JP2014051562A - Crosslinked product and crosslinking foamed product containing propylene polymer composition, and their manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinking foamed product good in crosslinking property, excellent in surface appearance of a foamed product and capable of weight saving, by using a propylene polymer composition.SOLUTION: A crosslinked product is obtained from a composition containing a propylene copolymer (A) containing a constitutional unit derived from propylene [i] of 50 to 95 mol%, a constitutional unit derived from α-olefin having 2 to 10 carbon atoms excluding propylene [ii] of 4.9 to 49.9 mol% and a constitutional unit derived from a non-conjugated polyene [iii] of 0.1 to 10 mol% (total of constitutional units [i], [ii] and [iii] is 100 mol%), and satisfying specific requirements (a) and (c), and a thermoplastic resin (B).

Description

  The present invention relates to a cross-linked product and a cross-linked foam containing a propylene-based polymer composition, and a method for producing them.

  Propylene polymers are widely used in various molding fields because they are excellent in mechanical properties and chemical resistance and are inexpensive. Polypropylene foam moldings are widely used as packaging materials, construction materials, and heat insulating materials because they can utilize the excellent mechanical strength, heat resistance, and workability of polypropylene, and can add cushioning and heat insulating properties.

  However, since the propylene-based polymer has a low viscosity at the time of melting, there is a problem that a foaming ratio at the time of foam molding is small, and foamed cells break up and are not uniform. As a method of increasing the melt viscosity of polypropylene, there is a method in which an organic peroxide and a crosslinking aid are reacted. However, when a crosslinking agent is added in the presence of oxygen to generate radicals, bonds between molecular chains are broken. However, there is a problem that the heat resistance of the crosslinked product is lowered and low molecular weight components are generated, and it is considered that there is a limit in practical use.

  For example, as disclosed in Patent Document 1 and Patent Document 2, it is possible to add a crosslinking aid or the like to polypropylene, to perform crosslinking by, for example, electron beam crosslinking, and to further foam to obtain a foam. is there.

Japanese Patent Publication No.46-38716 JP-A-1-244828

  Patent Document 1 is considered to be a technique for avoiding problems such as gelation accompanying the adjustment of the composition used for cross-linking foaming by lowering the melting point of the polypropylene used. Patent Document 2 is considered to have an aim of facilitating electron beam crosslinking by introducing a comonomer into the polypropylene to be used. However, such a method is considered to limit the properties of polypropylene used, such as heat resistance and mechanical properties.

Further, Patent Documents 1 and 2 do not examine in detail the mechanical properties and appearance of the obtained crosslinked body, in particular, the crosslinked foamed body.
That is, an object of the present invention is to provide a crosslinked foamed molded article having excellent surface appearance, high foaming and uniform foamed cells. Moreover, this invention makes it a subject to provide the manufacturing method of a crosslinked body which can manufacture the crosslinked body of a favorable property from various thermoplastic polymers.

As a result of intensive studies, the present inventors have completed the present invention as follows.
That is, in the crosslinked body according to the present invention, a composition containing the following propylene-based copolymer (A) and a thermoplastic resin (B) is used.

  The propylene-based copolymer (A) has a structural unit [i] derived from propylene of 50 to 95 mol% and a structural unit [ii] derived from an α-olefin having 2 to 10 carbon atoms excluding propylene. 49.9 mol% and structural unit [iii] derived from non-conjugated polyene [0.1] to 10 mol% (provided that the total of structural units [i], [ii] and [iii] is 100 mol%) And satisfies the following requirements (a) and (c), more preferably satisfies any one of the requirements (b) and (d), and particularly preferably satisfies the following requirements (a) to (d): Features.

(A) The intrinsic viscosity [η] measured at 135 ° C. in decalin is 0.1 to 5.0 (dL / g),
(B) The ratio (Mz / Mw) of z-average molecular weight (Mz) and weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 3.0 to 20.0,
(C) MFR ₁₀ obtained at 230 ° C. and 10 kg load according to JIS K-6721, and MFR _2.16 obtained at 230 ° C. and 2.16 kg load according to JIS K-6721 Ratio (MFR ₁₀ / MFR _2.16 ) is 8.0 to 150.0,
(D) Complex viscosity η * ₍ ω _{= 0.1)} of frequency (ω = _0.1 rad / s) obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, and frequency (ω = 100 rad / s) ) To the complex viscosity η * ₍ ω _{= 100)} (η * ₍ ω _{= 0.1)} / η * ₍ ω _{= 100)} ) is 5 to ₁₀₀ .

  The propylene copolymer composition (X) used in the present invention comprises 1 to 95 parts by weight of the propylene copolymer (A) and 5 to 99 parts by weight of the thermoplastic resin (B), preferably a propylene copolymer. 1 to 80 parts by weight of the union (A) and 20 to 99 parts by weight of the thermoplastic resin (B), more preferably 1 to 65 parts by weight of the propylene copolymer (A) and 99 to 35 parts by weight of the thermoplastic resin (B). Particularly preferably 1 to 45 parts by weight of the propylene copolymer (A) and 99 to 55 parts by weight of the thermoplastic resin (B), more particularly preferably 1 to 30 parts by weight of the propylene copolymer (A) and thermoplastic. It is characterized by comprising 99 to 70 parts by weight of the resin (B) (however, the sum of (A) and (B) is 100 parts by weight).

  In a preferred embodiment of the present invention, the propylene-based copolymer composition (X1) is used as the propylene-based copolymer composition (X), and the propylene-based copolymer (A) is derived from propylene. A structural unit derived from 50 to 95 mol% of structural units and at least one α-olefin selected from ethylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene 4.9 to 49. Propylene containing 9 mol% and 0.1 to 10 mol% of structural units derived from 5-vinyl-2-norbornene (provided that the total of the structural units [i], [ii] and [iii] is 100 mol%) 5 to 80 parts by weight of the copolymer (A1) and 95 to 20 parts by weight of polypropylene (B1) as the thermoplastic resin (B) (however, the total of (A1) and (B1) is 1 0 is that including a parts by weight) and.

The molded product of the present invention is obtained by processing a crosslinked product using the propylene-based copolymer composition (X).
The crosslinked product of the present invention may have a foam structure. Such a crosslinked foam is obtained by heating and foaming a crosslinked molded body obtained by crosslinking the propylene-based copolymer composition (X).

  The manufacturing method of the crosslinked body of this invention includes the process of heat-foaming the crosslinked molded object obtained by bridge | crosslinking the said propylene-type copolymer composition (X). Furthermore, in the production method according to the present invention, the composition (X) is preferably foamed after being crosslinked by electron beam irradiation or organic peroxide.

  According to the present invention, it is possible to provide a cross-linked foamed molded article having excellent surface appearance, high foaming and uniform foamed cells. Further, according to the present invention, a crosslinked product having good properties can be produced from various thermoplastic polymers.

1 is a cross-sectional SEM image of the foam obtained in Example 2. FIG. FIG. 2 is a cross-sectional SEM image of the foam obtained in Comparative Example 2.

The crosslinked body concerning this invention consists of a composition containing the propylene-type copolymer (A) shown below and a thermoplastic resin (B).
<Propylene-based copolymer (A)>
The propylene-based copolymer (A) according to the present invention comprises a structural unit [i] derived from propylene [i] 50 to 95 mol% and a structural unit selected from α-olefins having 2 to 10 carbon atoms excluding propylene [ii] 4.9 to 49.9 mol% and a structural unit [iii] derived from a non-conjugated polyene [0.1] to 10 mol% (provided that the structural units [i], [ii] and [iii] The total is 100 mol%). It is preferable that the structural units [i], [ii], and [iii] are in the above ranges because a copolymer (A) that is more excellent in moldability can be obtained.

As the propylene-based copolymer (A), preferably, the structural unit [i] is 55 to 95 mol%, the structural unit [ii] is 4.9 to 44.9 mol%, and the structural unit [iii]. Is a propylene-based copolymer consisting of 0.1 to 7.0 mol%, and is compatible with the thermoplastic resin (B), particularly when polypropylene is used as the thermoplastic resin (B), and a gel in production. It is preferable from the point that a component does not produce | generate (however, the total of structural unit [i], [ii], and [iii] shall be 100 mol%).
It should be noted that other copolymerization components may be included within the range not impairing the object of the present invention, and these are also within the scope of the present invention.

(Α-olefin)
The α-olefin having 2 to 10 carbon atoms excluding propylene may be linear, branched or cyclic. For example, ethylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1 Linear or branched α-olefins such as -butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-nonene, 1-decene; cyclopentene, cyclohexene And cyclic olefins such as cycloheptene. These α-olefins may be used alone or in combination of two or more.
Among these, ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable.

(Non-conjugated polyene)
Specific examples of the non-conjugated polyene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene. 4-ethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene 7-methyl-1,6-octadiene, 6-ethyl -1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl -1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl -1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl -1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl -1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-ethi 1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8- Non-conjugated dienes such as methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 9-methyl-1,8-undecadiene;
6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene (DMDT), 5,9-dimethyl-1,4,8-decatriene, 6,9 -Dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1 , 6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene- 1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4- Non-conjugated trienes such as ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene and the like can be mentioned. These non-conjugated polyenes can be used alone or in combination of two or more.

  Among these, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), 4-ethylidene-8-methyl- 1,7-nonadiene (EMND) is preferred, and 5-vinyl-2-norbornene (VNB) is more preferred.

(Conjugated polyene)
In the present invention, for example, a conjugated polyene may be included as another polymerization component as long as the object of the present invention is not impaired.

  Examples of the conjugated polyene include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3-butadiene, and 1-phenyl. -2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1,3-butadiene, 2 Conjugated dienes such as -hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-phenyl-1,3-butadiene; 1,3,5-hexa Examples thereof include conjugated trienes such as triene. It is also a preferred embodiment that no conjugated polyene is contained.

  The propylene-based copolymer (A) used in the present invention satisfies the following requirements (a) and (c), more preferably satisfies any of the requirements (b) and (d), and particularly preferably (a ) To (d) are satisfied, more preferably (a) to (e) are satisfied. Next, requirements (a) to (e) are shown.

