WO2015166666A2

WO2015166666A2 - Injection-molded article for packaging material, injection-molded article for automotive part, industrial film, and food packaging film

Info

Publication number: WO2015166666A2
Application number: PCT/JP2015/004235
Authority: WO
Inventors: Saho Nojiri; Hidekazu Yamada; Kenji Ikeda
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2015-08-24
Filing date: 2015-08-24
Publication date: 2015-11-05
Also published as: WO2015166666A3

Abstract

The present invention relates to an injection-molded article for a packaging material and an injection-molded article for an automotive part each comprising a propylene resin and each being excellent in the balance between rigidity and impact resistance, a food packaging film comprising a propylene resin and excellent in tensile property at a high temperature, and an industrial film comprising a propylene resin, being excellent in tensile property at a high temperature, and having a high dielectric constant. Provided is the injection-molded article that comprises a propylene resin represented by the following formula (1) or the following formula (2).

Description

INJECTION-MOLDED ARTICLE FOR PACKAGING MATERIAL, INJECTION-MOLDED ARTICLE FOR AUTOMOTIVE PART, INDUSTRIAL FILM, AND FOOD PACKAGING FILM

The present invention relates to an injection-molded article for a packaging material and an injection-molded article for an automotive part each comprising a propylene resin and each being excellent in the balance between rigidity and impact resistance, a food packaging film comprising a propylene resin and being excellent in tensile property at a high temperature, and an industrial film comprising a propylene resin, being excellent in tensile property at a high temperature, and having a high dielectric constant.

Propylene resins are applied to various uses such as automotive uses, food packaging uses, medical uses, optical uses, and electric and electronic uses by being formed into films, containers, etc. An injection-molded article used for a packaging material such as a container or an automotive part is traditionally required to be excellent in the balance between rigidity and impact resistance, and a film used for industrial uses and food packages is traditionally required to be excellent in tensile property at a high temperature. A film used for packaging an electronic part in the industries is required to have a high dielectric constant. Various propylene resins have therefore been developed each corresponding to its suitable use (Patent Documents 1 to 3).

[PTL1]Patent Document 1: Japanese Laid-Open Patent Publication No. 9-87479
[PTL2]Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-49012
[PTL3]Patent Document 3: WO 2011/013501 A1

The injection-molded article comprising the propylene resin described in each of the Patent Documents is not satisfactory in the balance between rigidity and impact resistance. The film comprising the propylene resin described in each of the Patent Documents is unsatisfactory in tensile property at a high temperature and is less prone to be high in dielectric constant.

An object of the present invention is to provide an injection-molded article for a packaging material and an injection-molded article for an automotive part each comprising a propylene resin and each being excellent in the balance between rigidity and impact resistance, a food packaging film comprising a propylene resin and being excellent in tensile property at a high temperature, and an industrial film comprising a propylene resin, being excellent in tensile property at a high temperature, and having a high dielectric constant.

The present invention is in one aspect thereof an injection-molded article for a packaging material comprising a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom; "X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety; "A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.

The present invention is in another aspect thereof an injection-molded article for an automotive part comprising a propylene resin represented by the following formula (1) or the following formula (2),

The present invention is in another aspect thereof an industrial film comprising a propylene resin represented by the following formula (1) or the following formula (2),

The present invention is in yet another aspect thereof a food packaging film comprising a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom; "X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety; "A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.
The propylene resin represented by the above formula (1) or the above formula (2) will hereinafter be referred to as "propylene resin of the present invention".

According to the present invention, there can be obtained an injection-molded article for a packaging material and an injection-molded article for an automotive part each comprising a propylene resin and each being excellent in the balance between rigidity and impact resistance, a food packaging film comprising a propylene resin and being excellent in tensile property at a high temperature, and an industrial film comprising a propylene resin, being excellent in tensile property at a high temperature, and having a high dielectric constant.

The "hydrocarbyl group" herein refers to a univalent group having a structure formed by removing one hydrogen atom from a carbon hydride. The "hydrocarbyloxy group" herein refers to a univalent group having a structure formed by substituting a hydrogen atom of a hydroxy group by a hydrocarbyl group. The "hydrocarbyl group substituted by a halogen atom" herein refers to a univalent group having a structure formed by substituting at least one hydrogen atom of a hydrocarbyl group by a halogen atom. The "hydrocarbyloxy group substituted by a halogen atom" herein refers to a univalent group having a structure formed by substituting at least one hydrogen atom of a hydrocarbyloxy group by a halogen atom. A "hydrocarbylene group" herein refers to a divalent group formed by removing two hydrogen atoms from a carbon hydride.

The propylene resin of the present invention is a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom;
"X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety; and
"A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.

The halogen atom represented by R¹ or R² may be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The hydrocarbyl group having 1 to 20 carbon atoms represented by R¹ or R² may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, a 1-methylbutyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a n-hexyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a n-octyl group, and a n-dodecyl group and, preferably, is a methyl group.
The cycloalkyl group having 3 to 20 carbon atoms may be a cyclopentyl group and a cyclohexyl group, and, preferably, is a cyclohexyl group.
The aryl group having 6 to 20 carbon atoms may be a phenyl group, a tolyl group, an ethylphenyl group, and a xylyl group.
The aralkyl group having 7 to 20 carbon atoms may be a benzyl group and a phenethyl group.

The hydrocarbyloxy group having 1 to 20 carbon atoms represented by R¹ or R² may be an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms.

The alkoxy group having 1 to 20 carbon atoms may be a methoxy group, an ethoxy group, a n-propoxy group, an isopuropoxy group, a n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.
The aryloxy group having 6 to 20 carbon atoms may be a phenyloxy group, a tolyloxy group, an ethylphenyloxy group, and a xylyloxy group.
The aralkyloxy group having 7 to 20 carbon atoms may be a benzyloxy group and a phenethyloxy group.

For the hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom represented by R¹ or R², the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
For the hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom that is represented by R¹ or R², examples of the hydrocarbyl group having 1 to 20 carbon atoms are similar to those provided as examples for the hydrocarbyl group having 1 to 20 carbon atoms represented by R¹ and R².

For the hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom represented by R¹ or R², the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
For the hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom represented by R¹ or R², examples of the hydrocarbyloxy group having 1 to 20 carbon atoms are similar to those provided as examples for the hydrocarbyloxy group having 1 to 20 carbon atoms represented by R¹ and R².

R¹ is, preferably, a hydrocarbyl group having 1 to 20 carbon atoms, is, more preferably, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms, and is, yet more preferably, a methyl group, an isopropyl group, a 1-ethylpentyl group, or a cyclohexyl group.
Preferably, R² is a hydrogen atom.

Preferably, X¹ or X² is a linking moiety having at least one type of linkage selected from the group including an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, a thioamide linkage, an imide linkage, a urea linkage, a thiourea linkage, a urethane linkage, and a thiourethane linkage.
X¹ and X² in the above formula (2) may be same linking moieties or may be linking moieties different from each other.

