JP2010111798A - Modified resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a crosslinked body showing specific viscosity performance during being melted while maintaining transparency and having satisfactory thermal stability and satisfactory foaming performance by crosslinking a propylene polymer composition, including a specific syndiotactic propylene polymer or the syndiotactic propylene polymer and a propylene-α-olefin copolymer, by irradiation with a radiation or in the presence of an organic peroxide and a crosslinking aid. <P>SOLUTION: A modified resin composition is obtained by crosslinking a resin composition (C), including 100 to 50 pts.wt. syndiotactic propylene polymer (A) and 0 to 50 pts.wt. propylene-α-olefin copolymer (B) (the total of (A) and (B) is 100 pts.wt.), by radiation or with a peroxide. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a modified resin composition obtained by crosslinking a specific propylene polymer composition.

  Polypropylene polymers are widely used in various molding fields because they are excellent in mechanical properties, chemical resistance, etc., are inexpensive and useful. However, since the viscosity at the time of melting is small, there is a problem that the expansion ratio in foam molding is low, the foam cells are defoamed and non-uniform, the neck-in at the time of film extrusion molding is large, and the width of the film is small. It was.

  In Patent Documents 1 and 2, as a method for increasing the melt tension and crystallization temperature of crystalline polypropylene, there is a method in which an organic peroxide and a crosslinking aid are reacted with crystalline polypropylene in a molten state. Since the agent is used, there is a problem that odor remains in the modified crystalline polypropylene. Furthermore, it was difficult to say that the melt tension was sufficiently improved. If the addition amount of the organic peroxide and the crosslinking aid is increased for the purpose of increasing the melt tension, a gel is generated, and there is a problem that the appearance of the film is deteriorated. Furthermore, the crystallinity is isotactic, and when a crosslinking agent is added in the presence of oxygen to generate radicals, some or all of the bonds between the molecular chains are broken, reducing the thermal stability of the crosslinked product, There were problems such as the generation of low molecular weight components.

Patent Document 3 discloses a method of irradiating an electron beam to polypropylene to which an acrylic ester crosslinking aid is added. This is also isotactic polypropylene, and a radical is obtained by adding a crosslinking agent in the presence of oxygen. When this occurs, some or all of the bonds between the molecular chains are broken, resulting in problems such as a decrease in the thermal stability of the crosslinked product and the generation of low molecular weight components.
JP 59-93711 A JP 61-152754 A JP-A-1-244828

  The present invention relates to a propylene-based polymer composition comprising a specific syndiotactic propylene polymer and a propylene / α-olefin copolymer in the presence of an organic peroxide and a crosslinking aid or a polyfunctional vinyl monomer. Alternatively, by maintaining the transparency by irradiating and irradiating with radiation, the decrease in viscosity at a low shear rate during melting is small, the increase in viscosity at a high shear rate is large, the thermal stability is good, and the foaming performance is high. It is an object of the present invention to provide a good modified resin composition or a modified resin composition comprising the composition.

  As a result of diligent studies to solve the above problems, the present inventors have developed a propylene-based polymer composition comprising a specific syndiotactic propylene polymer and a propylene / α-olefin copolymer as an organic peroxide. Crosslinking in the presence of a crosslinking aid or a polyfunctional vinyl monomer, or by irradiating with radiation to crosslink, while maintaining transparency, the decrease in viscosity at a low shear rate during melting is small and high shear. A modified resin composition having a large increase in viscosity at speed, showing good thermal stability and good foaming performance was found, and the present invention was completed.

That is, the present invention includes the following matters.
[1] Syndiotactic propylene polymer (A) 100 to 50 parts by weight;
Crosslinking a resin composition (C) comprising 0 to 50 parts by weight of a propylene / α-olefin copolymer (B) (provided that the total of (A) and (B) is 100 parts by weight) A modified resin composition obtained by
The ratio of η ^* _{100 (initial)} before crosslinking and η ^* _{100 (vulc)} after crosslinking satisfies the formula (Eq-1) at a shear rate of 100 rad / sec in melt viscoelasticity,
The ratio of η ^* _{0.1 (initial)} before cross-linking and η ^* _{0.1 (vulc)} after cross-linking satisfies the formula (Eq-2) at a shear rate of 0.1 rad / sec in melt viscoelasticity,
η ^* _{100 (vulc)} / η ^* _{100 (initial)} ≧ 0.85 (Eq-1)
η ^* _{0.1 (vulc)} / η ^* _{0.1 (initial)} ≧ 1.10 (Eq-2)
The boiling xylene extraction residual rate is 10 wt% or less,
The modified resin composition is characterized in that the syndiotactic propylene polymer (A) satisfies the following requirement (a) and the propylene / α-olefin copolymer (B) satisfies the following requirement (b). object.
(A) A syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, a melting point (Tm) determined by DSC is 145 ° C. or more, and derived from propylene The unit is contained in an amount exceeding 90 mol% (provided that the total amount of the structural units in the syndiotactic propylene polymer (A) is 100 mol%).
(B) Containing structural units derived from propylene in an amount of 55 to 90 mol%, and 10 to 45 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (provided that Contained in an amount of 100 mol% of the structural unit derived from propylene and the structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) and conforming to JIS K-6721 The MFR measured at 230 ° C. under a 2.16 kg load is in the range of 0.01 to 100 g / 10 minutes, and satisfies at least one of the following requirements (b-1) and (b-2) .
(B-1) The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2) The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) are expressed by the following relational expression (Eq-3) Meet.
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20) (Eq-3)

[2] Cross-linked in the presence of an organic peroxide (P) and, if necessary, one or more compounds selected from a crosslinking assistant (Q) and a polyfunctional vinyl monomer (R). The modified resin composition according to [1].
[3] The modified resin composition according to [1], which is crosslinked by irradiation with radiation.
[4] The resin composition (C) is a syndiotactic propylene polymer (A) 95 to 50 parts by weight and a propylene / α-olefin copolymer (B) 5 to 50 parts by weight (provided that (A) And (B) is 100 parts by weight.) The modified resin composition according to any one of claims [1] to [3].
[5] 1 to 100 parts by weight of the modified resin composition according to any one of [1] to [4], 0 to 99 parts by weight of the syndiotactic propylene polymer (A), and propylene / α-olefin copolymer A modified resin composition comprising 0 to 50 parts by weight of the combined body (B) (however, the total of the modified resin composition and (A) and (B) is 100 parts by weight).
[6] The half crystallization time (t _1/2 ) in isothermal crystallization at 110 ° C. determined by a differential scanning calorimeter (DSC) is 1000 sec or less, [1] to [5] The modified resin composition in any one.
[7] The modified resin composition according to any one of [1] to [6], wherein the needle penetration temperature is 145 ° C. or higher.
[8] The internal haze value of a 1 mm thick press sheet is 50% or less [
The modified resin composition according to any one of 1] to [7].
[9] The intrinsic viscosity [η] measured in decalin at 135 ° C. of the syndiotactic propylene polymer (A) is in the range of 0.1 to 10 dL / g, and determined by differential scanning calorimetry (DSC) measurement. The modified resin composition according to any one of [1] to [8], wherein the heat of fusion (ΔH) is 40 mJ / mg or more.
[10] The molecular weight distribution (Mw / Mn) determined by GPC of the propylene / α-olefin polymer (B) is 3.5 or less, according to any one of [1] to [9] Modified resin composition.

  One or more compounds selected from the specific resin composition (C) according to the present invention from an organic peroxide (P) and, if necessary, a crosslinking assistant (Q) and a polyfunctional vinyl monomer (R) In the presence of UV, or by irradiation to cause crosslinking, the viscosity decrease at the time of melting at the low shear rate is small while maintaining transparency, the viscosity increase at the high shear rate is large, and the thermal stability is good In addition, a modified resin composition having good foaming performance is provided.

The modified resin composition of the present invention includes the following first and second embodiments.
The modified resin composition of the first aspect of the present invention is a syndiotactic propylene polymer (A) 100 to 50 parts by weight,
Crosslinking a resin composition (C) comprising 0 to 50 parts by weight of a propylene / α-olefin copolymer (B) (provided that the total of (A) and (B) is 100 parts by weight) A modified resin composition obtained by
The ratio of η ^* _{100 (initial)} before cross-linking and η ^* _{100 (vulc)} after cross-linking satisfies the equation (Eq-1) at a shear rate of 100 rad / sec in melt viscoelasticity,
Η ^* _{0.1 (initial)} before crosslinking and η ^* ₀ after crosslinking at a shear rate of 0.1 rad / sec in melt viscoelasticity. 1 _(vulc) ratio satisfies the equation (Eq-2)
η ^* _{100 (vulc)} / η ^* _{100 (initial)} ≧ 0.85 (Eq-1)
_{^{η * 0.1 (vulc) / η}} * 0.1 (initial) ≧ 1.10 ··· (Eq-2)
The boiling xylene extraction residual rate is 10 wt% or less,
Further, the syndiotactic propylene polymer (A) satisfies the following requirement (a), and the propylene / α-olefin copolymer (B) satisfies the following requirement (b).