Requirement (a): [Intrinsic viscosity [η]]
In the propylene-based copolymer according to the present invention, the intrinsic viscosity [η] in decalin at 135 ° C. is usually in the range of 0.1 to 5.0 (dL / g). When the intrinsic viscosity is within this range, the balance between resin fluidity and melt tension is excellent.

Requirement (b): [Molecular weight distribution [Mz / Mw]]
The propylene copolymer according to the present invention generally has a ratio (Mz / Mw) of z-average molecular weight (Mz) and weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) to 3. It is in the range of 0 to 20.0. When the value of Mz / Mw is large, the amount of long chain branching is large and the melt tension becomes high.

Requirements (c): [ratio (MFR ₁₀ / MFR _2.16)]
The propylene-based copolymer according to the present invention includes MFR ₁₀ obtained at 230 ° C. and 10 kg load according to JIS K-6721, and 230 ° C. and 2.16 kg load according to JIS K-6721. The ratio (MFR ₁₀ / MFR _2.16 ) with MFR _2.16 obtained in the above is usually in the range of 8.0 to 150.0. When the ratio (MFR ₁₀ / MFR _2.16 ) is within the above range, the fluidity of the resin under two loads tends to change, and the rate of change in viscosity with respect to the shear rate is small. Therefore, when it exists in this range, the viscosity change of resin is small in the specific shear rate range, and it is excellent in workability.

Requirement (d): [ratio (η * ₍ ω _{= 0.1)} / η * ₍ ω _{= 100)} )]
Complex viscosity η * ₍ ω _{= 0.1)} of frequency (ω = _0.1 rad / s) and complex of frequency (ω = 100 rad / s) obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer. The ratio (η * ₍ ω _{= 0.1)} / η * ₍ ω _{= 100)} ) to the viscosity η * ₍ ω _{= 100)} is usually 5 to ₁₀₀ . When the ratio (η * ₍ ω _{= 0.1)} / η * ₍ ω _{= 100)} ) is in the above range, it means that it has a long-chain branched structure and is excellent in melt tension.

Requirement (e): [Melting point [Tm]]
The propylene-based copolymer according to the present invention preferably has a melting point (Tm) measured by DSC of 100 ° C. or lower or no melting point is observed because the resulting composition is excellent in flexibility. Here, that the melting point is not observed means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in the range of −150 to 200 ° C. The measuring method is the same as the examples described later.

  In a more preferred embodiment of the present invention, as the propylene copolymer (A), 50 to 95 mol% of structural units derived from propylene, ethylene, 1-butene, 4-methylpentene-1, 1-hexene and 1- 4.9 to 49.9 mol% of structural units derived from at least one α-olefin selected from octene and 0.1 to 10 mol% of structural units derived from 5-vinyl-2-norbornene (provided that And the total of the structural units [i], [ii] and [iii] is 100 mol%) and the propylene copolymer (A1).

[Propylene-based copolymer production method]
Next, the manufacturing method of the propylene-type copolymer which concerns on this invention is demonstrated. The production method of the copolymer of the present invention is not particularly limited.

  Next, the manufacturing method of the propylene-type copolymer which concerns on this invention is demonstrated. The production method of the copolymer of the present invention is not particularly limited, but is preferably synthesized using the following method.

Examples of the copolymer according to the present invention include (A) a bridged metallocene compound represented by the following general formula [I], and (B) (b-1) an organoaluminum oxy compound, (b-2) the metallocene compound. Existence of an olefin polymerization catalyst comprising a compound that reacts with (A) to form an ion pair, and (b-3) at least one compound selected from an organoaluminum compound (sometimes referred to as a promoter). Below, one or more monomers selected from propylene and α-olefin are usually solution polymerized in the presence of a solvent at a temperature of 50 to 300 ° C. (in the following description, sometimes referred to as “high temperature solution polymerization”). ) Can be manufactured. In the present invention, the copolymer production method may use, for example, a metallocene compound having a structure different from that of the general formula [I], as long as the above-mentioned requirements are satisfied, or an assistant different from the component (B). A catalyst may be used, and two or more types of known copolymers may be prepared by a method such as reactor blending or physical blending.

In the above general formula [I], M represents a transition metal, p represents the valence of the transition metal, X may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group, R ¹ and R ² represent a π-electron conjugated ligand coordinated to M, which may be the same or different, and Q represents a divalent group that bridges ^two π-electron conjugated ligands R ¹ and R ^2. Represents.

  In the general formula [I], examples of the transition metal represented by M include Zr, Ti, Hf, V, Nb, Ta, and Cr. Preferred transition metals are Zr, Ti, and Hf, and more preferable. The transition metal is Zr or Hf.

In the general formula [I], π-electron conjugated ligands represented by R ¹ and R ² include η-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure, and η-cyclo Examples thereof include a ligand having an octatetraene structure, and a particularly preferable ligand is a ligand having a η-cyclopentadienyl structure. Examples of the ligand having an η-cyclopentadienyl structure include a cyclopentadienyl group, an indenyl group, a hydrogenated indenyl group, and a fluorenyl group. These groups are further substituted with a hydrocarbon group such as a halogen atom, alkyl, aryl, aralkyl, alkoxy or aryloxy, a hydrocarbon group-containing silyl group such as a trialkylsilyl group, a chain or cyclic alkylene group, etc. Also good.

In general formula [I], the group that crosslinks R ¹ and R ² represented by Q is not particularly limited as long as it is a divalent group. For example, a linear or branched alkylene group, unsubstituted or Examples thereof include a substituted cycloalkylene group, an alkylidene group, an unsubstituted or substituted cycloalkylidene group, an unsubstituted or substituted phenylene group, a silylene group, a dialkyl-substituted silylene group, a germyl group, and a dialkyl-substituted germyl group.

  In the present invention, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene is used as the metallocene compound satisfying the above general formula [I]. (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (t-butylamido) -dimethyl (η5-2-methyl-s-indasen-1-yl) silane titanium (II) 1,3- Although pentadiene is preferable, it is not limited to this at all.

Next, a preferable embodiment when the metallocene compound (A) described above is used as a polymerization catalyst component for producing the copolymer of the present invention will be described.
When the metallocene catalyst containing the metallocene compound (A) is used as an olefin polymerization catalyst for producing a propylene copolymer, the polymerization catalyst is represented by (A) the general formula [I] as described above. A bridged metallocene compound, and (B) (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. It is preferably composed of at least one compound selected. Here, as the catalyst component (B), any one of the following [c1] to [c4] is preferably used from the viewpoint of the polymerization activity and the properties of the produced propylene-based copolymer.

[c1] Compound (b-1) only,
[c2] a mixture of compound (b-1) and compound (b-3),
[c3] a mixture of compound (b-2) and compound (b-3),
[c4] A mixture of compound (b-1) and compound (b-2).

  However, in the general formula [I] of the component (A), when a metallocene compound in which Q is a silylene group is used, the compound (b-2) is not used as the component (B). Among the above, [c1] and [c2] are adopted.

Hereinafter, each component which can comprise (B) component is demonstrated concretely.
(b-1) Organoaluminum Oxy Compound As the organoaluminum oxy compound (b-1), a conventionally known aluminoxane can be used as it is. Examples of the aluminoxane include the following general formula [II] and / or general formula [III].

In the formula [II] or [III], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

  In particular, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is used (in the general formula [II] or [III], an organoaluminum oxy compound in which R is a methyl group is represented by Sometimes called "methylaluminoxane".)

  Methylaluminoxane is an organoaluminum oxy compound that has been widely used in the polyolefin industry due to its availability and high polymerization activity, but it is difficult to dissolve in saturated hydrocarbons, and it has a huge environmental impact, such as toluene and benzene. Has been used as an aromatic hydrocarbon solution. Under such circumstances, methylaluminoxane analogues that are soluble in saturated hydrocarbons have been developed. Examples of such analogs include modified methylaluminoxanes represented by the following general formula [IV]. In the present invention, such a modified methylaluminoxane is also included as the organoaluminum oxy compound (b-1).

In the formula [IV], R represents a hydrocarbon group having 2 to 20 carbon atoms, and m and n represent an integer of 2 or more.

  The modified methylaluminoxane represented by the general formula [IV] is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum (for example, refer to patent publications US4960878 and US5041584). In addition, it is commercially produced under the trade names such as MMAO and TMAO, prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem, etc., where R is an isobutyl group (for example, “Tosoh Research and Technical Report”). 47th volume 55 (2003)). However, the present applicant has confirmed that even if MMAO or TMAO is polymerized in the form of a saturated hydrocarbon solution outside the technical scope of the high-temperature solution polymerization method of the present invention, the activity exceeding methylaluminoxane cannot be achieved. . The high temperature solution polymerization method according to the present invention exhibits high polymerization activity even when a saturated hydrocarbon solution of the modified aluminoxane represented by the general formula [IV] is used.

  In the high temperature solution polymerization according to the present invention, a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 can also be applied as the organoaluminum oxy compound (b-1).

  Furthermore, examples of the organoaluminum oxy compound (b-1) used in the present invention include an organoaluminum oxy compound containing boron represented by the following general formula [V].

In the formula [V], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Note that a slight amount of organoaluminum compound may be mixed in the above-described (b-1) organoaluminum oxy compound.

(b-2) Compound that reacts with metallocene compound (A) to form an ion pair Compound (b-2) that reacts with metallocene compound (A) to form an ion pair (hereinafter abbreviated as "ionic compound") Are disclosed in JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Kaihei 3-207704, Patent Publication US5321106, and the like. Furthermore, examples of the ionic compound (b-2) include heteropoly compounds and isopoly compounds.

  In the present invention, the ionic compound (b-2) preferably employed is a compound represented by the following general formula [VI].

In the formula [VI], R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Specific examples of the ionic compound (b-2) which is a carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5- Examples thereof include ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, and tris (3,5-dimethylphenyl) carbeniumtetrakis (pentafluorophenyl) borate.

  Examples of the ionic compound (b-2) that is an ammonium salt include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, and a dialkylammonium salt.

