WO2006054716A1

WO2006054716A1 - Extruded propylene resin foam

Info

Publication number: WO2006054716A1
Application number: PCT/JP2005/021283
Authority: WO
Inventors: Minoru Sugawara; Yasuhiko Otsuki; Motoki Yamada; Ryoichi Tsunori
Original assignee: Prime Polymer Co., Ltd.
Priority date: 2004-11-19
Filing date: 2005-11-18
Publication date: 2006-05-26
Also published as: JPWO2006054716A1

Abstract

An extruded propylene resin foam which can have a reduced average cell diameter while retaining a heightened expansion ratio and which hence has excellent heat-insulating performance and satisfactory vibration-damping performance. The extruded propylene resin foam is obtained by extrusion-foaming a propylene resin. The propylene resin constituting the extruded foam comprises an olefin polymer whose loss tangent (tanδ) as determined at a temperature of 298 K and a frequency of 10 Hz is 0.04-100. The foam has an expansion ratio of 10 or higher and an average cell diameter smaller than 400 µm. Due to the constitution, the extruded propylene resin foam combines excellent heat-insulating performance with excellent vibration-damping performance.

Description

Specification

Propylene resin extruded foam

Technical field

The present invention relates to a propylene-based resin extruded foam having both heat insulation performance and vibration damping performance.

Background art

[0002] Extruded foams obtained by extrusion foaming of thermoplastic resin and extrusion of these thermoplastic resin from a die having a large number of small holes are bundled into a strip of extruded resin. Extruded foam strips formed by so-called strand extrusion, in which the outer surfaces are fused and foamed, are lightweight and excellent in mechanical properties, so they are structural materials in the fields of construction, civil engineering, automobiles, etc. It is widely used as a thermal insulation material. As such an extruded foam of thermoplastic resin, an extruded foam made of polyurethane-based resin or polystyrene-based resin is known.

[0003] However, polyurethane-based resin is a material that does not necessarily have excellent recycling characteristics, so it is fully compatible with the Building Recycling Law (the Law Concerning Recycling of Materials Related to Construction Work). There was a problem that I could not do it. However, since polystyrene resins are inferior in heat resistance and chemical resistance, it has been desired to provide extruded foams using thermoplastic resins instead of these.

[0004] On the other hand, polypropylene-based resin is excellent in mechanical properties, heat resistance, chemical resistance, electrical properties, etc., and is a low-cost material, and is therefore widely used in various molding fields. Extruded foams based on rosin resin are also expected to be highly industrially useful. However, polypropylene, which is a straight chain resin, causes a sudden drop in viscosity when melted, resulting in a decrease in strength. It was difficult to obtain an extruded foam having a high closed cell ratio and a high expansion ratio equivalent to the thermoplastic rosin used. In order to improve the moldability, it is difficult to make the average cell diameter of the foamed cells (bubbles) of the extruded product obtained uniform. [0005] Furthermore, in the construction / civil engineering and automobile fields, in addition to heat insulation performance, vibration damping performance is also required. For example, vibration board surfaces such as automobile door panels, fender panels, ceiling panels, or trunk crates. On the other hand, if an extruded foam can be applied, it is possible to achieve light weight.

[0006] Here, the heat insulation performance when an extruded foam is used as a heat insulating material depends on the expansion ratio and the cell diameter at a certain expansion ratio (for example, 10 times or more). In other words, with regard to the expansion ratio, the heat transfer becomes smaller as the material wall in the extruded foam becomes thinner, so that the higher the expansion ratio, the better the heat insulation performance. Similarly, if the cell diameter is reduced at the same expansion ratio, the number of cell walls that block radiant heat increases, making it difficult to transfer heat and improving heat insulation. Therefore, the cell diameter is small! As the expansion ratio is increased and the average cell diameter is reduced to improve the heat insulation performance, the thickness of the molded product can be reduced, resulting in cost reduction. Even in the case of foams, while the above-described difficulty in moldability exists, studies have been made on improving the expansion ratio and reducing the cell diameter for polypropylene-based resin-extruded foams (for example, Patent Document 1 and Patent Document 2).

[0007] Patent Document 1: JP-A-9 25354

Patent Document 2: Japanese Patent Laid-Open No. 2001-1384

Disclosure of the invention

Problems to be solved by the invention

[0008] However, although the conventional propylene-based resin-extruded foam as disclosed in the above-mentioned patent document can achieve an improvement in the expansion ratio to some extent, the average cell diameter can be reduced to 400 m or less. It was difficult to further improve the heat insulation performance because it was difficult. For these propylene-based resin-extruded foams that have attempted to improve heat insulation performance, the vibration-damping performance has not been sufficient, so the propylene-based resin having both heat insulation performance and vibration damping performance. It has been desired to provide an extruded foam.

Accordingly, an object of the present invention is to provide a propylene-based resin-extruded foam having excellent heat insulation performance and good vibration damping performance because the average cell diameter can be reduced in a state where the expansion ratio is increased. It is to provide. Means for solving the problem

In order to achieve the above object, the propylene-based resin-extruded foam of the present invention is a propylene-based resin-extruded foam obtained by extruding and propylene-based resin, and constitutes an extruded foam. Propylene-based resin contains olefin-based polymer whose loss tangent (tan δ) at a temperature of 298K and frequency of 10Hz is 0.04 ~: LOO, foaming ratio is more than 10 times, and average cell diameter is It is less than m.

[0011] The propylene-based resin-extruded foam of the present invention has a foaming ratio of 10 times or more and an average cell diameter (bubble diameter) of less than 400 μm, and therefore has a large number of cell walls in the extruded foam. Therefore, it is possible to efficiently block radiant heat from the outside. As a result, an extruded foam excellent in heat insulation performance can be provided.

Furthermore, the propylene-based resin extruded foam of the present invention has a loss tangent (tan δ) at a temperature of 298 K and a frequency of 10 Hz of 0.04 to LOO or less with respect to the propylene-based resin as a constituent material. The olefin-based polymer (hereinafter sometimes referred to as “specific olefin-based polymer”) is added.

This particular olefinic polymer does not bind to the constituent propylene resin, so it is excluded from the crystal of polypropylene, which is a crystalline polymer, and as a result, the surface of the foam cell of the extruded foam is viscous. The specific olefin-based polymer that is a substance is uniformly present.

[0013] That is, propylene-based resin, which is a rigid part, has a property of propagating energy, while a substance having a viscosity near room temperature (a specific olefin-based polymer) uses vibration energy as a molecular molecule inside. Because it is used as thermal energy for movement, it has the property of absorbing vibration energy. In addition, in order to absorb vibration, the specific olefin-based polymer having a molecular structure close to that of the polypropylene-based resin, which is a vibration surface in which it is desirable to uniformly disperse the adhesive material on the vibration surface, Since it has a certain degree of compatibility with polypropylene-based resin, it can be uniformly dispersed on the surface of the cell wall to efficiently absorb vibration, and an extruded foam excellent in vibration damping performance can be provided. it can.

Thus, the present invention can suitably provide a propylene-based resin foam foam having both heat insulation performance and vibration damping performance. [0014] Further, the propylene-based resin, which is a constituent material, is excellent in recycling performance, and has good chemical resistance, heat resistance, and the like. The various performances (recycling performance, chemical resistance, heat resistance, etc.) will be enjoyed. Furthermore, by using propylene-based resin, which is a low-cost material, an extruded foam having the above-described effects can be provided at a low cost.

[0015] The propylene-based resin extruded foam of the present invention preferably has a weight ratio (aZb) force of lZl00 to 80Zl00 between the specific polyolefin polymer (a) and the propylene-based resin (b). Good.

According to the present invention, by including a specific olefin-based polymer such that the weight ratio (aZb) is 1Z100 to 80Z100 with respect to the constituent material, the foamed cell of the polypropylene-based resin has a foam cell. The olefin-based polymer is appropriately dispersed on the wall surface, so that the vibration damping performance can be improved.

[0016] The propylene-based resin-extruded foam of the present invention preferably uses the 1-butene-based copolymer of the following first or second aspect as the olefin-based polymer. By using a 1-butene polymer, vibration damping performance can be reliably imparted to the extruded foam.

[0017] First aspect: A 1-butene polymer having the following requirements (1) to (3).