Preferably, X¹ is a linking moiety represented by the following formula (3),

in the above formula (3),
"R³" represents a hydrocarbylene group having 1 to 20 carbon atoms,
"Y¹" represents an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, a thioamide linkage, an imide linkage, a urea linkage, a thiourea linkage, a urethane linkage, a thiourethane linkage, a linkage represented by the following formula (4), or a linkage represented by the following formula (5) (the linkages represented by the following formula (4) and the linkage represented by the following formula (5) are each attached to D¹ in the above formula (3) at *³ in the following formula (4) and *³ in the following formula (5), and are each attached to R³ in the above formula (3) at *⁴ in the following formula (4) and *⁴ in the following formula (5).),
"n" represents one or zero, and
"D¹" represents a hydrocarbylene group having 1 to 20 carbon atoms or a group represented by the following formula (6); the linking moiety represented by the above formula (3) is attached to A in the above formula (1) or A in the above formula (2) at *¹ in the formula (3) and a bond with a nitrogen atom in the above formula (1) or a nitrogen atom in the above formula (2) at *² in the above formula (3),

in the above formula (6),
"l" represents an integer equal to or greater than zero and equal to or smaller than 20,
"Y" represents an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, a thioamide linkage, an imide linkage, a urea linkage, a thiourea linkage, a urethane linkage, a thiourethane linkage, a linkage represented by the following formula (7), or a linkage represented by the following formula (8) (the linkage represented by the following formula (7) and the linkage represented by the following formula (8) are each attached to CH₂ in the above formula (6) at *⁷ in the following formula (7) and *⁷ in the following formula (8), and are each attached to R⁴ in the above formula (6) at *⁸ in the following formula (7) and *⁸ in the following formula (8)), and
"R⁴" represents a hydrocarbylene group having 1 to 20 carbon atoms;
the group represented by the above formula (6) is attached to A in the above formula (1) or A in the above formula (2) at *⁵ in the above formula (6) and is attached to Y¹ in the above formula (3) at *⁶ in the above formula (6).

The hydrocarbylene group having 1 to 20 carbon atoms represented by R³, R⁴, or D¹ may be an alkylene group, an alkenediyl group, an arylene group, and a group including an arylene group bonding to an alkylene group (hereinafter, may be referred to as "arylene-alkylene group"). The alkylene group may be a methylene group, an ethylene group, a propylene group, a 1-methylethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a 2,2,4-trimethylhexane-1,6-diyl group, a group represented by the following formula (a), and a group represented by the following formula (c). The alkenediyl group may be a propenylene group, a 3-methylpropenylene group, a 3,3-dimethylpropenylene group, and a propa-1-ene-2,3-diyl group. The arylene group may be a phenylene group, a naphthylene group, and a biphenylene group. The arylene-alkylene group may be a phenylene-alkylene group, a naphthylene-alkylene group, a biphenylene-alkylene group, and the group represented by the following formula (b).

R³ is, preferably, an alkylene group or an arylene-aklylene group and is, more preferably, a hexamethylene group, the group represented by the above formula (a), the group represented by the above formula (b), or the group represented by the above formula (c).
R⁴ is, preferably, an alkylene group and is, more preferably, a propylene group.
D¹ is, preferably, an alkylene group or an alkenediyl group and is, more preferably, a methylene group, a propenylene group, a 3-methylpropenylene group, a 3,3-dimethylpropenylene group, or a propa-1-ene-2,3-diyl group.

Preferably, X² is the linkage represented by the following formula (9),

in the above formula (9),
"R⁵" and "R⁶" each independently represent a hydrocarbylene group having 1 to 20 carbon atoms,
"Y²" and "Y³" each independently represent an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, a thioamide linkage, an imide linkage, a urea linkage, a thiourea linkage, a urethane linkage, a thiourethane linkage, the linkage represented by the following formula (10), or the linkage represented by the following formula (11) (when Y² is the linkage represented by the following formula (10) or the linkage represented by the following formula (11), this linkage is attached to D² in the above formula (9) at *¹¹ in the following formula (10) and *¹¹ in the following formula (11), and is attached to R⁵ in the above formula (9) at *¹² in the following formula (10) and *¹² in the following formula (11) and, when Y³ is the linkage represented by the following formula (10) or the linkage represented by the following formula (11), this linkage is attached to R⁵ in the above formula (9) at *¹¹ in the following formula (10) and *¹¹ in the following formula (11), and is attached to R⁶ in the above formula (9) at *¹² in the following formula (10) and *¹² in the following formula (11)),
"m" represents one or zero, and
"D²" represents a hydrocarbylene group having 1 to 20 carbon atoms or a group represented by the following formula (12).
The linking moiety represented by the above formula (9) establishes a bond with a carbon atom in the above formula (2) at *⁹ in the above formula (9) and established a bond with A in the above formula (2) at *¹⁰ in the above formula (9),

wherein "o" represents an integer equal to or greater than zero and equal to or smaller than 20,
"Y'" represents an ether linkage, a thioether linkage, an ester linkage, a thioester linkage, an amide linkage, a thioamide linkage, an imide linkage, a urea linkage, a thiourea linkage, a urethane linkage, a thiourethane linkage, the linkage represented by the following formula (13), or the linkage represented by the following formula (14) (the linkage represented by the following formula (13) and the linkage represented by the following formula (14) are each attached to CH₂ in the above formula (12) at *¹⁵ in the following formula (13) and *¹⁵ in the following formula (14) and are attached to R⁷in the above formula (12) at *¹⁶ in the following formula (13) and at *¹⁶ in the following formula (14)),
"R⁷" represents a hydrocarbylene group having 1 to 20 carbon atoms, and
the group represented by the above formula (12) is attached to A in the above formula (1) or A in the above formula (2) at *¹⁴ in the above formula (12) and establishes a bond with Y² in the above formula (9) at *¹³ in the above formula (12).

The hydrocarbylene group having 1 to 20 carbon atoms represented by R⁵, R⁶, R⁷, or D² may be an alkylene group, an alkenediyl group, an arylene group, and a group including an arylene group bonding to an alkylene group (hereinafter, may be referred to as "arylene-alkylene group"). The alkylene group may be a methylene group, an ethylene group, a propylene group, a 1-methylethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a 2,2,4-trimethylhexane-1,6-diyl group, the group represented by the above formula (a), and the group represented by the above formula (c). The alkenediyl group may be a propenylene group, a 3-methylpropenylene group, a 3,3-dimethylpropenylene group, a propa-1-ene-2,3-diyl group, and a pentane-2-ene-1.5-diyl group. The arylene group may be a phenylene group, a naphthylene group, and a biphenylene group. The arylene-alkylene group may be a phenylene-alkylene group, a naphthylene-alkylene group, a biphenylene-alkylene group, and the group represented by the above formula (b).

R⁵ is, preferably, an alkylene group or an arylene-alkylene group and is, more preferably, a hexamethylene group, the group represented by the above formula (a), the group represented by the above formula (b), or the group represented by the above formula (c).
R⁶ is, preferably, an alkylene group and is, more preferably, an ethylene group.
R⁷ is, preferably, an alkylene group and is, more preferably, a propylene group. D² is, preferably, an alkylene group or an alkenediyl group and is, more preferably, a methylene group, a propenylene group, a 3-methylpropenylene group, a 3,3-dimethylpropenylene group, or a propa-1-ene-2,3-diyl group.

The propylene polymer residue represented by "A" may be a propylene homopolymer residue, and a propylene copolymer residue including a monomer unit originated from propylene and a monomer unit originated from at least one selected from the group including ethylene and α-olefins each having four or more carbon atoms. The "polymer residue" means a moiety formed by removing one or two hydrogen atom(s) from a mother polymer.
The two "A"s in the above formula (2) may have the same structure or may have structures different from each other.

Because the propylene resin of the present invention includes the group represented by the following formula (A) or the following formula (B), hydrogen bonds may be formed between the molecules or in the molecule. The propylene resin therefore has a short molding cycle, is excellent in fluidity, and can provide an injection-molded article for a packaging material and an injection-molded article for an automotive part each excellent in the balance between rigidity and impact resistance, a food packaging film excellent in tensile property at a high temperature, and an industrial film excellent in tensile property at a high temperature and having a high dielectric constant.