  Specific examples of the ionic compound (b-2) which is a trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, and trimethylammonium. Tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro) Phenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n- Til) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, di Octadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2 , 4-Dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate Over DOO, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

  Specific examples of the ionic compound (b-2) which is an N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate, N, N-dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N , N-diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanily And nitrotetrakis (pentafluorophenyl) borate.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

As the other ionic compound (b-2), the ionic compounds described in JP-A-2004-51676 can be used without limitation.
Said ionic compound (b-2) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

(b-3) Organoaluminum compound As the organoaluminum compound forming the olefin polymerization catalyst (b-3), for example, an organoaluminum compound represented by the following general formula [VII], represented by the following general formula [VIII] And a complex alkylated product of a Group 1 metal and aluminum.

R ^a _m Al (OR ^b ) _n H _p X _q ... [VII]
In the formula [VII], R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m Is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3.

Specific examples of the organoaluminum compound represented by the general formula [VII] include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum;
Tri-branched alkyl aluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≦ 2x.) Isoprenyl represented by like Alkenyl aluminum such as aluminum;
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Partially alkoxylated alkylaluminum having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _0.5 ;
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

M ² AlR ^a ₄ ... [VIII]
In the formula [VIII], M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product of Group 1 metal of the periodic table and aluminum represented by the formula [VIII] include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) _4. .

A compound similar to the compound represented by the general formula [VII] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
In the polymerization, the method of using each component and the order of addition are arbitrarily selected. For example, a method of adding the catalyst component (A) and the catalyst component (B) to the polymerization vessel in any order can be exemplified. .

In the said method, two or more of each catalyst component may be contacted previously.
The reaction temperature can be raised to 100 ° C. because the catalyst is not deactivated even at high temperatures. The polymerization pressure is usually in the range of more than 0 MPa to 8 MPa (gauge pressure), preferably more than 0 MPa to 5 MPa (gauge pressure). The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 10 minutes to 3 hours. . Furthermore, molecular weight regulators such as hydrogen can be used.

  The molar ratio (charge ratio) ([A] / [B]) of propylene [A] to α-olefin [B] having 2 to 10 carbon atoms excluding propylene is usually 40/60 to 95/5, preferably Is 50/50 to 95/5.

  The molar ratio (preparation ratio) of propylene [A] and non-conjugated polyene [C] ([A] / [C]) is usually 99.9 / 0.1 to 90/10, preferably 99.5 / 0. .5 to 90/10.

Polymerization using the above catalyst is preferable because an appropriate amount of long chain branching can be introduced into the propylene-based copolymer.
Further, as a polymerization catalyst for producing the copolymer of the present invention, (i) a transition metal compound represented by the following general formula (I) or (II), and (ii) (b-1) the above transition metal At least one selected from a compound that reacts with the transition metal M in the compound (i) to form an ionic complex (also referred to as an ionized ionic compound), (b-2) an organoaluminum compound, and (b-3) an aluminoxane. It is also preferable to use a metallocene catalyst comprising a seed compound.

In the formulas (I) and (II), M represents Ti, Zr, Hf, Rn, Nd, Sm or Ru, and Cp ¹ and Cp ² represent a cyclopentadienyl group or indenyl which is π-bonded to M. A group, a fluorenyl group or a derivative group thereof, X ¹ and X ² are anionic ligands or neutral Lewis base ligands, and Y represents a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. And Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms.

In the general formula (I) of the transition metal compound, M represents Ti, Zr, Hf, Rn, Nd, Sm, or Ru, and preferably Ti, Zr, or Hf. Cp ¹ and Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof π-bonded to M. More specifically, Cp ¹ and Cp ² are ligands coordinated to a transition metal, such as cyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like. This is a ligand having a dienyl skeleton, and the ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, or a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, specifically, hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfonic acid-containing groups (—SO ₃ R ^a , wherein R ^a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group), a halogen atom And a hydrogen atom.

Z is C, O, B, S, Ge, Si or Sn, or a group containing these atoms, for example, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent group having 1 to 20 carbon atoms. A halogenated hydrocarbon group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —CO—, —SO—, —SO ₂ —, —BR ⁵ — (where R ⁵ is A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms) and the like.

Specific examples of the transition metal compound represented by the general formula (I) include, for example, paragraphs [0050] and [0051] of JP-A No. 2002-97228.
In the general formula (II) of the above transition metal compound, M is a Group 4 or lanthanide series transition metal, specifically, Ti, Zr, Hf, Rn, Nd, Sm or Ru. Preferably, Ti, Zr and Hf are used. Cp ¹ is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof that is π-bonded to M. More specifically, Cp ¹ is a ligand coordinated to a transition metal, and is a ligand having a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative group thereof. The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, or a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different from each other, and are hydrogen atoms or halogen atoms, or contain 20 or less carbon atoms Hydrocarbon group, silyl group containing 20 or less silicon atoms, or germanyl group containing 20 or less germanium atoms. Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom.

  Z is carbon, oxygen, sulfur, boron or an element belonging to Group 14 of the periodic table (for example, silicon, germanium or tin), preferably carbon, oxygen or silicon, and Z is an alkyl group, an alkoxy group or the like. These substituents may be bonded to each other to form a ring. Z and Y may form a condensed ring.

  Specific examples of the transition metal compound represented by the general formula (II) include, for example, paragraph [0056] of JP-A No. 2002-97228. In the present invention, among these, (1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenz (b , H) -fluorenyl) zirconium dichloride.

The transition metal compound (i) can be used alone or in combination of two or more. The transition metal compound (i) as described above can also be used by being supported on a particulate carrier. The particulate _{support, SiO 2, Al 2 O 3} , B 2 O 3, MgO, ZrO 2, CaO, TiO 2, ZnO, SnO 2, BaO, inorganic carriers such as ThO, polyethylene, polypropylene, poly-1 Organic carriers such as butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

  (Ii) (b-1) a compound that reacts with the transition metal M in the transition metal compound (i) to form an ionic complex, (b-2) an organoaluminum compound, and (b-3) an aluminoxane. Specific examples of the at least one compound selected from the above include those conventionally known in the field of olefin polymerization, such as the compounds described above and the specific examples described in WO 01/027124. .

In the present invention, these metallocene catalysts can be used singly or in combination of two or more.
In the present invention, propylene, an α-olefin having 2 to 10 carbon atoms other than propylene, and a non-conjugated polyene in the presence of the metallocene catalyst comprising the components (i) and (ii) described above are usually in a liquid phase. It can also be produced by copolymerization with. At this time, a hydrocarbon solvent is generally used, but an α-olefin such as propylene or 1-butene may be used as a solvent. Copolymerization can be carried out by either a batch method or a continuous method.

  When the above metallocene catalyst is used and a batch method is used, the transition metal compound (i) in the polymerization system is usually 0.00005 to 1 mmol, preferably 0.0001 to 0.5 mmol, per liter of polymerization volume. Used in such amounts.

  Here, when the ionized ionic compound (b-1) is used as the component (ii), the molar ratio of the ionized ionic compound (b-1) to the transition metal compound (i) ((b- It is desirable to use 1) / (i)) in such an amount that it is usually 0.5 to 20, preferably 1 to 10. When the organoaluminum compound (b-2) is used as the component (ii), the amount is usually about 0 to 5 mmol, preferably about 0 to 2 mmol per liter of polymerization volume. It is desirable.

When aluminoxane (b-3) is used as the component (ii), the aluminum atom (Al) in the organic aluminoxane (b-3) and the transition metal atom (M) in the transition metal compound (i) are used. It is desirable that the molar ratio (Al / M) is usually 1 to 10,000, preferably 10 to 5,000. The copolymerization reaction is usually performed at a temperature in the range of -20 to 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C, and a pressure exceeding 0 to 80 kg / cm ² or less, preferably exceeding 0. At 50 kg / cm ² or less.

  The reaction time (average residence time when polymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.5 hours. It is. In the copolymerization, a molecular weight regulator such as hydrogen can be used.

  In the present invention, in the presence of a metallocene catalyst, propylene, an α-olefin having 2 to 10 carbon atoms other than propylene, and a non-conjugated polyene are finally polymerized so as to have the above-described characteristics. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or solution polymerization, or a gas phase polymerization method.

  When performing such polymerization by liquid phase polymerization, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cyclopentane, cyclohexane, methylcyclohexane are used as the polymerization medium. Inert hydrocarbon solvents such as alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof can be used. Propylene can also be used as a solvent.

Further, when such polymerization is carried out by suspension polymerization, it is usually desirable to carry out at a temperature of −50 to 100 ° C., preferably 0 to 90 ° C. When carrying out solution polymerization, It is usually carried out at a temperature of 0 to 250 ° C, preferably 20 to 200 ° C. Moreover, when implementing a gas phase polymerization method, it is desirable that superposition | polymerization is normally performed at the temperature of 0-120 degreeC, Preferably it is 20-100 degreeC. The polymerization is usually performed under normal pressure to 100 kg / cm ² , preferably under normal pressure to 50 kg / cm ² .

  The polymerization can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the propylene copolymer used in the present invention thus obtained can be adjusted by allowing hydrogen to be present in the polymerization system, or by changing the polymerization temperature and polymerization pressure.

<Thermoplastic resin (B)>
Examples of the thermoplastic resin (B) include known resins and are not particularly limited, but a crystalline olefin resin (BB) is preferable, and polypropylene (B1) is more preferable.
Examples of the thermoplastic resin include polyolefin, polyamide, polyester, polyurethane, polystyrene, polyimide, and polyether.
The crystalline olefin resin (BB) is different from the copolymer (A). The melting point measured by DSC is usually 70 ° C. or higher, preferably 110 to 250 ° C.

  Examples of the crystalline olefin resin (BB) include low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1- Pentene, poly-3-methyl-1-butene, ethylene / α-olefin random copolymer, propylene / α-olefin random copolymer, 1-butene / α-olefin random copolymer, cyclic olefin copolymer, chlorine Polyolefin, vinyl acetate copolymer, ethylene / methacrylic acid acrylate copolymer, ionomer, ethylene / vinyl alcohol copolymer, and the like. In one embodiment, the thermoplastic resin (B) does not contain a non-conjugated polyene.