(1) Intrinsic viscosity [r?] Measured in a tetralin solvent at 135 ° C is 0.01 to 0.5dL / g

(2) Using a differential scanning calorimeter (DSC), hold the sample at 10 ° C for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C Z min. A crystalline resin with a melting point (T — D) defined as the peak top of the observed peak of 0 to: LOO ° C

(3) Stereoregularity index {(mmmm) / (mmrr + rmmr)} is 30 or less

[0018] Second aspect: A 1-butene polymer comprising the following (1), (2) and (3 ').

(1 ') Intrinsic viscosity [r?] Measured in a tetralin solvent at 135 ° C is 0.25 to 0.5 dL / g. (2) Using a differential scanning calorimeter (DSC), the sample is placed under a nitrogen atmosphere. The melting point (T — D) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by holding at 5 ° C for 5 minutes and then increasing the temperature at 10 ° CZ is 0. ~: Crystal of LOO ° C Resin

(3 ') Mesopentad fraction (mmmm) calculated from ¹³ C-nuclear magnetic resonance (NMR) spectrum is 73% or less

[0019] The extruded foam of the propylene-based resin of the present invention preferably has a closed cell ratio of 40% or more.

According to the present invention, since the independent foaming rate of the propylene-based resin-extruded foam is 40% or more, a large number of independent air bubbles make it difficult to conduct heat, so that the heat insulation performance is further improved and the impact strength, etc. The extruded foam has excellent mechanical strength and moisture resistance.

[0020] In the propylene-based resin-extruded foam of the present invention, the average cell diameter is preferably 200 µm or less.

According to the present invention, since the average cell diameter of the propylene-based resin-extruded foam is as small as 200 μm or less, it is possible to form more bubble walls in the extruded foam, thereby further improving the heat insulation performance. Excellent extruded foam.

[0021] The propylene-based resin-extruded foam of the present invention is preferably an extruded foam-strip bundling body in which a large number of extruded foams are bundled.

According to the present invention, the propylene-based resin-extruded foam has an extruded foam-strip converging body force in which a large number of strip-like extruded foams are concentrated, so that the expansion ratio of the extruded foam is increased. Thus, a foamed molded article having a sufficient foaming ratio and a sufficient thickness can be easily molded in various shapes.

[0022] In the propylene-based resin-extruded foam of the present invention, the propylene-based resin constituting the foam is preferably a propylene-based multistage polymer having the following (A) and (B) forces.

(A) A propylene homopolymer component having an intrinsic viscosity [7?] Of more than lOdLZg measured in a tetralin solvent at 135 ° C or a copolymer component of propylene and a-olefin having 2 to 8 carbon atoms Contain 5-20% by mass in the polymer

(B) Propylene homopolymer component having an intrinsic viscosity [r?] Of 0.5 to 3. OdLZg measured in a tetralin solvent at 135 ° C or propylene and α-olefin having 2 to 8 carbon atoms. The polymer component is contained in 80 to 95% by mass in the whole polymer.

[0023] This propylene-based multistage polymer comprises a component (i), that is, an ultrahigh molecular weight propylene-based heavy polymer. A linear propylene-based polymer that achieves high melt tension by imparting coalescence and has viscoelastic properties adjusted by adjusting the molecular weight distribution, and has excellent viscoelastic properties. Therefore, by using a propylene-based multistage polymer having excellent viscoelastic properties as a constituent material, a foaming ratio of 10 times or more and an average cell diameter of less than 00 m (preferably 200 m or less), propylene-based resin foam extrusion foaming The body can be obtained reliably. In addition, according to such a propylene-based multistage polymer, the ratio of closed cells in the extruded foam can be increased, and for example, the closed cell ratio can be reliably set to 40% or more.

[0024] The propylene-based resin-extruded foam of the present invention has the following relationship between the melt flow rate (MFR) at 230 ° C and the melt tension (MT) at 230 ° C of the propylene-based multistage polymer: It is preferable to have (I).

[0025] [Equation 1]

1 o g (M T)>-1. 3 3 1 o g (M F R) + 1.2 …… (I)

[0026] According to the present invention, the relationship between the melt flow rate (MFR) at 230 ° C and the melt tension (MT) at 230 ° C includes the formula (I). Molding becomes easy, and an extruded foam with an expansion ratio of 10 times or more can be obtained easily and reliably.

Brief Description of Drawings

[0027] FIG. 1 is a schematic diagram showing a morphology in which component (b) is selectively layered around bubbles in Example 2 of the present invention.

FIG. 2 is a schematic diagram showing a morphology in which component (b) is dispersed in component (a) in Example 2.

FIG. 3 is an image of a cross section of the foam of Example 2 taken by magnifying a wall portion between bubbles by a transmission electron microscope (TEM) at a magnification of 13000 times.

BEST MODE FOR CARRYING OUT THE INVENTION

[0028] The propylene-based resin extruded foam (hereinafter referred to as extruded foam) of the present invention has a loss tangent (tan δ) at a temperature of 298K and a frequency of 10Hz of propylene-based resin as a constituent material of 0.04 to 1. 00 is an olefin polymer (specific olefin polymer), and this specific olefin It is made by extrusion foaming of propylene-based resin containing in-series resin, and the expansion ratio is

The average cell diameter is 10 times or more and less than OO / z m. With such a configuration, an extruded foam having both excellent heat insulating performance and vibration damping performance can be provided.

[0029] Further, if the independent foaming ratio of the extruded foam is 40% or more, preferably 60% or more, a large number of independent bubbles transmit heat, so that the heat insulation performance is further improved and the impact strength is improved. The mechanical strength and moisture resistance such as are excellent.

[0030] The propylene-based resin forming the extruded foam of the present invention having such a structure includes a propylene-based resin having a high melt tension at the time of melting, such as JP-A-10-279632 and JP-A-2000. —Propylene-based resins described in 309670, JP-A 2000-336198, JP-A 2002-12717, JP 2002-542360, JP 2002-509575, and the like can be used.

[0031] Further, as described above, in order to obtain the extruded foam of the present invention, as the propylene-based resin, a resin material having excellent viscoelastic properties that is desired to increase the melt tension at the time of melting is used. It is preferable to use it.

Examples of the propylene-based resin having excellent viscoelastic properties include a propylene-based multistage polymer having the following component (A) and component (B) power as the propylene-based resin constituting the foam. Favored ,.

[0032] This propylene-based multistage polymer achieves high melt tension by adding component (i), that is, an ultra-high molecular weight propylene polymer, and the viscoelastic properties are adjusted by adjusting the molecular weight distribution. It is a straight-chain propylene polymer. By using such a propylene-based multistage polymer having excellent viscoelastic properties as a constituent material, the requirements of the present invention described above (the foaming ratio is 10 times or more and the average cell diameter is smaller than 00 μm (preferably 200 μ m or less), and a propylene-based resin-extruded foam having a closed cell ratio of 60% or more can be obtained with certainty.

[0033] Here, when the intrinsic viscosity of component (A) is 1OdLZg or less, the melt tension becomes insufficient, and the desired foaming performance may not be obtained.

On the other hand, if the mass fraction of component (A) is less than 5% by mass, the melt tension may be insufficient and the desired foaming performance may not be obtained, while if the mass fraction exceeds 20% by mass.

The so-called melt fracture may become intense, which may cause rough skin of the extruded foam and reduce the product quality.

[0034] The intrinsic viscosity of component (A) is preferably more than lOdLZg as described above,

It is more preferably within the range of 20 dLZg, and particularly preferably within the range of 13 to 18 dLZg.

The mass fraction of component (A) is preferably in the range of 8 to 18% by mass, particularly preferably in the range of 10 to 16% by mass.

[0035] If the intrinsic viscosity of component (B) is less than 0.5 dLZg, the melt tension may be insufficient and the desired foaming performance may not be obtained. On the other hand, if it exceeds 3. OdLZg, the viscosity will be high. In some cases, suitable extrusion cannot be performed.

If the mass fraction of component (B) is less than 80% by mass, it may be difficult to carry out suitable extrusion molding. If the mass fraction exceeds 95% by mass, the melt tension will be low, This may also make it difficult to perform suitable extrusion.

[0036] The intrinsic viscosity of component (B) is preferably in the range of 0.5 to 3. OdLZg as described above, but is preferably in the range of 0.8 to 2. OdLZg. It is particularly preferably within the range of 1.0 to 1.5 dLZg.

The mass fraction of the component (B) is preferably in the range of 82 to 92% by mass, particularly preferably in the range of 84 to 90% by mass.

