JP4808169B2 - Laminated glass interlayer and laminated glass - Google Patents

Description

  The present invention relates to an interlayer film for laminated glass used for a window glass of a building, an automobile windshield, a side glass, and the like, and a laminated glass using the interlayer film, and more specifically, a layer containing a specific propylene-based polymer. The present invention relates to an interlayer film for laminated glass having the above and a laminated glass using the interlayer film.

  The demand for laminated glass for building glass and other buildings is expanding from the standpoint of preventing the shattering of broken pieces and ensuring wind resistance when single glass cannot be used. Conventionally, polyvinyl butyral has been widely used as an interlayer film for laminated glass. However, a laminated glass having polyvinyl butyral as an interlayer film has room for improvement in terms of durability of appearance when used outdoors or for long periods of use indoors. That is, when a laminated glass having polyvinyl butyral as an intermediate film is used outdoors or used indoors for a long time, the peripheral portion of the glass is whitened.

Patent Document 1 proposes a method of wrapping the peripheral surface portion of a laminated glass laminate with a sealing material to suppress whitening of the peripheral portion due to moisture permeation and improving durability in outdoor or long-term use. However, labor and raw material costs are required to wrap the peripheral surface portion with the sealing material.
Patent Document 2 discloses a method in which polyvinyl butyral and polyethylene are laminated to form a laminated glass. However, polyethylene does not have properties such as vibration damping properties and is inferior in performance as a laminated glass.
JP-A-7-157344 JP-A-8-73244

  The problem to be solved by the present invention is to provide a laminated glass having less deterioration in appearance and maintaining the performance as a laminated glass without curing the peripheral surface of the laminated glass with an adhesive tape. It is to provide an interlayer film for laminated glass, and a laminated glass using the interlayer film for laminated glass.

The interlayer film for laminated glass of the present invention is
30 to 100 mol% of the structural unit (a) derived from propylene and 70 to 0 mol% of the structural unit (b) derived from an α-olefin having 2 to 20 carbon atoms excluding propylene [(a) And (b) is 100 mol%. ] A layer obtained from the propylene polymer (A) having a melting point measured by DSC of 90 ° C. or lower, or a melting point not observed, or the composition (X) containing the propylene polymer (A) It is characterized by having.

  In the interlayer film for laminated glass of the present invention, the composition (X) containing the propylene polymer (A) contains a propylene polymer (B) having a melting point measured by DSC of 100 ° C. or higher. It is preferable.

  In the interlayer film for laminated glass of the present invention, the composition (X) containing the propylene polymer (A) contains 100 to 40 parts by weight of the propylene polymer (A), and the propylene polymer. 0 to 60 parts by weight of the polymer (B) [the total of (A) and (B) is 100 parts by weight. It is preferable that the composition contains.

  The composition (X) containing the propylene polymer (A) is 99 to 40 parts by weight of the propylene polymer (A) and 1 to 60 parts by weight of the propylene polymer (B). [The total of (A) and (B) is 100 parts by weight. It is preferable that the composition contains.

  In the interlayer film for laminated glass of the present invention, the propylene polymer (A) contains 1 to 40 mol% of a structural unit derived from an α-olefin having 4 to 20 carbon atoms (wherein the structural unit and carbon derived from propylene). A propylene / co-α-olefin copolymer having 4 to 20 carbon atoms (A1) may be contained, and the propylene The polymer (A) contains 1 to 25 mol% of structural units derived from ethylene and 1 to 35 mol% of structural units derived from α-olefins having 4 to 20 carbon atoms (wherein the structural units derived from propylene and ethylene Propylene / ethylene / C4-C20 α-olefin copolymer (A2) containing 100% by mole of the structural unit derived from the α-olefin derived from C4-20 In In may.

The propylene polymer (A), (A1) or (A2) has an MFR measured at 230 ° C. and a 2.16 kg load in accordance with JIS K-6721 in the range of 0.01 to 100 g / 10 min. And satisfying any one or more of the following requirements (a-1) or (a-2);
(A-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more,
(A-2): The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression:
1.50 × MFR ^(−0.20 ) ≦ [η] ≦ 2.65 × MFR ^(−0.20)

  In the interlayer film for laminated glass of the present invention, when the composition containing the propylene polymer (A) contains the propylene polymer (B), (B) is about 23 ° C. n-decane insoluble part. More preferably, the isotactic pentad fraction measured by NMR method is 0.90 or more, preferably 0.95 or more.

  In the interlayer film for laminated glass of the present invention, the composition (X) containing the propylene polymer (A) is changed from the ethylene / α-olefin copolymer (C) to the propylene polymer (A). And 1 to 500 parts by weight with respect to a total of 100 parts by weight of the propylene polymer (B) as an optional component.

  In the composition (X), the ethylene / polar monomer copolymer (D) is added to a total of 100 parts by weight of the propylene polymer (A) and the propylene polymer (B) as an optional component. 1 to 500 parts by weight.

  In the interlayer film for laminated glass of the present invention, at least a part of the propylene polymer (A) is selected from the group consisting of a silane compound, a titanium compound, an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It can be graft-modified with more than one compound.

  In the interlayer film for laminated glass of the present invention, at least a part of the composition (X) containing the propylene polymer (A) is an anhydrous silane compound, titanium compound, unsaturated carboxylic acid and unsaturated carboxylic acid. It may be graft-modified with one or more compounds selected from the group consisting of products.

  In the interlayer film for laminated glass of the present invention, the composition (X) contains the radical generator (G), the propylene polymer (A), the optional propylene polymer (B), and the optional component. Composition containing 0.001 to 10 parts by weight with respect to a total of 100 parts by weight of the ethylene / α-olefin copolymer (C) as a component and the ethylene / polar monomer copolymer (D) as an optional component Can be a thing.

  In the interlayer film for laminated glass of the present invention, the composition (X) includes the propylene polymer (A), the propylene polymer (B) as an optional component, and the ethylene / α- as an optional component. The component containing the olefin copolymer (C) and the optional ethylene / polar monomer copolymer (D) is 100 parts by weight in total of (A) + (B) + (C) + (D). It is preferably obtained by heat treatment in the presence of 0.001 to 10 parts by weight of the radical generator (G).

  The interlayer film for laminated glass of the present invention can have a layer obtained from the propylene polymer (A) or the composition (X) and a layer made of plasticized polyvinyl butyral.

  The laminated glass of the present invention is characterized by using any of the interlayer films for laminated glass.

  The interlayer film for laminated glass according to the present invention contains a specific propylene polymer (A) having a melting point of 90 ° C. or less as measured by DSC or a melting point not observed, or the propylene polymer (A). Since it has a layer obtained from the composition (X), the laminated glass formed using the interlayer film for laminated glass has a durable appearance even without curing the peripheral surface of the laminated glass with an adhesive tape. In addition, a laminated glass having excellent performance (eg, vibration controllability) required as a laminated glass can be provided.

  In the interlayer film for laminated glass according to the present invention, the composition (X) containing the propylene polymer (A) contains a specific propylene polymer (B) having a melting point measured by DSC of 100 ° C. or higher. In this case, the laminated glass obtained from the interlayer film for laminated glass is particularly excellent in balance between vibration controllability and heat resistance.

  In the interlayer film for laminated glass according to the present invention, the composition (X) containing the propylene polymer (A) is further converted into an ethylene / α-olefin copolymer (C) and / or an ethylene / polar monomer copolymer. When (D) is contained, the laminated glass obtained from the interlayer film for laminated glass is particularly excellent in balance between vibration controllability and low temperature impact strength.

  In the interlayer film for laminated glass according to the present invention, when the composition (X) containing the propylene polymer (A) contains the radical generator (G), preferably the composition (X) is The propylene polymer (A), the optional propylene polymer (B), the optional ethylene / α-olefin copolymer (C), and the optional ethylene / polar monomer copolymer. In the presence of 0.001 to 10 parts by weight of the radical generator (G) with respect to a total of 100 parts by weight of (A) + (B) + (C) + (D), the component containing the polymer (D) When it is obtained by heat treatment, the laminated glass obtained using the composition (X) is particularly excellent in balance between vibration controllability and rubber elasticity.

  When at least a part of the propylene polymer (A) used in the interlayer film for laminated glass according to the present invention is graft-modified with one or more selected from a silane compound, a titanium compound, or a polar group-containing vinyl monomer In addition, the resin sheet can give a laminated glass that is particularly excellent in vibration controllability and also excellent in adhesion to the glass layer.

When at least a part of the composition (X) containing the propylene polymer (A) according to the present invention is graft-modified with one or more selected from a silane compound, a titanium compound or a polar group-containing vinyl monomer The laminated glass intermediate film can give a laminated glass that is particularly excellent in vibration controllability and also excellent in adhesion to the glass layer.
Since the laminated glass of the present invention uses the interlayer film for laminated glass described in any one of the above, it has excellent appearance durability and has the necessary properties as a laminated glass.

Hereinafter, the interlayer film for laminated glass and the laminated glass of the present invention will be described in more detail.
The interlayer film for laminated glass of the present invention has a layer obtained from the propylene polymer (A) or the composition (X) containing the propylene polymer (A). That is, the raw material used for the interlayer film for laminated glass of the present invention contains the propylene polymer (A) as an essential component, and further includes, for example, a propylene polymer (B), an ethylene / α-olefin copolymer. The composition may contain at least one of polymer (C), ethylene / polar monomer copolymer (D), foaming agent (F), and radical generator (G).

<Propylene polymer (A)>
The propylene-based polymer (A) used in the present invention is 30 to 100 mol% of the propylene-derived structural unit (a) and the structural unit (b) derived from an α-olefin having 2 to 20 carbon atoms excluding propylene. Is contained in a proportion of 70 to 0 mol%, preferably 35 to 98 mol% of the structural unit (a) and 65 to 2 mol% of the structural unit (b).

  Furthermore, the melting point of the propylene polymer (A) used in the present invention measured by DSC (differential scanning calorimeter) is 90 ° C. or lower, or no melting point is observed. For this reason, the resin sheet which comprises the laminated glass of this invention is excellent in vibration controllability (vibration control property, vibration insulation property, sound insulation property, sound absorption property, etc.).