"R¹" in the above formula (A) is synonymous with R¹ in the above formula (1), and "R¹" and "R²" in the above formula (B) are synonymous with R¹ and R² in the above formula (2).
The group represented by the above formula (A) is attached to X¹ in the above formula (1) at * in the formula (A), and the group represented by the above formula (B) is attached to X¹ in the above formula (2) at * in the formula (B) and establishes a bond with X² in the above formula (2) at ** in the formula (B).

Preferably, the propylene resin of the present invention is the propylene resin represented by the above formula (1).

The weight-average molecular weight (Mw) of the propylene resin of the present invention is, preferably, equal to or larger than 500 and is, more preferably, equal to or larger than 1,000 in order to improve the balance between the rigidity and the impact resistance of an injection-molded article for a packaging material and an injection-molded article for an automotive part and in order to improve the tensile property at a high temperature of an industrial film and a food packaging film.
The molecular weight distribution (Mw/Mn) of the propylene resin of the present invention is, preferably, 1 to 8 and is, more preferably, 1.5 to 7 in order to reduce the molding cycle of the propylene resin, in order to improve the fluidity of the propylene resin, and in order to improve the balance between the rigidity and the impact resistance of an injection-molded article for a packaging material and an injection-molded article for an automotive part, and in order to improve the tensile property at a high temperature of an industrial film and a food packaging film.
The weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the propylene resin of the present invention can be adjusted by adjusting the weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of a propylene polymer that is the raw material thereof.

The weight-average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of the propylene resin of the present invention are measured under the following conditions using a gel permeation chromatography.
<Measurement Conditions>
Instrument Model: 150C (manufactured by Waters Corporation)
Column: TSK-GEL GMH6-HT, 7.5 mm (diameter)×300 mm (length)×three pieces
Measurement Temperature: 140°C
Solvent: Orthodichlorobenzene
Measurement Concentration: 5 mg/5 ml

The limiting viscosity of the propylene resin of the present invention is 0.1 dl/g to 10 dl/g. The limiting viscosity is acquired using a calculation method described in Section 491 of "Study on High Molecule Solutions and High Molecule Experiments 11" (1982, Kyoritsu Shuppan Co., Ltd.), that is, an extrapolation method of plotting the reduced viscosity for each concentration and extrapolating the concentration to be zero, from the reduced viscosities measured at a temperature of 135°C using an Ubbelohde viscometer and tetrahydronaphthalene as the solvent.

The propylene resin of the present invention has a shear viscosity of 1 Pa.sec to 300 Pa.sec, and is superior in fluidity to a propylene polymer that does not include the group represented by the above formula (A) or the above formula (B).
The shear viscosity is a value measured with a capillary rheometer including a barrel to melt a specimen therein and attached with a capillary having a diameter of 1 mm, a length of 40 mm, and an inflow angle of 90° when the propylene resin is heated at 230°C by the capillary rheometer to be melted and is extruded thereby at a shear velocity of 2.432×10³ sec^-1.

The half-isothermal crystallization time period of the propylene resin of the present invention is 10 sec to 200 sec, and the propylene resin has a shorter molding cycle than that of the propylene polymer that does not include the group represented by the above formula (A) or the above formula (B).
The half-isothermal crystallization time period can be acquired from a differential scanning caloric curve. Using a differential scanning calorimeter, the differential scanning caloric curve is acquired by increasing the temperature from the room temperature to 220°C at a rate of 500 °C/min, maintaining the temperature at 220°C for 5 min, reducing the temperature thereafter from 220°C to the isothermal crystallization temperature (130°C) at a rate of 500 °C/min, and maintaining the temperature at 130°C. The half-isothermal crystallization time period is acquired from the curve. The half-isothermal crystallization time period is calculated as a time period for the value of the heat flow to reach its minima value, assuming that the isothermal crystallization process starting time (the time at which the temperature reaches the isothermal crystallization temperature from 220°C) t is t=0.

The production method of the propylene resin of the present invention may be a method of melting and kneading the modified propylene polymer and the compound represented by the following formula (15) or the following formula (16) with each other, and a method of mixing the modified propylene polymer and the compound represented by the following formula (15) or the following formula (16) with each other in a solvent,

wherein "Z¹" and "Z²" in the above formula (15) and "Z¹" and "Z²" in the above formula (16) each independently represent a halogen atom, a hydroxyl group, a thiol group, a group represented by -CO-O-CO-, a group represented by -CO-S-CO-, a group represented by -CO-X ("X" represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a carboxy group, a thiocarboxy group, a formyl group, a thioformyl group, a carbonyl group, a thiocarbonyl group, an amino group, an imino group, a nitro group, a group represented by RCONH-, a group represented by RCSNH-, a group represented by RCO(NR)CO-, a group represented by -COOR, a group represented by -COSR, a group represented by -CSOR, a group represented by -OR, a group represented by -SR (any "R" represents a hydrocalbyl group.), an epoxy group, a thioepoxy group, an isocyanate group, an isothiocyanate group, or an azi group.

A kneader used for the melting and the kneading may be any known apparatus such as a Banbury mixer, a plast mill, a Brabender plastgraph, a one-screw extruder, or a two-screw extruder. The set temperature of the kneader during the melting and the kneading is, preferably, a temperature of 160°C to 250°C, is, more preferably, 160°C to 230°C, and is, yet more preferably, 160°C to 210°C. The temperature during the mixing in a solvent is, preferably, a temperature of 50°C to 250°C, is, more preferably, 70°C to 230°C, and is, yet more preferably, 100°C to 200°C. The solvent used for the mixing in a solvent may be toluene, xylene, 1,2-dichlorobenzene, n-octylbenzene, tetrahydronaphthalene, decane, decahydronaphthalene, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.

The modifiedpropylene polymer is a propylene polymer including at least one reaction site capable of reacting with the compound represented by the above formula (15) or the above formula (16). The reaction site capable of reacting with the compound represented by the above formula (15) or the above formula (16) may be a halogen atom, a hydroxyl group, a thiol group, a group represented by -CO-O-CO-, a group represented by -CO-S-CO-, a group represented by -CO-X ("X" represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a carboxy group, a thiocarboxy group, a formyl group, a thioformyl group, a carbonyl group, a thiocarbonyl group, an amino group, an imino group, a nitro group, a group represented by RCONH-, a group represented by RCSNH-, a group represented by RCO(NR)CO-, a group represented by -COOR, a group represented by -COSR, a group represented by -CSOR, a group represented by -OR, a group represented by -SR (any "R" represents a hydrocalbyl group.), an epoxy group, a thioepoxy group, an isocyanate group, an isothiocyanate group, or an azi group.

The production method of the modified propylene polymer may be, for example, a method of reacting a propylene polymer including a carbon-carbon double bond at least at one end thereof and an organic compound into which the reaction site can be introduced, with each other, a method of copolymerizing a compound including a functional group or a linkage that includes an atom having electronegativity different from that of a carbon atom and a carbon-carbon double bond (hereinafter, referred to as "compound A") and propylene with each other, a method of reacting a compound acquired by copolymerizing the compound A and propylene with each other, and an organic compound into which the reaction site can be introduced, with each other, a method of reacting a propylene polymer and the compound A with each other, and a method of reacting a propylene polymer and the compound A with each other and reacting thereafter the acquired compound and an organic compound into which the reaction site can be introduced, with each other.