(A) A syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, a melting point (Tm) determined by DSC is 145 ° C. or more, and derived from propylene The unit is contained in an amount exceeding 90 mol% (provided that the total amount of the structural units in the syndiotactic propylene polymer (A) is 100 mol%).
(B) Containing structural units derived from propylene in an amount of 55 to 90 mol%, and 10 to 45 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (provided that Contained in an amount of 100 mol% of the structural unit derived from propylene and the structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) and conforming to JIS K-6721 The MFR measured at 230 ° C. under a 2.16 kg load is in the range of 0.01 to 100 g / 10 minutes, and satisfies at least one of the following requirements (b-1) and (b-2) .
^{(B-1) 13 C-} NMR method syndiotactic triad fraction measured by (rr fraction) is 60% or more.
(B-2) The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) are expressed by the following relational expression (Eq-3) Meet.

1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20) (Eq-3)
Hereinafter, the modified resin composition of the first aspect is referred to as a modified resin composition (D).
The modified resin composition of the second aspect of the present invention comprises 1 to 100 parts by weight of the modified resin composition (D), 0 to 99 parts by weight of the syndiotactic propylene polymer (A), and propylene / α-olefin. It is characterized by comprising 0 to 50 parts by weight of the copolymer (B) (however, the sum of (D), (A) and (B) is 100 parts by weight).

Hereinafter, the modified resin composition of the second aspect is referred to as a modified resin composition (E).
The components constituting the raw resin composition (C) of the modified resin composition of the present invention will be described in detail.

[Syndiotactic propylene polymer (A)]
The syndiotactic propylene polymer (A) used in the present invention may be a homopolypropylene or a random copolymer of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) Although it may be a propylene block copolymer, it is preferably a homopolypropylene or a random copolymer of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene), particularly preferably homopolypropylene or propylene and A random copolymer of α-olefins (excluding propylene) having 2 to 10 carbon atoms, and most preferably homopolypropylene from the viewpoint of heat resistance.

  Here, the α-olefin having 2 to 20 carbon atoms other than propylene includes ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.

  The structural unit derived from propylene is contained in an amount usually exceeding 90 mol%, preferably 91 mol% or more, out of a total of 100 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (including propylene). It is. When the syndiotactic propylene polymer (A) is a propylene / α-olefin random copolymer, the structural unit derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is usually 0. It is contained in an amount of 3 to 7 mol%, preferably 0.3 to 6 mol%, particularly preferably 0.3 to 5 mol%.

The syndiotactic propylene polymer (A) has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of 85% or more, preferably 90% or more, more preferably The syndiotactic propylene polymer (A) having 93% or more, more preferably 94% or more and having an rrrr fraction in this range is excellent in moldability, heat resistance and transparency, and is a crystalline polypropylene. It is preferable in terms of good characteristics. By using this syndiotactic propylene polymer (A), in the presence of oxygen, it becomes difficult for hydrogen at the β-position to be pulled out by organic peroxide or oxygen radicals generated by radiation, and the molecular chain is hardly broken. Therefore, the modified resin composition (D) obtained by crosslinking has a ratio between η ^* _{100 (initial)} before crosslinking and η ^* _{100 (vulc)} after crosslinking at a shear rate of 100 rad / sec in melt viscoelasticity. Satisfies the formula (Eq-1), and the ratio of η ^* _{0.1 (initial)} before cross-linking to η ^* _{0.1 (vulc)} after cross-linking is _0.1 -2) will be satisfied.
η ^* _{100 (vulc)} / η ^* _{100 (initial)} ≧ 0.85 (Eq-1)
_{^{η * 0.1 (vulc) / η}} * 0.1 (initial) ≧ 1.10 ··· (Eq-2)

The upper limit of the rrrr fraction is not particularly limited, but is usually 99% or less, for example.
This syndiotactic pentad fraction (rrrr fraction) is measured as follows.
The rrrr fraction is expressed as Prrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit in a site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (total methyl groups of propylene units). (Absorption intensity derived from the above) is determined by the following formula (Eq-4).
rrrr fraction (%) = 100 × Prrrr / Pw (Eq-4)

The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more.

  The intrinsic viscosity [η] of the syndiotactic propylene polymer (A) measured at 135 ° C. in decalin is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g, more preferably 0.5. 8 dL / g, particularly preferably 0.95 to 8 dL / g, further preferably 1 to 8, still more preferably 1.4 to 8 dL / g, and still more preferably 1.4 to 5 dL / g. The syndiotactic propylene polymer (A) having such an intrinsic viscosity [η] value exhibits good fluidity, is easy to be blended with other components, and mechanical strength is obtained from the obtained resin composition (C). There exists a tendency for the modified resin composition (D) excellent in to be obtained.

  Furthermore, melting | fusing point (Tm) obtained by the differential scanning calorimeter (DSC) measurement of a syndiotactic propylene polymer (A) is 145 degreeC or more, Preferably it is 147 degreeC or more, More preferably, it is 150 degreeC or more, Especially preferably, it is 155 degreeC or more, More preferably, it is 156 degreeC or more. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example. Further, the heat of fusion (ΔH) obtained by differential scanning calorimetry (DSC) measurement of the syndiotactic propylene polymer (A) is 40 mJ / mg or more, preferably 45 mJ / mg or more, particularly preferably 50 mJ / mg or more, More preferably, it is 52 mJ / mg or more, More preferably, it is 55 mJ / mg or more. It is preferable for the amount of heat of fusion (ΔH) to be in the above range because the resulting modified resin composition (D) has excellent heat resistance and mechanical strength.

  The differential scanning calorimeter measurement is performed as follows, for example. About 5.00 mg of sample is packed in a dedicated aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes, and then from 200 ° C. The temperature is lowered to 30 ° C. at 10 ° C./min, held at 30 ° C. for another 5 minutes, and then the melting point (Tm) and heat of fusion (ΔH) are determined from the endothermic curve when the temperature is raised at 10 ° C./min. When a plurality of peaks are detected during DSC measurement, the peak detected on the highest temperature side is defined as the melting point (Tm).

  The syndiotactic propylene polymer (A) having a melting point (Tm) in this range is excellent in moldability, heat resistance and mechanical properties, and has good properties as crystalline polypropylene. A syndiotactic propylene polymer (A) having a melting point (Tm) in this range can be produced by setting a polymerization condition using a catalyst system described in International Publication No. 2006/123759, which will be described later. it can.

  The syndiotactic propylene polymer (A) can be produced by a polymerization method using a crosslinked metallocene compound as a polymerization catalyst. Specifically, it can be produced by the method described in International Publication No. 2006/123759.

  The syndiotactic propylene polymer (A) in the resin composition (C) used in the present invention is a total of 100 weights of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B). In the part, 100 to 50 parts by weight, preferably 100 to 55 parts by weight, and more preferably 100 to 60 parts by weight are contained. It is preferable from a viewpoint of heat resistance and mechanical strength that content of a syndiotactic propylene polymer (A) exists in said range. Furthermore, in the case of imparting flexibility, it is contained in an amount of 95 to 50 parts by weight, preferably 95 to 55 parts by weight, and more preferably 95 to 60 parts by weight.

[Propylene / α-olefin copolymer (B)]
The propylene / α-olefin copolymer (B) used in the present invention contains a constitutional unit derived from propylene in an amount of 55 to 90 mol%, and an α-olefin having 2 to 20 carbon atoms (excluding propylene). Is contained in an amount of 10 to 45 mol%.