  The melting point measured by DSC is the temperature at the maximum melting peak position at the time of temperature rise determined from the exothermic / endothermic curve of DSC. More specifically, the sample is packed in an aluminum pan, and (i) After raising the temperature to 200 ° C. at 100 ° C./min and holding at 200 ° C. for 5 minutes, (ii) lowering the temperature to −150 ° C. at 10 ° C./min, and then (iii) raising the temperature at 10 ° C./min , (Iii) is the temperature at the maximum melting peak position determined from the exothermic / endothermic curve obtained in (iii). Further, that the melting point is not observed means that a melting peak having a heat of fusion of crystal of 1 J / g or more is not observed in the range of −150 to 200 ° C.

  In the DSC measurement of the propylene polymer (A), preferably a melting peak (melting peak of crystal having a heat of fusion of 1 J / g or more; the same applies hereinafter) is not observed, and more preferably the heat of crystallization is high. A crystallization peak of 1 J / g or more is not observed.

  The Tg of the propylene polymer (A) measured by DSC is preferably −10 ° C. or lower.

  Preferred embodiments of the propylene polymer (A) are propylene homopolymers in which no melting peak is observed in DSC measurement, propylene / C2-C20 α-olefin (excluding propylene) Examples are coalescence, in which no melting peak is observed in DSC measurement, and those having an atactic structure. These can be produced, for example, by the method described in JP 2000-52510 A, [0012] to [0039].

  This propylene polymer (A) has a Young's modulus of preferably 150 MPa or less, more preferably 100 MPa or less, and still more preferably 50 MPa or less.

The elastic modulus can be obtained by press-molding the copolymer (A) and then performing a tensile test by the method of Examples described later. The molding conditions, after preheating at a temperature of 190 ° C., under pressure (100 kg / ^cm 2) After molding at 2 minutes, the pressure at 20 ℃ (100kg / cm ²⁾ to produce a 1mm thick sheet by cooling To do.

  Such a propylene polymer (A) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 10 dl / g, preferably 0.5 to 10 dl / g, more preferably 1 to 1. It is desirable to be in the range of 8 dl / g.

  If the propylene polymer (A) is a copolymer, it is preferably a random copolymer.

  The molecular weight distribution (Mw (weight average molecular weight) / Mn (number average molecular weight)) measured by GPC (o-dichlorobenzene solvent, polystyrene conversion) of the propylene polymer (A) is, for example, 1.5 to 3.0. And preferably 1.8 to 2.5.

  A preferred embodiment of the propylene polymer (A) used in the present invention is a propylene / α-olefin copolymer having 4 to 20 carbon atoms, which is a structural unit derived from an α-olefin having 4 to 20 carbon atoms. Of 1 to 40 mol%, more preferably 1 to 35 mol% (hereinafter also referred to as "propylene-based polymer (A1)") (wherein propylene-derived structural units and carbon number) 4 to 20 α-olefin-derived structural units are summed to 100 mol%).

  It is preferable that the propylene polymer (A) used in the present invention is the propylene polymer (A1) from the viewpoints of excellent vibration controllability such as vibration damping and vibration proof performance and high breaking strength.

  Specific examples of the propylene polymer (A1) include a propylene homopolymer in which a melting peak is not observed by DSC measurement and a propylene / α-olefin copolymer in which a melting peak is not observed by DSC measurement.

  Another preferred embodiment of the propylene-based polymer (A) used in the present invention is a propylene / ethylene / α-olefin copolymer having 4 to 20 carbon atoms, and 30 to 84 structural units derived from propylene. Mol%, preferably 35-77 mol%, more preferably 43-72 mol%, ethylene-derived structural units 1-25 mol%, preferably 3-20 mol%, more preferably 5-17 mol%, Propylene polymer containing 15 to 50 mol%, preferably 20 to 45 mol%, more preferably 23 to 40 mol% of a structural unit derived from an α-olefin having 4 to 20 carbon atoms (hereinafter referred to as “propylene polymer”). (Also referred to as “A2)”) (wherein the total of the structural unit derived from propylene, the structural unit derived from ethylene, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is 1). And 0 mol%).

  It is preferable that the propylene polymer (A) used in the present invention is the propylene polymer (A2) in terms of a balance of flexibility, wear resistance, vibration damping, and vibration proof performance.

  The propylene polymer (A2) tends to be particularly excellent in the balance between flexibility and low-temperature characteristics when compared with a copolymer composed only of propylene and an α-olefin having 4 to 20 carbon atoms. When compared with a copolymer composed of ethylene and ethylene, the balance of vibration control performance such as vibration control and vibration control, strength, and wear resistance tends to be better.

  The α-olefin having 4 to 20 carbon atoms is not particularly limited, but an α-olefin having 4 to 12 carbon atoms is preferable and may be linear or branched.

  Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptane, 1-octene, 1-nonene, 1-decene, and 1-undecene. 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4 -Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like, such as 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene 1-butene, 1-hexene, 1-octene and 1-decene are preferable, and 1-butene is particularly preferable. These α-olefins can be used alone or in combination of two or more.

  The propylene-based polymer (A) includes only propylene-derived structural unit (a) from the viewpoint of weather resistance, flexibility, and vibration control performance (damping property, vibration proofing property, sound absorption property, soundproofing property, etc.). Or a structural unit (a) and a structural unit (b) derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) are preferably included.

  On the other hand, from the viewpoint of crosslinkability and vulcanizability, in addition to the structural unit (a) and the structural unit (b), the structural unit is derived from an aromatic vinyl compound such as styrene and has two or more double bonds. The structural unit derived from the said polyene unsaturated compound (polyene), the structural unit derived from alcohol, carboxylic acid, amine, and these derivatives, etc. may be contained. In this case, the content of the structural unit other than the structural unit (a) and the structural unit (b) is, for example, further 0.01 to 10 mol%, preferably 100 mol% with respect to the total of (a) and (b), 0.03 to 5 mol%.

As a particularly preferred embodiment of the propylene polymer (A), (A1) or (A2) used in the present invention,
MFR measured at 230 ° C. and 2.16 kg load in accordance with JIS K-6721 is in the range of 0.01 to 100 g / 10 minutes, and any of the following requirements (a-1) or (a-2) Or a propylene polymer satisfying one or more of these (hereinafter also referred to as a propylene polymer (A3)).
(A-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 60% or more,
(A-2): The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 min, 230 ° C., 2.16 kg load) satisfy the following relational expression.

1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20)
Such a propylene polymer (A3) tends to be excellent in transparency, flexibility, and abrasion resistance.

First, requirement (a-1) will be described.
(A-1) Syndiotactic triad fraction (rr fraction, triad syndiotacticity) measured by ¹³ C-NMR method is 60% or more, preferably 70% or more, more preferably 75% or more The propylene polymer (A) having an rr fraction in this range is preferable because of its good compatibility with the syndiotactic propylene polymer.

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

The rr fraction is expressed in terms of Prr in the ¹³ C-NMR spectrum (absorption intensity derived from the second unit methyl group at the site where three units of the propylene unit are continuously syndiotactically bonded) and Pw (total methyl group of the propylene unit). (Absorption intensity derived from the above) is determined by the following formula (2).

rr fraction (%) = 100 × Prr / Pw (2)
Here, mr-derived absorption (of 3 units of propylene units, absorption derived from at least both syndiotactic and isotactic bonds, used for determination of Pmr (absorption intensity)), rr-derived absorption (propylene Absorption derived from the methyl group of the second unit at the site where 3 units are continuously syndiotactically bonded, used for determination of Prr (absorption intensity)), or absorption derived from mm (3 units of propylene units are consecutive) If the absorption derived from the methyl group of the second unit at the isotactic bond site and Pmm (absorption intensity) overlap with the absorption derived from the comonomer, the contribution of the comonomer component is subtracted. Calculate as it is.

  Specifically, among the description of how to obtain the “syndiotacticity parameter (SP value)” described in JP-A-2002-097325, [0018] to [0031], [0018] to [0023] ] And calculating from the integrated intensity of the signals in the first region, the second region, and the third region by the above equation (2).

The rr fraction is measured as follows. That is, 50 mg of sample is o-
What was dissolved in about 0.5 ml of a mixed solvent of dichlorobenzene / deuterated benzene = 5/1 was measured in a single proton pulse decoupling measurement mode using a JEOL EX-400 type NMR measurement apparatus, and a pulse width of 4. ¹³ C-NMR measurement is performed at 120 ° C. in the observation range of 7 μs, pulse interval 5.5 s, and 180 ppm. The number of integration is 10,000 times or more.

Next, requirement (a-2) will be described.
(A-2): The propylene polymer (A) used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. and a load of 230 ° C. and 2.16 kg in accordance with JIS K-6721. The measured MFR satisfies the following relational expression.

1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20)
More preferably 1.80 × MFR ^(−0.20) ≦ [η] ≦ 2.50 × MFR ^(−0.19)
The propylene polymer satisfying (a-2) exhibits a large MFR at the same [η] as compared to the conventional isotactic propylene copolymer.

  As described in Macromolecules 31, 1335-1340 (1998), the molecular weight between the entanglement points of isotactic propylene (reported as Me = 6900 (g / mol) in the paper) and the syndiotactic propylene This is due to the difference in molecular weight between entanglement points (reported as Me = 2170 (g / mol) in the paper). That is, it is considered that the same [η] has a syndio structure, thereby increasing the number of entanglement points with respect to the material having an iso structure and increasing the MFR.

  It can be seen that the above formula can be distinguished from that of the isotactic structure according to FIG. 3 of Patent Document WO2006 / 123759.

  As described above, the propylene polymer (A) satisfying at least one of (a-1) and (a-2) is different in stereoregularity from the propylene polymer having an isotactic structure. It is considered that the polymer has a syndiotactic structure.