[0037] This propylene-based multistage polymer has an oc of 2 to 8 carbon atoms constituting the copolymer component.

Examples of olefins include ethylene, 1-butene and the like, which are olefins other than propylene. Among these, it is preferable to use ethylene.

Propylene-based multistage polymers have a melt flow rate (MFR) force at 230 ° C of 10 The OgZlO content or less is preferred. The 20gZlO content or less is particularly preferred. If MFR exceeds lOOgZlO, the melt tension and viscosity of the multistage polymer will be low, and molding may be difficult.

[0038] In the propylene-based multistage polymer, the relationship between the melt flow rate (MFR) at 230 ° C and the melt tension (MT) at 230 ° C preferably includes the following formula (I).

[0039] [Equation 2]

1 o g (MT)>-1. 3 3 1 o g (MF R) + 1. 2 ...... (I)

[0040] Here, if the relationship between the melt flow rate (MFR) at 230 ° C and the melt tension (MT) at 230 ° C does not satisfy the formula (I), high-magnification foaming It may be difficult to perform molding, and an extruded foam with an expansion ratio of 10 times or more may not be obtained. The above-mentioned constant (1.2) is preferably 1.3 or more, particularly preferably 1.4 or more.

In order for the propylene-based multistage polymer to have the relationship of the above formula (I), the component (A) should be contained in an amount of 5% by mass.

[0041] The propylene-based multistage polymer has a dynamic viscoelasticity in the molten state (angular frequency ω and storage modulus G

Specifically, it is preferable that the slope of the storage elastic modulus on the high frequency side is a certain amount or more. Specifically, the storage elastic modulus G when the angular frequency is lOmdZs (10 ) And G '(10) / G' (1), which is the ratio of the storage elastic modulus G '(1) when the angular frequency is IradZs, is preferably 2.5 or more. It is particularly preferred that If the ratio G ′ (10) ZG ′ (1) is less than 2.0, the stability of the extruded foam when an external change such as stretching is applied may decrease.

[0042] Similarly, it is preferable that the propylene-based multistage polymer preferably has a storage elastic modulus slope on the low frequency side of a certain amount or less as a dynamic viscoelasticity in a molten state. Is the ratio of the storage modulus G '(0.1) when the angular frequency is 0. IradZs to the storage modulus G' (0. 01) when the angular frequency is 0.01 rad / s. It is preferable that '(0. 1) / G' (0. 01) is 6.0 or less. Particularly preferable is 4.0 or less. If the ratio G ′ (0.1) / G ′ (0.01) exceeds 6.0, it may be difficult to increase the expansion ratio of the extruded foam. is there.

[0043] Such a propylene-based multistage polymer uses an olefin polymerization catalyst comprising the following components (a) and (b), or the following components (a), (b) and (c), and has two or more stages. In the polymerization step, it can be produced by polymerizing propylene or copolymerizing propylene and a-olefin having 2 to 8 carbon atoms.

(a) Solid catalyst component obtained by treating trisalt-titanium obtained by reducing tetrasalt-titanium with an organoaluminum compound with an ether compound and an electron acceptor.

(b) Organoaluminum compound

(c) Cyclic ester compound

[0044] Here, (a) a solid catalyst component obtained by treating trisalt titania obtained by reducing tetrasalt titanate with an organoaluminum compound with an ether compound and an electron acceptor (hereinafter, Simply “(a) Solid catalyst component”)! Examples of organic aluminum compounds that reduce titanium tetrachloride include (i) alkylaluminum dinos, rides, such as methylaluminum dichloride, ethylaluminum dichloride, and n-propylaluminum. Dichloride, (mouth) alkylaluminum sesquihalide, specifically, ethylaluminum sesquichloride mouthride, (ha) dialkylaluminum halide, specifically, dimethylaluminum chloride, jetylaluminum chloride, di-n-propyl Aluminum chloride and jetyl aluminum bromide, (2) trialkylaluminum, specifically, trimethylaluminum, triethylaluminum, and triisobutylaluminum, (e) dialkylaluminum hydra Id, specifically, jetylluminumuno, idride and the like can be mentioned. Here, “alkyl” is lower alkyl such as methyl, ethyl, propyl, butyl and the like. The “halide” is chloride or bromide, and the former is particularly common.

[0045] Further, the reduction reaction with an organoaluminum compound to obtain trisalt-titanium is usually carried out in a temperature range of -60 to 60 ° C, preferably 30 to 30 ° C. If the temperature in the reductive reaction is lower than 60 ° C, a long time is required for the reductive reaction. On the other hand, if the temperature in the reductive reaction exceeds 60 ° C, partial reduction may occur. The reduction reaction is performed using an inert hydrocarbon solvent such as pentane, heptane, octane and decane. I prefer to carry out!

[0046] In addition, it is preferable to further subject the titanium trichloride obtained by the reduction reaction of tetrachloride-titanium with an organoaluminum compound to ether treatment and electron acceptor treatment. the preferred Eterui匕合product to be used in processing, for example, Jeffrey Chino Les ether Honoré, di _n - propyl Honoré ether Honoré, di -n- butyl Honoré ether Honoré, diisoamyl ether, di-neopentyl ether, di-n hexyl ether Ether compounds in which each hydrocarbon residue is a chain hydrocarbon having 2 to 8 carbon atoms, such as di-octyl ether, di-2-ethylhexyl ether, methyl-n-butyl ether, and ethyl isobutyl ether. Among these, it is particularly preferable to use di-n-butyl ether.

[0047] As the electron acceptor used in the treatment of trisalt-titanium, it is preferable to use halogen compounds of Group III to Group IV and Group VIII elements of the periodic table. Titanium tetrachloride, tetrachloride-caine, boron trifluoride, trichloride-boron, pentachloride-antimony, gallium trichloride, iron trichloride, tellurium dichloride, tin tetrachloride, trichloride Examples thereof include phosphorus chloride, phosphorus pentachloride, tetrasalt / vanadium and tetrasalt / zirconium.

[0048] In preparing the solid catalyst component (a), the treatment of titanium trichloride with the ether compound and the electron acceptor may be performed using a mixture of both treatment agents, or with one treatment agent. After the treatment, the treatment with the other treatment agent may be performed. Of these, it is more preferable to perform the treatment with an electron acceptor after the ether treatment, which is preferred by the latter.

[0049] Prior to the treatment with the ether compound and the electron acceptor, it is preferable to wash the trisalt salt with a hydrocarbon. The ether treatment with the above-mentioned trisalt / titanium is performed by bringing titanium trichloride into contact with the ethery compound, and the treatment of the trisalt / titanium with the ethery compound is performed in the presence of a diluent. It is advantageous to do this by bringing them into contact. For such diluents, it is preferred to use inert hydrocarbon compounds such as hexane, heptane, octane, decane, benzene and toluene. The treatment temperature in the ether treatment is preferably 0 to 100 ° C. In addition, the processing time Although it is not particularly limited, it is usually performed in the range of 20 minutes to 5 hours.

[0050] The amount of the ether compound used may generally be in the range of 0.05 to 3.0 moles, preferably 0.5 to 1.5 moles per mole of titanium trichloride. When the amount of the ether compound used is less than 0.05 mol, the stereoregularity of the produced polymer cannot be sufficiently improved, which is not preferable. On the other hand, when the amount of the ether compound used exceeds 3.0 mol, the stereoregularity of the polymer produced is improved, but the yield is lowered. Strictly speaking, the trisalt-titanium treated with an organoaluminum compound or an etheric compound is a composition mainly composed of trisalt-titanium.

As such a solid catalyst component (a), Solvay-type trisalt-titanium can be preferably used.

[0051] As the organoaluminum compound (b), the same organoaluminum compound as described above may be used.

Examples of the cyclic ester compound (C) include γ-latathon, _δ -latathon, _£ -latathon, etc., and it is preferable to use ε-latathon.

Further, the olefin polymerization catalyst used for producing the propylene-based multistage polymer can be obtained by mixing the components (a) to (c) described above.