The propylene polymer including a carbon-carbon double bond at least at one end thereof can be produced using any of the following methods.
[1] A method of polymerizing propylene in the presence of a metallocene catalyst
[2] A method of introducing a double bond to an end of the propylene polymer using a pyrolytic reaction or a radical decomposition reaction

For the method of polymerizing propylene in the presence of a metallocene catalyst, the metallocene catalyst may be, for example, a catalyst described in International Patent Publication No. 2001-525461 and that described in Japanese Laid-Open Patent Publication No. 2009-299045.

The method of introducing a carbon-carbon double bond to an end of a propylene polymer using a pyrolytic reaction may be a method of melting and kneading the propylene polymer. For example, the method is a method according to which a reaction container such as the one made from stainless steel including a stirrer is filled with an inert gas such as nitrogen or argon, and the propylene polymer is thereafter added thereto to be melted and kneaded.

The radical decomposition reaction is a reaction that is caused to occur by heating a mixture of an organic peroxide and the propylene polymer at a temperature of 160°C to 300°C.
The method of introducing a carbon-carbon double bond to an end of the propylene polymer using a radical decomposition reaction may be a batch method or a fusion continuation method.

The method of introducing a carbon-carbon double bond to an end of the propylene polymer using a batch method may be, for example, a method according to which a reaction container such as the one made from stainless steel including a stirrer is filled with an inert gas such as nitrogen or argon, the propylene polymer is added thereto to be heated and melted, and an organic peroxide is added to the melted propylene polymer to be heated for a predetermined time period. The organic peroxide and the propylene polymer may each be dissolved in a solvent to be used. The solvent may be toluene, xylene, 1,2-dichlorobenzene, n-octylbenzene, tetrahydronaphthalene, decane, decahydronaphthalene, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.

The method of introducing a carbon-carbon double bond to an end of the propylene polymer using a fusion continuation method may be, for example, a method of impregnating the organic peroxide with the propylene polymer, and a method of mixing the propylene polymer and the organic peroxide with each other. The apparatus to be used therefor may be a one-screw extruder or a two-screw extruder.

The functional group or the linkage including an atom having electronegativity different from that of a carbon atom in the compound A may be a halogen atom, a hydroxyl group, a thiol group, an alkoxy group, a group represented by -CO-O-CO, a group represented by -CO-S-CO, a group represented by -CO-X ("X" represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a carboxy group, a thiocarboxy group, a formyl group, a thioformyl group, a carbonyl group, a thiocarbonyl group, an amino group, an imino group, an amide linkage, a thioamide linkage, an imide linkage, a nitro group, an ester linkage, a thioester linkage, a cyano group, an isocyano group, an ether linkage, a thioether linkage, an epoxy group, a thioepoxy group, an isocyanate group, an isothiocyanate group, an azi group, a silyl group, an alkylsilyl group, an alkoxysilyl group, a nitroso group, a hydrazide group, an oxime group, and a sulfide group. Examples of the compound A include unsaturated carboxylic acids such as maleic acid, fumaric acid, and itaconic acid, unsaturated carboxylic acid derivatives such as maleic acid anhydride, itaconic acid anhydride, maleimide, maleic hydrazide, methylnadic acid anhydride, dichloromaleic acid anhydride, and amide maleate, and unsaturated epoxy compounds such as glycidylacrylate, glycidylmethacrylate, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, and allylglycidyl ether.

The method of reacting the propylene polymer and the compound A with each other may be, for example, a method of reacting the propylene polymer, the compound A, and the organic peroxide with each other.

The method of reacting the propylene polymer, the compound A, and the organic peroxide with each other may be a method of melting and kneading the propylene polymer, the compound A, and the organic peroxide with each other, and a method of mixing the propylene polymer, the compound A, and the organic peroxide with each other in a solvent. The kneader used for the melting and the kneading may be any known apparatus such as a Banbury mixer, a plast mill, a Brabender plastgraph, a one-screw extruder, or a two-screw extruder. The solvent used for the mixing in a solvent may be toluene, xylene, 1,2-dichlorobenzene, n-octylbenzene, tetrahydronaphthalene, decane, decahydronaphthalene, 1,2-dichloroethane, and 1,1,2,2-tetrachloroethane.

The propylene polymer used in producing the propylene polymer including a carbon-carbon double bond at least at one end thereof, or the propylene polymer used in reacting the propylene polymer and the compound A with each other may be a propylene homopolymer, and a propylene copolymer including a monomer unit originated from propylene and a monomer unit originated from at least one selected from the group including ethylene and α-olefins each having four or more carbon atoms.

The polymerization catalyst used in producing the propylene polymer may be, for example, a Ziegler-type catalyst system, a Ziegler-Natta-type catalyst system, a metallocene catalyst system that includes a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring (a metallocene compound) and alkylalminoxan, a catalyst system that includes a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring, a compound forming an ionic complex by reacting with the compound of the transition metal, and an organic aluminum compound, and a supported metallocene catalyst system whose inorganic particles such as silica or a clay mineral support the catalyst components such as a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring, a compound forming an ionic complex by reacting with the compound of the transition metal, and an organic aluminum compound. An auxiliary polymerization catalyst may be used in the presence of any of the above catalyst systems. The auxiliary polymerization catalyst may be, for example, the catalyst systems described in Japanese Laid-Open Patent Publication Nos. 61-218606, 5-194685, 7-216017, 9-316147, 10-212319, and 2004-182981.

The production method of the propylene polymer may be, for example, bulk polymerization, solution polymerization, slurry polymerization, or gas phase polymerization. A solvent used in the solution polymerization and the slurry polymerization may be an inert carbon hydride such as propane, butane, isobutane, pentane, hexane, heptane, or decane. These polymerization methods may be executed in either the batch system or the continuous system, and some of these polymerization methods may be combined with each other. Preferably, a continuous gas phase polymerization method, or a bulk-gas phase polymerization method of continuously executing the bulk polymerization method and the gas phase polymerization method is used.

In the production of the propylene polymer, the propylene polymer may be dried at a temperature lower than the melting temperature of the propylene polymer to remove any residual solvent included in the propylene polymer, oligomers each having an ultra-low molecular weight and each formed as a by-product during the production. The method of drying the propylene polymer may be, for example, the methods described in Japanese Laid-Open Patent Publication No. 55-75410 and Japanese Patent Publication No. 2565753.

The compound represented by the above formula (15) is, preferably, a compound represented by the following formula (15a) and is, more preferably, a compound represented by the following formula (15b) or the following formula (15c),

wherein "Z³" in the above formula (15a) represents a halogen atom, a hydroxyl group, a thiol group, a group represented by -CO-O-CO-, a group represented by -CO-S-CO-, a group represented by -CO-X ("X" represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a carboxy group, a thiocarboxy group, a formyl group, a thioformyl group, a carbonyl group, a thiocarbonyl group, an amino group, an imino group, a nitro group, a group represented by RCONH-, a group represented by RCSNH-, a group represented by RCO(NR)CO-, a group represented by -COOR, a group represented by -COSR, a group represented by -CSOR, a group represented by -OR, a group represented by -SR (any "R" represents a hydrocalbyl group.), an epoxy group, a thioepoxy group, an isocyanate group, an isothiocyanate group, or an azi group. "R¹" and "R²" are synonymous with R¹ and R² in the above formula (1), and "R³" is synonymous with R³ in the above formula (3),

wherein "R¹" and "R²" in the above formula (15b) are synonymous with R¹ and R² in the above formula (1),

wherein "R¹" and "R²" in the above formula (15c) are synonymous with R¹ and R² in the above formula (1).