  Polypropylene (B1) is a propylene homopolymer or propylene such as propylene / ethylene block copolymer, propylene / ethylene random copolymer and propylene / ethylene / 1-butene random copolymer; Random copolymer or block copolymer of α-olefin (excluding propylene), and usually a constitutional unit derived from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) Constituent units derived from propylene are contained in an amount of 20 mol% or more, preferably 50 mol% or more in a total of 100 mol% of the units. The stereoregularity may be, for example, an isotactic structure or a syndiotactic structure.

  Polypropylene (B1) usually has a melting point obtained by differential scanning calorimetry (DSC) in the range of 110 to 170 ° C. It is preferable for the melting point of polypropylene (B1) to be in the above-mentioned range since the balance between heat resistance and mechanical properties is excellent.

  These thermoplastic resins can be used singly or in combination of two or more. Moreover, the manufacturing method of these thermoplastic resins is not specifically limited, It can manufacture with various catalysts and various well-known manufacturing methods.

<Propylene-based copolymer composition>
The propylene copolymer composition (X) used in the present invention comprises 1 to 95 parts by weight of the propylene copolymer (A) and a thermoplastic resin (B), preferably a crystalline olefin resin (BB). 99 to 5 parts by weight (provided that the total of (A) and (B) is 100 parts by weight), preferably 1 to 80 parts by weight of propylene copolymer (A) and thermoplastic resin (B ) 20 to 99 parts by weight, more preferably 1 to 65 parts by weight of the propylene copolymer (A) and 99 to 35 parts by weight of the thermoplastic resin (B), particularly preferably the propylene copolymer (A) 1 to 1 part. It comprises 45 parts by weight and 99 to 55 parts by weight of the thermoplastic resin (B), more preferably 1 to 30 parts by weight of the propylene copolymer (A) and 99 to 70 parts by weight of the thermoplastic resin (B). Within this range, a composition having excellent material strength and a good balance between moldability and melt tension can be obtained.

  If the propylene-based copolymer (A) is contained in the propylene-based copolymer composition (X) of the present invention, an effect such as promoting the crosslinking of the thermoplastic resin (B) can be expected. Although it is considered that a good cross-linked product can be obtained even in the number of blended parts, a region where the propylene-based copolymer (A) is less than the thermoplastic resin (B) is preferable because it is excellent in mechanical strength.

  The propylene-based copolymer composition (X1) of the present invention is 1 to 80 parts by weight of the propylene-based copolymer (A1) and 99 to 20 parts by weight of polypropylene (B1) as the thermoplastic resin (B). Preferably, it comprises 1 to 45 parts by weight of the propylene copolymer (A1) and 99 to 55 parts by weight of polypropylene (B1) (provided that the total of (A1) and (B1) is 100 parts by weight). . Such a copolymer composition (X1) is preferable because it is excellent not only in material strength but also in balance between moldability and melt tension.

[Other ingredients]
(Crosslinking agent and crosslinking aid)
Examples of the crosslinking agent used as necessary in the present invention include phenolic vulcanizing agents such as organic peroxides, sulfur, sulfur compounds, silane compounds (SiH group-containing compounds), and phenol resins. Organic peroxides are preferred.

  The cross-linking agent is preferably selected appropriately according to the apparatus used for the cross-linking reaction and the target cross-linking form. When using a crosslinking agent, it is used in an amount of 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the composition. When the crosslinking agent is used in the above-mentioned blending amount, it is preferable because characteristics as a foaming material can be obtained in the crosslinking foaming.

  In the case of crosslinking of the copolymer, the temperature at the time of crosslinking is usually 130 to 350 ° C., preferably 180 to 280 ° C. for an organic peroxide. 100 to 180 ° C. is preferable for sulfur and sulfur compounds, and 20 to 180 ° C. is preferable for silane compounds. In the present invention, the degree of freedom is large with respect to the crosslinking temperature.

  Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperbenzoate, t-butylperoxyisopropylcarbonate, diacetyl Examples thereof include peroxide, lauroyl peroxide and t-butylcumyl peroxide. Among them, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne in terms of odor and scorch stability -3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (t- Butylperoxy) valerate is preferred, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1, 3-bis (t-butylperoxyisopropyl) benzene is particularly preferred.

  Sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine and trimethylolpropane when crosslinking with organic peroxides -N, N'-m-Phenylenedimaleimide and other crosslinking aids, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate Functional methacrylate monomers and multifunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be included. By including such a compound, a uniform and mild crosslinking reaction can be expected.

  A compound such as the above-mentioned crosslinking aid or polyfunctional vinyl monomer is usually 0.001 to 50 parts by weight, preferably 0.001 to 30 parts by weight, particularly preferably 100 parts by weight of the composition. It is used in an amount of 0.005 to 10 parts by weight.

  In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, Decomposition accelerators such as naphthenates such as manganese, magnesium, lead, and mercury may be used.

  Sulfur compounds include low molecular disulfide compounds such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram disulfide, N, N'-dimethyl-N, N ' -Diphenylthiuram disulfide, N, N'-diethyl-N, N'-diphenylthiuram disulfide, dibenzothiazyl disulfide and the like.

  As a silane compound (a SiH group-containing compound or a hydrosilyl group-containing compound), a hydrogen atom directly bonded to at least 2, preferably 3 or more silicon atoms, that is, a SiH group, is contained in one molecule. The structure is not particularly limited, and any conventionally produced resinous material such as a linear, annular, branched structure or three-dimensional network structure can be used.

  The silane compound is usually 0.1 to 100 parts by weight, preferably 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, and still more preferably 0.2 to 100 parts by weight of the composition. -30 parts by weight, particularly preferably 0.2-20 parts by weight. Within the above range, it is possible to obtain a rubber composition that is excellent in compression set resistance and can form a crosslinked rubber molded article having an appropriate crosslinking density and excellent strength and elongation properties. Use of a silane compound in a proportion exceeding 100 parts by weight is not preferable because it is disadvantageous in terms of cost.

As specific silane compounds, reference can be made to paragraphs [0073] to [0116] of JP-A No. 2003-128851.
Examples of the phenol vulcanizing agent include phenol resin, alkylphenol formaldehyde resin, triazine-formaldehyde resin, melamine-formaldehyde resin, and the like.

Furthermore, when performing radiation crosslinking, the propylene copolymer composition (X) may contain a crosslinking aid or a polyfunctional vinyl monomer as necessary.
As the crosslinking aid or the polyfunctional vinyl monomer, known ones can be used. For example, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, Cross-linking aids such as 4-dinitrosoaniline, nitrobenzene, diphenylguanidine and trimethylolpropane-N, N'-m-phenylenedimaleimide, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, Examples include polyfunctional methacrylate monomers such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate, and polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate. By including the above-mentioned crosslinking aid or polyfunctional vinyl monomer, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene, triallyl isocyanurate, and trimethylolpropane trimethacrylate are preferable because they are inexpensive and easily available.

  The crosslinking aid or polyfunctional vinyl monomer is used usually in an amount of 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the propylene-based copolymer composition (X). .

(Foaming agent)
The composition (X) used in the present invention may contain a foaming agent. For example, inorganic foaming agents such as sodium bicarbonate and sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite; N, N Nitroso compounds such as' -dinitrosopentamethylenetetramine and N, N'-dinitrosoterephthalamide; azo compounds such as azodicarbonamide and azobisisobutyronitrile; benzenesulfonyl hydrazide and 4,4'-oxybis (benzenesulfonyl) Hydrazide compounds such as hydrazide; organic foaming agents such as calcium azide and azide compounds such as 4,4′-diphenyldisulfonyl azide. As commercially available products, for example, Cellmic MB1023 (trade name; manufactured by Sankyo Kasei Co., Ltd.), Bini Hall AC-2F (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd.), Bini Hall AC # LQ (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd.) , Azodicarbonamide (abbreviation ADCA)), Neocerbon N # 1000SW (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., 4,4′-oxybis (benzenesulfonylhydrazide (abbreviation: OBSH)), Cellular D (trade name; Eiwa Kasei Kogyo Co., Ltd.) Manufactured, N, N′-dinitrosopentamethylenetetramine (abbreviation DPT)) and the like.

Moreover, you may use the physical foaming agent which consists of inert gas, such as a carbon dioxide and nitrogen. Specific examples include argon, hydrogen, oxygen, butane, propane, water vapor, and the like, and two or more of them can be used as necessary. For example, air may be used. Among these, carbon dioxide is preferable from the viewpoints of inertness to raw materials, solubility in raw materials, and handling properties.
The blending amount of the foaming agent is usually 1 to 70 parts by weight, preferably 3 to 60 parts by weight with respect to 100 parts by weight as the total of the copolymer (A) and the thermoplastic polymer (B).

(Foaming aid)
In the present invention, in addition to the foaming agent, a foaming aid may be added as necessary. The foaming aid exhibits actions such as lowering the decomposition temperature of the foaming agent, promoting decomposition, or uniforming the bubbles.
Examples of the foaming aid include metal compounds such as zinc, calcium, lead, iron and barium, organic acids such as salicylic acid, phthalic acid, stearic acid, oxalic acid and citric acid or salts thereof, talc, barium sulfate and silica. Fine inorganic particles, urea or a derivative thereof. Also, polyvalent carboxylic acids such as citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, tartaric acid, lactic acid, cyclohexane 1,2-dicarboxylic acid, camphoric acid, ethylenediaminetetraacetic acid, triethylenetetramine hexaacetic acid and nitrilolic acid And inorganic carbonate compounds such as sodium hydrogen carbonate, sodium aluminum hydrogen carbonate and potassium hydrogen carbonate, and intermediates produced by these reactions, for example, salts of polycarboxylic acids such as sodium dihydrogen citrate and potassium oxalate And so on. Examples of commercially available products include cell paste K5 (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., urea) and FE-507 (trade name: manufactured by Eiwa Kasei Kogyo Co., Ltd., baking soda).

Although the compounding quantity of a foaming adjuvant is not specifically limited, It is 0.1-5 weight part normally with respect to 100 weight part of this composition, Preferably it is 0.5-4 weight part.
The foaming agent or foaming aid may be dry blended before extrusion molding of the foamed molded article and decomposed during extrusion molding, or may be melt blended into pellets in advance.