  The propylene polymer (A) satisfying any one or more of the above formulas (a-1) and (a-2) is a copolymer of propylene and α-olefin with a catalyst capable of producing, for example, syndiotactic propylene. For example, the method described in the pamphlet of International Publication No. 2005/103141, for example, the method described in [0053] (page 14) to [0064] (page 16) of the pamphlet, or international publication 2006 / No. 123759 pamphlet, for example, the method described in [0241] (page 55) to [0342] (page 84) of the same publication, the repeating unit derived from propylene is 40 to 100 mol%, from ethylene 0 to 25 mol% of repeating units derived, and 0 to 60 mol of repeating units derived from α-olefin. It can be obtained by copolymerizing propylene, ethylene and α-olefin so as to be 1%.

  When the propylene polymer (A) used in the present invention is a propylene polymer satisfying at least one of the formulas (a-1) and (a-2), the intermediate for laminated glass of the present invention It is preferable in terms of excellent vibration controllability (damping property, vibration proofing property, sound proofing property, sound absorbing property, etc.), flexibility, low temperature property, and transparency of the film. In particular, it is more preferable that the propylene polymer (A) is the propylene polymer (A2) and the propylene polymer (A2) is the propylene polymer (A3).

<Propylene polymer (B)>
The composition (X) used in the interlayer film for laminated glass of the present invention may further contain a propylene polymer (B).

  The melting point of this propylene polymer (B) measured by DSC is 100 ° C. or higher. The details of the “melting point measured by DSC” are as described above.

  The tensile elastic modulus of the propylene polymer (B) used in the present invention is preferably 400 MPa or more.

  The propylene polymer (B) is more preferably at least one selected from isotactic polypropylene (B1) and syndiotactic polypropylene (B2). The propylene polymer (B) is more preferably isotactic polypropylene (B1) from the viewpoint of balance between properties such as heat resistance, moldability and workability and vibration control performance. In this case, if necessary, the syndiotactic polypropylene (B2) is added in an amount of 10 parts by weight or less, preferably 100 parts by weight or less, based on a total of 100 parts by weight of the propylene polymer (A) and the isotactic polypropylene (B1). May be added in an amount of 0.1 to 10 parts by weight. Even in this case, the amount of (B) is considered to be the sum of (B1) and (B2). The elastic modulus can be obtained by press-molding the propylene polymer (B) and then performing a tensile test by the method of Examples described later. This press molding is performed by preheating the propylene-based polymer (B) at a temperature of 200 ° C., pressurizing for 3 minutes (10 MPa), and then cooling at 20 ° C. for 5 minutes (10 MPa) to cool down to 1 mm. This is done by making a thick sheet.

First, isotactic polypropylene (B1) will be described below.
The isotactic polypropylene (B1) is a polypropylene having an isotactic pentad fraction of 0.90 or more, preferably 0.95 or more, measured by NMR method for the 23 ° C. n-decane insoluble part.

The isotactic pentad (mmmm) fraction indicates the proportion of isotactic linkages in pentad units in the molecular chain measured using ¹³ C-NMR, and 5 consecutive propylene monomer units. The fraction of propylene monomer units at the center of the meso-bonded chain. Specifically, it is a value calculated as a fraction of the mmmm peak in the total absorption peak in the methyl carbon region observed in the ¹³ C-NMR spectrum. In addition, this isotactic pentad (mmmm) fraction is measured as follows.

The mmmm fraction is Pmmmm (absorption intensity derived from the methyl group of the third unit at a site where 5 units of propylene units are continuously isotactically bonded) and PW (total methyl groups of propylene units) in ¹³ C-NMR spectrum. (Absorption intensity derived from the above) is obtained by the following formula (2).

mmmm fraction = Pmmmm / PW (2)
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.

  In the isotactic polypropylene (B1), the amount of the 23 ° C. n-decane insoluble component is not particularly limited, but is, for example, 99.9 wt% to 80 wt%. Here, the 23 ° C. n-decane insoluble component was dissolved by immersing 5 g of the sample in 200 cc of boiling n-decane for 5 hours, cooled to room temperature, and filtered the precipitated solid phase with a G4 glass filter. The value calculated from the solid phase weight measured after drying.

  Examples of the isotactic polypropylene (B1) include a propylene homopolymer or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms other than propylene. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, Examples thereof include 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like, and ethylene or α-olefin having 4 to 10 carbon atoms is preferable.

  These α-olefins may form a random copolymer with propylene or a block copolymer. The structural unit derived from these α-olefins may be contained in the polypropylene in a proportion of 40 mol% or less, preferably 20 mol% or less.

  The melt flow rate (MFR) of the isotactic polypropylene (B1) measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D 1238 is 0.01 to 1000 g / 10 minutes, preferably 0.05. It is desirable to be in the range of ˜500 g / 10 minutes.

  The isotactic polypropylene (B1) is, for example, a Ziegler 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 be produced by polymerization using a catalyst system. The same can be obtained by using a metallocene catalyst.

Next, syndiotactic polypropylene (B2) will be described below.
The syndiotactic polypropylene (B2) may be copolymerized with ethylene, an α-olefin having 4 or more carbon atoms, and the like in a small amount, for example, 10 mol% or less, preferably 5 mol% or less. As the syndiotactic polypropylene (B2), syndiotactic homopolypropylene is particularly preferable. Examples of the catalyst used in the production of such syndiotactic polypropylene include metallocene catalysts described in JP-A-10-300084.

  Here, the syndiotactic pentad (rrrr, pentad syndiotacticity) fraction is 0.5 or more, preferably 0.6 or more, more preferably 0.7 or more, and particularly preferably 0.8 or more. Those of 0.5 or more are preferable because they are excellent in heat resistance and moldability and have good properties as crystalline polypropylene.

The syndiotactic pentad fraction (rrrr) is measured as follows. The rrrr fraction is expressed in terms of Prrrr (absorption intensity derived from the third unit methyl group at a site where 5 units of propylene units are continuously syndiotactically bonded) and PW (all methyl groups of propylene units) in the ¹³ C-NMR spectrum. (Absorption intensity derived from the above) is determined by the following formula (3).

rrrr fraction = Prrrr / PW (3)
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 melt flow rate (MFR, 190 ° C., 2.16 kg load) of the syndiotactic polypropylene (B2) is 0.01 to 1000 g / 10 minutes, preferably 0.05 to 500 g / 10 minutes. . When the MFR is in such a range, a good flowability is exhibited, the syndiotactic polypropylene (B2) can be easily blended with other components, and a molded product having excellent mechanical strength can be obtained from the obtained composition. There is a tendency to be obtained.

  The propylene polymer (B) has a weight ratio [(A) :( B)] of the propylene polymer (A) and the propylene polymer (B) of 100 to 40: 0 to 60, preferably Is preferably used in an amount of (A) :( B) = 99 to 40: 1 to 60, more preferably 90 to 50:10 to 50 [total of (A) and (B) is 100 wt. Part. ].

  When the composition (X) used in the present invention contains the propylene polymer (B), the resulting interlayer film for laminated glass has particularly vibration controllability (vibration control, vibration control, soundproofing). In terms of balance between heat resistance and sound resistance) and heat resistance.

<Ethylene / α-olefin copolymer (C)>
The composition (X) containing the propylene polymer (A) used in the present invention further contains an ethylene / α-olefin copolymer (C) (hereinafter also referred to as “component (C)”). It may be. This ethylene / α-olefin copolymer (C) is an amorphous or low crystalline random or block copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms, and its density (ASTM D1505 ) Is usually 0.857 g / cm ³ or more and 0.910 g / cm ³ or less, preferably 0.860 to 0.905 g / cm ³ , more preferably 0.880 to 0.905 g / cm ³ , and its melt The flow rate (MFR; ASTM D 1238, 190 ° C., load 2.16 kg) is usually 0.1 to 40 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes.

  The α-olefin copolymerized with ethylene is an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Examples include octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 4-methyl-1-pentene and the like. Of these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, and 1-octene are particularly preferable. These α-olefins may be used alone or in combination of two or more.

  In addition, the ethylene / α-olefin copolymer (C) is not particularly limited in the amount of structural units derived from ethylene, but it is, for example, 75 to 95 mol% and an α-olefin having 3 to 20 carbon atoms. It is desirable that the structural unit derived from is contained in an amount of 5 to 25 mol%. Here, the total amount of the structure derived from ethylene and the structure derived from α-olefin is 100 mol%.

  Further, the ethylene / α-olefin copolymer (C) may contain, in addition to these structural units, structural units derived from other polymerizable monomers as long as the object of the present invention is not impaired. .

  Specific examples of the ethylene / α-olefin copolymer (C) include an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / propylene / 1-butene copolymer, and an ethylene / propylene copolymer. Examples thereof include an ethylidene norbornene copolymer, an ethylene / 1-hexene copolymer, and an ethylene / 1-octene copolymer. Among these, ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene / 1-octene copolymers, etc. are preferably used, especially ethylene / 1-butene. A copolymer is preferably used. These copolymers are random or block copolymers, but are preferably random copolymers.

  The degree of crystallinity of the ethylene / α-olefin copolymer (C) measured by X-ray diffraction is usually 40% or less, preferably 10 to 30%.

  The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (C) determined by gel permeation chromatography (GPC) is preferably in the range of 1.5 to 3.0, preferably It is desirable to be within the range of 1.7 to 2.5. When the ethylene / α-olefin copolymer (C) having a molecular weight distribution (Mw / Mn) within the above range is used, the compression set and the shapeability are excellent particularly at the time of crosslinking. The ethylene / α-olefin copolymer (C) as described above usually exhibits properties as an elastomer.

Melt flow rate (MFR ₁₀ ) of ethylene / α-olefin copolymer (C) measured at 190 ° C. under a load of 10 kg and a melt flow rate measured at a load of 2.16 kg in accordance with ASTM D 1238 (MFR ₂₎ ratio of _(MFR 10 / MFR ₂₎ is the following formula MFR ₁₀ / MFR ₂ ≦ 6.0
Preferably 7 ≦ MFR ₁₀ / MFR ₂ ≦ 15
And the molecular weight distribution (Mw / Mn) and the melt flow rate ratio are as follows: Mw / Mn + 5.0 <MFR ₁₀ / MFR ₂
When the above relationship is satisfied, it is possible to prepare a foamed resin sheet (crosslinked foamed molded article) that has a high foaming ratio, that is, a low specific gravity at the time of cross-linking foaming, and is highly elastic and excellent in compression set and formability. Composition (X) is obtained.