The compound represented by the above formula (16) is, preferably, the compound represented by the following formula (16a) and is, more preferably, the compound represented by the following formula (16b) or the following formula (16c),

wherein "Z⁴" and "Z⁵" in the above formula (16a) each independently represent a halogen atom, a hydroxyl group, a thiol group, an alkoxy group, a group represented by -CO-O-CO-, a group represented by -CO-S-CO-, a group represented by -CO-X ("X" represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.), a carboxy group, a thiocarboxy group, a formyl group, a thioformyl group, a carbonyl group, a thiocarbonyl group, an amino group, an imino group, a nitro group, a group represented by RCONH-, a group represented by RCSNH-, a group represented by RCO(NR)CO-, a group represented by -COOR, a group represented by -COSR, a group represented by -CSOR, a group represented by -OR, a group represented by -SR (any "R" represents a hydrocalbyl group.), an epoxy group, a thioepoxy group, an isocyanate group, an isothiocyanate group, or an azi group. "R¹" is synonymous with R¹ in the above formula (2). "R³" is synonymous with R³ in the above formula (3). "R⁵", "R⁶", and "Y³" are synonymous with R⁵, R⁶, and Y³ in the above formula (9),

wherein "R¹" in the above formula (16b) is synonymous with R¹ in the above formula (2),

wherein "R¹" in the above formula (16c) is synonymous with R¹ in the above formula (2).

The production method of the compound represented by the above formula (15) or (16) may be, for example, a method described in Japanese Laid-Open Patent Publication No. 2007-522261 or Journal of Applied Polymer Science, Vol. 123, 1755-1763 (2012).

The propylene resin of the present invention is acquired by an addition reaction or a condensation reaction occurring between the modifiedpropylene polymer and the compound represented by the above formula (15) or (16) by the above production method.

The propylene resin of the present invention may be mixed with a propylene polymer (X) to be used. The mixture of the propylene resin and the propylene polymer (X) will hereinafter be referred to as "propylene resin composition".
The propylene polymer (X) may be a propylene homopolymer, a propylene random copolymer including a monomer unit originated from propylene and a monomer unit originated from at least one selected from the group including ethylene and α-olefins each having four or more carbon atoms, a propylene polymerized material, and a modified propylene polymer.
The propylene polymerized material is a material including a polymer component (I) and a copolymer component (II). The polymer component (I) may be a propylene homopolymer component. The copolymer component (II) may be a copolymer component including a constituent unit originated from propylene and a monomer unit originated from at least one selected from the group including ethylene and α-olefins each having four or more carbon atoms. The modified propylene polymer is similar to the above modifiedpropylene polymer used in the production of the propylene resin of the present invention.
The propylene polymer (X) may be used alone or two or more types thereof may concurrently be used.

The α-olefins each having four or more carbon atoms in the propylene random copolymer and the α-olefins each having four or more carbon atoms in the copolymer component (II) of the propylene polymerized material can each be 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimety-1-pentene, ethyl-1-pentene, triethyl-1-butenne, methylethyl-1-butenen, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentenen, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene and, preferably, are each an α-olefin having four or more and eight or less carbon atoms.

The polymerization catalyst used in the production of the propylene homopolymer in the propylene polymer (X) and the propylene random copolymer can each be, for example, a Ziegler-type catalyst system, a Ziegler-Natta-type catalyst system, a metallocene catalyst system that includes a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring (a metallocene compound) and alkylalminoxan, a catalyst system that includes a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring, a compound forming an ionic complex by reacting with the compound of the transition metal, and an organic aluminum compound, and a supported metallocene catalyst system whose inorganic particles such as silica or a clay mineral support the catalyst components such as a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring, a compound forming an ionic complex by reacting with the compound of the transition metal, and an organic aluminum compound. An auxiliary polymerization catalyst may be used in the presence of any of the above catalyst systems. The auxiliary polymerization catalyst may be, for example, the catalyst systems described in Japanese Laid-Open Patent Publication Nos. 61-218606, 5-194685, 7-216017, 9-316147, 10-212319, and 2004-182981.

The production method of the propylene polymerized material may be a method of executing multi-stage polymerization using a polymerization catalyst. The method may be, for example, a method of producing the homopolymer component (I) at a pre-stage polymerization step and producing the copolymer component (II) at a post-stage polymerization step.
The polymerization catalyst used in the production of the propylene polymerized material may be, for example, a Ziegler-type catalyst system, a Ziegler-Natta-type catalyst system, a metallocene catalyst system that includes a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring (a metallocene compound) and alkylalminoxan, a catalyst system that includes a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring, a compound forming an ionic complex by reacting with the compound of the transition metal, and an organic aluminum compound, and a supported metallocene catalyst system whose inorganic particles such as silica or a clay mineral support the catalyst components such as a compound of a transition metal in the Group 4 of the periodic table including a cyclopentadienyl ring, a compound forming an ionic complex by reacting with the compound of the transition metal, and an organic aluminum compound. An auxiliary polymerization catalyst may be used in the presence of any of the above catalyst systems. The auxiliary polymerization catalyst may be, for example, the catalyst systems described in Japanese Laid-Open Patent Publication Nos. 61-218606, 5-194685, 7-216017, 9-316147, 10-212319, and 2004-182981.

The content of the propylene resin in the propylene resin composition is 20% by weight to 99% by weight and is, preferably, 25% by weight to 99% by weight in order to improve the tensile property at a high temperature of the industrial film and the food packaging film. The content of the propylene polymer (X) is 1% by weight to 80% by weight and is, preferably, 1% by weight to 75% by weight in order to improve the tensile property at a high temperature of the industrial film and the food packaging film. It is assumed that the total amount of the propylene resin and the propylene polymer (X) corresponds to 100% by weight.

The propylene resin composition of the present invention may include resins and additive agents other than the propylene resin.

The resins other than the propylene resin may be an ethylene homopolymer, an α-olefin homopolymer having four or more carbon atoms such as a butene homopolymer, and an ethylene-α-olefin copolymer including a monomer unit originated from ethylene and a monomer unit originated from an α-olefin having four or more carbon atoms. These substances may each be produced using a heterogeneous catalyst or may each be produced using a homogeneous catalyst such as a metallocene-system catalyst. The other resins can also be a styrene-based elastomer such as a styrene-butadiene-styrene copolymer, a styrene-isoprene-styrene copolymer, a hydrogen-added styrene-butadiene-styrene copolymer, and a hydrogen-added styrene-isoprene-styrene copolymer, a polyester-based elastomer, a polyurethane-based elastomer, and a polyvinylchloride-based elastomer. Two or more of the other resins may concurrently be used.

The additive agents may be, for example, an inorganic filler, an oxidation inhibitor, a heat resistance stabilizing agent, a neutralizer, an ultraviolet absorbing agent, a flame retarder, a flame retarding auxiliary agent, a dispersing agent, an antistatic agent, a smoothing agent, a nucleating agent, an adhesive agent, an antifogging agent, an antiblocking, a coloring agent, a plasticizing agent, and a crystallization promoting agent. Two or more of these additive agents may concurrently be used.

The inorganic filler may be, for example, calcium carbonate, barium sulfate, mica, crystalline calcium silicate, talc, magnesium sulfate fiber, glass flake, glass powder, glass beads, clay, alumina, carbon black, and wollastonite. Two or more of these inorganic fillers may concurrently be used.