(Other additives)
The propylene-based copolymer composition (X) used in the present invention includes a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, an anti-fogging agent as long as the object of the present invention is not impaired. Additives such as agents, lubricants, pigments, dyes, plasticizers, anti-aging agents (stabilizers), hydrochloric acid absorbents, antioxidants, secondary antioxidants may be blended as necessary. The blending amount is not particularly limited, but is usually about 0.001 to 10 parts by weight with respect to 100 parts by weight of the composition.

  Furthermore, if necessary, a dispersant, a dispersion aid, a dispersion strengthener, a nucleating agent, a vulcanizing agent, a vulcanization accelerator, a vulcanizing aid, a reinforcing agent, a filler, a softening agent, a processing aid, an activator, Other additives such as a hygroscopic agent, a pressure-sensitive adhesive, a flame retardant, a release agent, a pigment, and a dye can be blended.

These additives may be used alone or in combination of two or more.
These additives are added to the present composition melted in the extruder and kneaded into the resin particles, for example, when the resin particles are produced by cutting the strand extruded by the extruder. Can do.

[Propylene-based copolymer composition production method]
The propylene-based copolymer composition used in the present invention can be produced by employing any known method. For example, the propylene-based copolymer, a thermoplastic resin, and other components added as desired, A modified body is mixed with various known methods such as a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender or the like, or after mixing, a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a roll, etc. It can be produced by adopting a method of granulating or pulverizing after melt-kneading.

<Crosslinked product>
The cross-linked product in the present invention refers to a product obtained by irradiating the propylene-based copolymer composition with an electron beam or a chemical reaction with a cross-linking agent.

  Any known method may be used as the crosslinking method of the crosslinked product of the present invention, and specific examples include electron beam crosslinking and peroxide crosslinking. Electron beam crosslinking has the advantage of producing less volatile matter in the manufacturing process, and peroxide crosslinking is widely used because it has the advantage of not requiring special equipment in the crosslinking process. The crosslinked product obtained by these methods can be widely used for conventionally known polyolefin applications, and can be suitably used for a crosslinked molded product, a crosslinked foamed molded product, and the like. As a molding method, it can be molded by a known molding method such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, press molding, vacuum molding, calendar molding, and foam molding. Applications include, for example, sheets, films, pipes, hoses, electric wire coatings and filaments. In addition, the copolymer or the composition of the present invention can be used as a part of a molded product to be used as a multilayer laminate. The multilayer laminate is a laminate in which at least one layer thereof is a layer comprising the copolymer or the composition, and is a component of the multilayer film and sheet, multilayer container, multilayer tube, water-based paint Multilayer coating film laminated body etc. which are contained as are mentioned.

  The degree of cross-linking of the cross-linked product can be expressed by the gel fraction described below. Usually, the gel fraction of a crosslinked body is 10 to 80%. However, the crosslinked body in this patent is not limited to this range, and the present invention is applicable to a crosslinked body having a gel fraction of less than 10%, particularly less than 0.5% and having a low degree of crosslinking. As in the case of the crosslinked product having a high degree of crosslinking, effects such as excellent surface appearance can be obtained.

(Crosslinked molded product)
The crosslinked molded product of the present invention comprises a crosslinked product obtained by crosslinking a propylene-based copolymer composition by the above method.

  According to this invention, the crosslinked body which shows the outstanding characteristic is obtained. This is because radicals generated during crosslinking of the propylene-based copolymer composition are consumed for crosslinking of unsaturated groups, particularly vinyl groups of the propylene-based copolymer (A), and decomposition of the main chain is suppressed. It seems that one of the reasons is that the crosslinkability is improved. The cross-linked product of the present invention is excellent in, for example, mechanical properties (rigidity, surface hardness, etc.). When the thermoplastic polymer (B) is an α-olefin (co) polymer, particularly an α-olefin (co) polymer having 3 or more carbon atoms, particularly excellent characteristics are exhibited. It is estimated that this is because the propylene-based polymer used in the present invention has good compatibility with the component (B), for example, an α-olefin (co) polymer, particularly preferably polypropylene. Therefore, it is estimated that the crosslinkability is good even when compared with the case where, for example, an ethylene-propylene-nonconjugated diene copolymer is blended with the component (B). This is also due to the suppression of main chain degradation. Further, when the crosslinked body is foamed, a uniform foamed cell with excellent surface appearance and high foaming can be obtained. It is also excellent in hardness such as surface hardness and compression hardness. Moreover, it is thought that the same effect is acquired also when bridge | crosslinking and foaming are performed simultaneously so that it may mention later.

  According to the present invention, not only the deterioration of the thermoplastic resin (B) is particularly suppressed, but the gel fraction of a resin that should normally be difficult to crosslink may be improved. This is considered that not only (A) itself is easily cross-linked, but also (A) works on (B) to promote the cross-linking of (B). Further, (A) and (B) are considered to be one of the causes of the above-mentioned unique behavior because of excellent compatibility.

(Electron beam cross-linked compact)
First, radiation crosslinking will be described in detail. The radiation may be an electron beam or any of X-rays, γ-rays, α-rays and β-rays. The propylene-based copolymer composition crosslinked by a method of irradiating with radiation such as electron beam or γ-ray is more excellent in surface appearance and foaming than the propylene-based copolymer composition obtained only by ordinary melt-kneading. Excellent cell uniformity. "
Further, when performing radiation crosslinking, the propylene copolymer composition (X) is melt-kneaded with a crosslinking aid or a polyfunctional vinyl monomer in advance using an extruder, a roll, or the like, if necessary. Also good.

  The crosslinking aid or polyfunctional vinyl monomer is used usually in an amount of 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the propylene-based copolymer composition (X). .

  As an electron beam irradiation method, first, a mixer such as a Banbury mixer is used, and a propylene-based copolymer (A), a thermoplastic resin (B) and, if necessary, a seed additive and a crosslinking aid are added at 80 to 170 ° C. After kneading at a temperature of 3 to 10 minutes, using rolls such as an open roll, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensing, ribbon-like or sheet-like propylene copolymer composition A product (X) is prepared. Alternatively, the propylene copolymer composition (X) is prepared by blending in a plastic bag or the like. The propylene-based copolymer composition (X) thus prepared remains in the form of a sheet, or is formed into a desired shape by an extruder, a calender roll, an injection molding machine or a press, or a strand from the extruder. Extruded into a shape and pulverized with a cutter or the like to form pellets and irradiated with an electron beam. Alternatively, propylene-based copolymer composition (X) is prepared by directly irradiating powder such as propylene-based copolymer (A) and thermoplastic resin (B) impregnated with a compound such as a crosslinking aid. May be. Irradiation with an electron beam is usually 0.1 to 10 MeV (megaelectron volts), preferably 0.3 to 5 MeV, and the absorbed dose is usually 0.5 to 100 kGy (kilogrey), preferably 0.5. Performed to be ~ 70 kGy.

  The γ-ray irradiation has a higher permeability to the propylene-based copolymer composition (X) than the electron beam irradiation. In particular, when the propylene-based copolymer composition (X) is irradiated to a pellet-shaped electron, Irradiation effects can be expected only on the surface portion of the beam irradiation, but γ rays can be sufficiently crosslinked to the inside of the pellet by directly irradiating a small amount. The γ-ray irradiation is performed so that the propylene copolymer composition (X) has a γ-ray irradiation amount of usually 0.1 to 50 kGy, preferably 0.3 to 50 kGy.

  According to the present invention, in order to improve the crosslinkability of the thermoplastic resin (B), for example, it is not always necessary to introduce a site having excellent crosslinkability, and the degree of freedom regarding the thermoplastic resin is large. In addition, when the crosslinking assistant or polyfunctional vinyl monomer is melt-kneaded with the propylene-based copolymer composition (X), if necessary, using an extruder, a roll or the like before the radiation crosslinking, I think there are fewer constraints such as conditions.

(Peroxide cross-linked molded product)
Next, the peroxide crosslinking method will be described in detail. In the peroxide crosslinking, the propylene-based copolymer composition (X) is crosslinked using an organic peroxide and a crosslinking aid or a polyfunctional vinyl monomer. At this time, the following organic peroxide, crosslinking aid and polyfunctional vinyl monomer are used.

  Any of the above-mentioned organic peroxides may be used. From the viewpoint of odor and scorch stability, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5- Dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethyl Cyclohexane and n-butyl-4,4-bis (tert-butylperoxy) valerate are preferred, and 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane is particularly preferred.

  The organic peroxide is usually 0.001 to 10 parts by weight, preferably 0.001 to 5 parts by weight with respect to 100 parts by weight as a total of the propylene-based copolymer (A) and the thermoplastic resin (B). Used in an amount.

  When crosslinking is performed using an organic peroxide, the above-described various crosslinking aids and polyfunctional vinyl monomers can be included. By including such a compound, a uniform and mild crosslinking reaction can be expected.

  The above-mentioned crosslinking aid or compound such as a polyfunctional vinyl monomer is usually 0.001 to 50 parts by weight, preferably 100 parts by weight in total for the propylene copolymer (A) and the thermoplastic resin (B). Is used in an amount of 0.001 to 30 parts by weight, particularly preferably 0.005 to 10 parts by weight.

  In order to accelerate the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine and 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium, zirconium, Decomposition accelerators such as naphthenates such as manganese, magnesium, lead and mercury may be used.

  The crosslinking method is not particularly limited, and for example, it can be carried out by dynamically heat-treating the propylene-based copolymer composition (X) in the presence of a crosslinking agent and a crosslinking aid. Here, “dynamic heat treatment” means kneading in a molten state.

  The dynamic heat treatment may be performed in either an open type or non-open type apparatus. The reaction may be performed in the presence of oxygen or in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of heat processing is 130-350 degreeC normally, Preferably it is 180-280 degreeC. The kneading time is usually 0.5 to 10 minutes, preferably 0.5 to 5 minutes. Further, the applied shearing force is usually in the range of 0.05 to 1000 sec-1, preferably 0.1 to 500 sec-1 in terms of shear rate.

