer.

Production Example 8

[Synthesis of maleic anhydride-modified propylene polymer]

In Production Example 3, maleic anhydride was produced in the same manner as in Production Example 3 except that the propylene polymer synthesized in Production Example 7 (1) was used instead of the propylene polymer synthesized in Production Example 2 (3). Modified propylene polymer (acid-modified PP

9) was synthesized.

Table 5 shows the physical properties of this polymer.

Example 4 5

Unmodified PP synthesized in Production Example 2 (4) —5 pellets of ground product: 380 g, APTE S: 1.0 g, Acid-modified PP synthesized in Production Example 3—20 g And blended well.

This powder blend was melt-kneaded at 230 ° C. using a 20 mm twin screw extruder to produce a polymer composition.

Table 5 shows the manufacturing conditions and measurement results of various physical properties.

Examples 46 to 48

In Example 45, the amount of the acid-modified PP-7 was changed to 10 g (Example 461), 30 g (Example 47) and 40 g (Example 48) by adding unmodified PP-7. Polymer was prepared in the same manner as in Example 45, except that the compounding amount of 5 was changed to 390 g (Example 46), 370 g (Example 47), and 360 g (Example 48). A composition was produced.

[0 0 7 8]

Example 4 9 to 50

A polymer was prepared in the same manner as in Example 45 except that the amount of APTE S was changed to 0.3 g (Example 49) and 0.6 g (Example 50) in Example 45. A composition was prepared.

Example 5 1

In Example 45, a polymer composition was produced in the same manner as in Example 45, except that the unmodified PP-6 synthesized in Production Example 4 was used instead of the unmodified PP-5.

Example 5 2

In Example 45, the unmodified PP-7 synthesized in Production Example 5 was used instead of the unmodified PP-5, and the acid-modified PP-8 synthesized in Production Example 6 was used instead of the acid-modified PP-7. A polymer composition was prepared in the same manner as in Example 45 except that the polymer composition was used. Was manufactured.

Example 5 3

In Example 10, the unmodified PP-5 synthesized in Production Example 7 was used in place of the unmodified PP-5, and the acid-modified PP-9 synthesized in Production Example 8 was replaced with the acid-modified PP-7 in place of the acid-modified PP-7. Except for using, a polymer composition was produced in the same manner as in Example 10.

Comparative Example 1 4

A polymer composition was produced in the same manner as in Example 45 except that APTES was not used in Example 45.

Comparative Example 15

A polymer composition was produced in the same manner as in Example 45 except that the acid-modified PP-7 was not used.

Comparative Example 16

A polymer composition was produced in the same manner as in Example 45 except that acid-modified PP-4 was used in place of acid-modified PP-7.

Five

* 1: The amount is based on 1 part by weight of unmodified polypropylene (C4). * 2: Amount based on 100 parts by weight of propylene-based polymer (C2) mmmm: Mesopentad (molar fraction) rrrr: Racemic pentad (molar fraction)

(D) Irganox 1010 + Irgafoss 168

P picture 003/010513 Example 54

Unmodified PP-5 pellets: 100 parts by weight, irganox 101: 0.03 parts by weight, irgafos 168: 0.07 parts by weight, stearic acid strength: 0.025 parts by weight, APTE S: 0.25 parts by weight was added, and the mixture was melt-kneaded at 230 ° C. using a 20 mni twin screw extruder to produce pellets containing 2,500 ppm of APTE S.

Subsequently, 100 parts by weight of the pellets and 5 parts by weight of the acid-modified PP-7 were melt-kneaded at 230 ° C. using a 20 mm twin-screw extruder to produce a polymer composition. did.

Table 6 shows the manufacturing conditions and measurement results of various physical properties.

Example 55 to 57

Except that the amount of the acid-modified PP-7 used in Example 54 was changed to 3 parts by weight (Example 55), 8 parts by weight (Example 56), and 12 parts by weight (Example 57). A polymer composition was produced in the same manner as in Example 54.

Example 5 8 ~ 5 9

A polymer was prepared in the same manner as in Example 54 except that a pellet containing 800 ppm of APTES (Example 58) and a pellet containing 1,600 ppm (Example 59) were used. A composition was prepared.

Example 6 0

A polymer composition was produced in the same manner as in Example 54, except that in place of the unmodified PP-5, the unmodified PP-6 synthesized in Production Example 4 was used.

Example 6 1 In Example 54, the unmodified PP-7 synthesized in Production Example 5 was used instead of the unmodified PP-5, and the acid-modified PP-8 synthesized in Production Example 6 was used instead of the acid-modified PP-7. Except for using, a polymer composition was produced in the same manner as in Example 54.