The intensity ratio (Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer (C) is 0.5 or less, preferably 0.4 or less.

Here, Tαα and Tαβ in the ¹³ C-NMR spectrum are the peak intensities of CH _{2 in} the structural unit derived from the α-olefin having 3 or more carbon atoms, and the positions with respect to the tertiary carbon are different as shown below. Two types of CH ₂ are meant.

Such a Tαβ / Tαα intensity ratio can be obtained as follows. The ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer (C) is measured using, for example, a JEOL-GX270 NMR measuring apparatus manufactured by JEOL Ltd. The measurement was performed on the basis of 67.8 MHz, 25 ° C., d6-benzene (128 ppm) using a mixed solution of hexachlorobutadiene / d6-benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight. Do. The measured ¹³ C-NMR spectrum is analyzed according to the proposal of Lindeman Adams (Analysis Chemistry 43, p1245 (1971)) and JCRandall (Review Macromolecular Chemistry Physics, C29, 201 (1989)) to obtain the Tαβ / Tαα intensity ratio.

The B value determined from the ¹³ C-NMR spectrum and the following general formula (4) of the ethylene / α-olefin copolymer (C) is 0.90 to 1.5, preferably 0.95 to 1.2. Is preferred.

B value = [POE] / (2.multidot. [PE] [PO]) (4)
(Wherein [PE] is the mole fraction of structural units derived from ethylene in the copolymer (C), and [PO] is derived from α-olefins in the copolymer (C)) (The mole fraction of the structural unit, and [POE] is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer (C).)

  This B value is an index representing the distribution state of ethylene and an α-olefin having 3 to 20 carbon atoms in the ethylene / α-olefin copolymer. JCRandall (Macromolecules, 15, 353 (1982)), J It can be calculated based on the report of .Ray (Macromolecules, 10, 773 (1977)).

The B value of the ethylene / α-olefin copolymer (C) is usually ¹³ C- of a sample prepared by uniformly dissolving about 200 mg of ethylene / α-olefin copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube. The NMR spectrum was measured at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, and a pulse repetition time of 4.2 sec. , Pulse width 6 μsec. Measured under the following conditions.

  As the B value is larger, the block chain of ethylene or α-olefin copolymer becomes shorter, the distribution of ethylene and α-olefin is more uniform, and the composition distribution of the copolymer rubber is narrower. It should be noted that as the B value becomes smaller than 1.0, the composition distribution of the ethylene / α-olefin copolymer becomes wider and the handling properties are worse.

  The ethylene / α-olefin copolymer (C) as described above can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst. In particular, the solution polymerization method described in JP-A-62-1121709 is preferable.

  When the ethylene / α-olefin copolymer (C) is used, the ethylene / α-olefin copolymer (C) is composed of the propylene-based copolymer (A) and a propylene-based copolymer used as necessary. It is used in a proportion of 1 to 500 parts by weight, preferably 10 to 100 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer (B).

  When the composition (X) used in the present invention contains the ethylene / α-olefin copolymer (C) in such an amount, the resulting interlayer film for laminated glass has particularly vibration controllability and low temperature. It is preferable in that it has an excellent balance with impact resistance.

<Ethylene / polar monomer copolymer (D)>
The composition (X) used in the present invention may further contain an ethylene / polar monomer copolymer (D). As this polar monomer, unsaturated carboxylic acid, its salt, its ester, its amide, vinyl ester, carbon monoxide etc. can be illustrated. More specifically, an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride, itaconic anhydride; lithium, sodium of these unsaturated carboxylic acids, Salts of monovalent metals such as potassium and polyvalent metals such as magnesium, calcium and zinc; methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, isooctyl acrylate, methyl methacrylate Unsaturated carboxylic acid esters such as ethyl methacrylate, isobutyl methacrylate, dimethyl maleate, etc., vinyl esters such as vinyl acetate and vinyl propionate; carbon monoxide, sulfur dioxide, etc. are exemplified, and these are used alone. Or even two or more There.

  More specifically, the ethylene / polar monomer copolymer (D) is an ethylene / acrylic acid copolymer, an ethylene / unsaturated carboxylic acid copolymer such as an ethylene / methacrylic acid copolymer; An ionomer in which part or all of the carboxyl groups of the carboxylic acid copolymer are neutralized with the above metal; ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methyl methacrylate copolymer; Ethylene / unsaturated carboxylic acid ester copolymer such as ethylene / isobutyl acrylate copolymer, ethylene / n-butyl acrylate copolymer; ethylene / isobutyl acrylate / methacrylic acid copolymer, ethylene / n-butyl acrylate・ Ethylene such as methacrylic acid copolymer ・ Unsaturated carboxylic acid ester ・ Unsaturated carboxylic acid Some or all of the copolymer and its carboxyl groups neutralized ionomers above metals; can be exemplified as a representative example of ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer.

  Among these, a copolymer of ethylene and a polar monomer selected from an unsaturated carboxylic acid, a salt thereof, an ester thereof and vinyl acetate is preferable. In particular, an ionomer of ethylene / (meth) acrylic acid copolymer or ethylene / An ionomer of a (meth) acrylic acid / (meth) acrylic ester copolymer and an ethylene / vinyl acetate copolymer are preferred, and an ethylene / vinyl acetate copolymer is most preferred.

  The ethylene / polar monomer copolymer (D) varies depending on the kind of the polar monomer, but preferably contains 1 to 50% by weight, particularly 5 to 45% by weight of the polar monomer.

  As such an ethylene / polar monomer copolymer, in consideration of molding processability, mechanical strength, etc., the melt flow rate at 190 ° C. under a load of 2160 g is 0.05 to 500 g / 10 min, particularly 0.5 to The thing of 20 g / 10 minutes is preferable. A copolymer of ethylene and unsaturated carboxylic acid, unsaturated carboxylic acid ester, vinyl ester or the like can be obtained by radical copolymerization at high temperature and high pressure. A copolymer (ionomer) of ethylene and a metal salt of an unsaturated carboxylic acid can be obtained by reacting an ethylene / unsaturated carboxylic acid copolymer with a corresponding metal compound.

  When the ethylene / polar monomer copolymer (D) used in the present invention is an ethylene / vinyl acetate copolymer, the vinyl acetate content in the ethylene / vinyl acetate copolymer is 10 to 30% by weight, preferably It is 15 to 30% by weight, more preferably 15 to 25% by weight.

  Further, the melt flow rate (MFR; ASTM D 1238, 190 ° C., load 2.16 kg) of this ethylene / vinyl acetate copolymer is 0.1 to 50 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes, more preferably 0.5 to 5 g / 10 minutes.

  When the ethylene / polar monomer copolymer (D) is used, the ethylene / polar monomer copolymer (D) is composed of the propylene copolymer (A) and a propylene polymer used as necessary. It is used in a proportion of 1 to 500 parts by weight, preferably 10 to 100 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the total of (B).

  When the composition (X) of the present invention contains the ethylene / polar monomer copolymer (D) in such an amount, the resulting interlayer film for laminated glass has particularly vibration controllability and low-temperature impact resistance. This is preferable because of its excellent balance.

(Modification of polymer)
The propylene polymer (A) used in the interlayer film for laminated glass of the present invention is a group in which a part or all of the propylene polymer (A) is composed of a silane compound, a titanium compound, an unsaturated carboxylic acid, and an unsaturated carboxylic acid anhydride. It may be graft-modified with one or more selected compounds. Further, the composition (X) containing the propylene polymer (A) used in the interlayer film for laminated glass of the present invention is partially or entirely composed of a silane compound, a titanium compound, an unsaturated carboxylic acid, and It may be graft-modified with one or more compounds selected from the group consisting of anhydrides of unsaturated carboxylic acids. When a part or all of the composition (X) is graft-modified, for example, the propylene polymer (A), the propylene polymer (B), the ethylene / α-olefin copolymer ( C), or any one or more of ethylene / polar monomer copolymer (D), part or all of which are anhydrous silane compounds, titanium compounds, unsaturated carboxylic acids, and unsaturated carboxylic acids It may be graft-modified with one or more compounds selected from the group consisting of products, and all components may be graft-modified. Of the silane compounds, titanium compounds, unsaturated carboxylic acids, and unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, or silane coupling agents are preferred. By graft modification, adhesion between the laminated glass interlayer film of the present invention and, for example, glass can be further improved. The graft rate is not particularly limited and may be grafted in an amount necessary to obtain the required adhesion performance. For example, the component (A), the component (B) used as necessary, and the component are used as necessary. When the total of component (C), component (D) used as needed, and compounds grafted on (A) to (D) is 100 parts by weight, the silane compound, titanium compound, unsaturated One or more compounds selected from the group consisting of carboxylic acids and anhydrides of unsaturated carboxylic acids may be grafted in an amount of 0.01 to 10 parts by weight, for example, 0.05 to 6 parts by weight. The amount of parts is preferred. Graft modification can be performed by a method such as melt kneading in the presence of an unsaturated carboxylic acid or the like and a radical initiator. The graft ratio is the amount of the unsaturated carboxylic acid or silane coupling agent grafted with respect to the entire graft-modified product, expressed in% by weight. The graft ratio can be determined by using ¹³ C-NMR.

  Examples of the unsaturated carboxylic acid or its anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylic acid, itaconic anhydride Acid, citraconic anhydride, hymic anhydride, bicyclo (2,2,2) oct-5-ene-2,3-dicarboxylic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, bicyclo (2,2,1) oct-7-ene-2,3,5 , 6-tetracarboxylic acid-2,3,5,6-dianhydride, 7-oxabicyclo (2,2,1) hept-5-ene-2,3-dicarboxylic anhydride, etc. . These metal salts can also be used. Of these, maleic anhydride is particularly preferably used.

  Examples of the silane coupling agent include vinyltriethoxysilane, methacryloyloxytrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, methacryloyloxycyclohexyltrimethoxysilane, γ-methacryloyloxypropyltriacetyloxysilane, methacryloyloxytriethoxy. Examples include silane and γ-methacryloyloxypropyltriethoxysilane.