[0052] In order to obtain a propylene-based multistage polymer, among the two-stage polymerization methods, it is preferable to polymerize propylene or copolymerize propylene and a-olefin having 2 to 8 carbon atoms in the absence of hydrogen. Here, “in the absence of hydrogen” means substantially in the absence of hydrogen, and includes cases in which a trace amount of hydrogen is present only when no hydrogen is present (for example, about 10 mol ppm). . In short, even if hydrogen is contained to the extent that the intrinsic viscosity [7?] Of the first-stage propylene polymer or propylene copolymer measured in 135 ° C tetralin solvent does not fall below lOdLZg, It is included in the meaning of “in the absence of hydrogen”.

[0053] By carrying out the polymerization of propylene or the copolymer of propylene and α-olefin in the absence of hydrogen, an ultrahigh molecular weight propylene polymer, that is, a component of the propylene multistage polymer (多) Can be manufactured. Ingredient (Α) is, in the absence of hydrogen, the raw material monomer as the polymerization temperature, preferably 20 to 80 ° C, more preferably 40 to 70 ° C, and the polymerization pressure is generally normal pressure to 1.47 MPa. Preferably 0.39 ~: under the condition of L 18MPa It is preferable to manufacture by slurry polymerization.

[0054] In this production method, it is preferable that the component (B) of the propylene-based multistage polymer is produced in the second and subsequent stages. The production conditions for component (B) are not particularly limited except that the above-mentioned catalyst for olefin polymerization is used, but the raw material monomer is preferably used at a polymerization temperature of 20 to 80 ° C, more preferably 60. ~ 70 ° C, polymerization pressure is generally normal pressure ~ 1.47 MPa, preferably 0.19-1.18 MPa, preferably polymerized under the presence of hydrogen as a molecular weight regulator, .

[0055] In the above-described production method, preliminary polymerization may be performed before the main polymerization. When the prepolymerization is carried out, the powder morphology can be maintained well. In general, the prepolymerization generally has a polymerization temperature of preferably 0 to 80 ° C, more preferably 10 to 60 ° C, and a polymerization amount. As an example, it is preferable to polymerize 0.01 to 100 g, more preferably 0.1 to 10 g of propylene or copolymerize propylene and α-talin having 2 to 8 carbon atoms per lg of the solid catalyst component. Better ,.

[0056] In addition, propylene-based resin, which is a constituent material of the extruded foam, is used as a propylene-based resin composition, and the above-mentioned propylene-based multistage polymer and a melt flow rate (MFR) force at 230 ° C ^ OgZlO And the ratio between the weight average molecular weight (M) and the number average molecular weight (M).

w n

A propylene polymer having M / M of 5.0 or less may be included. Said pro w n

By blending a pyrene-based multistage polymer with other materials to obtain a resin composition, it is possible to improve the moldability of the extruded foam, increase its functionality, and reduce cost.

By using this resin composition, the extruded foam has excellent viscoelastic properties with high melt tension. The extruded foam has a high foaming ratio, good surface appearance, and stretching during sheet formation. When cutting is prevented, an effect can be imparted.

[0057] In this resin composition, the weight ratio of the propylene polymer to the propylene multistage polymer is 6 times or more, more preferably 10 times or more. If the weight ratio is less than 8 times, the surface appearance of the extruded foam may be poor.

The melt flow rate (MFR) of the propylene-based polymer is preferably 30 gZlO or less, more preferably 15 gZlO or less, and even more preferably lOgZlO or less. If the MFR exceeds 30gZlO, molding failure of the extruded foam may occur. is there.

[0058] The M / M of the propylene-based polymer is preferably 5.0 or less, and 4.5 or less.

w n

It is particularly preferred. When M / M exceeds 5.0, the surface appearance of the extruded foam deteriorates.

w n

There is a case.

The propylene-based polymer can be produced by a polymerization method using a known catalyst such as a Ziegler-Natta catalyst or a metamouth catalyst.

[0059] This rosin composition has a dynamic elastic viscoelasticity in a molten state (relation between angular frequency ω and storage elastic modulus G '), and the slope of the storage elastic modulus on the high frequency side is larger than a certain amount. In addition, it is preferable that the slope of the storage elastic modulus on the low frequency side is a certain amount or less.

Specifically, G '(10) / G is the ratio of the storage elastic modulus G' (10) when the angular frequency is lOradZs and the storage elastic modulus G '(1) when the angular frequency is 1 radZs. '(1) is preferably 5.0 or more, particularly preferably 5.5 or more. If G '(10) ZG' (1), which is a strong ratio, is less than 5.0, stability may be reduced when an extrudate foam is subjected to external changes such as stretching.

[0060] Further, the storage elastic modulus G ′ (0.1) when the angular frequency is 0.1 IradZs and the storage elastic modulus G, (0.01) when the angular frequency is 0.01 radZs. It is preferable that a certain G, (0. 1) / G ′ (0. 01) is 14.0 or less, and particularly preferably 12.0 or less. When the ratio G ′ (0.1) / G ′ (0.01) exceeds 14.0, it may be difficult to increase the expansion ratio of the extruded foam.

[0061] Here, when the extruded foam is stretched, a component having a relaxation time in the range of 1 to 10 s generally results in poor stretch characteristics of the extruded foam. The greater the contribution of the relaxation time in this region, the smaller the slope of the storage elastic modulus G ′ (1) near the angular frequency ω IradZs. Therefore, as an index of this slope, if the storage elastic modulus G when the angular frequency ω is lOmdZs, and G, (10) ZG, (1), which are the ratios to (10), are set, the results of numerical simulation and experimental analysis Therefore, it was found that the smaller this value, the greater the rupture during extrusion foaming. Therefore, it is preferable that G ′ (10) ZG ′ (1) is 5.0 or more in the above-described rosin composition. [0062] In addition, a certain degree of strain hardening is required for bubble breakage at the final stage of bubble growth and for bubble breakage caused by high-speed elongation deformation in the vicinity of the die lip in extrusion foam molding. An appropriate amount of high molecular weight component in the time domain is required, and for this purpose, the storage elastic modulus G ′ in the low frequency domain must be large to some extent. Therefore, as an index, the storage elastic modulus G ′ (0.1) when the angular frequency ω is 0.1 IradZs, and the storage elastic modulus G, (0.01) when the angular frequency is 0. Olr adZs. If G, (0. 1) / G '(0. 01) is set, the foaming ratio will decrease significantly due to bubble breakage. Was found to be. Therefore, it is preferable that G, (0.1) / G, (0.01) be 14.0 or less in the above-described rosin composition.

[0063] It should be noted that the propylene-based resin constituting the extruded foam of the present invention, including this resin composition, may contain an antioxidant, a medium as long as it does not interfere with the effects of the present invention, if necessary. Stabilizers or cross-linking agents such as neutralizers, crystal nucleating agents, metal deactivators, phosphorus processing stabilizers, UV absorbers, UV stabilizers, fluorescent brighteners, metal stalagmites, antacid absorbers, chain transfer Additives such as additives, nucleating agents, lubricants, plasticizers, fillers, reinforcing agents, pigments, dyes, flame retardants and antistatic agents can be added. The addition amount of these additives may be appropriately determined according to various properties and molding conditions required for the extruded foam to be molded.

[0064] Further, when the propylene-based multistage polymer having excellent melt viscoelasticity is used as the propylene-based resin, it is known in advance in a state where the above-mentioned additives are added as necessary. It is also possible to form a desired extruded foam after melt-kneading using a melt-kneader to form a pellet.

[0065] The propylene-based resin extruded foam of the present invention has a propylene-based resin, which is a constituent material, having a loss tangent (tan δ) at a temperature of 298K and a frequency of 10Hz of 0.04 to LOO. It is characterized by containing a polymer (specific olefin polymer). By adding such a specific olefinic polymer as a constituent material to propylene-based resin, a specific olefin-based weight which is a viscous substance is applied to the wall surface of the foamed cell of the extruded foam composed of propylene-based resin. Since the coalescence is uniformly dispersed, the extruded foam has excellent vibration damping performance.

[0066] A specific olefin-based polymer has a loss tangent (ta 11 3) is from 0.04: It is particularly preferable that the force is 0.04 to 10 as LOO. If the loss tangent is from 0.04 to L00, it exhibits a viscous behavior and can exhibit excellent vibration damping performance when it is included in a propylene-based resin to form an extruded foam. On the other hand, if the loss tangent is less than 0.04, sufficient vibration damping performance cannot be obtained, and if the loss tangent is greater than 100, it exhibits solid properties, does not absorb energy inside, and is a rigid propylene-based resin. Since it vibrates with fat, it cannot exhibit vibration control performance.