Example 6 2

In Example 54, the unmodified PP-5 synthesized in Production Example 7 was used instead of the unmodified PP-5, and the acid-modified PP-9 synthesized in Production Example 8 was used instead of the acid-modified PP-7. Except for using, a polymer composition was produced in the same manner as in Example 54.

Comparative Example 1 7

A polymer composition was produced in the same manner as in Example 54, except that the acid-modified PP-7 was not used.

Comparative Example 1 8

A polymer composition was produced in the same manner as in Example 54, except that the acid-modified PP-7 was used instead of the acid-modified PP-7.

Table 6 shows the manufacturing conditions and measurement results of various physical properties. FIG. 3 shows the relationship between M I and M T for the compositions of Examples 45 to 62, Comparative Examples 14 to 18, Native PP-5 to 8, and Reference Examples 1 to 8.

In the figure, the calculated value represents MT / 7 X (M l)-° · ⁸ = 1.

From this figure, it can be seen that the compositions of the examples have higher melt tension, show better fluidity, and are more practical than the compositions of the comparative examples. Resin composition

Polypropylene resin (C2)

MAH - unmodified polypropylene (G4) MAH-modified polypropylene (C5) modification rate Ml (mmmm) lOO X rrrr / Δ Η APTES (B) antioxidant base / formulation (wt%) Type (g / 10 min) (moles ⁰ / 0) (1-mmmm) (l / g) 3 Yes (D) Content Type (dl / g) Polymer chain (weight

() (Ppm) vppm) (molar ratio) Example 54 5.24 X 10 "" ³ native ΡΡ-5 6.5 69.2 20.5 76.2 2500 2000 acid-modified PP - 7 0.11 1.34 1.1 Example 55 3.20 X 10- ³ unmodified ro-ro -5 6.5 69.2 20.5 76.2 2500 2000 acid娈性pp- ₇ 0.11 1.34 1.1 example 56 8.15 x 10- ³ unmodified [rho _[rho one ₅ 6.5 69.2 20.5 76.Zeta 2500 2000 acid-modified PP- 7 0.11 1.34 1.1 example 57 t.t8 ΐ0 ~ ³ native ΡΡ-5 6.5 ■ 69.2 20.5 76.2 2500 2000 acid-modified PP- 7 0.11 1.34 1.1 1 example 58 5.24 X 10 one ³ native ΡΡ-5 6.5 69.2 20.5 76.2 800 2000 acid-modified PP - 7 0.11 1.34 1.1 example 59 5.24 X 10 one ³ native ΡΡ-5 6.5 69.2 20.5 76.2 1600 2000 acid-modified PP - 7 0.11 1.34 1.1 example 60 5.24 X 10- ³ native ΡΡ-6 2.5 69.2 20.5 76.2 2500 2000 acid-modified PP- 7 0.11 1.34 1.1 example 61 4.76 X 10- ³ native ΡΡ-7 6.7 61.0 22.3 67.4 2500 2000 acid-modified PP-8 0.10 t.27 0.9 example 62 5.71 κ ΐ (Γ ³ unmodified ΡΡ- 5 6.4 53.6 26.3 56.4 2500 2000 Acid modified pp- _{9 9} 0.12 1.42 1.0 Comparative 17 0 Unmodified ΡΡ-5 6.5 69.2 20.5 7¾2 2500 2000 Not used

Comparative Example 18 0.195 Undenatured ΡΡ-5 6.5 69.2 20.5. ■ 76.2 2500 2000 Acid-modified PP-5 4.1 0.56 12

* 1: The amount added to 100 parts by weight of the propylene-based polymer (G2).

mmmm: mesopentad (molar fraction) mr: racemic pentad (molar fraction) (D) irganox 1010 + irgafoss 168

&

Production example 9 '

[Synthesis of maleic anhydride-modified propylene polymer]

(1) Preparation of solid catalyst component

After replacing a 0.5-liter, three-necked flask with a stirrer with a nitrogen gas, 60 ml of dehydrated octane and 16 g of magnesium ethoxy were added.

This was heated to 40 ° C., 2.4 milliliters of silicon tetrachloride was added, and the mixture was stirred for 20 minutes, and then 1.6 milliliters of dibutyl phthalate was added.

The temperature of the solution was raised to 80 ° C., followed by dropwise addition of 77 milliliters of titanium tetrachloride, followed by stirring at an internal temperature of 125 ° C. for 2 hours to perform a contact operation.