The production method of the propylene resin composition may be any known method such as, for example, a method of melting and kneading the propylene resin and the propylene polymer (X) with each other, and a method of mixing the propylene resin and the propylene polymer (X) with each other in a solvent.

The method of melting and kneading the propylene resin and the propylene polymer (X) with each other may be a method using any known kneading apparatus. The method may be, for example, a method according to which the propylene resin, the propylene polymer (X), and, when necessary, the other resins and the additive agents are mixed with each other using a kneading apparatus such as a Henschel mixer, a ribbon blender, or a tumble mixer to be thereafter melted and kneaded, and a method according to which the propylene resin, the propylene polymer (X), and, when necessary, the other resins and the additive agents are each continuously supplied to a kneading apparatus using a volumetric feeder to thereby acquire a homogeneous mixture and the mixture is thereafter melted and kneaded using a one-screw or a two or more-screw extruder, a Banbury mixer, a plast mill, a Brabender plastgraph, a roll kneader, etc. The set temperature of the kneader during the melting and the kneading is, preferably, a temperature of 160°C to 250°C, is, more preferably, 160°C to 230°C, and is, yet more preferably, 160°C to 210°C.

From the propylene resin of the present invention or the propylene resin composition comprising the propylene resin, a molded article may be acquired using any known method such as, for example, injection molding, extrusion molding, calender molding, inflation molding, blow molding, or vacuum molding.

The molded article may be an injection-molded article for a packaging material, an injection-molded article for an automotive part, an industrial film, or a food packaging film.

Surface treatment may be applied to the industrial film and the food packaging film, such as corona discharge treatment, flame treatment, plasma treatment, or ozone treatment, or a metal vapor-deposition film may be deposited thereon. These films may each be used as a single-layer film or may each be used as one layer of a composite film. The "composite film" is a film including the film of the present invention and other films. The other films may be, for example, a polypropylene two-screw stretched film, a non-stretch nylon film, a stretched polyethylene terephthalate film, and an aluminum foil. The production method of the composite film may be dry laminating and extrusion laminating.

The injection-molded article for a packaging material may be a food packaging material such as a pudding cup, a container for a boxed lunch or prepared food, or a cap of a PET bottle, an ink cartridge, a medical syringe, a packing or packaging material for cosmetic products, a packaging material for clothes, and a packing or packaging material for general merchandises.

The molded article for an automotive part may be an automotive inner part such as a door trim, a pillar, an instrumental panel, a console, a locker panel, an arm rest, a door panel, or a spare tire cover, an automotive outer part such as a bumper, a spoiler, a fender, or a side step, a part such as an air intake duct, a coolant reserve tank, a fender liner, a fan, or an under deflector, and a molded part integrally including a metal, and a rubber or a plastic such as a front-end panel.

The industrial film may be a release film, an enamel paper sheet for printing, a transfer film, a transfer foil, a dielectric film for a film capacitor, a battery separator film, a mold releasing film, a gas permeating film, an agricultural film, a protect film, a medical film for a sterilized bag and an infusion bag, a paper carton, and a cloth.

The food packaging film may be a film adhered to a container for a boxed lunch or prepared food, a bread packaging film, a noodle packaging film, a fresh vegetable packaging film, a fresh flower packaging film, a retort pouch, a film for packaging a sweet stuff such as a snack, a rice cake, or a candy, a dried food packaging film, a frozen and processed food packaging film, a film for packaging powder food such as sugar, salt, or cereals, a packaging film for food boiled in soy sauce, seaweed, or fish cakes, and a heavy-duty packaging bag such as a bag for rice or wheat and a bag for fertilizer or animal feed.

The present invention will be descried in more detail with reference to Examples while the present invention is not limited to Examples. The measurements of the items in the detailed description of the invention, Examples, and Comparative Examples were measured using the following methods.

(1) Limiting Viscosity ([η], unit: dl/g)
The reduced viscosity was measured for three points of the concentration of 0.1 g/dl, 0.2 g/dl, and 0.5 g/dl using an Ubbelohde viscometer. The limiting viscosity was acquired using a calculation method described in Section 491 of "Study on High Molecule Solutions and High Molecule Experiments 11" (1982, Kyoritsu Shuppan Co., Ltd.), that is, an extrapolation method of plotting the reduced viscosity for each concentration and extrapolating the concentration to be zero. The reduced viscosities were measured at 135°C using tetrahydronaphthalene as the solvent.

(2) Weight-Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw/Mn)
The weight-average molecular weight (Mw) and the number average molecular weight (Mn) were acquired under the following measurement conditions using a gel permeation chromatography, and the molecular weight distribution (Mw/Mn) was calculated.
<Measurement Conditions>
Instrument Model: 150C (manufactured by Waters Corporation)
Column: TSK-GEL GMH6-HT, 7.5 mm (diameter)×300 mm (length)×three pieces
Measurement Temperature: 140°C
Solvent: Orthodichlorobenzene
Measurement Concentration: 5 mg/5 ml

(3) Chemical Shift Value (δ)
A chemical shift value (δ) was acquired by measuring a proton nuclear magnetic resonance (¹H-NMR) spectrum under the following conditions, using a proton nuclear magnetic resonance method.
<Measurement Conditions>
Instrument Model: JEOL JNM-AL400 (manufactured by JEOL Ltd.)
Measurement Temperature: 135°C
Measurement Solvent: 1,1,2,2-tetrachloroethane-d2 (chemical shift reference value: 6.0 ppm)

(4) Content Rate of Hydroxyl Group in Hydroxyl Group-Denatured Propylene Polymer (Unit: mol%)
<Content Rate of Hydroxyl Group in Hydroxyl Group-Denatured Propylene Polymer (1)>
From the ¹H-NMR spectrum measured in (3) above, the integral value (H¹) of the peaks (the peaks observed between 3.6 and 3.4 ppm) originated from a methylene group (-CH₂-OH) adjacent to a hydroxyl group included in the hydroxyl group-modified propylene polymer (1) was acquired assuming that the total of the integral values of the peaks (all the peaks observed between 2.0 and 0.2 ppm) originated from the alkyl group included in the hydroxyl group-modified propylene polymer (1) was 1,000, and the content rate of the hydroxyl group was calculated from the following equation (i).
The content rate of the hydroxyl group (mol%)=100×{(H¹/2)/(1,000/6)} Eq. (i)
<Content Rate of Hydroxyl Group in Hydroxyl Group-Denatured Propylene Polymer (2)>
From the ¹H-NMR spectrum measured in (3) above, the integral value (H²) of the peaks (the peaks observed between 4.0 and 3.2 ppm) originated from a propylene group (-(CH₂)₃-OH) adjacent to a hydroxyl group included in the hydroxyl group-modified propylene polymer (2) was acquired assuming that the total of the integral values of the peaks (all the peaks observed between 2.0 and 0.2 ppm) originated from the alkyl group included in the hydroxyl group-modified propylene polymer (2) was 1,000, and the content rate of the hydroxyl group was calculated from the following equation (ii).
The content rate of the hydroxyl group (mol%)=100×{(H²/6)/(1,000/6)} Eq. (ii)

(5) Content Rate of Group Expressed by Formula (U) in Propylene Resin (Hereinafter, Referred to as "Substituent Group (U)") (Unit: mol%)