The loss tangent can be measured with, for example, a commercially available solid viscoelasticity measuring device (for example, DMS 6100, manufactured by Seiko Instruments Inc.)! ,.

[0067] Further, such a specific olefin polymer (a) is preferably added to the polypropylene resin (b) so that the weight ratio (aZb) is 1Z100 to 80Z100. It is particularly preferable to add such that it is 5, 100 to 60 to 100. By including an olefin polymer such that the weight ratio is 1/100 to 80/100, the polyolefin polymer is appropriately dispersed on the wall surface of the foam cell in the foamed molded article made of polypropylene resin, and the Vibration performance can be improved.

[0068] As this specific olefin-based polymer, for example, a resin material disclosed in WO 03-070788 and WO 03-070790, a resin material disclosed in Japanese Patent No. 3255697, and the like can be used. Specific examples include high-flow 1-butene copolymers disclosed in WO 03-070788 or similar 1-butene polymers.

[0069] As the 1-butene copolymer, specifically, those shown in the following first embodiment or second embodiment can be used. By using these, it is possible to reliably impart vibration damping performance to the extruded foam.

First, as the first embodiment, the following requirements (1) to (3) are satisfied.

(2) Using a differential scanning calorimeter (DSC), hold the sample at 10 ° C for 5 minutes in a nitrogen atmosphere, and then raise the temperature at 10 ° C Z min. A crystalline resin with a melting point (T — D) defined as the peak top of the observed peak from 0 to L00 ° C

(3) Stereoregularity index {(mmmm) / (mmrr + rmmr)} is 30 or less [0070] Further, the 1-butene polymer comprises the following (1 '), (2) and (3') as the second form.

(1 ') Intrinsic viscosity [r?] Measured in tetralin solvent at 135 ° C is 0.25 to 0.5dL / g. (2) Using a differential scanning calorimeter (DSC), the sample is placed in a nitrogen atmosphere. The melting point (T — D) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by holding at 10 ° C for 5 minutes and then raising the temperature at 10 ° CZ is 0 to: LOO ° C crystalline resin

(3 ') Mesopentad fraction (mmmm) determined from ¹³ C nuclear magnetic resonance (NMR) spectrum is 73% or less

[0071] Of these, the 1-butene polymer of the first embodiment has an intrinsic viscosity [7?] Measured in a tetralin solvent at 135 ° C of 0.01 to 0.5dLZg, and this intrinsic viscosity [7? ] Is preferably 0.1 to 0.5 dL. If the intrinsic viscosity [7?] Is less than 0. OldLZg, the physical properties (strength) may decrease. On the other hand, if it exceeds 0.5 dL, the fluidity may deteriorate.

[0072] Further, the 1-butene polymer of the second embodiment has an intrinsic viscosity [r?] Of 0.25-0. 5dLZg measured in a tetralin solvent at 135 ° C, and this intrinsic viscosity [7? ] Is preferably 0.3 to 0.5 dLZg.

If the intrinsic viscosity [7?] Is smaller than 0.25dLZg, the molecules that connect the crystals are insufficient and the toughness (tensile elongation at break) decreases, and if it exceeds 0.5dLZg, the viscosity increases too much, causing fluidity. The moldability may be deteriorated and molding defects may occur.

The 1-butene-based polymer of the first and second embodiments described above must be a crystalline rosin having a melting point (TD) that is soft and has a point strength of 0 to 100 ° C. using a differential scanning calorimeter (DSC). The temperature is preferably 0 to 80 ° C.

[0073] The melting point (T-D) is determined by DSC (abbreviation for Differential Scanning Calorimetry). In other words, using a differential scanning calorimeter (DSC-7: manufactured by Perkin 'Elma Ichi), 10 mg of the sample was held in a nitrogen atmosphere at 10 ° C for 5 minutes and then heated at 10 ° CZ for 5 minutes. This is the peak top 1S melting point (TD) of the peak observed on the highest temperature side of the melting point endothermic curve. Here, the “crystalline resin” in the present specification means a resin in which this TD is observed. [0074] Further, in such a 1-butene polymer of the first aspect, the stereoregularity index {(mm mm) Z (mmrr + rmmr)} is 30 or less, preferably 20 or less, more preferably 15 or less. If this stereoregularity index exceeds 30, the flexibility of the viscous material may decrease and the vibration absorption effect may decrease.

Here, the mesopentad fraction (mmmm) is preferably 90% or less, more preferably 85%, and even more preferably 80% or less. When the mesopentad fraction (mmm m) exceeds 90%, the flexibility and the secondary cache property may be reduced.

[0075] The 1-butene polymer of the second embodiment has a mesopentad fraction (mmmm) of 73% or less. When the mesopentad fraction (mmmm) exceeds 73%, the physical cross-linking point becomes excessive, and the flexibility may decrease.

[0076] In such 1-butene-based polymers, the mesopentad fraction (mmmm) was reported by "Polymer Journal, 16, 717 (1984)" reported by Asakura et al., J. Randall et al. In accordance with the method proposed in “Macromol. Chem. Phys., C29, 201 (1989)” and “Marcomol. Chem. Phys., 198, 1257 (1997)” reported by V. Busico et al. Asked. That is, the signals of methylene group and methine group were measured using ¹³ c-nuclear magnetic resonance spectrum to determine the mesopentad fraction in the poly (1-butene) molecule.

[0077] The ¹³ C nuclear magnetic resonance spectrum may be measured by the following equipment and conditions: Equipment: JEOL (Building) S ^ NM- EX400 type 13C-NMR equipment

Method: Proton complete decoupling method

Concentration: 230mgZ ml

Solvent: 1, 2, 4 90:10 (volume ratio) mixed solvent of triclonal benzene and heavy benzene Temperature: 130 ° C

Panores width: 45 °

Pulse repetition time: 4 seconds

Calculation: 10,000 times

[0078] Further, the stereoregularity index {(mmmm) / (mmrr + rmmr)} of such a 1-butene-based polymer can be expressed as (mmmm), (mmrr) and ( rmmr) What is necessary is just to calculate the value power.

[0079] In addition to the above-mentioned requirements, the 1-butene-based polymer of the first and second embodiments has a weight average molecular tatami (M) measured by the GPC method of 10,000 to 100,000. Is preferred

w

Yes. If the M force is less than 000, the physical properties (strength) may decrease. Meanwhile, M force S100,

If it exceeds 000, the fluidity is lowered and the workability may be poor.

The above M / M was measured by the GPC method using the following equipment and conditions.

w n

It is a value calculated from the weight average molecular weight (M) and number average molecular weight (M) in terms of styrene.

w n

The

[0080] (GPC measurement device)

Column: TOSO GMHHR—H (S) HT

Detector: RI detector for liquid chromatogram WATERS 1500C measurement conditions [0081] (50C measurement conditions)

Solvents: 1, 2, 4 Trichrome mouth benzene

Measurement temperature: 145 ° C

Flow rate: 1.0ml Z min

Sample concentration: 2. 2mgZ ml

Injection volume: 160 microliters

Calibration curve: Universal Calibration

Analysis program: HT— GPC (Ver. 1. 0)

[0082] The 1-butene polymer of the first embodiment preferably has a tensile modulus of 300 MPa or less, preferably 500 MPa or less, as measured by a tensile test in accordance with JIS K7113. If the tensile modulus exceeds 500 MPa, sufficient softness may not be obtained.

[0083] When the 1-butene polymer is a copolymer, it is preferably a random copolymer. Further, the structural unit from which 1-buteneca is obtained is preferably 50% mol or more, more preferably 70 mol% or more. If the structural unit derived from 1-butene is smaller than 50 mol%, there is a possibility that a secondary cache property will be adversely affected.

Further, when the 1-butene polymer is a copolymer, the following formula ( The randomness index R obtained by V) is preferably 1 or less.

[0084] [Equation 3]

R = 4 [α a] [BB] / [α B] ^2- "… (V)

([α α] is the α-olefin chain fraction, [Β Β] is the butene chain fraction, and [α Β] is the one-year-old lefin-butene chain fraction.)

[0085] Here, R is an index representing randomness, and the smaller R is, the higher the isolation of a-olefin (comonomer), and the more uniform the composition. This R is preferably 0.5 or less, and more preferably 0.2 or less.

When R is 0, the chain is lost and the α-olefin chain is completely isolated.