100 milliliters of dehydrated otatan was added, the temperature was increased to 125 with stirring, and the temperature was maintained for 1 minute. After stirring was stopped, the solid was settled and the supernatant was extracted.

This washing operation was repeated seven times.

Thereafter, 122 milliliters of titanium tetrachloride was further added, and the mixture was stirred at an internal temperature of 125 for 2 hours to perform a second contact operation.

(2) Preparation of prepolymerized catalyst component

After replacing a 0.5-liter three-necked flask with a stirrer with a nitrogen gas, dehydrated heptane (400 ml), triisobutylaluminum dimethyl (25) .5 milliliter and 4 g of the solid catalyst component prepared in the above (1) were added.

To this, propylene was introduced at room temperature with stirring.

After 1 hour, the stirring was stopped, resulting in 4 g of pro A prepolymerized catalyst component in which pyrene was polymerized was obtained.

(3) Synthesis of propylene polymer ''

A stainless steel autocrepe with an internal volume of 10 liters equipped with a stirrer was thoroughly dried and purged with nitrogen. Was.

After the inside of the system was stabilized at a temperature of 80 ° C and a total pressure of 0.8 MPa, 50 ml of a heptane slurry containing 0.08 mmol of the prepolymerized catalyst component prepared in (2) above in terms of Ti atoms was added. In addition, polymerization was carried out at 80 ° C. for 3 hours while continuously supplying propylene.

After the completion of the polymerization, 50 ml of methanol was added, and the temperature and depressurized contents of the _c were transferred to a filter tank equipped with a filter, and the temperature was raised to 85 ° C to perform solid-liquid separation.

Further, the solid portion was washed twice with 6 liters of heptane at 85 ° C. twice and dried under vacuum to obtain 2.5 kg of a propylene polymer having an intrinsic viscosity [η] of 7.65 d 1 / g.

The catalytic activity per gram of the solid catalyst component was 9.8 kg / g-cat. · 3 hr in 3 hours of polymerization.

(4) Synthesis of maleic anhydride-modified propylene polymer

Propylene polymer synthesized in (3) above: 100 parts by weight, maleic anhydride (denaturing agent): 0.3 parts by weight, and perhexin 25 BZ 40 (2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3, inert solid 40% dilution product) (trade name, radical initiator, manufactured by NOF Corporation): Add 0.05 parts by weight and add a 20 mm twin screw extruder. Melt and knead at 180 ° C 0513

To 100 parts by weight of the obtained pellet-like sample, 50 parts by weight of heptane and 50 parts by weight of acetone were added, and washed in a pressure-resistant reactor at 85 ° C. for 3 hours.

After washing, the pellet was filtered off, added to 200 parts by weight of acetone, and allowed to stand for 16 hours.

Next, the pellet was filtered off, air-dried, and vacuum-dried at 90 ° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer (acid-modified PP-10).

Table 7 shows the physical property values of this polymer.

Production Example 10

[Synthesis of maleic anhydride-modified propylene polymer]

In Example 9 (4), a maleic anhydride-modified propylene polymer (acid-modified PP_1 1) was obtained in the same manner as in Example 9 except that the amount of maleic anhydride used was changed to 1.2 parts by weight. Was.

Table 7 shows the physical property values of this polymer. .

Production example 1 1

[Synthesis of maleic anhydride-modified propylene polymer]

In Preparation Example 9 (4), maleic anhydride-modified propylene polymer (acid-modified PP-12) was prepared in the same manner as in Preparation Example 9 except that the amount of perhexin 25 BZ40 was changed to 0.1 part by weight. ).

Table 7 shows the physical property values of this polymer.

Production example 1 2

[Synthesis of maleic anhydride-modified propylene polymer]

In Preparation Example 9 (4), maleic anhydride-modified propylene polymer (acid-modified PP-13) was prepared in the same manner as in Preparation Example 9 except that the amount of perhexin 25 BZ40 was changed to 0.2 parts by weight. ). · Table 7 shows the physical property values of this polymer.

Production example 1 3

[Synthesis of maleic anhydride-modified propylene polymer]

Production Example 9 Except that in Example 4 (4), the amount of maleic anhydride used was changed to 1.2 parts by weight, and the amount of perhexin 25 B / 40 was changed to 0.2 part by weight, Production Example 9 In the same manner as described above, a maleic anhydride-modified propylene polymer (acid-modified PP-14) was obtained.

Table 7 shows the physical property values of this polymer.