<Content Rate of Substituent Group (U) in Propylene Resin (1)>
From the ¹H-NMR spectrum measured in (3) above, the integral value (U¹) of the peak (the peak observed at 4.6 ppm) originated from a urethane bond (-NHCOO-) included in the propylene resin (1) was acquired assuming that the total of the integral values of the peaks (all the peaks observed between 2.0 and 0.2 ppm) originated from the alkyl group included in the propylene resin (1) was 1,000, and the introduction rate of the substituent group (U) was calculated from the following equation (iii).
The content rate of the substituent group (U) (mol%)=100×{U¹/(1,000/6)} Eq. (iii)
<Content Rate of Ureidopyrimidinone Group in Propylene Resin (2)>
From the ¹H-NMR spectrum measured in (3) above, the integral value (U²) of the peak (the peak observed at 4.1 ppm) originated from a methylene group (-NHCOO-CH₂-) adjacent to the urethane bond included in the propylene resin (2) was acquired assuming that the total of the integral values of the peaks (all the peaks observed between 2.0 and 0.2 ppm) originated from the alkyl group included in the propylene resin (2) was 1,000, and the introduction rate of the substituent group (U) was calculated from the following equation (iv).
The content rate of the substituent group (U) (mol%)=100×(U²/2)/(1,000/6) Eq. (iv)

(6) Half-Isothermal Crystallization Time Period (Unit: sec)
The half-isothermal crystallization time period was acquired from a differential scanning caloric curve that was acquired using a differential scanning calorimeter by increasing the temperature from the room temperature to 220°C at a rate of 500 °C/min, maintaining the temperature at 220°C for five min, reducing the temperature thereafter from 220°C to the isothermal crystallization temperature (130°C) at a rate of 500 °C/min, and maintaining the temperature at 130°C. The half-isothermal crystallization time period was calculated as a time period for the value of the heat flow to reach its minima value, assuming that the isothermal crystallization process starting time (the time at which the temperature reaches the isothermal crystallization temperature from 220°C) t is t=0.

(7) Young's Modulus (Unit: MPa)
The propylene resin composition was injection-molded at a cylinder temperature of 230°C and the barrel temperature of 40°C using a small injection-molding machine (Xplore; manufactured by DSM) to acquire an injection-molded article having a thickness of 2 mm. Using the acquired injection-molded article, the Young's modulus was measured based on ISO527-2-1BA under the following conditions. The rigidity becomes more excellent as the value of the Young's modulus becomes greater.
Measurement Temperature: 23°C
Pulling Rate: 50 mm/min
Gripping Interval: 58mm

(8) Izod Impact Strength (Unit: KJ/m²)
The propylene resin composition was injection-molded at a cylinder temperature of 230°C and the barrel temperature of 40°C using a small injection-molding machine (Xplore; manufactured by DSM) to acquire an injection-molded article having a thickness of 4 mm. Using a test piece with a notch acquired by notch-processing the acquired injection-molded article, the Izod impact strength was measured at the measurement temperature of 23°C based on JIS-K-7110. The impact resistance becomes more excellent as the value of the Izod impact strength becomes greater.

(9) Tensile Test (Elongation at Breakage, Unit: %)
The propylene resin composition was press-molded under the conditions of the temperature of 190°C, the pressure of 10 MPa, and five min to acquire a pressed sheet having a thickness of 0.1 mm. A test piece was produced from the acquired pressed sheet and the elongation at breakage was measured based on JIS-K-6251-7 under the following conditions. The tensile property at a high temperature is more excellent as the value of the elongation at breakage is greater.
Measurement Temperature: 140°C
Pulling Velocity: 50 mm/min

(10) Shear Viscosity (Unit: Pa.sec)
Using the propylene resin composition, the shear viscosity was measured at the set temperature of 230°C and the shear rate of 2.432×10³ sec^-1 by Capillograph 1B (manufactured by Toyo Seiki Manufacturing Co., Barrel diameter: 9.55 mm) to which a capillary having a diameter of one mm, a length of 40 mm, and an inflow angle of 90° was attached. The fluidity is more excellent as the value of the shear viscosity becomes smaller.

(11) Specific Dielectric Constant
The propylene resin composition was press-molded under the conditions of the temperature of 190°C, the pressure of 10 MPa, and five min to acquire a pressed sheet having a thickness of 0.1 mm. A test piece was produced from the acquired pressed sheet to measure the specific dielectric constant under the following conditions.
Instrument Model: DES 100U (SII manufactured by SII Nano Technology Inc.)
Measurement Temperature: 20°C
Measurement Frequency: 1 kHz
Highest Excitation Voltage: 10 V
Specimen Size: Diameter 45 mm, thickness 0.1 mm

The resins and the compounds described below were used in Examples and Comparative Examples.

<Propylene Polymer (X)>
A propylene polymer (X-1), a propylene polymer (X-2), and a propylene polymer (X-4) were produced under the production conditions for the physical properties thereof to be those described below, according to the production method of a propylene homopolymer described in Examples in Japanese Laid-Open Patent Publication No. 2002-012734. A propylene polymer (X-3) was produced by producing a propylene homopolymer component at a pre-stage polymerization step and producing an ethylene-propylene copolymer component at a post-stage polymerization step according to the production method of a propylene-ethylene block copolymer described in Examples in Japanese Laid-Open Patent Publication No. 2002-012734.
Propylene polymer (X-1): The propylene homopolymer having a limiting viscosity [η] of [η]=2.1 dl/g
Propylene polymer (X-2): The propylene homopolymer having a limiting viscosity [η] of [η]=0.93 dl/g
Propylene polymer (X-3): The propylene polymerized material ([η]_T=1.4 dl/g) including 80% by weight of the propylene homopolymer component (having a limiting viscosity [η]p of [η]p=1.06 dl/g) and 20% by weight of the ethylene-propylene copolymer component ([η]ep=2.8 dl/g and the content of monomer unit originated from ethylene=35% by weight)
[η]p represents the limiting viscosity of the propylene homopolymer component in the propylene polymerized material. [η]ep represents the limiting viscosity of the ethylene-propylene copolymer component in the propylene polymerized material. [η]_T represents the limiting viscosity of the propylene polymerized material.
Propylene Polymer (X-4): The propylene homopolymer having a limiting viscosity [η] of [η]=0.69 dl/g

Ureidopyrimidinone Compound (1): 2-(6-isocyanatehexylaminocarbonylamino)-6-methyl-4[1H]pyrimidinone (manufactured by SupraPolxB. V., the compound represented by the following formula)

The propylene resin (1) was produced according to Production Example 1 and Production Example 2 as below.

[Production Example 1] Synthesis of Hydroxyl Group-Denatured Propylene Polymer (1)
10 g of a propylene homopolymer including a carbon-carbon double bond at an end thereof (Viscol 660P, produced by Sanyo Chemical Industries Ltd.) was dissolved in 50 mL of toluene at 90°C and 10 mL of a borane-tetrahydrofuran solution was thereafter dripped therein to be heated and stirred at 90°C for three hours. The solution was cooled for its temperature to reach the room temperature. 35 mL of 30%-hydrogen peroxide water and 70 mL of 2-N-sodium hydroxide were mixed with each other in advance and this mixture was dripped into the cooled solution to be stirred for two hours at the room temperature. 200 mL of 17%-sodium thiosulfate water solution was dripped into the stirred solution and the mixture solution was filtered. An acquired white solid substance was dried in vacuum for three hours at 80°C to acquire the hydroxyl group-modified propylene polymer (1) represented by the following formula (I). (The content rate of the hydroxyl group: 0.99mol%)

("PP" in the formula (I) represents the propylene homopolymer.)
¹H NMR: δ 3.6 to 3.4 ppm (2H) and 2.0 to 0.2 ppm (PP).