[0086] Note that the butene content and R when the 1-butene polymer is a propylene'-butene copolymer may be measured as follows.

Specifically, butene content and R were calculated by the following method by measuring ¹³ C-NMR spectrum under the following measurement conditions using JNM-—400 type NMR equipment manufactured by JEOL Ltd. do it.

[0087] (Measurement conditions)

Sample concentration: 220mg / NMR solution 3ml

NMR solution: 1, 2, 4-Trichloro-necked benzene Z benzene one d6 (90Zl〇vol%) Measurement temperature: 130 ° C

Panores width: 45 °

Pulse repetition time: 10 seconds

Integration count: 4000 times

[0088] Under the above measurement conditions, PP, PB, and BB chains conform to the method proposed in JC Randall, Macromolecules, 197 8, 11, 592, and the ¹³ C-nuclear magnetic resonance spectrum of So; The signal was measured to determine the PP, PB, and BB diamond chain fractions in the copolymer molecular chain.

The butene content and randomness index R were determined from the following formula chain fractions (mol%) from the following formulas (W) and (X). [0089] [Equation 4] Putene content (mol%) = [BB] + [PB] / 2 …… (W) [0090] [Equation 5] Randomness index R = 4 [PP] [BB] / [ PB] 2 ...... (X) (in formula (W) and formula (X), [PP] is the propylene chain fraction, [BB] is the butene chain fraction, and [PB] is the propylene-butene chain fraction. )

[0091] The butene content and R when the 1-butene polymer is a octyne 'butene copolymer may be measured as follows. Specifically, the butene content and R can be calculated by the following method by measuring a ¹³ C-NMR spectrum under the following measurement conditions using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. Good.

[0092] (Measurement conditions)

Sample concentration: 220mg / NMR solution 3ml

NMR solution: 1, 2, 4-Trichloro-neck benzene Z benzene one d6 (90Zl〇vol%) Measurement temperature: 130 ° C

Panores width: 45 °

Pulse repetition time: 10 seconds

Integration count: 4000 times

[0093] Under the above measurement conditions, the signal of the Saa carbon in the ¹³ C-nuclear magnetic resonance spectrum was measured, and the BB chain, 41.3 to 40.8 ppm [this] The observed OB chain, the peak intensity force derived from the OO chain observed at 42.5-41.3 ppm, and the 00, OB and BB diamond chain fractions in the copolymer molecular chain were determined.

The butene content and randomness index R were determined from the following formula chain fractions (mol%) from the following formulas (Y) and (Z).

[0094] [Equation 6] Butene content (mol./.) = [BB] + [OB] / 2 …… (Y)

[0095] [Equation 7] Randomness index R = 4 [OO] [BB] / [OB] ² …… (Z)

(In formulas (Y) and (Ζ), [O O] represents the octene chain fraction, [B B] represents the butene chain fraction, and [O B] represents the octene butene chain fraction)

[0096] The 1-butene copolymer can be easily obtained by the method for producing a 1-butene copolymer disclosed in WO 03Z070788.

[0097] The extruded foam of the present invention can be obtained by extrusion foaming a mixed material of the above-described propylene-based resin and a specific olefin-based polymer. A known extrusion foaming apparatus that can be heated to a state, kneaded while applying an appropriate shear stress, and foam-extruded can be used. Further, as the extruder constituting the production apparatus, either a single screw extruder or a twin screw extruder can be adopted. As such an extrusion foam molding apparatus, for example, a tandem type extrusion foam molding apparatus disclosed in JP-A-2004-237729, to which two extruders are connected, may be used.

[0098] As the foaming means for foaming the molded body, physical foaming in which a fluid (gas) is injected into the molten resin material at the time of molding or chemical foaming in which a foaming agent is mixed with the resin material is employed. be able to.

For physical foaming, the fluid to be injected includes an inert gas, such as carbon dioxide (carbon dioxide gas), nitrogen gas, or the like. As chemical foaming, usable foaming agents include, for example, azodicarbonamide, azobisisobutyric-tolyl and the like.

[0099] In the above-described physical foaming, if a supercritical carbon dioxide gas or nitrogen gas is injected into the molten resin material, the average cell diameter is less than OO / zm, Preferably, it is preferable to form a large number of fine foam cells of 200 μm or less because it can be surely performed.

Here, the supercritical state refers to a state where the density of the gas and the liquid becomes equal and the two layers cannot be distinguished by exceeding the limit temperature and pressure at which the gas and the liquid can coexist. The fluid generated in is called a supercritical fluid. In addition, the temperature and pressure in the supercritical state are the supercritical temperature and the supercritical pressure. For example, in the case of carbon dioxide, it is, for example, 31 ° C. and 7.4 MPa. In addition, carbon dioxide gas and nitrogen gas in a supercritical state are, for example, a resin material If about 4 to 15% by mass is injected, the molten resin material can be injected into the cylinder.

[0100] The shape of the extruded foam may be a known shape as a structural material that is not particularly limited, for example, a known shape such as a plate shape, a cylindrical shape, or a rectangular shape, and may be a cylindrical shape, a rectangular shape, a convex shape, or the like. A known shape such as a shape or a concave shape can be employed.

[0101] In addition, the extruded foam is formed by, for example, extruding and foaming a large number of strips with a die force for extrusion in which a plurality of extrusion holes are formed. It is good also as an extrusion foaming strip bundling body. In this way, by forming an extruded foam strip converging body in which a large number of strip extruded foams are converging, the foaming ratio of the extruded foam can be increased, and a sufficient thickness for increasing the foaming ratio can be obtained. The foamed molded product can be easily molded in various shapes.

The production of such an extruded foamed strip bundle is known, for example, from JP-A-53-1262 in addition to Patent Document 1 and Patent Document 2 described above.

[0102] The shape of the strips constituting such an extruded foamed strip converging body depends on the shape of the extrusion holes formed in the extrusion die, and the shape of the extrusion holes is circular, rhombus, or slit shape. It can be made into arbitrary shapes, such as. In molding, it is preferable that the pressure loss at the outlet of the extrusion die be 3 MPa to 50 MPa! /.

Also, the shape of the extrusion holes formed in the extrusion die may be the same shape, or multiple types of extrusion holes may be formed in one extrusion die.

Furthermore, for example, even when a circular extrusion hole is used, there may be a plurality of types of diameters, and a large number of circular extrusion holes having different diameters may be formed.

[0103] According to the propylene-based resin extruded foam of the present invention obtained in this way, the foaming magnification force S is 10 times or more and the average cell diameter is less than 00 m, so the cell walls in the extruded foam Therefore, it is possible to efficiently block the radiant heat of the external force, and it is possible to provide an extruded foam excellent in heat insulation performance.

The average cell diameter of the propylene-based resin-extruded foam is preferably 200 μm or less. If the average cell diameter is further reduced to 200 m or less, more cell walls are formed in the extruded foam. Propylene-based extrusion with better thermal insulation performance It becomes a foam.

[0104] In addition, since the loss tangent (tan δ) at a temperature of 298K and a frequency of 10Hz is 0.04 to the propylene-based resin that is a constituent material, it is made to contain an olefin-based polymer that is LOO. Since the olefin-based polymer, which is a viscous material, is present in a uniformly dispersed state on the wall surface of the foam cell that constitutes the molded body, vibrations are efficiently absorbed and vibration suppression is performed. An extruded foam having excellent performance can be provided.

Thus, the present invention can suitably provide a propylene-based resin foam foam having both heat insulation performance and vibration damping performance.

[0105] The propylene-based resin extruded foam of the present invention is a constituent material of which the propylene-based resin is excellent in recycling performance and also has good chemical resistance and heat resistance. The bright propylene-based resin-extruded foam also enjoys these performances (recycling performance, chemical resistance, heat resistance). Furthermore, by using propylene-based resin, which is a low-cost material, an extruded foam having the above-described effects can be provided at low cost.

In this way, the extruded foam of the present invention has both excellent heat insulation performance and vibration control performance, so it can be used for structural materials in the automotive field (components such as ceilings, doors, floors, cowls, etc.), construction, and civil engineering. It can be applied to structural materials (building materials, etc.) in the field.

[0106] Since the extruded foam of the present invention has a small average cell diameter of less than 00 µm (preferably less than 200 µm), it has excellent heat insulation performance and the same heat insulation performance. The thickness can be made thinner than the conventional one. Therefore, for example, when it is applied to the above-described fields, the secondary effect that the living space can be made larger than that of the conventional heat insulating material can be suitably achieved.