  When used in the present invention, the syndiotactic propylene polymer (A) is contained in 50 parts by weight or more in a total of 100 parts by weight of (A) and (B), so that the propylene / α-olefin copolymer (B ) Is derived from 55 to 90 mol%, preferably from 55 to 85 mol%, more preferably from 60 to 85 mol%, and an α-olefin having 2 to 20 carbon atoms (excluding propylene) derived from propylene. The structural unit is contained in an amount of 10 to 45 mol%, preferably 15 to 45 mol%, more preferably 15 to 40 mol%. When the content of the syndiotactic propylene polymer (A) is less than 50 parts by weight in the total of 100 parts by weight of (A) and (B), the propylene / α-olefin copolymer (B) is A structural unit derived from propylene in an amount of 55 to 90 mol%, preferably 65 to 85 mol%, more preferably 70 to 85 mol%, and an α-olefin having 2 to 20 carbon atoms (excluding propylene). 10 to 45 mol%, preferably 15 to 35 mol%, more preferably 15 to 30 mol%.

The total of structural units derived from propylene and structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is 100 mol%.
Examples of the α-olefin having 2 to 20 carbon atoms (excluding propylene) include ethylene, 3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, Examples include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene. Particularly preferred are ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.

  Of the propylene / α-olefin copolymer (B), a propylene / ethylene copolymer is preferably used, specifically, a structural unit derived from propylene / ethylene copolymer or propylene, It is derived from a structural unit derived from ethylene and at least one monomer selected from 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene (hereinafter also referred to as “HAO comonomer”). A propylene / ethylene / HAO copolymer is used which is composed of structural units and has a proportion (mol%) of structural units derived from ethylene larger than a proportion (mol%) of structural units derived from HAO comonomer. Further, the structural unit derived from ethylene and the HAO comonomer is more preferably 15 to 45 mol%, and particularly preferably 15 to 40 mol%. Within this range, the resin composition (C) used in the present invention is particularly excellent in the balance of heat resistance, transparency and impact resistance.

The propylene / α-olefin copolymer (B) used in the present invention has an MFR measured at 230 ° C. under a 2.16 kg load in the range of 0.01 to 100 g / min in accordance with JIS K-6721. And at least one of the following requirements (b-1) and (b-2) is satisfied.
(B-1) the syndiotactic triad fraction measured by ¹³ C-NMR method (rr) of 60% or more.
(B-2) Intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and MFR (g / 10 min) measured at 230 ° C. and 2.16 kg load according to JIS K-6721 Satisfies the following relational expression (Eq-3).
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20) (Eq-3)

  The propylene / α-olefin copolymer (B) preferably has an MFR measured at 230 ° C. under a load of 2.16 kg in accordance with JIS K-6721, usually in the range of 0.01 to 100 g / 10 min. Is in the range of 0.02 to 100 g / 10 min.

The requirement (b-1) is described below.
(B-1) Syndiotactic triad fraction (rr fraction, triad syndiotacticity) measured by ¹³ C-NMR method of propylene / α-olefin copolymer (B) is 60% or more, preferably 70 % Or more, more preferably 75% or more. The propylene / α-olefin copolymer (B) having an rr fraction in this range is preferable because it has good compatibility with the syndiotactic propylene polymer (A).

  The polymer satisfying (b-1) can be obtained, for example, by copolymerizing propylene and α-olefin in the presence of a catalyst capable of producing syndiotactic polypropylene. It can also be manufactured.

The rr fraction is Prr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the second unit at the site where three units of propylene units are continuously syndiotactically bonded) and Pw (total methyl groups of propylene units). (Absorption intensity derived from the above) is determined by the following formula (Eq-4).
rr fraction (%) = 100 × Prr / Pw (Eq-4)

  Here, absorption derived from mr (used to determine Pmr (absorption intensity), absorption derived from at least syndiotactic bond and isotactic bond among 3 units of propylene unit), absorption derived from rr ( Absorption derived from the methyl group of the second unit at a site where 3 units of propylene units are continuously syndiotactically bonded, used for determination of Prr (absorption intensity)), or absorption derived from mm (3 units of propylene units are continuous) If the absorption derived from the methyl group of the second unit at the isotactic bond site and the absorption derived from the comonomer overlap with the absorption derived from the second unit methyl group, the contribution of the comonomer component Calculate without any deduction.

  Specifically, among the description of how to obtain the “syndiotacticity parameter (SP value)” described in paragraphs [0018] to [0031] of JP-A-2002-097325, [0018] to [0023] ] Paragraph, and it calculates | requires by calculating from Formula (1) from the integrated intensity | strength of the signal of 1st area | region, 2nd area | region, and 3rd area | region.

In the present invention, the rr ₁ value is obtained particularly according to the method for obtaining the “syndiotacticity parameter (SP value)” described in paragraphs [0018] to [0031] of JP-A-2002-097325. The value is usually 60% or more, preferably 65% or more, more preferably 70% or more. In other words, in the calculation of the rr value, the rr ₁ value is obtained by subtracting the contribution of the comonomer component when the mr-derived absorption, the rr-derived absorption or the mm-derived absorption overlaps with the comonomer-derived absorption. It is.

In the measurement of the rr value and the rr ₁ value, the NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120 ° C. using a GX-400 NMR measurement apparatus manufactured by JEOL. The number of integration is 8,000 times or more.

Next, requirement (b-2) is explained.
(B-2) The propylene / α-olefin copolymer (B) has an intrinsic viscosity [η] (dL / g) measured in decalin of 135 ° C. and 230 ° C. in accordance with JIS K-6721. MFR (g / 10 min) measured with a .16 kg load satisfies the following relational expression (Eq-3).
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20) (Eq-3)
More preferably, the following relational expression (Eq-3 ′) is satisfied.
1.80 x MFR ^(-0.20) ≤ [η] ≤ 2.50 x MFR ^(-0.19) (Eq-3 ')
The propylene / α-olefin copolymer (B) satisfying this relational expression is preferable because of good compatibility with the syndiotactic propylene polymer (A).

  The propylene / α-olefin copolymer (B) satisfying the above formula may be obtained by copolymerizing propylene and α-olefin using a catalyst capable of producing a syndiotactic propylene polymer, for example. You may superpose | polymerize using a catalyst. The propylene / α-olefin copolymer (B) thus obtained has good compatibility with the syndiotactic propylene polymer (A).

The propylene / α-olefin copolymer (B) satisfying (b-2) has the same intrinsic viscosity [η] and a high MFR value as compared with the conventional isotactic propylene-based copolymer.
This is described in “Macromolecules” 1998, Vol. 31, p. The molecular weight between entanglement points of isotactic polypropylene (reported as Me = 6900 (g / mol) in the paper) and the molecular weight between entanglement points of syndiotactic polypropylene as described in 1335-1340. In this case, it is considered that this is caused by a difference from Me = 2170 (g / mol). That is, when [η] is the same, having a syndiotactic structure increases the number of entanglement points as compared with a material having an isotactic structure, and thus the MFR value is considered to be high.

  As described above, the propylene / α-olefin copolymer (B) satisfying at least one of the requirements (b-1) and (b-2) is a steric rule different from the isotactic structure. It is considered to have a syndiotactic structure that is a sex. Therefore, it is considered that the propylene / α-olefin copolymer (B) exhibits good compatibility with the component (A).

  In the propylene / ethylene copolymer and propylene / ethylene / HAO copolymer, which are preferred embodiments of the propylene / α-olefin copolymer (B), the above requirements (b-1) and (b-2) It is preferable to satisfy both.

  The intrinsic viscosity [η] of the propylene / α-olefin copolymer (B) measured in decalin at 135 ° C. is 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g, more preferably 0.8. It is desirable to be 5 to 7.0 dL / g.

  This propylene / α-olefin copolymer (B) has a single glass transition temperature, and the glass transition temperature (Tg) obtained by DSC measurement is usually preferably 0 ° C. or lower. When the glass transition temperature (Tg) of the propylene / α-olefin copolymer (B) is within the above range, the cold resistance and the low temperature characteristics are excellent.

The differential scanning calorimetry is performed as follows, for example. About 10.00 mg of sample is packed in a special aluminum pan, and the temperature is increased from 30 ° C. to 200 ° C. at 200 ° C./min using a DSCRDC220 manufactured by Seiko Instruments Inc. The temperature is lowered to −100 ° C. at 10 ° C./min, held at −100 ° C. for another 5 minutes, and then the glass transition temperature (Tg) is obtained from an endothermic curve when the temperature is raised at 10 ° C./min.

  Moreover, the molecular weight distribution (Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC of this propylene / α-olefin copolymer (B) is usually 3.5 or less, preferably Is 3.0 or less, more preferably 2.5 or less.

  The propylene / α-olefin copolymer (B) can be produced by a polymerization method using a crosslinked metallocene compound as a polymerization catalyst. Specifically, it can be produced by the method described in International Publication No. 2006/123759.