<Radical generator (G)>
The composition (X) according to the present invention may further contain a radical generator (G). Specific examples of the organic peroxide suitably used as the radical generator (G) include dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di- (t-butylperoxy). Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy)- 3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t -Butyl perbenzoate, t-butyl peroxyisopropyl carbonate, dia Chill peroxide, lauroyl peroxide, etc. t- butyl cumyl peroxide.

When the radical generator (G) is used, the radical generator (G) includes a propylene copolymer (A), an optional propylene polymer (B), and an optional ethylene / α -0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of the olefin copolymer (C) and the optional ethylene / polar monomer copolymer (D) Parts, more preferably 0.1 to 1.5 parts by weight, still more preferably 0.2 to 1.0 parts by weight. However, since components other than (A) are optional components, one or more of components (B), (C), and (D) may be 0 parts by weight. When the organic peroxide is used in the above ratio, it is preferable that a radical reaction occurs moderately.
The composition (X) comprises the propylene polymer (A), the propylene polymer (B) as an optional component, the ethylene / α-olefin copolymer (C) as an optional component, and an optional component. A component containing the ethylene / polar monomer copolymer (D) is 0.001 to 10 parts by weight of radical generator with respect to 100 parts by weight in total of (A) + (B) + (C) + (D). It is more preferable that it is obtained by heat treatment in the presence of (G). Also in this case, since components other than (A) are optional components, one or more of components (B), (C), and (D) may be 0 parts by weight.
The heat treatment method is not particularly limited. For example, the components containing the above (A), (B), (C), and (D), the radical generator (G), the reaction aid (g), etc. There is a method in which a predetermined amount is charged into a kneading apparatus such as an extruder or a kneader and melt kneaded.
The melt kneading temperature is not particularly limited, and is, for example, 170 ° C. or higher and the decomposition temperature of the polyolefin resin or lower, preferably 180 ° C. or higher and 300 ° C. or lower, more preferably 180 ° C. or higher and 250 ° C. or lower.
Further, when the radical generator (G) is used together with the reaction aid (g), a more appropriate radical reaction can be performed.

(Reaction aid (g))
Specific examples of the reaction aid (g) include sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, and diphenyl. Peroxy reaction aids such as guanidine and trimethylolpropane-N, N′-m-phenylenedimaleimide; or divinylbenzene, triallyl cyanurate (TAC), triallyl isocyanurate (TAIC) are preferred. Also listed are 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. It is done. Of these, triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC) are preferable.

  In the present invention, the reaction aid (g) as described above has a weight ratio [(G) / (g)] of the reaction aid (g) to the radical generator (G) of 1/30 to 20. / 1, preferably in an amount of 1/20 to 10/1.

<Tackifier (H)>
The composition (X) according to the present invention may further contain a tackifier (H). Examples of the tackifier (H) include rosin, modified rosin, rosin ester, terpene resin, terpene phenol resin, aromatic hydrocarbon modified terpene resin, aliphatic petroleum resin, alicyclic petroleum resin, aromatic Examples include petroleum resins, coumarone / indene resins, styrene resins, cyclopentadiene resins, phenol resins, and xylene resins.

  These tackifiers (H) have a molecular weight in the range of about 100 to 10,000 and exhibit a plasticizing effect on the olefin resin. This molecular weight is a number average molecular weight (Mn) that can be measured by GPC. Conventionally, a large amount of plasticizers and softeners had to be added to vibration-damping and vibration-proofing materials for lightweight materials in order to reduce the hardness. By using resinous materials that fall into the category, the hardness can be reduced without deterioration of compression set characteristics and bleeding at high temperatures, and at the same time vibration control (soundproofing, sound absorption, vibration control, vibration control) It becomes possible to improve. The tackifier (H) preferably has a softening point measured by the ring and ball method in the range of 50 ° C to 160 ° C, and more preferably in the range of 60 to 160 ° C.

  When the tackifier (H) is used, the tackifier (H) includes a propylene copolymer (A), an optional propylene polymer (B), and an optional ethylene / α -5 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 100 parts by weight of the total amount of the olefin copolymer (C) and the optional ethylene / polar monomer copolymer (D) Is used in a proportion of 10 to 20 parts by weight.

<Inorganic filler (Z)>
The composition (X) according to the present invention may further contain an inorganic filler (Z). However, when importance is attached to transparency, the amount used may be adjusted as appropriate or may not be used.

  The inorganic filler is not particularly limited, and examples thereof include metal hydrated oxide, natural silicic acid or natural silicate, carbonate, sulfate, oxide, synthetic silicic acid or synthetic silicate.

Examples of the metal hydrated oxide include aluminum hydroxide and magnesium hydroxide.
As natural silicic acid or silicate, natural silicic acid or silicate such as talc, fine powder talc, kaolinite, calcined clay, mica, virophilite, sericite, wollastonite,
Carbonates include carbonates such as calcium carbonate, precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate,
The sulfates include barium sulfate and magnesium sulfate, and the oxides include zinc oxide, zinc white, magnesium oxide, and antimony oxide.
Examples of synthetic silicic acid or silicate include hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and anhydrous silicic acid.

  The inorganic filler (Z) may be an inorganic flame retardant, and examples of the inorganic flame retardant include an antimony flame retardant (eg, antimony trioxide) and a metal hydrated oxide flame retardant (eg, magnesium hydroxide). Well-known flame retardants, such as, can be mentioned.

  When the inorganic filler (Z) is used, the inorganic filler (Z) includes a propylene copolymer (A), an optional propylene polymer (B), and an optional ethylene / α -Ratio of usually 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, based on 100 parts by weight of the total of the olefin copolymer (C) and the optional ethylene / polar monomer copolymer (D) Used in

<Flame retardant (E)>
The composition (X) according to the present invention may further contain a flame retardant (E). However, when importance is attached to transparency, the amount used may be adjusted as appropriate or may not be used.

  The flame retardant (E) is not particularly limited as long as it is a flame retardant other than the flame retardant listed as the inorganic filler (Z). For example, a halogen flame retardant (eg decabromodiphenyl ether), a phosphorus flame retardant A well-known compound flame retardant, such as a flame retardant, can be mentioned. Preferred examples of the flame retardant include those other than the inorganic filler.

  When the flame retardant (E) is used, the flame retardant (E) comprises a propylene copolymer (A), an optional propylene polymer (B), and an optional ethylene / α-olefin. Used in a proportion of usually 1 to 1,000 parts by weight, preferably 10 to 500 parts by weight, based on 100 parts by weight of the total of copolymer (C) and optional ethylene / polar monomer copolymer (D). It is done.

<Foaming agent (F)>
The composition (X) according to the present invention may further contain a foaming agent (F). However, when importance is attached to transparency, the amount used may be adjusted as appropriate or may not be used. As the foaming agent (F), chemical foaming agents, specifically, azodicarbonamide (ADCA), 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl-2,2′-azobis Butyrate, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (cyclohexane-1-carbonitrile), 2, Azo compounds such as 2'-azobis [N- (2-carboxyethyl) -2-methyl-propionamidine];
Nitroso compounds such as N, N′-dinitrosopentamethylenetetramine (DPT);
Hydrazine derivatives such as 4,4′-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3′-disulfonylhydrazide;
semicarbazide compounds such as p-toluenesulfonyl semicarbazide;
Organic pyrolytic foaming agents such as trihydrazinotriazine, and bicarbonates such as sodium bicarbonate and ammonium bicarbonate; carbonates such as sodium carbonate and ammonium carbonate;
Examples thereof include inorganic pyrolytic foaming agents such as nitrites such as ammonium nitrite and hydrogen compounds. Among these, azodicarbonamide (ADCA) and sodium hydrogen carbonate are particularly preferable.

  In the present invention, physical foaming agents (foaming agents not necessarily accompanied by chemical reaction during foaming), for example, various aliphatic hydrocarbons such as methanol, ethanol, propane, butane, pentane and hexane; dichloroethane, dichloromethane, tetrachloride Various chlorohydrocarbons such as carbon; organic physical foaming agents such as chlorofluorocarbons such as chlorofluorocarbons, and inorganic physical foaming agents such as air, carbon dioxide, nitrogen, argon, and water. ). Among these, carbon dioxide, nitrogen, and argon are the most excellent because they do not need to be vaporized, are inexpensive, and have a very low possibility of environmental pollution and ignition.

  The physical foaming agent used as the foaming agent (F) in the present invention has no decomposition residue of the foaming agent, and therefore can prevent mold contamination during the crosslinking and foaming of the composition. In addition, since the physical foaming agent is not in powder form, it has excellent kneadability. In addition, when this physical foaming agent is used, it is possible to prevent off-flavors (such as ammonia odor generated during ADCA decomposition) of the resulting crosslinked foam.

  In the present invention, the chemical foaming agent as described above can be used in combination as long as no adverse effects such as odor and mold contamination occur.

  As a physical foaming agent storage method, for small-scale production, carbon dioxide, nitrogen, etc. can be used in a cylinder and supplied to an injection molding machine and an extrusion molding machine through a pressure reducing valve. In some cases, the pressure is increased by a pump or the like and supplied to an injection molding machine, an extrusion molding machine, or the like.

  In addition, if it is a facility that manufactures foamed products on a large scale, a storage tank for liquefied carbon dioxide, liquefied nitrogen, etc. is installed, passed through a heat exchanger, vaporized, piping, injection molding machine and extrusion molding machine with a pressure reducing valve Etc.

  In the case of a liquid physical foaming agent, the storage pressure is preferably in the range of 0.13 to 100 MPa. If the pressure is too low, the pressure cannot be reduced and cannot be injected into an injection molding machine, an extrusion molding machine or the like. If the pressure is too high, the pressure resistance of the storage equipment needs to be increased. The storage pressure defined here refers to the pressure that is vaporized and supplied to the pressure reducing valve.

  When a chemical foaming agent is used as the foaming agent (F), the chemical foaming agent is composed of a propylene-based copolymer (A), an optional component, a propylene-based polymer (B), and an optional component, an ethylene / α-olefin copolymer. A ratio of usually 0.0001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, based on 100 parts by weight of the total amount of the polymer (C) and the optional ethylene / polar monomer copolymer (D). Used in However, the amount of the chemical foaming agent used can be appropriately increased or decreased depending on the target foaming ratio because the amount of generated gas varies depending on the type and grade of the foaming agent used.