  The gel fraction is less than 10%, preferably less than 0.5% by adjusting the content of the propylene-based copolymer (A), the addition amount of the peroxide and the addition amount of the crosslinking aid. A finely cross-linked molded article having an extremely small gel content can be obtained. Compared to a crosslinked product having a gel fraction of 10% to 80%, which is obtained by a normal crosslinking method, the finely crosslinked molded product having an extremely small gel content described above has good extrusion moldability and is easy to reuse.

A case where a so-called microcrosslinked molded body having a gel content of less than 10% is produced will be described. In the crosslinked product, the amount of peroxide used is preferably 3.0 parts by weight or less based on 100 parts by weight of the raw material propylene copolymer composition (X). Adjustment of the gel fraction to be suppressed to 10% or less because the addition of a crosslinking aid for suppressing the direction of decomposition of the coalesced composition (X) is not always necessary or a small amount is required. Is easy. Moreover, if the usage-amount of a peroxide is 0.1 weight part or more, especially the propylene which has a foaming ratio of 3-30 times (it will be 0.3-0.03 g / cm < ³ > when converted into a foam density). It is considered that melt-processability suitable for producing the extruded copolymer composition (X) can be sufficiently imparted to the propylene-based copolymer composition (X). On the other hand, the addition amount of the crosslinking aid is 5.0 parts by weight or less with respect to 100 parts by weight of the propylene-based copolymer composition (X), and the gel fraction is 10% or less, preferably 0.5. It is more desirable to suppress it to less than or equal to%, and 0.01 parts by weight or more is more preferable because the resin is difficult to decompose.

  As a more specific example of finely cross-linking the propylene-based copolymer composition (X), as will be described in the examples described later, for example, the propylene-based copolymer composition (X), a cross-linking agent, and the like Accordingly, a crosslinking aid, a heat stabilizer, and the like may be mixed by a method such as dry blending, and then supplied to an extruder and subjected to dynamic heat treatment.

  Also, the propylene-based copolymer composition (X), peroxide, and crosslinking aid are dispersed in an aqueous medium such as water and stirred to suppress decomposition of the peroxide as much as possible. If the temperature and time at which half or more of the total amount of the product remains, preferably 4/5 or more (for example, the decomposition temperature at which the half-life of the peroxide is 10 hours (10-hour half-life temperature)) The propylene copolymer composition (X) is impregnated with a peroxide and a crosslinking aid by heating and holding for about 6 hours (preferably 1.5 to 4.5 hours). 5 at a temperature lower than the melting point of the system copolymer composition (X) and at or above the temperature at which substantial decomposition of the peroxide takes place, preferably at or above the 10-minute half-life temperature of the peroxide. Hold for 120 to 120 minutes, preferably 15 to 60 minutes By decomposing the peroxide impregnated in the propylene copolymer composition (X), the propylene copolymer composition (X) is slightly cross-linked without completely melting, and the gel fraction is extremely high. The method of obtaining a low polypropylene resin is mentioned. By impregnating and decomposing the peroxide without completely melting the propylene-based copolymer composition (X), the main chain of the propylene-based copolymer composition (X) is hardly broken by the peroxide. Since the amount of the crosslinking aid used can be relatively reduced, there is no possibility of causing non-uniform physical properties due to the incorporation of a large amount of the crosslinking aid.

  The above-described crosslinking reaction is performed in a sealed container, but after the contents are put into the sealed container, the upper gas phase space in the container is inert so that the oxygen concentration becomes 1% by volume or less. It is desirable to replace with gas.

  In preparing the propylene-based copolymer composition (X), in addition to the method of impregnating the propylene-based copolymer composition (X) with the crosslinking aid using the aqueous medium as described above, It is also possible to employ a method in which an auxiliary agent is previously contained in the propylene-based copolymer composition (X) and then the composition is impregnated with a peroxide using an aqueous medium. In order to make the propylene-based copolymer composition (X) contain a crosslinking aid in advance, for example, after the propylene-based copolymer composition (X) and the crosslinking aid are melt-kneaded in an extruder, A method of extruding the melt-kneaded product in a linear form from an extruder and cutting the linear resin into a particulate form can be employed. However, in this case, since a part of the crosslinking aid may be vaporized and dissipated from the propylene-based copolymer composition (X) with time, the content of the crosslinking aid may be reduced. After granulating the propylene-based copolymer composition (X) contained, it is preferable to impregnate the propylene-based copolymer composition (X) with a peroxide at a relatively early stage for fine crosslinking.

  In the present specification, an embodiment in which the composition (X) is first produced from (A) and (B) and then subjected to the crosslinking step has been described. However, the present invention is not necessarily limited thereto. B) and a crosslinking agent, a crosslinking aid, and other necessary additives are separately supplied to a molding machine such as an extruder, and mixing and crosslinking are performed simultaneously in the same molding machine, for example. It doesn't matter.

Cross-linked foamed molded product A cross-linked foamed molded product is obtained by foaming a cross-linked molded product that has been cross-linked using a crosslinking agent such as electron beam cross-linking or peroxide.

  In addition, the propylene-based copolymer composition (X) and a crosslinking agent, a foaming agent, and a crosslinking aid, a heat-resistant stabilizer, a foaming aid, and the like are blended as necessary, heated in a molding machine, and the like. Foaming may be performed simultaneously. In the present invention, a method of foaming a crosslinked crosslinked product can be given as a preferred example.

  There is no restriction | limiting in particular as a method of manufacturing the foam of this invention, Extrusion molding, press molding, injection molding, blow molding, extrusion blow molding, injection blow using the molding machine used for the well-known resin processing method It can be produced by molding, inflation molding, stamping mold molding, compression molding, bead molding and the like.

In addition to a known method, the foam may be mixed by contact with a high-pressure gas (also referred to as a physical foaming agent).
Specifically, the desired raw material can be impregnated with the high pressure gas by contacting with the high pressure gas. The form of the raw material when contacting with the high-pressure gas may be a molded product such as a film or a sheet, or may be a molten raw material, but is preferably a film or a sheet. As a method for bringing the raw material and the high-pressure gas into contact, for example, the molded body may be put in a pressure-resistant container, and the high-pressure gas may be injected into the molded body, or the molten raw material may be injected into the pressure-resistant container, the extruder, or the injection It may be put in a molding machine or the like, and high pressure gas may be injected into it.

  Examples of the high-pressure gas include carbon dioxide, nitrogen, argon, hydrogen, oxygen, butane, propane, water vapor, and the like, and two or more of them can be used as necessary. For example, air may be used. . Among these, carbon dioxide is preferable from the viewpoints of inertness to raw materials, solubility in raw materials, and handling properties. When carbon dioxide is used, the concentration is usually 80% by volume or more.

  The pressure of the high-pressure gas brought into contact with the raw material is usually 1 MPa or more, preferably 20 MPa or more. The upper limit is not particularly limited, but is usually 50 MPa or less from the viewpoint of economy and operability. The higher the pressure, the smaller the bubble diameter of the resulting foam, which is preferable.

  The temperature of the high-pressure gas is appropriately selected depending on the form of the raw material, and is usually 300 ° C. or lower, preferably 200 ° C. or lower. Although it does not specifically limit about a minimum, From a viewpoint of economical efficiency or operativity, it is 0 degreeC or more normally. The lower the temperature, the smaller the bubble diameter of the resulting foam, which is preferable.

  The contact time between the raw material and the high-pressure gas is appropriately selected depending on the form of the raw material. When a melt is used, it is usually 1 second or longer, preferably 1 minute or longer, and when a film or sheet-shaped molded body is used, Usually, it is 1 hour or more, preferably 3 hours or more. The upper limit is not particularly limited, but after the high-pressure gas is sufficiently impregnated and diffused in the raw material, and the dissolved gas in the raw material reaches the saturated dissolution amount, the effect corresponding to the time is poor. Within 100 hours.

  The state of the high-pressure gas includes a supercritical state or a liquid state, but a supercritical state is preferable. Note that the high-pressure gas is in a supercritical state means that the temperature and pressure of the high-pressure gas are above the critical point. In this state, the density, viscosity, diffusion coefficient, etc. are close to gas by changing the pressure. Can vary widely from liquid to liquid. The critical point of high-pressure gas varies depending on the type of high-pressure gas. For example, carbon dioxide has a critical temperature of 304.2 K and a critical pressure of 7.4 MPa, and nitrogen has a critical temperature of 126.2 K and a critical pressure of 3.4 MPa. . In the case of two or more kinds of mixed gas, a critical point exists according to the kind of gas component and the mixing ratio.

  A raw material or a sheet-like or film-like molded body that is contacted with or impregnated with a high-pressure gas can usually be foamed by lowering the ambient pressure to about the normal pressure, that is, reducing the pressure. In the process of depressurization, usually, a part of the dissolved gas in the raw material escapes to the outside and the raw material is cooled by the Joule-Thomson expansion. The pressure reduction rate may be adjusted as appropriate, but the slower the pressure reduction rate, the more the dissolved gas in the raw material escapes to the outside, and the number of bubbles in the foam decreases. After completion of the decompression, the following low temperature holding is usually performed within 1 hour, preferably within 5 minutes.

  The foamed raw material is then held at a temperature of 15 ° C. or lower, preferably 10 ° C. or lower, more preferably 5 ° C. or lower. By performing such low-temperature holding, a highly transparent foam can be obtained. The lower limit of the holding temperature is not particularly limited, but is usually 0 ° C. or higher from the viewpoint of operability.

  The low temperature holding time is usually 1 minute or longer, preferably 5 minutes or longer, and more preferably 1 hour or longer for the purpose of allowing the dissolved gas to sufficiently escape outside. The upper limit of the holding time is not particularly limited, but is usually within 24 hours from the viewpoint of operability. Further, examples of the medium used for the holding include liquids such as cold water and oil, and gases such as chlorofluorocarbons, and may be directly or indirectly brought into contact with the raw material.

  As another example, there is a method of producing a foam by a press molding method. That is, the chemical foaming agent (inorganic foaming agent, organic foaming agent, etc.) and the copolymer or pellets of the composition are placed in a heated mold of a press molding machine, Alternatively, without applying mold pressure, the copolymer or composition is melted and then foamed to form a foam. At this time, the temperature of the mold is preferably in the range of 110 to 250 ° C.