[0107] The aspect described above shows one aspect of the present invention. The present invention is not limited to the above-described embodiment, and has the configuration of the present invention. Needless to say, it is included in the content of the present invention. In addition, the specific structure and shape in carrying out the present invention may be any other structure or shape as long as the object and effect of the present invention can be achieved. Example

Hereinafter, the present invention will be described more specifically with reference to examples and production examples. However, the present invention is not limited to the contents of the examples and the like.

The physical properties in the following production examples and examples were measured by the following methods.

[0109] (1) Mass fraction of the first stage propylene polymer component (component 1) and the second stage propylene polymer component (component 2):

The mass balance using the flow meter integrated value of propylene continuously supplied during polymerization was determined.

(2) Intrinsic viscosity [τ?]:

Measurements were made in a 135 ° C. tetralin solvent. The intrinsic viscosity [7?] Of component 2 is given by the following formula (II

2

).

[0110] [Equation 8]

_{[Η 2] = ([TJ} total] XI 0 0- ί J XWJ / W 2 ...... (II) [r?]: Propylene

total Intrinsic viscosity of the entire polymer (dLZg)

[r?]: Intrinsic viscosity of component 1 (dLZg)

W: Mass fraction of component 1 (mass%)

W: Mass fraction of component 2 (mass%)

2

[0111] (3) Melt flow rate (MFR):

In accordance with JIS K7210, the temperature was measured at 230 ° C and the load was measured at 2.16 kgf. (4) Melt tension (MT):

The measurement was performed using Capillograph 1C (manufactured by Toyo Seiki Co., Ltd.) at a measurement temperature of 230 ° C., an extrusion speed of 10 mm Zmin, and a take-up temperature of 3. lmZ. For the measurement, a talented face with a length of 8 mm and a diameter of 2.095 mm was used.

[0112] (5) Viscoelasticity measurement:

The measurement was performed with an apparatus having the following specifications. The storage elastic modulus G ′ can be obtained from the real part of the complex elastic modulus.

Equipment: RMS—800 (Rheometrics) Temperature: 190 ° C

Distortion: 30%

Frequency: 100radZs ~ 0.01rad / s

[0113] [Production Example 1]

Propylene-based multistage polymer production:

(i) Preparation of prepolymerization catalyst component:

Thoroughly dry the 5-liter flask equipped with a stirrer with an internal volume of 5 liters, and replace with nitrogen gas. 20 Titanium catalyst (Tosohichi Finechem Co., Ltd.) 20g was burned. While maintaining this at 20 ° C. with stirring, propylene was continuously introduced. After 80 minutes, stirring was stopped to obtain a pre-catalyst component in which 0.8 g of propylene was polymerized per lg of trisalt / titanium catalyst.

[0114] (ii) Polymerization of propylene (first stage):

A stainless steel autoclave with a stirrer with an internal volume of 10 liters was thoroughly dried and replaced with nitrogen gas, 6 liters of dehydrated heptane was added, and nitrogen in the system was replaced with propylene. Thereafter, propylene was introduced while stirring to stabilize the inside of the system at an internal temperature of 60 ° C and a total pressure of 0.78 MPa, and then the prepolymerized catalyst component obtained in (i) above was converted to a solid catalyst equivalent of 0.75. The polymerization was started by adding 50 ml of heptane slurry containing gram. When propylene was continuously fed for 35 minutes, the amount of propylene flow rate obtained was also found to be 151 g. As a result of sampling and analyzing a part of the polymer, the intrinsic viscosity was 14. Id LZg. Thereafter, the internal temperature was lowered to 40 ° C or lower, the stirring was loosened, and the pressure was released.

[0115] (iii) Polymerization of propylene (second stage):

After depressurization, the internal temperature was again set to 60 ° C, and propylene was introduced with stirring while adding 0.15 MPa of hydrogen. While propylene was continuously supplied at a total pressure of 0.78 MPa, polymerization was carried out at 60 ° C for 2.8 hours. At this time, as a result of sampling and analyzing a part of the polymer, the intrinsic viscosity was 1.16 dL / g.

[0116] After completion of the polymerization, 50 ml of methanol was added, and the temperature was lowered and the pressure was released. Transfer the entire contents to the filter tank equipped with a filter, add 100 ml of 1-butanol, and stir at 85 ° C for 1 hour. After that, solid-liquid separation was performed. Further, the solid part was washed twice with 6 liters of heptane at 85 ° C. and vacuum-dried to obtain 3.1 kg of a propylene polymer.

[0117] From the above results, the polymerization weight ratio of the first stage and the second stage was 12. 2 / 87.8, and the intrinsic viscosity of the propylene polymer component produced in the second stage was determined to be 1.08dLZg. .

Based on 100 parts by weight of the resulting propylene-based multi-stage polymer powder, Irganox 1010 (manufactured by Tinoku Specialty Chemicals Co., Ltd.) as an antioxidant is 600 ppm, and calcium stearate is 500 ppm as a neutralizer. In addition, the mixture was mixed and melt-kneaded at a temperature of 230 ° C. with a lab plast mill single screw extruder (manufactured by Toyo Seiki Co., Ltd., φ20 mm) to prepare propylene polymer pellets.

Table 1 shows the physical properties and oil properties of the resulting propylene-based multistage polymer.

[0118] (Physical properties and oil properties of propylene-based multistage polymer)

[table 1]

[Example 1]

Manufacture of Polypropylene Extrusion Foam (Extruded Foam Strips):

The 1-butene copolymer (a) disclosed in Example 1 of WO 03Z070788 is added to the pellet-shaped propylene-based multistage polymer (b) obtained in Production Example 1 described above in a weight ratio (a / b) was mixed as 15Z85 (85% by mass of a propylene-based multistage polymer and 15% by mass of a 1-butene copolymer) to obtain a molding material. 1-Butene copolymer physical properties and grease properties Shown in 2.

For the measurement items shown in Table 2, the loss tangent (t an δ) at a temperature of 298K and a frequency of 10Hz! /, A solid viscoelasticity measuring device (DMS 6100: manufactured by Seiko Instruments Inc.) ), And other items were measured in accordance with the method described in WO 038870788.

[0120] (Physical property value and grease property of 1-butene copolymer)

[Table 2]

(Note 1) Loss tangent at temperature 298K, frequency 10Hz (tan S)

(Note 2) {mmmm / (mrnrr + rmmr;}

• Measurement methods shall be in accordance with those described in WO 03/070788, except for loss tangent measurement.

[0121] This molding material was applied to two tandem extrusion foaming molding machines disclosed in JP-A-2004-237729 (a single-screw extruder with a screw diameter of φ50 mm and a single-screw extruder with a screw diameter of φ35). Equipped with a single-screw extruder), and a die having a large number of circular extrusion holes (circular tube die) assembled together, and a number of extruded foam strips are collected by the following method. A propylene-based resin-extruded foam, which is a plate-like extruded foam bundle, was produced.

Foaming is performed by injecting a CO supercritical fluid with a φ50mm single screw extruder.

2

I

[0122] That is, the CO supercritical flow while melting the molding material with a φ50mm single screw extruder

2

The body is injected and the fluid is sufficiently dissolved in the molten molding material to be uniform. Thereafter, the extruded foam was molded from the connected φ35 mm single screw extruder so that the temperature of the resin at the die outlet in the φ35 mm single screw extruder was S180 ° C. Details of the manufacturing conditions are given below.

The resin temperature at the die outlet of the φ35mm single screw extruder is measured with a thermocouple thermometer, and this resin temperature can be considered as the temperature of the molten resin extruded while foaming.

[0123] (Production conditions)

CO supercritical fluid: 7% by mass

2

Extrusion amount: 8kgZhr

Die upstream oil pressure: 8MPa

Extrusion temperature at die outlet: 180 ° C

When the expansion ratio, average cell diameter, and independent cell ratio of the propylene-based resin-extruded foam thus obtained were measured according to the following conditions, they were 28 times, 120 m, and 50%, respectively.

[0124] (Measurement conditions)

Foaming ratio: The density was determined and calculated by dividing the weight of the obtained foamed molded article by the volume determined using the water casting method.

Average cell diameter: Measured according to ASTM D3576—3577.

Closed cell ratio: Measured according to ASTM D 2856.