  The propylene / α-olefin copolymer (B) in the resin composition (C) according to the present invention is a total of 100 of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B). In the parts by weight, 0 to 50 parts by weight, preferably 0 to 50 parts by weight, particularly preferably 0 to 40 parts by weight are contained. When the content of the propylene / α-olefin copolymer (B) is in the above range, it is preferable from the viewpoint of heat resistance and mechanical strength. Further, in the case of imparting flexibility, it is usually contained in an amount of 5 to 50 parts by weight, preferably 5 to 45 parts by weight, and more preferably 5 to 40 parts by weight.

[Isotactic polypropylene]
The resin composition (C) comprising the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B) according to the present invention has a level that does not impair the object of the present invention. Isotactic polypropylene may be included as necessary. By including isotactic polypropylene, the mechanical strength of the resulting modified resin composition (D) is increased.

  As the isotactic polypropylene, commercially available ones can be used without particular limitation, but the isotactic pentad fraction measured by NMR method is 0.9 or more, preferably 0.95 or more. It is preferable to use polypropylene.

  Specifically, a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms other than propylene can be used. Examples of the α-olefin having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and 1-dodecene. , 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Among them, ethylene and an α-olefin having 4 to 10 carbon atoms are preferable. These α-olefins may form a random copolymer with propylene or a block copolymer. The structural unit derived from the α-olefin may be contained in the isotactic polypropylene at a ratio of 40 mol% or less, preferably 20 mol% or less.

  The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D 1238 of the isotactic polypropylene according to the present invention is usually 0.01 to 1000 g / 10 minutes, preferably 0.05 to The range is 500 g / 10 minutes.

The isotactic polypropylene is, for example, a Ziegler catalyst comprising (a) a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (b) an organoaluminum compound, and (c) an electron donor. It can manufacture by superposing | polymerizing using a system. It can also be produced similarly using a metallocene catalyst.

  The isotactic polypropylene is preferably a propylene / ethylene random copolymer or a propylene / ethylene block copolymer having a good balance of whitening resistance and impact resistance among polypropylene copolymers produced by a Ziegler catalyst.

[Other ingredients]
The resin composition (C) used in the present invention has a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, and an antifogging agent as required, as long as the object of the invention is not impaired. In addition, additives such as a nucleating agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, and an antioxidant may be blended.

[Resin composition (C)]
The resin composition (C) obtained as described above is excellent in moldability and heat resistance, and is also excellent in transparency, flexibility and scratch resistance.

  Here, “excellent in moldability” indicates that when molding such as injection, inflation, blow, foaming, hollow, vacuum compression, extrusion or pressing is performed, the time from solidification to solidification is short. When moldability is good, it is excellent in molding cycle performance, shape stability, long-term productivity, and formation of foamed cells.

Specifically, the time until solidification is a half crystallization time (t _1/2 ) obtained from isothermal crystallization measurement at 110 ° C. by a differential calorimeter (DSC) (hereinafter also referred to as “physical property (1)”). However, it is 1000 sec or less, preferably 500 sec or less. The resin composition (C) used in the present invention contains a specific syndiotactic propylene polymer (A) and a propylene / α-olefin copolymer (B), so that t _1/2 Has been dramatically improved, and can be molded by the same molding method as that of normally used isotactic polypropylene. Therefore, the resin composition (C) can be molded freely by irradiating with radiation such as electron beam or γ-ray, or by crosslinking with an organic peroxide and a crosslinking aid or a polyfunctional vinyl monomer. A crosslinked product can be formed efficiently while maintaining the degree.

The half crystallization time (t _1/2 ) obtained by isothermal crystallization measurement reached 50% heat when the area between the DSC calorimetric curve and the baseline in the isothermal crystallization process is the total heat. Time (see New Polymer Experiment Lecture 8 Physical Properties of Polymers (Kyoritsu Shuppan Co., Ltd.)). The half crystallization time (t _1/2 ) is measured as follows. That is, about 5.00 mg of a sample is packed in a special aluminum pan, heated to 320 ° C./min from 30 ° C. to 200 ° C. using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes. It was obtained from a DSC curve obtained by lowering the temperature from 320 ° C. to an isothermal crystallization temperature of 110 ° C. at 320 ° C./min and maintaining the temperature at 110 ° C. Here, the half crystallization time (t _1/2 ) was determined by assuming that the isothermal crystallization process start time at 110 ° C. (time when the temperature reached from 110 ° C. to 110 ° C.) t = 0. The resin composition (C) used in the present invention can determine t _1/2 as described above. However, when it is not crystallized at 110 ° C., it is conveniently measured at an isothermal crystallization temperature of 110 ° C. or less. The half crystallization time (t _1/2 ) is obtained from the extrapolated value.

The needle penetration temperature (hereinafter also referred to as “physical property (2)”) measured for the resin composition (C) used in the present invention is 145 ° C. or higher, preferably 147 ° C., more preferably 150 ° C. or higher. . When the needle penetration temperature is in the above range, the resulting modified resin composition is preferable because it has excellent heat resistance. The needle penetration temperature (sometimes referred to as the softening point determined by TMA measurement) can be measured as follows. That is, using a Seiko SS-120 or TA Instrument Q-400, a press sheet test piece having a thickness of 1 mm and a flat indenter of 1.8 mmφ at a heating rate of 5 ° C./min is 2 Kgf / cm. A pressure of ² was applied, and the needle penetration temperature (° C.) was determined from the TMA curve.

The internal haze (hereinafter also referred to as “physical properties (3)”) is 50% or less, more preferably 40% or less. The measuring method of internal haze is shown below.
The internal haze was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd., using a 1 mm thick press sheet test piece, and the average value was obtained twice.

  In each of the above tests, the test piece was heated in a press molding machine at 200 ° C. for 5 to 10 minutes, then molded in 10 to 2 minutes under 10 MPa pressure, and then cooled at 20 ° C. under 10 MPa pressure. It was obtained by preparing a sheet having a predetermined thickness.

In the case of the above resin composition (C), the half crystallization time (1) is preferably 1000 sec or less, more preferably 500 sec or less, and the needle penetration temperature (2) is preferably 145 ° C. or more, more preferably 147 ° C or higher,
Compounding the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B) obtained by the polymerization conditions and catalyst system described in WO 2006/123759 pamphlet in the above-mentioned ratio. Thus, a propylene-based polymer composition satisfying the physical properties (1) to (3) is obtained.

  When the physical properties (2) to (3) are in the above range, the resulting modified resin composition is preferable because it has excellent heat resistance and transparency, and the physical properties (1) to (3) are in the above range. The modified resin composition obtained is particularly preferable because it has excellent heat resistance, transparency and moldability.

[Modified resin composition (D)]
The modified resin composition (D) of the present invention comprises a syndiotactic propylene polymer (A), a propylene / α-olefin copolymer (B) and, if necessary, the above isotactic polypropylene and various additives. The resin composition (propylene polymer composition) (C) obtained is irradiated with radiation, or one or more selected from organic peroxides and, if necessary, a crosslinking aid and a polyfunctional vinyl monomer. Cross-linked using a compound.

  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 modified resin composition (D) crosslinked by a method of irradiating radiation such as an electron beam or γ-ray is more transparent, heat resistant and melted than a propylene polymer composition obtained only by ordinary melt kneading. Excellent viscosity characteristics, expansion ratio, and cell uniformity during foaming. Further, γ-ray irradiation has an antibacterial action when forming a crosslinked body.

  Furthermore, when performing radiation crosslinking, the syndiotactic propylene polymer (A), the propylene / α-olefin copolymer (B) and, if necessary, the above-mentioned isotactic polypropylene and various additives are added. In the resin composition (C) to be formed, a crosslinking aid or a polyfunctional vinyl monomer may be melt-kneaded in advance using an extruder, a roll or the like, if necessary.

Cross-linking aids or multifunctional vinyl monomers include sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine and trimethylol Cross-linking aids such as propane-N, N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, triallyl isocyanurate,
Examples include polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, 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 above-mentioned crosslinking aid or polyfunctional vinyl monomer is usually 0 to 10 parts by weight with respect to a total of 100 parts by weight of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B), Preferably it is used in an amount of 0.05 to 5 parts by weight.