  Moreover, when using a physical foaming agent as a foaming agent (F), the addition amount of a physical foaming agent is suitably determined according to a desired foaming ratio.

  In this invention, you may use a foaming auxiliary agent (f) with a foaming agent (F) as needed. The foaming aid (f) acts to lower the decomposition temperature of the foaming agent (F), accelerate the decomposition, and make the bubbles uniform. Examples of the foaming aid (f) include zinc oxide (ZnO), zinc stearate, salicylic acid, phthalic acid, stearic acid, oxalic acid and other organic acids, urea or derivatives thereof.

The propylene polymer (A) or the composition (X) containing the propylene polymer (A) according to the present invention further comprises a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent, an antislip agent, An additive such as a blocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, an anti-aging agent, a hydrochloric acid absorbent, or an antioxidant may be included as necessary.
The method for producing the composition (X) containing the propylene polymer (A) used in the present invention is not particularly limited. For example, the necessary components are melted and kneaded together with (A) into an extruder or a kneader. Can be manufactured.

The composition (X) according to the present invention contains one or more of the following (a) to (c) in a state in which neither the radical generator (G) nor the foaming agent (F) is contained. Preferably two or more, more preferably three requirements are satisfied;
(A) In dynamic viscoelasticity measurement (frequency = 10 rad / s) in torsion mode, it has a loss tangent (tan δ) peak in the range of −25 ° C. to 25 ° C., and the value is 0.5 or more. is there,
(B) The needle penetration temperature (° C) measured according to JIS K7196 is 100 ° C to 168 ° C.
(C) The distance between chucks is set to 30 mm, the tensile speed is set to 30 mm / min, 100% strain is applied, the load is unloaded after 10 minutes, and the residual strain after 10 minutes is 20% or less.

  Here, the test piece at the time of measuring physical properties in the above (a) and (b) is a press-molded body having a width of 10 mm, a length of 45 mm, and a thickness of 2 mm. In press molding, the composition (X) is preheated at a temperature of 200 ° C., pressed for 3 minutes (10 MPa) and then molded, and then cooled at 20 ° C. for 5 minutes (10 MPa) to cool the sheet to a thickness of 2 mm. It is done by making.

Further, the test piece when measuring the physical properties in (c) above, the length _(L 0) 50 mm, width 5 mm, 1mm thick pressed bodies (dumbbell specimens). In press molding, the vibration control material is preheated at a temperature of 200 ° C., pressed for 3 minutes (10 MPa), and then pressed at 20 ° C. for 5 minutes (10 MPa) to cool a 1 mm thick sheet. It is done by making it.

<Interlayer film for laminated glass>
The interlayer film for laminated glass according to the present invention has a layer obtained from the above-described propylene polymer (A) or composition (X) containing the propylene polymer (A),
It can be obtained by a method of forming a sheet by a normal film forming method such as an extrusion method, a calendar method, or a press method.

  The film thickness of the interlayer film for laminated glass of the present invention is not particularly limited, but in consideration of the minimum penetration resistance and weather resistance required for laminated glass, it is practically a normal transparent interlayer film for laminated glass and Similarly, a film thickness range of 0.3-5 mm is generally preferred.

  The surface of the interlayer film for laminated glass prevents blocking between the films, handling workability when laminating the glass plate and the interlayer film (sliding property with the glass plate), and deaeration property when bonding with the glass plate In order to improve, it is preferable that the surface is rough, for example, has some unevenness. It is also a preferred embodiment that a large number of fine embosses are formed using an embossing roll or the like.

The embossing is preferably performed on at least one side, preferably both sides of the sheet, that is, the interlayer film for laminated glass, from the viewpoint that deaeration can be efficiently performed during the production of laminated glass. Furthermore, it is preferable that the entire surface in contact with the glass is embossed to enable efficient deaeration.
Embossing rolls used to form embossing on an interlayer film are generally manufactured by a method of forming irregularities by subjecting the surface of a metal roll to blasting, etching, engraving, engraving mill (mother mill), etc. The

  The interlayer film for laminated glass according to the present invention includes a layer obtained from the propylene polymer (A) or the composition (X) containing the propylene polymer (A), and a layer made of plasticized polyvinyl butyral. May be laminated. Plasticized polyvinyl butyral has a water absorption property, but the composition (X) has a very low water absorption property and excellent vibration controllability (vibration control properties, etc.). Therefore, it is possible to reduce the amount of plasticized polyvinyl butyral used by laminating with the sheet made of composition (X), and to suppress deterioration in appearance such as devitrification and whitening due to water absorption of PVB when used as laminated glass. Is preferable.

  The film thickness of the plasticized polyvinyl butyral sheet is not particularly limited. In consideration of the minimum penetration resistance and weather resistance required for laminated glass, a layer obtained from the propylene polymer (A) or the composition (X) containing the propylene polymer (A) of the present invention; In general, the laminated glass interlayer film including a layer obtained from plasticized polyvinyl butyral is practically preferably in a film thickness range of 0.3 to 5 mm in total, in the same manner as an ordinary transparent interlayer film for laminated glass.

  Of the film thickness of the laminated glass interlayer film of the present invention, the thickness ratio of the plasticized polyvinyl butyral sheet is preferably 80% or less and more preferably 50% or less in order to suppress deterioration of the appearance of the laminated glass due to water absorption. Although there is no particular lower limit, when using plasticized polyvinyl butyral, 5% or more is preferable.

  Examples of the plasticizer used for the polyvinyl butyral resin include known plasticizers used for the polyvinyl butyral resin, such as triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, Ethylene glycol-di-caprylate, triethylene glycol-di-n-octate, triethylene glycol-di-n-heptate, tetraethylene glycol-di-n-heptate are preferably used.

  Such a plasticizer is generally contained in the range of 20 to 60 parts by weight, particularly preferably in the range of 30 to 55 parts by weight, with respect to 100 parts by weight of the resin. If the content of the plasticizer is less than 20 parts by weight, film formation becomes difficult, and elongation of the resulting resin film becomes poor. On the other hand, when the plasticizer content exceeds 60 parts by weight, the plasticizer bleeds from the resulting resin film, resulting in poor transparency.

  The surface of the plasticized polyvinyl butyral sheet has anti-blocking between films, handling workability when laminating a glass plate and an intermediate film (sliding property with a glass plate), and deaeration at the time of bonding with a glass plate In order to improve, it is preferable that the surface is rough, for example, has some unevenness. It is also a preferred embodiment that a large number of fine embosses are formed using an embossing roll or the like.

  The embossing of the sheet surface is preferable in that it can be efficiently deaerated at least on one side, preferably on both sides. Furthermore, it is preferable that the surface in contact with the resin of the present invention is entirely embossed in order to enable efficient deaeration.

  The laminated laminated glass intermediate film which is one aspect of the present invention is formed by, for example, molding each resin film separately, and heating and pressurizing each of these resin films between two glass plates. A method of integrally forming and laminating simultaneously with the production of laminated glass, or a method of integrally laminating and molding each resin film by a multilayer extrusion method, or a method of integrally laminating and molding each resin film by heating and pressing. It can be manufactured by a method or the like.

  In this laminated glass interlayer film, the propylene polymer (A) or the composition (X) containing the propylene polymer (A) may be a single layer or two or more layers. Good. Moreover, when the layer which consists of plasticized polyvinyl butyral is laminated | stacked, the layer which consists of plasticized polyvinyl butyral may be one layer, or may be two or more layers.

<Laminated glass>
The laminated glass according to the present invention uses the laminated glass interlayer film according to the present invention described above. Specific examples of the laminated glass according to the present invention include the following structures;
A multilayer laminate in which the interlayer film for laminated glass is laminated on a base glass;
A multilayer laminate in which the interlayer film for laminated glass is laminated on a substrate glass, and further a substrate layer is laminated thereon. Base glass / interlayer film for laminated glass / substrate glass / intermediate film for laminated glass / base Multi-layer laminated body laminated in the order of material glass Multi-layer laminated body laminated in order of base glass / laminated glass (/ base glass / interlayer film for laminated glass) n / base glass (n is 2) The above integer, for example, 2 to 10).

  In the above illustration, when the laminated glass interlayer film has two or more layers, the compositions of the laminated glass interlayer films may be the same or different. Moreover, when it has two or more base glass layers, the base glass layers may be the same or different.

  In the laminate according to the present invention, on the surface of the laminated glass interlayer of the present invention, an ethylene / methacrylic acid copolymer, an ionomer thereof, an ethylene / vinyl acetate copolymer, and other polymers (for example, modified nylon, An adhesive layer of modified polyolefin or the like can also be provided.

  In addition, it does not specifically limit as a base glass layer, The glass plate generally used can be used. Examples of such glass plates include various types of inorganic glass such as float plate glass, heat ray absorbing glass, polished plate glass, mold plate glass, mesh plate glass, and wire plate glass: polycarbonate plate, polymethyl methacrylate plate, polyethylene terephthalate plate, acrylic An organic glass plate such as a plate may be mentioned. These glass plates may be used independently and two or more types may be used together. In addition, the thickness of these glass plates should just be suitably selected according to a use, and although it does not specifically limit, The thickness of one sheet of 1-3 mm is desirable. Further, the glass used may be opaque when transparency is not important.

<Method for producing laminated glass>
Although there is no restriction | limiting in particular in manufacturing the laminated glass which concerns on this invention, It can manufacture by the method similar to the manufacturing method of a normal laminated glass. For example, the interlayer film for laminated glass described above is sandwiched between at least two base glass plates, and this is passed through a pressing roll, or preferably placed in a rubber bag and sucked under reduced pressure, and the glass plate and the interlayer film Pre-adhering at about 70 to 110 ° C. while deaerating the air remaining between the layers, and then placing the degassed laminate in an autoclave or pressing, at about 120 to 150 ° C., It can manufacture by performing this adhesion | attachment with the pressure of about 1-1.5 MPa.
The interlayer film for laminated glass of the present invention is preferably a sheet having embossed on at least one side, preferably both sides, and is preferably used for producing laminated glass. Moreover, when manufacturing this laminated glass, it is preferable to manufacture by laminating | stacking the laminated body which interposed the said sheet | seat between the glass plates, depressurizing and depressurizing.