[Production Example 2] Synthesis of Propylene Resin (1)
An amount as a catalyst of dibutytin dillaurate was added to 50 g of the hydroxyl group-modified propylene polymer (1) acquired in Production Example 1 and 2.8 g of the ureidopyrimidinone compound (1) to be heated and stirred in 225 mL of toluene at 110°C for one hour. The solvent was thereafter vaporized at a reduced pressure to be removed to acquire a white solid substance. The acquired white solid substance was crushed and Soxhlet extraction was executed therefor for three hours using chloroform. The remaining white solid substance was dried in vacuum for three hours at 80°C to acquire the propylene resin (1) represented by the following formula (II). (The content rate of the substituent group (U): 0.35 mol%)

("PP" in the formula (II) represents the propylene homopolymer.)
Mw=17,000, Mw/Mn=2.1
¹H NMR: δ 5.9 ppm (1H), 4.6 ppm (1H), 4.0 ppm (2H), 3.4 to 3.0 ppm (4H), 2.3 ppm (3H), and 2.0 to 0.2 ppm (8H and PP). The introduction of the substituent group (U) was recognized from the peak (the peak observed at 4.6 ppm) originated from a urethane bond (-OCONH-).

The propylene resin (2) was produced according to Production Example 3 and Production Example 4 as below.

[Production Example 3] Synthesis of Hydroxyl Group-Denatured Propylene Polymer (2)
15 g of a maleic acid anhydride-modified propylene polymer (Polybond PB3000, produced by Uniroyal Chemical Co., Inc.) was heated in 300 mL of xylene at 140°C to be dissolved therein and the mixture was added to 1.5 L of acetone for the polymer to again be precipitated. The acquired polymer was dried in vacuum for three hours at 80°C. 10 g of the acquired polymer was heated in 300 mL of xylene to be dissolved therein. 0.5 mL of 3-amino-1-propanol dissolved in advance in 10 mL of xylene was dripped into the polymer mixture. The mixture was thereafter heated and stirred for one hour being concurrently refluxed. The mixture was added to 1.5 L of acetone for the polymer to be precipitated. The polymer acquired as a white solid substance was dried in vacuum for three hours at 80°C. The hydroxyl group-modified propylene polymer (2) of the following formula (III) was thereby acquired. (The content rate of the hydroxyl group: 0.16 mol%)

("PP" in the formula (III) represents the propylene homopolymer.)
¹H NMR: δ 4.0 to 3.2 ppm (6H) and 2.0 to 0.2 ppm (PP).

[Production Example 4] Synthesis of Propylene Resin (2)
An amount as a catalyst of dibutytin dillaurate was added to 100 g of the hydroxyl group-modified propylene polymer (2) acquired in Production Example 3 and 3.7 g of the ureidopyrimidinone compound (1) to be heated and stirred in 450 mL of toluene at 110°C for one hour. The solvent was vaporized at a reduced pressure to be removed to acquire a white solid substance. The acquired white solid substance was crushed and Soxhlet extraction was executed therefor for three hours using chloroform as the solvent. The white solid substance remaining as an insoluble substance was dried in vacuum for three hours at 80°C to acquire the propylene resin (2) represented by the following formula (IV). (The content rate of the substituent group (U): 0.14 mol%)

("PP" in the formula (IV) represents the propylene homopolymer.)
Mw=91,000, Mw/Mn=2.2
¹H NMR: δ 5.9 ppm (1H), 4.8 ppm (1H), 4.1 ppm (2H), 3.6 ppm (2H), 3.4 to 3.0 ppm (6H), 2.3 ppm (3H), 2.0 to 0.2 ppm (8H and PP). The introduction of the substituent group (U) was recognized from the peak (the peak observed at 4.1 ppm) originated from a methylene group (-CH₂-OCONH-) adjacent to an urethane bond.

A total amount of 100 parts by weight of the propylene resin (1) and the propylene polymer (X-3) including 25% by weight of the propylene resin (1) and 75% by weight of the propylene polymer (X-3) was melted and kneaded with 0.05 parts by weight of calcium stearate, 0.20 parts by weight of di-tert-butylhydroxytoluene, and 0.20 parts by weight of Irganox 1010 (produced by Ciba Specialty Chemicals Co., Ltd.) under the conditions of the set temperature of 210°C, the kneading time period of five min, and the screw rotation velocity of 200 rpm, using a small kneader (Xplore; manufactured by DSM) to acquire a propylene resin composition. The acquired propylene resin composition was injection-molded at a cylinder temperature of 230°C and the barrel temperature of 40°C using a small injection-molding machine (product name: Xplore (manufactured by DSM)) to acquire an injection-molded article.
The physical properties of the acquired propylene resin composition and the injection-molded article are shown in Table 1.
[Example 2] and [Comparative Examples 1 to 4]

Melting and kneading were executed similarly to those in Example 1 using the components and the contents shown in Table 1 to acquire a propylene resin composition. The acquired propylene resin composition was injection-molded similarly to that in Example 1 to acquire an injection-molded article. The physical properties of the acquired propylene resin composition and the injection-molded article are shown in Table 1.

100 parts by weight of the propylene resin (2) were melted and kneaded with 0.05 parts by weight of calcium stearate, 0.20 parts by weight of di-tert-butylhydroxytoluene, and 0.20 parts by weight of Irganox 1010 (produced by Ciba Specialty Chemicals Co., Ltd.) under the conditions of the set temperature of 190°C and the kneading time period of five min, using a test roll mill (HR-20, manufactured by Nisshin Kagaku Co., Ltd.) to acquire a propylene resin composition. The acquired propylene resin composition was press-molded under the conditions of the temperature of 190°C, the pressure of 10 MPa, and five min to acquire a pressed sheet. The physical properties of the pressed sheet of the acquired propylene resin composition are shown in Table 2.
[Examples 4 to 6] and [Comparative Example 5]

The propylene resin composition was acquired similarly to that in Example 3 using the components and the blending amounts shown in Table 2. The acquired propylene resin composition was press-molded under the same conditions as those in Example 3 to acquire a pressed sheet. The physical properties of the acquired pressed sheet are shown in Table 2.
[Example 10] and [Comparative Example 8]

The propylene resin shown in Table 3 was press-molded under the conditions of the temperature of 190°C, a pressure of 15 MPa, and five min to acquire pressed sheets each having a thickness of 0.1 mm. The specific dielectric constants of the acquired pressed sheets are shown in Table 3.

Claims

An injection-molded article for a packaging material, the injection-molded article comprising a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom;
"X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety; and
"A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.
An injection-molded article for an automotive part, the injection-molded article comprising a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom;
"X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety and
"A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.
An industrial film comprising a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom;
"X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety; and
"A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.
[Corrected under Rule 26, 09.09.2015]
A food packaging film comprising a propylene resin represented by the following formula (1) or the following formula (2),

wherein "R¹" in the above formula (1), "R¹" in the above formula (2), and "R²" in the above formula (1) each independently represent a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbyl group having 1 to 20 carbon atoms and substituted by a halogen atom, or a hydrocarbyloxy group having 1 to 20 carbon atoms and substituted by a halogen atom;
"X¹" in the above formula (1), "X¹" in the above formula (2), and "X²" in the above formula (2) each independently represent a linking moiety; and
"A" in the above formula (1) and "A" in the above formula (2) each independently represent a propylene polymer residue.