  As the electron beam irradiation method, first use a mixer such as a Banbury mixer, syndiotactic propylene polymer (A), propylene / α-olefin copolymer (B), and if necessary, isotactic polypropylene and various additions Kneading agent and crosslinking aid or polyfunctional vinyl monomer at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and then kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes using rolls such as an open roll Thereafter, dispensing is performed to prepare a ribbon-shaped or sheet-shaped resin composition (C). Alternatively, the resin composition (C) is prepared by blending in a plastic bag or the like. The resin composition (C) thus prepared is molded into a desired shape by an extrusion molding machine, a calender roll, an injection molding machine or a press, or is extruded into a strand from the extruder and pulverized by a cutter or the like. The pellet is irradiated with an electron beam. Alternatively, powders such as a syndiotactic propylene polymer (A) and a propylene / α-olefin copolymer (B) impregnated with a compound such as a crosslinking aid or a polyfunctional vinyl monomer are directly irradiated with an electron beam. A resin composition (C) or a modified resin composition (D) may be prepared. Irradiation with an electron beam usually involves electrons having an energy of 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.

  γ-ray irradiation has a higher permeability to the resin composition (C) than electron beam irradiation. In particular, when the resin composition (C) is irradiated into pellets, only the surface portion is irradiated with the electron beam. Although the irradiation effect cannot be expected, the inside of the pellet can be sufficiently cross-linked by directly irradiating a small amount with γ rays. The γ-ray irradiation is performed so that the resin composition (C) has a γ-ray irradiation amount of usually 0.1 to 50 kGy, preferably 0.3 to 50 kGy.

  Next, the peroxide crosslinking method will be described in detail. In the peroxide crosslinking, the resin composition (C) 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.

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

  The organic peroxide is usually 0.001 to 10 parts by weight, preferably 0.001 parts by weight with respect to 100 parts by weight in total of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B). Used in an amount of 001-5 parts by weight.

  Sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine and trimethylol when crosslinking using organic peroxides Crosslinking aids such as propane-N, N'-m-phenylene dimaleimide, divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate Multifunctional methacrylate monomers and polyfunctional 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.

  The above-mentioned crosslinking aid or compound such as a polyfunctional vinyl monomer is usually 0.001 with respect to 100 parts by weight in total of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B). It is used in an amount of ˜50 parts by weight, preferably 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 method for crosslinking is not particularly limited, but can be carried out by dynamically heat-treating the resin composition (C) in the presence of a crosslinking agent and a crosslinking aid or a polyfunctional vinyl monomer. 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 modified resin composition (D) thus obtained by irradiation with an electron beam or γ-ray, or using an organic peroxide and a crosslinking aid or a polyfunctional vinyl monomer has a melt viscoelastic shear rate of 100 rad. The ratio of η ^* _{100 (initial)} before crosslinking and η ^* _{100 (vulc)} after crosslinking at / sec satisfies the following formula (Eq-1).
_{^{η * 100 (vulc) / η}} * 100 (initial) ≧ 0.85 ··· (Eq-1)
The above formula (Eq-1) indicates the degree of cleavage of the molecular chain. If the above formula is not satisfied, the molecular chain is severely cut, low molecular weight components are generated, and stickiness of the surface of the molded product is generated.

Furthermore, in the modified resin composition (D) of the present invention, the ratio of η ^* _{0.1 (initial)} before crosslinking and η ^* _{0.1 (vulc)} after crosslinking at a shear viscoelastic shear rate of 0.1 rad / sec is as follows. The equation (Eq-2) is also satisfied.
η ^* _{0.1 (vulc)} / η ^* _{0.1 (initial)} ≧ 1.10 (Eq-2)
The above formula (Eq-2) indicates the degree of crosslinking, and if the above formula is not satisfied, the foaming performance of the resulting modified resin composition (D) is lowered, the foam expansion ratio of the foam is low, or the foam cell Degassing occurs and becomes non-uniform. Furthermore, in film forming, the neck-in at the time of film forming is large and the width of the film is narrowed. Also, the increase in heat resistance is insufficient.

The measurement of melt viscoelasticity is performed, for example, as follows. As an apparatus, MCR-301 manufactured by Arton Co., Ltd. is used, a sample is sandwiched between 2.5 cm cone plates at a measurement temperature of 230 ° C., and the shear rate is changed from 0.01 rad / sec to 500 rad / sec. The η ^* of the resin composition after crosslinking was measured.

  The modified resin composition (D) of the present invention is characterized in that the residual ratio in a Soxhlet extraction operation using boiling xylene is 10 wt% or less, preferably 9.5 wt% or less, more preferably 9 wt% or less. If it exceeds this range, the strength of the modified resin composition (D) decreases. Further, when used in a film or the like, the residual ratio is 1.0 wt% or less, preferably 0.95 wt% or less, and more preferably 0.9 wt% or less. When this range is exceeded, surface irregularities occur due to the generation of gel, and the film appearance deteriorates or the impact resistance of the film decreases.

  Thus, the modified resin composition (D) obtained by irradiating with an electron beam or γ-ray, or by crosslinking with an organic peroxide and a crosslinking aid or a polyfunctional vinyl monomer, Compared with the resin composition (C), the decrease in viscosity in the high shear region is small, the increase in viscosity in the low shear region is large, transparency, heat resistance, wear resistance, dimensional stability, expansion ratio, and foam cell Good uniformity and thermal stability.

[Modified resin composition (E)]
The modified resin composition (E) of the present invention comprises 1 to 100 parts by weight of the resin composition (D), 0 to 99 parts by weight of a syndiotactic propylene polymer (A), and a propylene / α-olefin copolymer. (B) 0 to 50 parts by weight (however, the sum of (D), (A) and (B) is 100 parts by weight), preferably 3 to 100 parts by weight of the resin composition (D). Part, syndiotactic propylene polymer (A) 0 to 97 parts by weight, and propylene / α-olefin copolymer (B) 0 to 50 parts by weight, particularly preferably the resin composition (D) 5 -100 parts by weight, syndiotactic propylene polymer (A) 0 to 95 parts by weight, and propylene / α-olefin copolymer (B) 0 to 30 parts by weight. When the composition is in the above range, the heat resistance, mechanical strength, expansion ratio and uniformity of the expanded cells are good.

The modified resin composition (E) of the present invention is obtained by syndiotactic pentad fraction (rrrr fraction), intrinsic viscosity [η], and differential scanning calorimeter (DSC) measurement measured by ¹³ C-NMR. melting point (Tm), heat of fusion ([Delta] H), MFR and [eta] of relations, personnel syndiotactic triad fraction measured by ¹³ C-NMR (rr fraction), the molecular weight distribution (Mw / Mn), differential scanning calorimetry Regarding the half crystallization time (t _1/2 ) in the isothermal crystallization at 110 ° C., the needle penetration temperature, and the internal haze value of the press sheet having a thickness of 1 mm obtained by a total (DSC), the above-described modified resin composition (D ).

In the modified resin composition (E) of the present invention, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, and an anti-fogging agent are added to the modified resin composition (E) as necessary. Further, additives such as a nucleating agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent and an antioxidant may be blended.
The modified resin composition (E) of the present invention can be produced by arbitrarily adopting a known method, and can be obtained by melting and kneading all together using an extruder, a kneader or the like.

[Molded body]
The modified resin composition (D) and the modified resin composition (E) of the present invention can be widely used for conventionally known polyolefin applications. In particular, sheets, unstretched or stretched films, foams, pipes, wire coatings, It can be formed into filaments and other shaped articles.

  Specifically, the molded body can be obtained by a known thermoforming method such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. A molded body is mentioned. Hereinafter, the molded body will be described with several examples.

  When the molded body according to the present invention is, for example, an extrusion molded body or an injection molded body, the shape and the type of product are not particularly limited, but for example, a sheet, a film (unstretched), a pipe, a hose, a wire coating, a filament, and the like In particular, sheets, skin materials, automobile inner and outer layer materials, building materials, and the like are preferable. The obtained molded body is excellent in transparency, transparency, heat resistance, wear resistance and dimensional stability.

  When performing extrusion molding or injection molding, conventionally known extrusion apparatuses, injection apparatuses, and molding conditions can be employed. Further, at the time of extrusion molding, a crosslinking treatment can also be performed with an electron beam or γ-ray.

  When the molded body according to the present invention is a foam, the method for producing the foam is not particularly limited, but the modified resin composition (D) or the modified resin composition (E) is extrusion molded or injection molded. As a result, a foam-molded article having a desired shape can be obtained. In extrusion foam molding which is one of the molding methods suitable for this resin, the modified resin composition (D) or the modified resin composition (E) is supplied to a uniaxial or biaxial extruder and melted. Producing foam by supplying gas or liquid inert gas from the center of the cylinder of the machine, mixing them well, and extruding molten resin mixed with inert gas from the end of the extruder into the atmosphere Can do. In addition, an unfoamed molded body is once molded from a propylene-based polymer composition in which a foaming agent has been added in advance to the modified resin composition (D) or the modified resin composition (E) of the present invention, and then the temperature is raised to foam. A method of changing to a molded body may be employed, or a method of directly obtaining a foamed molded body from the resin composition (C) to which a foaming agent has been added may be used. The molded body is not limited to the two types of molding methods described above, and can be shaped from a sheet shape to a filament shape, a net shape, a strand shape, or the like depending on the shape of the die attached to the tip of the extruder.