Production Example 14

[Synthesis of maleic anhydride-modified propylene polymer]

(1) Preparation of prepolymerized catalyst component

After replacing a 0.5-liter three-necked flask with a stirrer with nitrogen gas, dehydrated heptane: 400 milliliters, getyl aluminum chloride: 18 g, commercially available Solvay-type titanium trichloride Catalyst (manufactured by Tosoh I-Finchem): 2 g was added. .

The temperature was maintained at 20 ° C, and propylene was introduced with stirring.

After 80 minutes, stirring was stopped to obtain a prepolymerized catalyst component in which 0.8 g of propylene was polymerized per 1 g of the solid catalyst.

(2) Synthesis of propylene polymer

A stainless steel autoclave with an internal volume of 10 liters equipped with a stirrer was sufficiently dried and purged with nitrogen. Then, 6 liters of dehydrated heptane was added, and nitrogen in the system was replaced with propylene.

Then, hydrogen: 0.06 MPaG was added, and propylene was introduced with stirring.

Inner temperature: 65 ° C, Propylene pressure: 0.75 MPa After the inside of the system became stable, the prepolymerized catalyst component prepared in (1) above was contained in an amount of 0.5 g in terms of solid catalyst. Heptane slurry: 50 milliliters was added, and polymerization was carried out at 65 ° C for 1.5 hours while continuously supplying propylene.

After the completion of the polymerization, 50 milliliters of methanol was added, and the temperature was reduced and the pressure was released.

The entire contents were transferred to a filtration tank equipped with a filter, and the temperature was raised to 85 ° C to perform solid-liquid separation.

Further, the solid portion was washed twice with 6 liters of heptane at 85 ° C. twice and dried under vacuum to obtain a propylene polymer having an intrinsic viscosity [η] of 4.02 d 1 Zg: 2.1 kg.

The catalytic activity per gram of solid catalyst was 4.2 kg / g—cat. * 7.5 hr in 7.5 hours of polymerization.

(3) Synthesis of maleic anhydride-modified propylene polymer

20 parts by weight of the propylene polymer synthesized in (2) above, 1.2 parts by weight of maleic anhydride, and 0.0125 parts by weight of perhexine 25 BZ40 were dry-blended. The mixture was melt-kneaded at 180 ° C using a millimeter twin screw extruder.

To 100% by weight of the obtained pellet-like sample, 50 parts by weight of acetone and 50 parts by weight of heptane were added, and the mixture was heated and stirred at 85 ° C. for 2 hours. The heating and stirring were performed in a pressure vessel.

After the operation was completed, the pellets were collected with a wire mesh and immersed in 100 parts by weight of acetone for 15 hours.

Thereafter, the pellets are collected with a wire mesh, air-dried, and then vacuum-dried at 80 ° C for 6 hours and at 130 ° C for 6 hours to obtain a maleic anhydride-modified propylene polymer (acid-modifiable PP-15). Got.

Table 7 shows the physical property values of this polymer.

Production example 1 5 PT / JP2003 / 010513

[Synthesis of maleic anhydride-modified propylene polymer]

In Production Example 14 (3), the maleic anhydride-modified propylene polymer (acid-modified PP-16) was prepared in the same manner as in Production Example 14 except that the amount of perhexin 25BZ40 used was changed to 0.05 parts by weight. ).

Table 7 shows the physical property values of this polymer.

Production Example 1 6

[Synthesis of maleic anhydride-modified propylene polymer]

In Preparation Example 14 (3), the maleic anhydride-modified propylene polymer (acid-modified) was prepared in the same manner as in Preparation Example 14 except that the amount of the protein toxin 25 B / 40 was changed to 0.1 part by weight. PP-1 7) was obtained.

Table 7 shows the physical property values of this polymer.

Production Example 1 7

[Synthesis of maleic anhydride-modified propylene polymer]

In Preparation Example 9 (4), maleic anhydride-modified propylene polymer (acid-modified PP-1) was prepared in the same manner as in Preparation Example 9 except that the amount of perhexin 25 BZ40 was changed to 0.025 parts by weight. 8) was obtained.

Table 7 shows the physical property values of this polymer.

Comparative Production Example 1

[Synthesis of propylene polymer]

A propylene polymer (unmodified PP) was obtained in the same manner as in Production Example 9 except that maleic anhydride was not used in Production Example 9 (4).

Table 7 shows the physical property values of this polymer.