Furthermore, when the extruded foam of Example 1 was evaluated for heat insulation performance and vibration damping performance using conventional methods, good results were obtained for both, and the extruded foam of the present invention had excellent heat resistance performance and It has been confirmed that it has vibration control performance.

[0125] [Examples 2 and 3]

Evaluation with MuCell injection molding machine

(Molding method)

Ingredients (a) and (b) described above were blended so as to be Examples 2 and 3 and Comparative Examples 1 and 2 in Table 1, and were simply extruded and foamed from the following injection molding machines and tested from the molded bodies. By cutting out the pieces, we evaluated the foaming characteristics and vibration damping. Molding machine: Japan Steel, J180EL—MuCell

Injection time: 5 seconds

Injection fat amount: lOOg

Cylinder set temperature: 180 ° C

Foaming agent: CO supercritical fluid

2

Gas amount: 5wt%

It should be noted that there is a correlation between the foam moldability of the tandem-type extrusion molding apparatus of Example 1 and the foam moldability of the simple extrusion from the injection molding machine of this example, and the result of this example is a general extrusion. It can be judged that it represents the foam moldability in foam molding.

[Table 3]

Example 1 Example 2 Comparative Example 1 Comparative Example 2

W003 / 070788 W003 / 070790 W003 / 070788 Disclosed in Component (a) Disclosed in-Resin material Resin material Resin material Disclosed in Production Example 1 Production Example 1 Production Example 1 Use of Production Example 1

Component (b) Propylene Propylene Propylene Propylene

Multi-stage polymer Multi-stage polymer Multi-stage polymer Multi-stage polymer Material

Ingredient (a)

Fee

Loss tangent of 0.35 0.50 ― 0.35

(tan δ)

15/85 5/95 0/100 100/100

(a / b)

Foaming ratio 30 times 29 times 32 times-average cell diameter

100 110 80 ―

(β m)

Foam

Loss tangent 0. 070 0. 063 0. 053 one (tan 6)

Formability by melting in raw material supply section---

Can not be molded

(Vibration damping ability)

The extruded foam of this example was evaluated for heat insulation capacity and vibration suppression performance using a conventional method, and both of them were able to obtain good evaluation results, and the extruded foam of the present invention had excellent heat insulation performance and It has been confirmed that it has vibration control performance.

As shown in Table 3, it is generally known that the tangent loss tan δ of solid viscoelasticity is a measure of vibration damping, that is, a measure of damping performance! The elastic tan δ was evaluated as an index of the damping performance of the foam. As tan δ increases, the vibration absorption capacity improves. The extruded foam of Example 1 showed a large increase in tan δ as compared with the extruded foam of the propylene-based multistage polymer (b) obtained in Production Example 1. It was confirmed that the bright extruded foam showed excellent vibration damping performance.

[0128] (Relationship between morphology and damping performance)

Morphology of olefin polymer (b) with loss tangent (tan δ) of 0.04 to 100 at a temperature of 298 ° C and a frequency of 10Hz mixed with propylene resin (a) (Form)!

Morphology in the foam varies depending on the compatibility and molecular weight of component (b) with component (a), but when component (b) tends to bleed at the bubble interface or bubbles are preferentially generated from component (b). When this occurs, it is considered that the morphology is such that the component (b) is selectively layered around the bubbles as shown in FIG. On the other hand, if different from the above, it is considered that the morphology is such that component (b) is dispersed in component (a) as shown in FIG. In any case, the component (b) vibrates in the same way with the vibration of the component (a), so that the vibration damping performance of the component (b) improves the damping performance. In the case of the same morphology as in a), it is considered that a more effective vibration damping effect is exhibited by increasing the magnitude of the generated strain according to the vibration of the bubble wall surface.

[0129] FIG. 3 shows a transmission electron microscope showing the wall portion between the bubbles in the cross section of the foam of Example 2.

(TEM) shows the result of shooting at 13000 times magnification. In this image, the foam is dyed with ruthenium tetrachloride, so that the portion made of component (a) is blackened. In this way, component (a) with damping effect can effectively block the propagation of vibration through component (b)! / You can see how you speak.

[0130] (Change due to blending ratio)

As the blending ratio of the component (a) to the component (b) is increased, the vibration damping characteristics improve, but if the weight ratio (aZb) exceeds 80Z100, molding under the same conditions becomes difficult. Comparative example 2 in Table 1 shows the results when the weight ratio (aZb) is 100Z100. In this case, the ratio of the component (a), which is a low-melting point material, is too high, so the force of the raw material supply unit (hopper) is also high. In the process up to you, clogging occurred due to dissolution of component (a), making molding impossible.

Industrial applicability

[0131] The propylene-based resin-extruded foam of the present invention is, for example, in the fields of architecture, civil engineering, and automobiles. Can be advantageously used for structural materials that require heat insulation performance and vibration control performance.

Claims

Claims [1] A propylene-based resin extruded foam obtained by extruding propylene-based resin, wherein the propylene-based resin constituting the extruded foam has a loss tangent (tan) at a temperature of 298 K and a frequency of 10 Hz. A propylene-based resin-extruded foam comprising an olefin-based polymer in which δ) is 0.04: LOO, having an expansion ratio of 10 times or more, and an average cell diameter of less than 400 μm. [2] The propylene-based resin extruded foam according to claim 1, wherein the weight ratio (aZb) of the olefin-based polymer (a) to the propylene-based resin (b) is 1Z100 to 80/80. A propylene-based extruded resin foam characterized by being 100. [3] The propylene-based resin extruded foam according to claim 1 or 2, wherein the olefin-based polymer comprises the following (1), (2) and (3): A propylene-based resin-extruded foam, which is a polymer.

(3) Stereoregularity index {(mmmm) / (mmrr + rmmr)} is 30 or less

[4] The propylene-based resin extruded foam according to claim 1 or claim 2, and

A propylene-based resin-extruded foam, wherein the olefin-based polymer is a 1-butene-based polymer having the following (1 '), (2) and (3').

(1 ') Intrinsic viscosity [r?] Measured in a tetralin solvent at 135 ° C is 0.25 to 0.5 dL / g. (2) Using a differential scanning calorimeter (DSC), the sample is placed under a nitrogen atmosphere. The melting point (T — D) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by holding at 5 ° C for 5 minutes and then increasing the temperature at 10 ° CZ is 0. ~: Crystalline resin at L00 ° C

[5] In the propylene-based resin-extruded foam according to any one of claims 1 and 4!

A propylene-based resin-extruded foam having a closed cell ratio of 40% or more.

[6] The propylene-based resin-extruded foam according to any one of claims 1 and 5! ,,,

A propylene-based resin-extruded foam, wherein the average cell diameter is 200 μm or less.

[7] The propylene-based resin-extruded foam according to any one of claims 1 and 6! ,,,

A propylene-based resin-extruded foam characterized in that it is an extruded foam-strip bundling body in which a large number of extruded foam strips are bundled.

[8] The propylene-based resin-extruded foam according to any one of claims 1 and 7! ,,,

A propylene-based resin-extruded foam characterized in that the propylene-based resin constituting the extruded foam is a propylene-based multistage polymer having the following (A) and (B) forces.

(A) A propylene homopolymer component having an intrinsic viscosity [7?] Of more than lOdLZg measured in a tetralin solvent at 135 ° C or a copolymer component of propylene and a-olefin having 2 to 8 carbon atoms Contain 5-15% by mass in the polymer

(B) Propylene homopolymer component having an intrinsic viscosity [r?] Of 0.5 to 3. OdLZg measured in a tetralin solvent at 135 ° C or propylene and α-olefin having 2 to 8 carbon atoms. 85 to 95% by mass of the polymer component is contained in the total polymer.

[9] The propylene-based resin extruded foam according to claim 8,

The propylene-based polymer is characterized in that the relationship between the melt flow rate (MFR) at 230 ° C. and the melt tension (MT) at 230 ° C. of the propylene-based multistage polymer has the following formula (I): Fat extrusion foam.

[Number 1]

1 og (MT)>-1. 3 3 1 og (MFR) + 1.2 …… (I)

[10] The propylene based resin extruded foam according to any one of claims 1 to 7 and claim 7! ,,,

[11] The propylene-based resin-extruded foam according to claim 10,

[Equation 2]

1 o g (M T)>-1.3 3 3 1 o g (M F R) + 1.2… "-(I)