The foaming agent is appropriately selected from chemical foaming agents and gas foaming agents based on the molding method and molding temperature of the foamed molded product according to the present invention.
Chemical blowing agents include azo compounds such as azodicarboxylic amide and azobisisobutyronitrile, hydrazide compounds such as benzosulfonyl hydrazide, toluenesulfonyl hydrazide and p, p'-oxybis (benzenesulfonyl hydrazide), dinitrosopentamethylene Examples thereof include nitroso compounds such as tetramine, and alkali metal hydrogen carbonates such as sodium hydrogen carbonate and sodium carbonate, alkali metal carbonates or a mixture thereof. It generates gas. Moreover, you may use a foaming adjuvant with these foaming agents as needed. Examples of the foaming aid include organic acids such as zinc oxide, zinc stearate, calcium stearate, salicylic acid, phthalic acid, oxalic acid and citric acid.

Examples of gas blowing agents include halogenated hydrocarbons such as carbon dioxide and difluorodichloromethane, and hydrocarbons such as butane, pentane, hexane, cyclobutane and cyclohexane, which are themselves gases under molding conditions. Contributes to foam molding. One type of foaming agent may be used, or a plurality of types may be used in combination.

Next, an example of a method for producing a highly foamed molded product will be described. First, two extruders are prepared, a mixing unit (adapter) including a static mixer is provided between the two extruders, and the respective extruders are connected. Next, the modified resin composition (crosslinked propylene polymer) (D) or the modified resin composition (propylene polymer composition) (E) is supplied from the hopper of the first extruder, and melt kneading is advanced. On the other hand, carbon dioxide gas is supplied to an accumulator prepared separately, and is preferably set to a temperature higher than the critical temperature of carbon dioxide gas and higher than a critical pressure. Carbon dioxide gas whose temperature and pressure are adjusted in this way is supplied from the center of the cylinder of the first extruder, and the carbon dioxide gas is uniformly mixed with the molten resin in the extruder. The amount of carbon dioxide supplied is appropriately adjusted within the range of 0.1 to 30 parts by weight per 100 parts by weight of the resin. Next, the molten mixture is passed through an adapter to further improve the uniform mixing of the resin and carbon dioxide gas, and then transferred to the second extruder while maintaining the pressurized state. The resin temperature is gradually lowered and suitable for foam molding. The temperature. Then, the foam can be continuously produced by extruding the molten mixture into the atmosphere from a die provided at the tip of the second extruder and taking it out while cooling.
The expansion ratio of the foamed molded product of the present invention is usually 0.5 to 20 times, preferably 0.5 to 18 times, and more preferably 1 to 10 times.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the examples, each physical property was measured as follows.

Physical property measurement method [Intrinsic viscosity [η]]
It measured at 135 degreeC using the decalin solvent. That is, about 20 mg of polymer powder, pellets or resin mass is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η _sp is measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η] = lim (η _sp / C) (C → 0)

[Amount of soluble part of n-decane]
200 ml of n-decane was added to 5 g of a sample of syndiotactic propylene polymer (A), and the polymer was dissolved by heating at 145 ° C. for 30 minutes. The resulting solution was allowed to cool to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (n-decane insoluble part) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate was filtered off from acetone and then dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following equation.
n-decane soluble part amount (wt%) = [precipitate weight / sample weight] × 100

[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Use dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, move at 1.0 ml / min, set the sample concentration to 15 mg / 10 mL, and set the sample injection volume to 500 μL A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Ethylene, propylene, α-olefin content in polymer]
Quantification of ethylene, propylene, and α-olefin content was measured as follows using a JNM GX-400 NMR measuring apparatus manufactured by JEOL Ltd. A 0.35 g sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. The solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is placed in an NMR tube having an inner diameter of 10 mm, and ¹³ C-NMR measurement is performed at 120 ° C. The number of integration is 8,000 times or more. The composition of ethylene, propylene, and α-olefin was quantified by the obtained ¹³ C-NMR spectrum.

[Melting point (Tm) of component (A), heat of fusion (ΔH)]
Using DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg was heated to 200 ° C., held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peaks.

When two peaks are observed in the propylene polymer described in the examples, the low temperature side peak is Tm ₁ and the high temperature side peak is Tm ₂ . Incidentally, Tm is defined by the appended claims 1 (a) is a Tm _2.

[Stereoregularity rrrr, rr, mmmm]
Stereoregularity (rrrr, rr, mmmm) was calculated from ¹³ C-NMR spectrum.
[Semi-isothermal crystallization time (t _1/2 )]
About 5 mg of sample is packed in a special aluminum pan, heated to 320 ° C./min from 30 ° C. to 200 ° C. using DSCPyris 1 or DSC 7 manufactured by Perkin Elmer, held at 200 ° C. for 5 min, and then isothermal crystal from 200 ° C. the to a temperature 110 ° C. and cooled at 320 ° C. / min, it was determined half-crystallization time (t _1/2) from the DSC curve obtained by holding the respective isothermal crystallization temperature. The half crystallization time (t _1/2 ) was obtained by setting the isothermal crystallization process start time (time when the isothermal crystallization temperature was reached from 200 ° C.) as t = 0. When not crystallizing at an isothermal crystallization temperature, for example, 110 ° C., for convenience, several measurements are performed at an isothermal crystallization temperature of 110 ° C. or less, and from the extrapolated value, the half crystallization time (t _1/2 ) is calculated. Asked.

[Glass point transfer (Tg) of component (B), melting point (Tm)]
Using a DSC manufactured by Seiko Instruments Inc., about 5 mg of sample was packed in a measurement aluminum pan, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 min, and then −150 ° C. at 10 ° C./min. Then, the temperature was obtained from an endothermic curve that was raised to 200 ° C. at 10 ° C./min.

[MFR]
The MFR of the syndiotactic propylene polymer (A) and the propylene / α-olefin copolymer (B) was measured at 230 ° C. under a load of 2.16 kg according to JIS K-6721.

[density]
Density measurement was performed according to ASTM D1505.
[Electron beam crosslinking]
Using an electron beam irradiation facility owned by Japan Electron Beam Irradiation Service Co., Ltd., the pellet was irradiated with an electron beam under irradiation conditions of an acceleration voltage of 2 MeV and an irradiation dose of 20 to 60 kGy to obtain an electron beam cross-linked propylene polymer. About the irradiation dose, the film of the oxidized cellulose triacetate was stuck on the upper and lower sides of the polyethylene bag which packed the pellet, the light absorbency in 280 nm of the film was measured after the irradiation test, and the irradiation dose was calculated | required. Irradiation dose is 20-60 both above and below the bag.
kGy, and the sample was uniformly irradiated with an electron beam.

[Viscoelasticity measurement]
Using MCR-301 manufactured by Arton, sandwich a 2 mm thick press sheet into a cone plate with a measurement temperature of 230 ° C. and 2.5 cm, and push the sample to a distance between caps of 0.056 mm. The measurement was carried out while changing to 500 / sec.

[Boiling xylene extraction residual rate]
Soxhlet extraction with boiling xylene was performed for 3 hours, filtered through a 325 mesh stainless steel mesh, the mesh was dried under reduced pressure at 110 ° C. for 1 hour, and calculated from the residual amount on the mesh.

[Internal haze]
Using a hydraulic heat press machine manufactured by Kondo Metal Industry Co., Ltd. set at 200 ° C., pressurizing for 4 minutes at a residual heat of 4 minutes and 10 MPa, and then using another hydraulic heat press machine manufactured by Kondo Metal Industry Co., Ltd. set at 20 ° C. And cooled for about 5 minutes to form a 1 mm sheet. A 5 mm thick brass plate was used as the thermal plate. Using the sample prepared by the above method, measurement was performed with a digital turbidity meter “NHD-20D” manufactured by Nippon Denshoku Industries Co., Ltd.

[Foaming ratio]
The specific gravity of the foam is measured with a submersible density meter, and the modified resin composition (crosslinked propylene polymer) (D) or the modified resin composition (propylene polymer composition) (E) as the raw material before foaming ).