Example 63

[Production of propylene polymer composition]

Production example 9 Acid-modified PP-10 synthesized in (4): 100 parts by weight, 3-aminopropyltriethoxysilane (APTES): 0.05 parts by weight, GANOX 100 (trade name, phenolic antioxidant, Ciba Specialty Chemicals): 0.06 parts by weight, ilgafos 1668 (trade name, phosphorus antioxidant, chiba) 'Specialty' Chemicals): 0.14 parts by weight, stearic acid resin: 0.06 parts by weight, dry blended, and melted at 230 ° C using a 20 mni twin screw extruder The mixture was kneaded to produce a propylene polymer composition.

Table 7 shows the physical property values of this composition.

Examples 64 to 6 7

In Example 63, the amounts of APTE S were changed to 0.025 parts by weight (Example 64), 0.01 parts by weight (Example 65), and 0.1 parts by weight (Example A propylene polymer composition was produced in the same manner as in Example 63, except that 66) and 0.2 parts by weight (Example 67) were used.

Table 7 shows the physical property values of these compositions.

Example 6 8

A propylene polymer composition was produced in the same manner as in Example 63 except that 3-aminopropyltrimethoxysilane (APTMS) was used instead of APTES.

Table 7 shows the physical property values of this composition.

Example 6 9

A propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-11 synthesized in Production Example 10 was used instead of the acid-modified PP-10 in Example 63. Manufactured.

The physical properties of this composition are shown in Table 2.

Example 7 0

In Example 63, propylene was prepared in the same manner as in Example 63, except that the acid-modified PP-12 synthesized in Production Example 11 was used instead of the acid-modified PP-10. A polymer composition was produced.

Table 7 shows the physical property values of this composition.

Example 7 1

A propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-13 synthesized in Production Example 12 was used instead of the acid-modified PP-10 in Example 63. Manufactured.

Table 7 shows the physical property values of this composition.

Example 7 2

A propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP_14 synthesized in Production Example 13 was used instead of the acid-modified PP-10 in Example 63. Manufactured.

Table 7 shows the physical property values of this composition.

Example 7 3

A propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-15 synthesized in Production Example 14 was used instead of the acid-modified PP-10 in Example 63. Manufactured.

Table 7 shows the physical property values of this composition.

Example 7 4

A propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-16 synthesized in Production Example 15 was used instead of the acid-modified PP-10 in Example 63. Manufactured.

Table 7 shows the physical property values of this composition.

Example 7 5.

In Example 63, a propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP- 17 synthesized in Production Example 16 was used instead of the acid-modified PP-10. Manufactured. Table 7 shows the physical property values of this composition.

Comparative Example 1 9

A propylene polymer composition was produced in the same manner as in Example 63 except that APTES was not used.

Table 7 shows the physical property values of this composition.

Comparative Example 20 '

A propylene polymer composition was produced in the same manner as in Example 63 except that the unmodified PP synthesized in Comparative Production Example 1 was used in place of the acid-modified PP-10 in Example 63. .

Table 7 shows the physical property values of this composition.

Comparative Example 2 1

Example 6 Example 6 was repeated except that in place of the acid-modified PP-10, Toyo Tac 100 P (trade name, manufactured by Toyo Gosei Co., Ltd.) was used as the maleic anhydride-modified propylene polymer. A propylene polymer composition was produced in the same manner as in 3.

Table 7 shows the physical property values of this composition.

Comparative Example 22

Example 6 Example 6 was repeated except that Eunox 110 (trade name, manufactured by Sanyo Chemical Co., Ltd.) was used as the maleic anhydride-modified propylene polymer in place of the acid-modified PP-10. A propylene polymer composition was produced in the same manner as in 3.

Table 7 shows the physical property values of this composition.

Example 7 6

A propylene polymer composition was produced in the same manner as in Example 63 except that the amount of APTES was changed to 0.25 part by weight. Next, this composition was added to a homopolyp of intrinsic viscosity []: 1.70 dl Zg. Add propylene (F7044NP, manufactured by Idemitsu Petrochemical Co., Ltd.) to homopolypropylene / composition = 20Z80 (weight ratio), melt blend at 200 ° C, and mix propylene polymer composition. Was manufactured.

Table 7 shows the physical property values of this composition.

Example 7 7, 7 8

In Example 76, except that the homopolypropylene Z composition (weight ratio) was changed to 40/60 (Example 77) and 60/40 (Example 77), respectively, A propylene polymer composition was produced in the same manner as in Example 76. Table 7 shows the physical property values of this composition. '' Example 7 9

A propylene polymer composition was prepared in the same manner as in Example 63 except that the acid-modified PP-18 synthesized in Production Example 17 was used instead of the acid-modified PP-10 in Example 63. Was manufactured.