  Furthermore, a method for producing a foam by an injection molding method will be described as an example. That is, there is a method in which the crosslinked composition is heated and melted with an injection molding machine and then injected into a mold so as to be foamed at the tip of a nozzle to form a foam. The resin temperature during injection is preferably in the range of 110 to 250 ° C.

The foam of the present invention can be obtained by the foaming method described above.
The foaming ratio of the foamed material is preferably 1.5 to 50 times when foamed at a foaming temperature of usually 100 to 170 ° C, preferably 120 to 165 ° C, more preferably 140 to 165 ° C. More preferably, it is 2 to 50 times, and most preferably 2 to 30 times. The expansion ratio can be obtained by dividing the density of the obtained foam by the density of the raw material.

The average cell diameter of the foam of this invention is 0.1-100 micrometers normally, Preferably it is 0.5-50 micrometers, More preferably, it is 0.5-20 micrometers.
The foam of the present invention may be laminated with various other materials, for example, laminated with a polyolefin-based resin substrate.

In the foaming, a crosslinking step may be performed in advance, foaming may be performed simultaneously with crosslinking, and crosslinking may be performed after foaming.
The crosslinked product obtained by the present invention can be used for applications such as tubes, electric wires, cables, electrical insulating materials, heat resistant films and the like. Moreover, it can use widely also for the uses which were mentioned to the following foaming molding. The crosslinked foamed molded product can be used for various applications in which a foamed molded product is generally used, such as a heat insulating material, a shock-absorbing packaging material, an automobile interior member, and a core material for an automobile bumper.

Automotive materials include bumper cores, seat core cushioning materials, automotive floor cushioning materials such as trunk floor spacers;
Door rim, console BOX, seat bag garnish, instrument panel, ceiling material, seat pad, ceiling cushion material, sound absorbing material, soundproof material, headrest, armrest, floor mat, trunk mat, floor spacer, door trim, instrument panel, door mirror packing, Pillar garnish, engine sound absorbing material, fuel tank safety foam, in-filter material, element material, side impact pad, door panel, seat back cover, instrument panel skin, cooler, freezer, tank truck, steering wheel, etc. (including semi-rigid products) ), Car cooler insulation, instrument panel lining, trunk mat, floor mat cowl side, ceiling material, wheel house cover, seat back, sun visor, molded door, pillar trim, door trim, wiring pro Compactors and the like automobile interior materials such as.

Moreover, a seat pad, a seat cushion, a floor soundproof material, a helmet lining, an oil filter, a saddle, etc. are mentioned.
As construction and earth and timber, folded plate roof, rooftop insulation sheet, various packing materials, unit bath insulation, roof insulation waterproofing material, uneven surface adjustment material, folded plate roofing material, various joint materials, long roof insulation, Examples include dew-proof materials, carpet underlays, water and hot water pipe heat-insulating materials, bath heat-insulating materials, sink dew-proof materials, soft lay construction, and sash table materials.

As packaging and cushioning materials, cushioning and packaging materials for tableware containers such as food containers for microwave ovens, precision equipment, electrical products (notebook PCs, flat-screen TVs), etc .;
Packing materials such as alcoholic beverages (sake, whiskey, shochu, domestic wine, etc.) and toiletries (shampoos, treatments, pump bottles for liquid detergents, etc.) can be mentioned.
Further, the foamed molded body may be subjected to secondary processing such as thermoforming such as vacuum molding, compression molding, hot stamping molding, etc. to obtain a molded body.

[Example]
The present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
In addition, the physical-property value etc. in an Example and a comparative example were measured with the following method.

[Various measurement conditions in Examples]
[Comonomer composition]
The contents of propylene, α-olefin and non-conjugated polyene in the propylene copolymer were measured by ¹³ C-NMR and ¹ H-NMR.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] was measured at 135 ° C. using a decalin solvent.
[Molecular weight distribution (Mz / Mw)]
The molecular weight distribution is a liquid chromatograph (Waters) in which TSKgelGMH ⁶ -HT × 2 and TSKgelGMH ⁶ -HTL × 2 columns (both column sizes are 7.5 mm in diameter and 300 mm in length) are connected in series as columns. Measurement was performed using an alliance / GPC2000 type). The obtained chromatogram was analyzed using a calibration curve using a standard polystyrene sample by a known method using the data processing software Empower2 manufactured by Waters, and Mz / Mw was calculated.

[MFR (g / 10 min)]
MFR was measured according to JIS K-6721 with a load of 2.16 kg at 230 ° C. and a load of 10 kg at 230 ° C.
From the measurement result, the ratio (MFR ₁₀ / MFR _2.16 ) was calculated.

[Melting point (Tm)]
A differential scanning calorimeter (device: DSC220C, manufactured by Seiko Instruments Inc.) was used to obtain an exothermic / endothermic curve, and the temperature at the maximum melting peak position at the time of temperature rise was defined as Tm. For measurement, about 5 mg of the sample is packed in an aluminum pan for measurement, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 minutes, and then (ii) −150 at 10 ° C./min. The temperature was lowered to ° C., then (iii) the temperature was raised to 200 ° C. at 10 ° C./min, and the obtained endothermic curve was analyzed and determined.

(Linear viscoelasticity measurement)
A press sheet having a thickness of 2 mm was punched into a disk shape of 25 mmφ and used as a sample. MCR301 (rheometer) manufactured by ANTONPaar was used for measurement, and a 25 mmφ parallel plate was used as the jig.

From the measurement results, the ratio (η * ₎ between the complex viscosity η * ₍ ω _{= 0.1)} at the frequency (ω = _0.1 rad / s) and the complex viscosity η * ₍ ω _{= 100)} at the frequency (ω = 100 rad / s). ₍ ω _{= 0.1)} / η * ₍ ω _{= 100)} ) was calculated.

[Methods for preparing various measurement samples for the composition]
A sheet for measuring physical properties was prepared from the propylene-based copolymer composition prepared by any one of the above production methods. Pellets of the above composition are put into a mold, a 5 mm thick brass plate is used as a hot plate, preheated for 5 to 7 minutes with a hydraulic hot press (manufactured by Shinto Metal Industry Co., Ltd.), and then applied at a pressure of 10 MPa for 1 to 2 minutes. Pressed. Further, the mold was transferred to another hydraulic hot press machine (manufactured by Shinfuji Metal Industry Co., Ltd.) set at 20 ° C. and cooled and pressed at a pressure of 10 MPa for 5 minutes to obtain sheets for evaluating various physical properties.

  A sheet having a length and width of 80 × 80 mm and a thickness of 1 mm or 5 mm was prepared. A 1 mm thick sheet was used for the tensile elasticity test described later, and a 5 mm thick sheet was used for the foaming test and density measurement.

[Gel fraction (%)]
About 100 mg of the sample was weighed, wrapped in a 325 mesh screen, 30 ml of p-xylene sufficient for the pellet was added in a sealed container, and immersed at 140 ° C. for 24 hours. Next, this sample was taken out on a filter paper and dried at 80 ° C. until a constant weight was obtained for 2 hours or more. The gel fraction was calculated based on the following formula.
Gel fraction [wt%] = [sample dry weight after p-xylene immersion / sample weight before p-xylene immersion] × 100

[Tensile modulus (MPa)]
Using a universal material testing machine AG-X manufactured by Shimadzu Corporation according to JIS K7113, the tensile modulus of the sample was measured under the conditions of a test piece temperature of 23 ° C. and a test speed of 30 mm / min.

[Batch foaming]
A 20 × 20 × 5 mmt press sample was charged into a 1 L autoclave (inner diameter 140 mmφ × height 90 mm), heated with a heater, and further adjusted to a pressure of 25 MPa while injecting and pressurizing carbon dioxide gas. While keeping the inside of the autoclave at 25 MPa, it was held at a predetermined temperature for 2 hours, and then the pressure was released to obtain a foamed sample.

[Density (g / cm ³ ) and foaming ratio]
The obtained molded body and foam were cut into appropriate shapes, and density measurement was carried out by an underwater displacement method (based on JISK7112) using an electronic hydrometer (manufactured by Alpha Mirage, MD-200S).
The value obtained by dividing the density of the press sheet before foaming by the density of the molded article after foaming was taken as the foaming ratio.

[SEM observation]
After cutting the cross section of the foam sample with a razor and depositing platinum on the cross section with an auto fine coater (JFC-1600) manufactured by JEOL Ltd., a scanning electron microscope manufactured by JEOL Ltd. ( JSM-6510LV) was used to observe the cross section.

[Cell shape]
SEM observation of the cross section of the foam sample was performed to evaluate the cell size uniformity.
“Level 4”: The cells are fine and uniform, and the distribution is narrow.
"Level 3": The cells are almost uniform and the distribution is narrow.
“Level 2”: Cell shape is non-uniform and distributed.
"Level 1": The cell shape is non-uniform and there are many broken bubbles.

〔Surface condition〕
The surface of the foam sample was observed and the surface condition was evaluated at the following level.
“Level 5”: The surface of the molded article is smooth.
“Level 4”: The surface of the molded product is almost smooth.
"Level 3": There is a slight unevenness on the surface of the molded product.
"Level 2": There are many irregularities on the surface of the molded product.
"Level 1": The shape is unstable.

〔hardness〕
The center portion of the foam sample was a core layer, the surface portion was a skin layer, and the hardness of the core layer and the skin layer was measured with an Asker C hardness meter.

[25% compressive strength (MPa)]
Using a universal material testing machine AG-X manufactured by Shimadzu Corporation according to JIS K6767, the 25% compression hardness and compression set of the foamed sample were measured under the conditions of a test piece temperature of 23 ° C. and a load speed of 10 mm / min. It was measured.

[Example 1]
A SUS polymerization apparatus with a stirring blade with a capacity of 1500 ml that was sufficiently purged with nitrogen was charged with 750 ml of dry hexane, 10 ml of 5-vinyl-2-norbornene, and 0.75 mmol of triisobutylaluminum (TIBAl) at 23 ° C. at room temperature. The internal temperature of the polymerization apparatus was raised to 80 ° C., 200 ml of hydrogen was inserted, the internal pressure was increased to 0.5 MPa with propylene, and the internal pressure was adjusted to 0.55 MPa with ethylene.