Catalyst synthesis example [Synthesis Example 1]
Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was produced by the method described in Synthesis Example 3 of Japanese Patent Application Laid-Open No. 2004-189666.

[Synthesis Example 2]
Di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was produced by the method described in Synthesis Example 3 of JP-A-2007-321102.

[Synthesis Example 3]
Isopropylidene (3-tert-butyl-5-ethylcyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride is produced by the method described in Synthesis Example 2 of WO 06/025540. Then, a slurry of the supported catalyst was produced by the method described in Synthesis Example 2 of the same publication.

Polymerization Example <Polymerization Example 1> Production of Syndiotactic Propylene Polymer (A-1) 250 ml of toluene was charged into a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, and propylene was charged at 150 L / hour and hydrogen was added at a rate of 0.1. It was circulated in an amount of 3 L / hour and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branch flask with sufficient nitrogen substitution, and 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), followed by dibenzylmethylene (cyclopentadienyl). ) 5.0 μmol of a toluene solution of (3,6-di-tert-butylfluorenyl) zirconium dichloride was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene and hydrogen had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 L / hour and hydrogen was continuously supplied at a rate of 0.3 L / hour. Polymerization was carried out at 25 ° C. for 45 minutes under normal pressure, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 5.77 g of polymer was obtained. The polymerization activity is 1.25 kg-PP / mmol-Zr · hr. [Η] of the obtained polymer is 1.5 dl / g, Tm ₁ = 152 ° C., Tm ₂ = 158 ° C., and rrrr = 93. It was 5%, and Mw / Mn = 1.9. This operation was repeated to obtain the required amount of polymer and used in the examples.
The results are shown in Table 1.

Syndiotactic propylene polymer (A-2)
Syndiotactic polypropylene (trade name: FINAPLAS 1471, MFR = 5.0 g / 10 min) manufactured by Total was used in the comparative example.

<Polymerization Example 2> Production of Propylene / α-Olefin Copolymer (B-1) After charging 1834 ml of dry hexane and triisobutylaluminum (1.0 mmol) to a 4000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature. The internal temperature of the polymerization apparatus was raised to 70 ° C., and the pressure in the system was increased to 0.66 MPa with propylene, and then the system pressure was adjusted to 1.36 MPa with ethylene. Next, 0.001 mmol of di (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum are brought into contact. The toluene solution was added to the polymerization vessel and polymerized for 15 minutes while maintaining the internal temperature at 70 ° C. and the internal pressure at 1.36 MPa with ethylene, 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 polymer was 105 g, the MFR was 0.7 (g / 10 min), and [η] = 2.5 (dL / g) measured in decalin at 135 ° C. The rr ₁ value was 78%. This operation was repeated to obtain the required amount of polymer and used in the examples.
The results are shown in Table 1.

Isotactic propylene polymer (F-1)
Isotactic polypropylene (trade name: F-107BV, MFR = 7.0 g / 10 min) manufactured by Prime Polymer Co., Ltd. was used in the comparative example.

<Polymerization Example 3> Production of Isotactic Propylene Polymer (F-2) A magnetic stirrer chip was placed in a 50 ml branch flask thoroughly purged with nitrogen, and 341 mg of the supported catalyst slurry prepared in Synthesis Example 3 above. And 1.0 mmol of a hexane solution of triisobutylaluminum (Al = 1.0 M) and 5.0 ml of dehydrated hexane were added, and the mixture was introduced into a SUS autoclave having an internal volume of 2000 ml which was sufficiently purged with nitrogen. Thereafter, 500 g of liquid propylene and 0.1 NL of hydrogen were charged and polymerization was carried out at 70 ° C. for 40 minutes, and then the autoclave was cooled and purged with propylene and hydrogen to stop the polymerization. The polymer was dried under reduced pressure at 80 ° C. for 10 hours. The obtained polymer was 75.5 g of isotactic polypropylene, the polymerization activity was 158.7 kg-PP / mmol-Zr · hr, [η] = 2.1 dl / g, Mw / Mn = 2.4, mmmm = 95.3% and Tm = 158.1 ° C. This operation was repeated to obtain the required amount of polymer and used in the examples.
The results are shown in Table 1.

[Example 1]
The polymer (A-1) obtained in Polymerization Example 1 was irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy to obtain a crosslinked propylene polymer (D-1).
Table 2 shows the physical properties of the obtained polymer.

[Example 2]
An accelerating voltage was applied to pellets obtained by previously melt-kneading 0.5 parts by weight of triallyl isocyanurate (trade name: Tyke) manufactured by Nippon Kasei Co. An electron beam was irradiated under conditions of 2 MeV and an irradiation dose of 60 kGy to obtain a crosslinked propylene polymer (D-2).
Table 2 shows the physical properties of the obtained polymer.

Example 3
The pellet obtained by melting and kneading 1.0 part by weight of the polymer (A-1) obtained in Polymerization Example 1 in advance with 1.0 part by weight was irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy, and crosslinked propylene. A system polymer (D-3) was obtained.
Table 2 shows the physical properties of the obtained polymer.
The measurement result of melt viscoelasticity is shown in FIG.

Example 4
1.0 part by weight of Thaik was added to 100 parts by weight of the composition (C) composed of 85 wt% of the polymer (A-1) obtained in Polymerization Example 1 and 15 wt% of the polymer (B-1) obtained in Polymerization Example 2. The pellets melted and kneaded in advance were irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy to obtain a crosslinked propylene-based polymer (D-4).
Table 2 shows the physical properties of the obtained polymer.

Example 5
1.0 parts by weight of Thai is obtained with respect to 100 parts by weight of the composition (C) composed of 70% by weight of the polymer (A-1) obtained in Polymerization Example 1 and 30% by weight of the polymer (B-1) obtained in Polymerization Example 2. The pellets melted and kneaded in advance were irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy to obtain a crosslinked propylene polymer (D-5).
Table 2 shows the physical properties of the obtained polymer.

[Comparative Example 1]
A pellet obtained by previously melting and kneading 1.0 part by weight of 100 parts by weight of polymer (A-2) was irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy to produce a crosslinked propylene polymer (G-1 )
Table 3 shows the physical properties of the obtained polymer.

[Comparative Example 2]
A pellet obtained by previously melting and kneading 1.0 part by weight of Thailand with respect to 100 parts by weight of the polymer (F-1) was irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy, and a crosslinked propylene polymer (G-2 )
Table 3 shows the physical properties of the obtained polymer.
The measurement result of melt viscoelasticity is shown in FIG.

[Comparative Example 3]
The polymer (F-2) obtained in Polymerization Example 3 was irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy to obtain a crosslinked propylene polymer (G-3).
Table 3 shows the physical properties of the obtained polymer.

[Comparative Example 4]
To 100 parts by weight of the polymer (F-2) obtained in Polymerization Example 3, 1.0 part by weight of Thailand was melt-kneaded in advance and irradiated with an electron beam under the conditions of an acceleration voltage of 2 MeV and an irradiation dose of 40 kGy. A propylene polymer (G-4) was obtained.
Table 3 shows the physical properties of the obtained polymer.

Example 6
2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 (trade name: manufactured by NOF Corporation) with respect to 100 parts by weight of the polymer (A-1) obtained in Polymerization Example 1. 0.025 part by weight of perhexine 25B) and 0.5 part by weight of divinylbenzene manufactured by Wako Pure Chemical Industries, Ltd. were melt-kneaded to obtain a crosslinked propylene polymer (D-6).
Table 4 shows the physical properties of the obtained polymer.

Example 7
To 100 parts by weight of the polymer (A-1) obtained in Polymerization Example 1, 0.025 part by weight of perhexine 25B and 1.0 part by weight of divinylbenzene are melt-kneaded to obtain a crosslinked propylene-based polymer (D-7). Obtained.
Table 4 shows the physical properties of the obtained polymer.

Example 8
With respect to 100 parts by weight of the polymer (A-1) obtained in Polymerization Example 1, 0.025 part by weight of perhexine 25B and 1.0 part by weight of Thailand are melt-kneaded to obtain a crosslinked propylene polymer (D-8). It was.
Table 4 shows the physical properties of the obtained polymer.

Example 9
For 100 parts by weight of the composition (C) composed of 70 wt% of the polymer (A-1) obtained in Polymerization Example 1 and 30 wt% of the polymer (B-1) obtained in Polymerization Example 2, 0.025 wt. And 0.5 parts by weight of divinylbenzene were melt-kneaded to obtain a crosslinked propylene polymer (D-9).
Table 4 shows the physical properties of the obtained polymer.