Next, the homopolypropylene used in Example 76 was added to this composition so that homopolypropylene / composition = 90 to 10 (weight ratio), and the mixture was melt-blended at 200 ° C. A polymer composition was produced.

Table 7 shows the physical property values of this composition.

Examples 80, 8 1.

Same as Example 79 except that the homopolypropylene composition (weight ratio) in Example 79 was changed to 80Z20 (Example 80) and 70/30 (Example 81), respectively. To produce a propylene polymer composition.

Table 7 shows the physical property values of this composition. Table tied o

o

* 1: The amount is based on 100 parts by weight of the maleic anhydride-modified propylene polymer (# 6).

Industrial applicability

According to the present inventions 1 and 2, an α-olefin polymer composition is obtained in which the generation of gel is suppressed, the melt tension is increased, and the moldability is greatly improved.

According to the third aspect of the present invention, it is possible to provide a modified polypropylene pyrene-based resin composition excellent in balance between melt tension and fluidity, and a method for producing the same.

According to the fourth aspect of the present invention, it is possible to use the # 1 method for producing a modified phosphorescent polymer pirates having an excellent melting balance and excellent bacterial balance.

Claims

The scope of the claims

1. (A) Intrinsic viscosity measured in tetralin at 135 ° C [η] Force ^s 0.7 to 5 d1 / g, α-olefin polymer having 2 to 20 carbon atoms 1 0 0 parts by mass, (Β 1) General formula (1)

X _n S i Y _m (OR) ₄ ( _{n + m} ) (1)

0.01 to 1 part by mass of an organic silicon compound represented by the following formula: and 0.01 to 1 part by mass of a polar group derived from a compound containing (C 1) an ethylenic double bond and a polar group in the same molecule. Modified α-olefin polymer having an intrinsic viscosity [] of 0.7 d 1 / g or more and having 2 to 20 carbon atoms at a temperature of 135 ° C in tetralin containing 0.1 to 1% by mass. An α-olefin polymer composition obtained by mixing (contacting) 0 parts by mass.

2. (Β 1) General formula (1)

X „S i Y _m (OR) ₄ _{Cn + m)} (1)

(A) 1 containing 1 to 1 parts by mass of an organosilicon compound represented by the formula:

Intrinsic viscosity measured in tetralin at 35 ° C [77] Force S O. 100 parts by mass of α-olefin polymer having 2 to 20 carbon atoms in the range of 7 to 5 dl / g, and

(C 1) ethylenic double bond and a polar group the polar base derived from a compound 0.0 0 1-1 mass ^_0/0 containing containing in the same molecule, 1 3 5 ° C, in tetralin The measured intrinsic viscosity ₇ ] is obtained by contacting 0.1 to 30 parts by mass of an acid-modified polyolefin polymer having 2 to 20 carbon atoms with a d of at least 0.7 d 1 / g, and a melt tension (MT) and melt flow rate (M l) is, ΜΎ / 7 X (M l ) - 0 · 8> α- old Refuin polymer composition of claim 1 that satisfies one relationship.

3. In the same molecule, X of the general formula (1) contains a substituent containing a group capable of reacting with a carboxylic acid or an anhydride thereof, and an ethylenic double bond and a polar group of the component (C1). 3. The monoolefin polymer composition according to claim 1, wherein the polar group derived from the compound is an acid derived from an unsaturated carboxylic acid and / or an anhydride thereof.

4. The olefin polymer composition according to claim 1 or 2, which satisfies the following (1) to (3).

(1) 0.001 to 1 part by mass of a silicon compound derived from the organic silicon compound as the component (B1);

② melt tension (ΜΤ) and melt flow rate (Ml), MT / '7x (MI) - ° - 8> to satisfy the first relation,

③ 1 Less than 1 mass of insoluble in paraxylene at 30 ° C

5. —The olefin polymer according to claim 1 or 2, wherein X in the general formula (1) is at least one substituent selected from substituents including an amino group, a hydroxyl group, an epoxy group, and an isocyanate group. Composition.

6. The α-olefin polymer composition according to claim 1, wherein the α-olefin polymer modified with the polar group of the component (C1) further satisfies the following (1) to (3). (1) The polar group content and the molar ratio of the chain of the polyolefin polymer), 0.5: 1.0 to 3.0: 1.0

②Weight average molecular weight (Mw) Z ⁷ Number average molecular weight (Mn) is 2.5 or less

(3) Component with Mw of 10,000 or less is 0.5% by mass or less

7. The α-olefin polymer composition according to claim 1, wherein the polar group derived from the compound containing the ethylenic double bond and the polar group in the component (C 1) in the same molecule is maleic anhydride. object.