[Example]
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the examples.

1. Heat resistance (TMA): softening temperature (° C);
In accordance with JIS K7196, using a 1 mm thick test piece, a pressure of 0.2 MPa was applied to a 1.8 mmφ flat indenter at a heating rate of 5 ° C./min, and the softening temperature (° C.) was obtained from the TMA curve. It was. In the present specification, this softening temperature is sometimes referred to as TMA.
2. Haze (%);
Using a test piece having a thickness of 1 mm, measurement was performed with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd.
3. Rebound resilience (%);
Using a circular press sheet having a thickness of 15 mm and a diameter of 30 mm, the resilience modulus (%) was calculated in accordance with JIS K6255. The measurement temperature is 23 ° C. The smaller this value, the better the vibration damping.
4). Izod impact strength;
Using an injection molding machine (IS55EPN manufactured by Toshiba Machine Co., Ltd.), a test piece was created at an injection temperature of 200 ° C and a mold temperature of 40 ° C, and an impact test was performed under the following conditions in accordance with ASTM D-256. Asked to go.

<Test conditions>
Test piece: 12.7 mm (width) x 6.4 mm (thickness) x 64 mm (length)
Notch: machining Measurement temperature: 0 ° C and -30 ° C.
5. Melting point (Tm) and glass transition temperature (Tg);
An endothermic curve of DSC is obtained, and the temperature at the maximum peak position is defined as Tm.

The measurement is performed using a measuring device manufactured by Perkin Elmer Co., Ltd., and the sample is packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, held at 200 ° C. for 10 minutes, and then kept at −150 ° C. to 10 ° C. / It was determined from the endothermic curve when the temperature was decreased at min and then increased at 10 ° C./min.
6). Intrinsic viscosity [η];
Measurements were made in decalin at 135 ° C.
7). Mw / Mn;
Using GPC (gel permeation chromatography), measurement was performed at 140 ° C. using orthodichlorobenzene as a solvent.
8). (H) softening point of component;
It was measured by the ring and ball method (ASTM-D36).
9. Dynamic viscoelasticity measurement;

  Using RDS-II made by Rheometric, the torsion mode (twist) between 10mm in width and 38mm in length, the heating rate is 2 ℃ / min, the frequency is 10rad in the range from -100 ℃ to 100 ℃ / S was measured, and the value of loss tangent tan δ and storage elastic modulus G ′ at each temperature were obtained. A large maximum value of tan δ indicates excellent vibration damping properties, vibration proof properties, sound proof properties, and sound absorption properties.

[Synthesis Example 1]
(Synthesis of syndiotactic polypropylene)
According to the method described in JP-A-2-274863, syndiotactic by propylene bulk polymerization in the presence of hydrogen using a catalyst comprising diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and methylaluminoxane. Polypropylene was synthesized. The obtained syndiotactic polypropylene (hereinafter also referred to as “synPP”) had a melt flow index of 4.4 g / 10 min, a molecular weight distribution by GPC of 2.3, and was measured by ¹³ C-NMR. The tic pentad fraction (rrrr) was 0.823, Tm measured by differential scanning calorimetry was 127 ° C., and Tg was 57 ° C.

Example 1
[Synthesis of propylene / butene / ethylene copolymer (1)]
Into a polymerization apparatus (polymerizer) having a volume of sufficiently nitrogen-substituted 2000 ml, 500 ml of dry hexane, 240 g of 1-butene and 1.0 mmol of triisobutylaluminum were charged at room temperature, and then the temperature inside the polymerizer was adjusted. The temperature was raised to 35 ° C., the inside of the polymerization vessel was pressurized to 0.6 MPa with propylene, and then ethylene was supplied to pressurize to 0.62 MPa. Thereafter, a toluene solution in which 0.005 mmol of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and 1.5 mmol of methylaluminoxane (produced by Tosoh Finechem Co., Ltd.) in contact with aluminum was added to the polymerization vessel. Then, the polymerization was carried out for 5 minutes while supplying ethylene at an internal temperature of 35 ° C. and maintaining the polymerization vessel pressure at 0.62 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours.

  The weight of the obtained polymer (hereinafter also referred to as “sPBER (1)”) was 39.2 g. The composition of sPBER (1) is that propylene content is 67.9 mol%, ethylene content is 5.1 mol%, 1-butene content is 27.0 mol%, and intrinsic viscosity [η] is 2.89 dl / g. The glass transition temperature Tg was −19.7 ° C., there was no melting peak, and the molecular weight distribution by GPC was 2.0.

The sPBER (1) is molded under the conditions of a hot plate temperature of 190 ° C., a preheating of 6 minutes, and a pressure (10 MPa) of 2 minutes, and then transferred to a press molding machine having a hot plate temperature of 20 ° C. and cooled by pressurization (10 MPa) Thus, a press sheet was prepared and various physical properties were measured. The low temperature impact strength was measured using an injection test piece of sPBER (1).
The resin obtained in Example 1 was sandwiched between Teflon (registered trademark) sheets to form a 1 mm thick press sheet, and laminated glass was formed by the following method.

Float glass (30 cm square, 2 mm thickness) was used as the base material, and the base material, the composition 1 and the base material were laminated in this order, and pressure bonding (conditions: pressure: 2 kg / cm ² , 160 ° C. × 3 minutes) ) To produce a laminate (three-layer laminate).
Next, the obtained laminated glass was stored at 50 ° C. and 95% RH for 1 week, and the appearance of the edge portion was observed. The measurement results are shown in Table 1.

(Example 2)
[Synthesis of propylene / butene / ethylene copolymer (2)]
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the inside of the polymerization vessel was pressurized to 0.54 MPa with propylene, then ethylene was supplied and the pressure was increased to 0.62 MPa. The weight of the obtained polymer (hereinafter also referred to as “sPBER (2)”) was 82.6 g. The composition of sPBER (2) is that propylene content is 61.3 mol%, ethylene content is 10.3 mol%, 1-butene content is 28.4 mol%, and intrinsic viscosity [η] is 2.67 dl / g. The glass transition temperature Tg was −24.7 ° C., there was no melting peak, and the molecular weight distribution by GPC was 2.0.
Using the sPBER (2), a press sheet and an injection test piece were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 2-2)
[Synthesis of propylene / butene / ethylene copolymer (2-2)]
Polymerization was carried out in the same manner as in Synthesis Example 1 except that the inside of the polymerization vessel was pressurized to 0.50 MPa with propylene, then ethylene was supplied and the pressure was increased to 0.62 MPa. The weight of the obtained polymer (hereinafter also referred to as “sPBER (2-2)”) was 91.2 g. The composition of sPBER (2) is that propylene content is 61.3 mol%, ethylene content is 15.3 mol%, 1-butene content is 26.2 mol%, and intrinsic viscosity [η] is 2.89 dl / g. The glass transition temperature Tg was −31.4 ° C., there was no melting peak, and the molecular weight distribution by GPC was 2.0.
Using the sPBER (2-2), a press sheet and an injection test piece were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 3)
[Synthesis of propylene / ethylene copolymer (3)]
750 ml of heptane was added to a 1.5 liter autoclave that had been dried under reduced pressure and purged with nitrogen at room temperature, and then a 1.0 mmol / ml toluene solution of triisobutylaluminum (hereinafter abbreviated as “TIBA”) was converted to aluminum atoms. Then, 0.3 ml was added so that the amount became 0.3 mmol, 50.7 liters of propylene (25 ° C., 1 atm) was inserted with stirring, and the temperature was raised to reach 30 ° C. Thereafter, ethylene was supplied to pressurize the system to 0.55 MPa, and a heptane solution of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride synthesized by a known method (0.0002 mmol / ml) And 3.75 ml of toluene solution (0.002 mmol / ml) of (triphenylcarbenium tetra (pentafluorophenyl) borate) were added to initiate copolymerization of propylene and ethylene. The catalyst concentrations at this time were 0.001 mmol / liter of diphenylmethylene (cyclopentadienyl) fluorenylzirconium dichloride and 0.004 mmol / liter of triphenylcarbenium tetra (pentafluorophenyl) borate relative to the total system. Liters.

During the polymerization, the pressure in the autoclave was maintained at 0.55 MPa by continuously supplying ethylene. 30 minutes after the start of the polymerization, the polymerization reaction was stopped by adding 20 ml of methanol. After depressurization, the polymer solution was taken out, and this polymer solution was washed with the same volume as this polymer solution “an aqueous solution in which 5 ml of concentrated hydrochloric acid was added to 1 liter of water”, and the catalyst residue was transferred to the aqueous phase. After this catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Subsequently, the polymer liquid phase separated from oil and water is brought into contact with 3 times the volume (volume ratio) of acetone under strong stirring to precipitate a polymer, and then the precipitate is sufficiently washed with acetone to obtain a solid part (co-polymer). Polymer) was collected by filtration. Subsequently, this solid part was dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow. The yield of the propylene / ethylene copolymer (hereinafter also referred to as “sPER (3)”) obtained as described above was 50.0 g. In addition, the composition of sPER (3) has a propylene content of 76.0 mol% and an ethylene content of 24.0 mol%, and an intrinsic viscosity [η] measured in decalin at 135 ° C. is 2.4 dl / g. The glass transition temperature Tg was −28 ° C., no melting peak was present, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.9.
Using the sPER (3), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