[Comparative Example 5]
With respect to 100 parts by weight of the polymer (A-2), 0.025 part by weight of perhexine 25B and 0.5 part by weight of divinylbenzene were melt-kneaded to obtain a crosslinked propylene polymer (H-5).
Table 5 shows the physical properties of the polymer obtained.

[Comparative Example 6]
With respect to 100 parts by weight of the polymer (F-1), 0.025 part by weight of perhexine 25B and 0.5 part by weight of divinylbenzene were melt-kneaded to obtain a crosslinked propylene polymer (H-6).
Table 5 shows the physical properties of the polymer obtained.

[Comparative Example 7]
With respect to 100 parts by weight of the polymer (F-1), 0.025 part by weight of perhexine 25B and 1.0 part by weight of divinylbenzene were melt-kneaded to obtain a crosslinked propylene polymer (H-7).
Table 5 shows the physical properties of the polymer obtained.

[Comparative Example 8]
With respect to 100 parts by weight of the polymer (F-2) obtained in Polymerization Example 3, 0.025 part by weight of perhexine 25B and 0.5 part by weight of divinylbenzene are melt-kneaded to obtain a crosslinked propylene polymer (H-8). Obtained.
Table 5 shows the physical properties of the polymer obtained.

Example 10
100 parts by weight of the polymer (D-3) obtained in Example 3 was blended with 1.5 parts by weight of sodium bicarbonate and 1.5 parts by weight of citric acid, and equipped with a nozzle having a diameter of 5 mm at the tip of the single screw extruder. Then, strand extrusion foam molding was performed under the temperature conditions of a cylinder temperature of 170 ° C., a cylinder head temperature of 220 ° C., and a nozzle temperature of 150 ° C.
Table 6 shows the expansion ratio of the obtained foam.

Example 11
100 parts by weight of the polymer (D-4) obtained in Example 4 was blended with 1.5 parts by weight of sodium bicarbonate and 1.5 parts by weight of citric acid, and subjected to strand extrusion foam molding under the same conditions as in Example 10. did.
Table 6 shows the expansion ratio of the obtained foam.

Example 12
Propylene polymer composition (modified resin composition) (E-1) comprising 80 wt% of the polymer (D-3) obtained in Example 3 and 20 wt% of the polymer (A-1) obtained in Polymerization Example 1 To 100 parts by weight, 1.5 parts by weight of sodium bicarbonate and 1.5 parts by weight of citric acid were blended, and strand extrusion foam molding was carried out under the same conditions as in Example 10.
Table 6 shows the expansion ratio of the obtained foam.

Example 13
100 parts by weight of the polymer (D-7) obtained in Example 7 was blended with 1.5 parts by weight of sodium bicarbonate and 1.5 parts by weight of citric acid, and subjected to strand extrusion foam molding under the same conditions as in Example 10. did.
Table 6 shows the expansion ratio of the obtained foam.

[Comparative Example 9]
100 parts by weight of the polymer (G-2) obtained in Comparative Example 2 was blended with 1.5 parts by weight of sodium bicarbonate and 1.5 parts by weight of citric acid, and subjected to strand extrusion foam molding under the same conditions as in Example 10. did.
Table 7 shows the expansion ratio of the obtained foam.

[Comparative Example 10]
100 parts by weight of the polymer (H-7) obtained in Comparative Example 7 was blended with 1.5 parts by weight of sodium bicarbonate and 1.5 parts by weight of citric acid, and subjected to strand extrusion foam molding under the same conditions as in Example 10. did.
Table 7 shows the expansion ratio of the obtained foam.

[Comparative Example 11]
1.5 weight of baking soda with respect to 100 weight part of the propylene polymer composition composed of 80 wt% of the polymer (G-2) obtained in Comparative Example 2 and 20 wt% of the polymer (A-1) obtained in Polymerization Example 1 Part and 1.5 parts by weight of citric acid were blended and subjected to strand extrusion foam molding under the same conditions as in Example 10.

  Table 7 shows the expansion ratio of the obtained foam.

FIG. 1 is a diagram showing measurement results of melt viscoelasticity of a crosslinked propylene-based polymer (D-3) and a syndiotactic propylene polymer (A-1). FIG. 2 is a graph showing the measurement results of the melt viscoelasticity of the crosslinked propylene polymer (G-2) and the isotactic propylene polymer (F-1).

Claims (10)

100-50 parts by weight of syndiotactic propylene polymer (A),
Crosslinking a resin composition (C) comprising 0 to 50 parts by weight of a propylene / α-olefin copolymer (B) (provided that the total of (A) and (B) is 100 parts by weight) A modified resin composition obtained by
The ratio of η ^* _{100 (initial)} before cross-linking and η ^* _{100 (vulc)} after cross-linking satisfies the equation (Eq-1) at a shear rate of 100 rad / sec in melt viscoelasticity,
The ratio of η ^* _{0.1 (initial)} before cross-linking and η ^* _{0.1 (vulc)} after cross-linking satisfies the formula (Eq-2) at a shear rate of 0.1 rad / sec in melt viscoelasticity,
η ^* _{100 (vulc)} / η ^* _{100 (initial)} ≧ 0.85 (Eq-1)
η ^* _{0.1 (vulc)} / η ^* _{0.1 (initial)} ≧ 1.10 (Eq-2)
The boiling xylene extraction residual rate is 10 wt% or less,
The modified resin composition is characterized in that the syndiotactic propylene polymer (A) satisfies the following requirement (a) and the propylene / α-olefin copolymer (B) satisfies the following requirement (b). object.
(A) A syndiotactic pentad fraction (rrrr fraction) measured by ¹³ C-NMR is 85% or more, a melting point (Tm) determined by DSC is 145 ° C. or more, and derived from propylene The unit is contained in an amount exceeding 90 mol% (provided that the total amount of the structural units in the syndiotactic propylene polymer (A) is 100 mol%).
(B) Containing structural units derived from propylene in an amount of 55 to 90 mol%, and 10 to 45 mol% of structural units derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) (provided that Contained in an amount of 100 mol% of the structural unit derived from propylene and the structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) and conforming to JIS K-6721 The MFR measured at 230 ° C. under a 2.16 kg load is in the range of 0.01 to 100 g / 10 minutes, and satisfies at least one of the following requirements (b-1) and (b-2) .
(B-1) The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more.
(B-2) The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) are expressed by the following relational expression (Eq-3) Meet.
1.50 × MFR ^(-0.20) ≦ [η] ≦ 2.65 × MFR ^(-0.20) (Eq-3)   The crosslinking is carried out in the presence of an organic peroxide (P) and, if necessary, one or more compounds selected from a crosslinking aid (Q) and a multifunctional vinyl monomer (R). 1. The modified resin composition according to 1.   The modified resin composition according to claim 1, which is crosslinked by irradiation with radiation. The resin composition (C) is
95-50 parts by weight of syndiotactic propylene polymer (A),
The propylene / α-olefin copolymer (B) is contained in an amount of 5 to 50 parts by weight (provided that the total of (A) and (B) is 100 parts by weight). 4. The modified resin composition according to any one of 3 above. 1 to 100 parts by weight of the modified resin composition according to any one of claims 1 to 4,
Syndiotactic propylene polymer (A) 0 to 99 parts by weight;
The propylene / α-olefin copolymer (B) is 0 to 50 parts by weight (provided that the total of the modified resin composition and (A) and (B) is 100 parts by weight). Modified resin composition. 6. The half crystallization time (t1 _{/ 2} ) in isothermal crystallization at 110 [deg.] C. determined by a differential scanning calorimeter (DSC) is 1000 sec or less. Modified resin composition.   The modified resin composition according to claim 1, wherein the needle penetration temperature is 145 ° C. or higher.   The modified resin composition according to any one of claims 1 to 7, wherein an internal haze value of a press sheet having a thickness of 1 mm is 50% or less.   The intrinsic viscosity [η] of the syndiotactic propylene polymer (A) measured in decalin at 135 ° C. is in the range of 0.1 to 10 dL / g, and the heat of fusion determined by differential scanning calorimetry (DSC) ( (DELTA) H) is 40 mJ / mg or more, The modified resin composition in any one of Claims 1-8 characterized by the above-mentioned.   The modified resin composition according to any one of claims 1 to 9, wherein a molecular weight distribution (Mw / Mn) obtained by GPC of the propylene / α-olefin polymer (B) is 3.5 or less. .

Images