8. (C 1) component, the propylene polymer or a butene polymer according to claim 1 or 2 which is obtained et the acid-modified a- Orefin polymers with _alpha - O les fin polymer composition .

9. The a-olefin polymer composition according to claim 1 or 2, wherein the component (ii) is a pyrene polymer or a 1-butene polymer having a mesopentad fraction [mmmm] of 97 mol% or more.

1 0. (A) an average particle diameter of 5 0~2 0 0 0 zm component, bulk specific gravity of 0. 2 ~ 0. 6 g / cm 3, non Orefuin polymer according to claim 9 Composition.

1. The o-olefin polymer composition according to claim 1, wherein X in the general formula (1) is a component (B 1) that is a substituent containing an amino group.

1 2. The component (B1) is dispersed in the component (A) under a temperature condition equal to or lower than the melting point of the component (A), and then the component (C1) is mixed (reacted). Or the a-olefin polymer thread according to 2 above.

1 3. The preparation of a mixture of the component (A) and the component (B 1) may be carried out in a drying step and a transferring step in the production of a propylene polymer or a 1-butene polymer, or in a forming step of the polymer. 3. The α-olefin polymer composition according to claim 1, which supplies a component.

1 4. The composition of claim 1, wherein the component (に), the component (B1) and the component (C1) are melt-kneaded or mixed in a solvent. Production method.

1 5. The monoolefin polymer according to claim 1 or 2, wherein the component (Α) containing the component (Β 1) and the component (C 1) are melt-kneaded or mixed in a solvent. A method for producing the composition.

1 6. Melt tension (ΜΤ) and Menoleto flow rate (Ml), MT / 7 X (Ml) “° · ⁸ > obtained by mixing the following components (C 2) and (Β) A modified polypropylene resin composition that satisfies the relationship 1 and has a paraxylene-insoluble component amount of 130 ° C. (G value) force S 1% by weight or less.

(C 2) ethylenic double bond and a polar group polypropylene-based resin compound containing in the same molecule include ^{1 x 1 0- 6 ~ 0. 2} 5 wt% polar base that - derived fat: 1 0 0 parts by weight

(B) Silane coupling agent: 0.01

17 7. In addition to the polypropylene resin (C 2) and the silane coupling agent (B), further add a phosphorus and / or phenolic antioxidant (D) 17. The modified polypropylene resin composition according to claim 16, which is obtained by mixing 1 part by weight.

18. The modified polypropylene resin composition according to claim 16, wherein the compound containing an ethylenic double bond and a polar group in the same molecule is maleic anhydride.

1 9. The modification according to claim 16 or 17, wherein the polypropylene resin (C2) is a mixture of the following (C3) and (C5) or the following (C4) and (C5). Polypropylene resin composition. .

(C 3) Unmodified polypropylene resin having a melt flow rate of 0.01 to 100 g / 10 minutes and a melting point of 145 to 170 ° C .: 100 parts by weight

(C 4) a melt flow rate is that 0. 0 1~ 1 0 0 g / 1 0 min, ¹ ³ C-NMR was measured to seek the main Sopenta' de fraction ([mmmm]) is 4 0-9 unmodified polypropylene resin is 0 mole ^_0/0: 1 00 parts by weight

(C 5) 135 containing 0.001 to 1% by weight of a polar base. C, modified polypropylene resin whose intrinsic viscosity measured in tetralin is 0.7 d1 Zg or more: 0.7 to! 30 parts by weight

20. The unmodified polypropylene resin (C4) has a melting enthalpy of less than 100 JZ g as measured by differential scanning calorimetry (DSC) and a mesopentad determined by measuring ¹³ C—N MR. The modified polypropylene-based resin composition according to claim 19, wherein the ratio ([mmmm] and [rrr1:]) satisfies the relationship of [rrrr] / (1-[mmmm]) ≥ 20%.

2 1. Model of polar group of modified polypropylene resin (C5) and polymer chain 22. The modified polypropylene resin composition according to claim 20, wherein the composition ratio is 0.8 to 2.

22. The modified polypropylene resin according to claim 16 or 17, wherein the modified silane coupling agent (B) is an organic silicon compound represented by the general formula (1).

X _n S i Y _m (OR) ₄ — _{(n + m} ) (1)

23. The modified polypropylene resin composition according to claim 22, wherein X in the general formula (1) is a substituent containing an amino group.