  Next, di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride 0.0005 mmol and 0.0025 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added in the polymerization vessel. Polymerization was carried out for 10 minutes while maintaining the internal temperature at 80 ° C. and the internal pressure at 0.55 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 4 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained propylene copolymer (A-1) was 21.6 g. The physical properties of the polymer are shown in Table 1.

[Example 2] (X-1)
5 parts by weight of a propylene copolymer (A-1) and a propylene copolymer (B-1) (Prime Polymer Pro Primer E-200GP, MFR (230 ° C., 2.16 kg load)) = 2.0 (G / 10 min)) A sample for electron beam irradiation was prepared using 95 parts by weight. To 100 parts by weight in total, 0.1 part by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as a heat-resistant stabilizer and 1,3,5- 1 part by weight of tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione was added. Thereafter, after melt-kneading using a biaxial extruder BT-30 (screw diameter 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd. under the conditions of a set temperature of 200 ° C., a resin extrusion rate of 65 g / min and 200 rpm. A pellet was obtained.

  The pellet was taken out and a sheet for evaluating physical properties was obtained by a method for preparing various measurement samples for the composition. The pellets and sheets were each irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 60 kGy to obtain a crosslinked sample. The MFR, gel fraction, and intrinsic viscosity of the pellet sample were measured. Moreover, the tensile elasticity modulus, the density, the expansion ratio, the cell shape, the surface state, the hardness, and the 25% compression hardness were measured using a sheet sample and a sample obtained by batch foaming at 157 ° C. The evaluation results are shown in Table 2.

[Example 3] (X-2)
10 parts by weight of propylene-based copolymer (A-1) and propylene-based copolymer (B-1) (Prime Polymer Pro Primer E-200GP, MFR (230 ° C., 2.16 kg load)) = 2.0 Table 2 shows the results of various physical properties obtained by measuring the physical properties of the sample obtained in the same manner as in Example 2 using 90 parts by weight of (g / 10 minutes).

[Example 4] (X-3)
Example 3 except that 1 part by weight of 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione as a crosslinking aid was removed Table 2 shows the results of various physical properties obtained by measuring the physical properties of the samples obtained in the same manner as described above.

[Comparative Example 1] (X-4)
Table 2 shows various physical property results obtained by measuring physical properties of a sample obtained in the same manner as in Example 2 using 100 parts by weight of the propylene-based copolymer (B-1).

[Comparative Example 2] (X-5)
Comparative Example 1 except that 1 part by weight of 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione as a crosslinking aid was removed Table 2 shows the results of various physical properties obtained by measuring the physical properties of the samples obtained in the same manner as above.

[Reference Example 1] (X-6)
Table 2 shows the physical properties before crosslinking of the sample having the same resin composition as (X-1) of Example 2 and the batch foaming evaluation result of the sheet at 157 ° C.

[Reference Example 2] (X-7)
Table 2 shows the physical properties before cross-linking of the sample having the same resin composition as (X-2) of Example 3 and the results of batch foaming evaluation at 157 ° C. of the sheet.

[Reference Example 3] (X-8)
100 parts by weight of propylene copolymer (B-1) 0.1 parts by weight of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] as a heat-resistant stabilizer, crosslinked 1 part by weight of 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione was added as an auxiliary agent in the same manner as in Example 2. To obtain pellets and sheets. Table 2 shows the physical properties before cross-linking and the results of batch foaming evaluation at 157 ° C. of the sheet.

[Example 5] (X-9)
A micro-crosslinked sample was produced with the same resin composition as (X-1) of Example 2.
To a total of 100 parts by weight of 5 parts by weight of the propylene copolymer (A-1) and 95 parts by weight of the propylene copolymer (B-1), pentaerythritol tetrakis [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate] and 0.1 part by weight of perhexa25B (2,5-dimethyl-2,5-di (t-butylperoxy) hexane) as a crosslinking agent As a crosslinking aid, 0.1 part by weight of 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione was blended. Thereafter, after melt-kneading using a biaxial extruder BT-30 (screw diameter 30 mmφ, L / D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd. under the conditions of a set temperature of 200 ° C., a resin extrusion rate of 65 g / min and 200 rpm. A pellet was obtained.
The pellet was taken out and a sheet for evaluating physical properties was obtained by a method for preparing various measurement samples for the composition. Table 2 shows the results of various physical property evaluations.

[Example 6] (X-10)
A microcrosslinked sample was produced with the same resin composition as (X-2) in Example 3.
Various samples obtained in the same manner as in Example 5 except that 10 parts by weight of the propylene copolymer (A-1) and 90 parts by weight of the propylene copolymer (B-1) were used in total. The physical property evaluation results are shown in Table 2.

[Example 7] (X-11)
5 parts by weight of propylene-based copolymer (A-1) and propylene-based copolymer (B-2) (Prime Polymer Pro Primer J232WA, MFR (230 ° C., 2.16 kg load)) = 1.5 (g Table 2 shows the evaluation results of various physical properties of samples obtained in the same manner as in Example 5 using 95 parts by weight.

[Example 8] (X-12)
5 parts by weight of propylene-based copolymer (A-1) and propylene-based copolymer (B-3) (Prime Polymer Pro Prime Polypropylene BJS-MU, MFR (230 ° C., 2.16 kg load)) = 1.6 Table 2 shows the evaluation results of various physical properties of samples obtained in the same manner as in Example 5 using 95 parts by weight (g / 10 minutes).

[Comparative Example 3] (X-13)
Table 2 shows the results of evaluating various physical properties of samples obtained in the same manner as in Example 5 using 100 parts by weight of the propylene-based copolymer (B-1).

[Comparative Example 4] (X-14)
Table 2 shows the results of evaluating various physical properties of samples obtained in the same manner as in Example 5 using 100 parts by weight of the propylene-based copolymer (B-2).

[Comparative Example 5] (X-15)
Table 2 shows the results of evaluating various physical properties of samples obtained in the same manner as in Example 5 using 100 parts by weight of the propylene-based copolymer (B-3).

Thus, all of the crosslinked products of the present invention shown in the examples are excellent in surface appearance and cell uniformity. On the other hand, the crosslinked body which does not contain a propylene-based copolymer shown in the comparative example is inferior in surface appearance and cell uniformity. Furthermore, the foamed body foamed without cross-linking the same composition as the example shown as a reference example has a low expansion ratio and inferior surface condition.

Claims (7)

A structural unit derived from propylene [i] 50 to 95 mol%, a structural unit derived from an α-olefin having 2 to 10 carbon atoms excluding propylene [ii] 4.9 to 49.9 mol%, and a non-conjugated polyene Derived structural unit [iii] 0.1 to 10 mol% (provided that the total of structural units [i], [ii] and [iii] is 100 mol%), and the following requirements (a) and ( 1 to 95 parts by weight of a propylene-based copolymer (A) characterized by satisfying c);
A crosslinked product obtained from the composition comprising 5 to 99 parts by weight of the thermoplastic resin (B) (however, the sum of (A) and (B) is 100 parts by weight).
(A) The intrinsic viscosity [η] measured at 135 ° C. in decalin is 0.1 to 5.0 (dL / g),
(C) MFR ₁₀ obtained at 230 ° C. and 10 kg load according to JIS K-6721, and MFR _2.16 obtained at 230 ° C. and 2.16 kg load according to JIS K-6721 Ratio (MFR ₁₀ / MFR _2.16 ) is 8.0 to 150.0. A structural unit derived from propylene [i] 50 to 95 mol%, a structural unit derived from an α-olefin having 2 to 10 carbon atoms excluding propylene [ii] 4.9 to 49.9 mol%, and a non-conjugated polyene Derived structural unit [iii] 0.1 to 10 mol% (provided that the total of structural units [i], [ii] and [iii] is 100 mol%), and the following requirements (a) and ( 1 to 45 parts by weight of a propylene-based copolymer (A) characterized by satisfying c);
The cross-linked product according to claim 1, obtained from a composition comprising 55 to 99 parts by weight of the thermoplastic resin (B) (provided that the total of (A) and (B) is 100 parts by weight).
(A) The intrinsic viscosity [η] measured at 135 ° C. in decalin is 0.1 to 5.0 (dL / g),
(C) MFR ₁₀ obtained at 230 ° C. and 10 kg load according to JIS K-6721, and MFR obtained at 230 ° C. and 2.16 kg load according to JIS K-6721 _{. 16} (MFR ₁₀ / MFR _2.16 ) is 8.0 to 150.0. The cross-linked product according to claim 1 or 2, wherein the propylene-based copolymer (A) is a propylene-based copolymer composition further satisfying the following requirements (b) and (d).
(B) The ratio (Mz / Mw) of z-average molecular weight (Mz) and weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 3.0 to 20.0,
(D) Complex viscosity η * (ω = 0.1) of frequency (ω = 0.1 rad / s) obtained by linear viscoelasticity measurement (190 ° C.) using a rheometer, and frequency (ω = 100 rad) / S) to the complex viscosity η * (ω = 100) (η * (ω = 0.1) / η * (ω = 100)) is 5 to 100. The propylene-based copolymer (A) satisfies the above requirements (a) to (d), and is composed of 50 to 95 mol% of structural units derived from propylene, ethylene, 1-butene, 4-methylpentene-1, 1 -4.9 to 49.9 mol% of structural units derived from at least one α-olefin selected from hexene and 1-octene and 0.1 to 10 mol% of structural units derived from 5-vinyl-2-norbornene (Provided that the total of the structural units [i], [ii] and [iii] is 100 mol%), a propylene-based copolymer (A1),
The crosslinked product according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is polypropylene (B1).   It has a foam structure, The crosslinked body in any one of Claims 1-4 characterized by the above-mentioned.   The manufacturing method of the crosslinked body in any one of Claims 1-5 which has the process of irradiating the said composition with an electron beam.   The molded object obtained by processing the crosslinked body in any one of Claims 1-5.