24. Silane coupling agent (B) force S 10-: L 000, pp, phosphorus-based and / or phenol-based antioxidant (D) mosquito 500-10, OOO pm A silane coupling agent (B), a phosphorus-based and / or phenol-based antioxidant (D), and the following polypropylene-based resin (C3) or (C4) are mixed, and 100 parts by weight of the mixture is mixed. On the other hand, a method for producing a modified polypropylene resin composition comprising mixing 0.1 to 30 parts by weight of the following modified polypropylene resin (C5).

(C 3) An unmodified polypropylene resin having a methanol flow rate of 0.01 to 1.0 L / Og / 10 minutes and a melting point of 144 to 170 ° C

(C 4) a melt flow rate is that 0. 0 1~ 1 00 g / 1 0 min, ¹ ³ C-NMR Mesopenta' de fraction was determined by measuring the ([mmmm]) is 4 0-90 moles ⁰ / ₀ unmodified polypropylene resin (C5) A modified polypropylene resin containing 0.001 to 1% by weight of a polar group and having an intrinsic viscosity of 0.7 d1 Zg or more at 135 ° C in tetralin '

2 5. Phosphorous and / or phenolic antioxidants so that the phosphorus and / or phenolic antioxidants (D) are contained at 500 to 10,000 ppm

(D) is mixed with the following polypropylene resin (C 3) or (C 4), and the silane coupling agent (B) is reacted with the following modified polypropylene resin (C 5). A method for producing a modified polypropylene resin composition, comprising mixing 0.1 to 30 parts by weight of the reactant with 0 part by weight.

(C 3) Menoleto flow rate force S O. 01 to: Unmodified polypropylene resin with lOOg / 10 min and melting point of 144 to 170 ° C

(C 4) Melt flow rate is from 0.01 to: L 0 g / 10 min, ¹

³ C-NMR was measured to seek the main source Bae Nta' de fraction ([mmmm]) is the unmodified polypropylene resin which is a 4 0-9 0 mole ^_0/0

2 6. The following component (C6) and component (B) are mixed, and the following component (A) is added to the mixture [(B) + (C6)], and the mixture is added to (A) / [(B) + (C 6)] (Weight ratio) A method for producing a modified hypoolefin polymer composition, which comprises mixing so that the force S becomes 0/100 to 99/1.

(C 6) Modified _α- olefin polymer having 2 to 20 carbon atoms, satisfying the following (a) to (d): 100 parts by weight

(a) A compound containing an ethylenic double bond and a polar group in the same molecule Coming polar base content: 0.001 to 0.4 weight.

(b) Intrinsic viscosity measured at 135 ° C in tetralin: 0.9 to 5.0 d1 / g

(c) Weight average molecular weight Z number average molecular weight (Mw / Mn): 3 or less (d) Molar ratio between the polar group and the polymer chain: 0.1 to 3.0 (Β) Silane coupling agent: 0.0 0 1 to 0.5 parts by weight

(A) α-olefin polymer having 2 to 20 carbon atoms having an intrinsic viscosity of 0.7 to 5.0 d 1 / g measured in tetralin at 135 ° C.

2 7. Modification-Melt tension (ΜΤ), melt flow rate (M l), MT / 7 X (M l) of the polymer composition. 27. The production of the modified α-olefin polymer composition according to claim 26, wherein the relationship of ⁸ > 1 is satisfied and the amount of paraxylene-insoluble component (G value) at 130 ° C. is 1% by weight or less. Method.

28. The process for producing a modified α-olefin polymer composition according to claim 26 or 27, wherein the modified monoolefin polymer (C 6) and the silane coupling agent (Β) are melt-mixed.

29. The method for producing a modified _α -olefin polymer composition according to claim 28, wherein the molten mixture [(Β) + (C 6)] and the c-olefin polymer (A) are melt-mixed.

30. The modified α-olefin polymer according to claim 26 or 27, wherein the modified α-olefin polymer (C 6) is a modified S, modified propylene (co) polymer or modified 1-butene (co) polymer. A method for producing the composition. .

31. The process for producing a modified monoolefin polymer composition according to claim 26 or 27, wherein the compound containing an ethylenic double bond and a polar group in the same molecule is maleic anhydride.

32. The modified a-olefin polymer composition according to claim 26 or 27, wherein the silane coupling agent (B), (B1) is an organic silicon compound represented by the general formula (1). Production method.

X n S i Ym (OR) ₄ — _{(n + m)} (1)

3. The method for producing a modified α-olefin polymer composition according to claim 32, wherein X in the general formula (1) is a substituent containing an amino group.