Example 4
Mitsui Chemicals Co., Ltd. isotactic polypropylene (hereinafter also referred to as “isoPP”) (grade: E110G, MFR = 0.5, melting point 165 ° C., mmmm = 95.8%, decane soluble part 0.3 weight) %) 20 parts by weight and 80 parts by weight of sPBER (2) obtained in Example 2 were mixed and melt-kneaded at 200 ° C. to obtain a thermoplastic resin composition (hereinafter also referred to as “composition (4)”). .)
Using the composition (4), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 5)
Yashara Chemical Co., Ltd. hydrogenated terpene resin P125 (softening point 125 ° C. by ring and ball method) 20 weights with respect to 100 weight parts in total of 20 weight parts of isoPP and 80 weight parts of sPBER (2) obtained in Example 2 A thermoplastic resin composition (hereinafter also referred to as “composition (5)”) was obtained by adding parts and melting and kneading at 200 ° C.
A press sheet and an injection test piece were prepared using the composition (5) in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 6)
20 parts by weight of synPP obtained in Synthesis Example 1 and 80 parts by weight of sPBER (2) obtained in Example 2 were melt-kneaded at 200 ° C. to obtain a thermoplastic resin composition (hereinafter “composition (6 ) ").
Using the composition (6), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 7)
20 parts by weight of hydrogenated terpene resin P125 manufactured by Yashara Chemical Co., Ltd. was added to 100 parts by weight of the total amount of 20 parts by weight of synPP obtained in Synthesis Example 1 and 80 parts by weight of sPBER (2) obtained in Example 2. Then, a thermoplastic resin composition (hereinafter also referred to as “composition (7)”) was obtained by melt-kneading at 200 ° C.
A press sheet and an injection specimen were prepared using the composition (7) in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 8)
20 parts by weight of isoPP and 20 parts by weight of hydrogenated terpene resin P125 manufactured by Yashara Chemicals Co., Ltd. and 100 parts by weight of sPBER (2) 80 parts by weight obtained in Example 2 and Mitsui Chemicals, Inc. Tuffmer (registered trademark) A4070 (density 0.872 g / cm ³ , MFR = 7 g / 10 min) (in Table 1, “(C) EBR”) 20 parts by weight are mixed and melt-kneaded at 200 ° C. As a result, a thermoplastic resin composition (hereinafter also referred to as “composition (8)”) was obtained.
Using the composition (8), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

Example 9
To a total amount of 100 parts by weight of 20 parts by weight of isoPP and 80 parts by weight of sPBER (2) obtained in Example 2, Tafmer (registered trademark) A4070 (density 0.872 g / cm ³ , manufactured by Mitsui Chemicals, Inc.) 20 parts by weight of MFR = 7 g / 10 min), 20 parts by weight of hydrogenated terpene resin P125 manufactured by Yasuhara Chemical Co., Ltd., and 0.05 parts by weight of peroxide PH25B manufactured by Nippon Oil & Fats Co., Ltd. were melted at 200 ° C. By kneading, a thermoplastic resin composition (hereinafter also referred to as “composition (9)”) was obtained.
Using the composition (9), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 10)
To a total amount of 100 parts by weight of 20 parts by weight of isoPP and 80 parts by weight of sPBER (2) obtained in Example 2, an ethylene / vinyl acetate copolymer (EVAFLEX: P1905, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 20 parts by weight of density 0.940 g / cm ³ , MFR = 2.5 g / 10 min) and 20 parts by weight of hydrogenated terpene resin P125 manufactured by Yasuhara Chemical Co., Ltd. are mixed and melt-kneaded at 200 ° C. A composition (hereinafter also referred to as “composition (10)”) was obtained.
Using the composition (10), a press sheet and an injection test piece were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 11)
Yashara Chemical Co., Ltd. hydrogenated terpene resin P125 20 parts by weight and Ajinomoto Fine Chemicals Co., Ltd. with respect to a total of 100 parts by weight of isoPP 20 parts by weight and sPBER (2) 80 parts by weight obtained in Example 2 Magnesium hydroxide (referred to as “(Z) inorganic filler (inorganic flame retardant)” in Table 1) 300 parts by weight are added and melt-kneaded at 200 ° C. to form a thermoplastic resin composition (hereinafter “composition”). Product (11) ").
Using the composition (11)), press sheets and injection test pieces were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 1.

(Example 12)
20 parts by weight of synPP obtained in Synthesis Example 1 and 80 parts by weight of sPER (3) obtained in Example 3 were melt-kneaded at 200 ° C. to obtain a thermoplastic resin composition (hereinafter “composition (12 ) ").
Using the composition (12), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 2.

(Example 13)
To a total amount of 100 parts by weight of 20 parts by weight of isoPP and 80 parts by weight of sPBER (2) obtained in Example 2, Tafmer (registered trademark) A4070 (density 0.872 g / cm ³ , manufactured by Mitsui Chemicals, Inc.) MFR = 7 g / 10 min) 20 parts by weight were mixed and melt-kneaded at 200 ° C. to obtain a thermoplastic resin composition (hereinafter also referred to as “composition (13)”).
Using the composition (13), a press sheet and an injection test piece were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 2.

(Example 14)
In Example 13, a thermoplastic resin composition was prepared in the same manner as in Example 13, except that 80 parts by weight of sPBER (2) obtained in Example 2 was changed to sPBER (1) obtained in Example 1. (Hereinafter also referred to as “composition (14)”).
Using the composition (14), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 2.

(Example 15)
70 parts by weight of sPBER (1) obtained in Example 1 was mixed with 30 parts by weight of Tuffmer (registered trademark) A4070 (density 0.872 g / cm ³ , MFR = 7 g / 10 min) manufactured by Mitsui Chemicals, Inc. Then, a thermoplastic resin composition (hereinafter also referred to as “composition (15)”) was obtained by melt-kneading at 200 ° C. In other words, sPBER (1) was 100 parts by weight, and Tafmer (registered trademark) A4070 was 42.8 parts by weight.
Using the composition (15), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 2.

(Example 16)
80 parts by weight of sPBER (1) obtained in Example 1 and 20 parts by weight of isoPP were kneaded in a single-screw extruder at a set temperature of 190 ° C., and the thermoplastic resin composition (hereinafter referred to as “Composition (16)”). Say). 3 parts by weight of zinc oxide (referred to as “(f) foaming aid” in Table 1) and azodicarbonamide (“(F) foaming agent in Table 1) relative to 100 parts by weight of the composition (16). The mixture containing 2 parts by weight was kneaded for 10 minutes with a kneader having a set temperature of 100 ° C., and further kneaded for 10 minutes with a roll having a roll surface temperature of 100 ° C., and then formed into a sheet shape.

The obtained sheet was filled in a press die and pressurized and heated under the conditions of 150 kgf / cm ² , 155 ° C. and 30 minutes to obtain a foam. The size of the press mold was 15 mm thick, 150 mm long, and 200 mm wide.
Subsequently, the resilience of this foam was measured according to the above method. The results are shown in Table 2.

(Example 17)
To 100 parts by weight of the total amount of 80 parts by weight of sPBER (1) obtained in Example 1 and 20 parts by weight of isoPP, Tafmer (registered trademark) A4070 (density 0.872 g / cm ³ ) manufactured by Mitsui Chemicals, Inc. (MFR = 7 g / 10 min) 30 parts by weight was mixed and kneaded in a single screw extruder at a set temperature of 190 ° C. to obtain a thermoplastic resin composition (hereinafter also referred to as “composition (17)”). Using a mixture in which 3.9 parts by weight of zinc oxide and 2.6 parts by weight of azodicarbonamide were blended with 130 parts by weight of the composition (17), a foam was prepared in the same manner as in Example 16. Physical properties were measured. The results are shown in Table 2.

(Example 18)
70 parts by weight of sPBER (1) obtained in Example 1 was mixed with 30 parts by weight of Tuffmer (registered trademark) A4070 (density 0.872 g / cm ³ , MFR = 7 g / 10 min) manufactured by Mitsui Chemicals, Inc. The mixture was kneaded with a single screw extruder at a set temperature of 190 ° C. to obtain a thermoplastic resin composition (hereinafter also referred to as “composition (18)”). In other words, sPBER (1) was 100 parts by weight, and Tafmer (registered trademark) A4070 was 42.8 parts by weight.

  In addition, a foam was prepared in the same manner as in Example 16 using a mixture in which 3 parts by weight of zinc oxide and 2 parts by weight of azodicarbonamide were blended with 100 parts by weight of the composition (18), and physical properties were measured. It was. The results are shown in Table 2.

(Example 19)
A thermoplastic resin composition (hereinafter also referred to as “composition (19)”) was obtained in the same manner as in Example 8, except that sPBER (2) obtained in Example 2 was changed to sPBER (2-2). Got.
Using the composition (19), a press sheet and an injection specimen were prepared in the same manner as in Example 1, and various physical properties were measured. The measurement results are shown in Table 2.

(Example 20)
The resin composition obtained in Example 4 was formed into a sheet having a thickness of 0.6 mm by press molding.
In addition, 100 parts by weight of polyvinyl butyral (BM-SZ) manufactured by Sekisui Chemical Co., Ltd. was kneaded with 39 parts by weight of triethylene glycol-bis-2-ethylhexanoate as a plasticizer using a plastmill at 150 ° C., A press sheet having a thickness of 0.2 mm was prepared.
Subsequently, the glass substrate, the plasticized polyvinyl butyral, the resin sheet obtained in Example 4, the plasticized polyvinyl butyral, and the glass substrate were laminated in this order, and a laminated glass was prepared and evaluated in the same manner as in Example 1.
The results are shown in Table 2.

(Comparative Example 1)
A laminated glass was prepared and evaluated in the same manner as in Example 20 except that the thickness of the plasticized polyvinyl butyral sheet was 1 mm and the composition (X) of the present invention was not used.
The edge was whitened.
The results are shown in Table 2.

(Comparative Example 2)
The whole peripheral surface of the laminated glass obtained in Comparative Example 1 was tightly sealed with a polyester adhesive tape to produce a laminated glass and evaluated.
Whitening of the edge was suppressed. The results are shown in Table 2.

Claims (15)

30 to 100 mol% of the structural unit (a) derived from propylene and 70 to 0 mol% of the structural unit (b) derived from an α-olefin having 2 to 20 carbon atoms excluding propylene [(a) And (b) is 100 mol%. ] The propylene polymer (A) having a melting point measured by DSC of 90 ° C. or lower, or no melting point being observed and satisfying the following requirement (a-1 ), or the propylene polymer (A): An interlayer film for laminated glass comprising a layer obtained from the composition (X) to be contained.
(A-1): The syndiotactic triad fraction (rr fraction) measured by ¹³ C-NMR method is 70% or more. The interlayer film for laminated glass according to claim 1, wherein the composition (X) contains a propylene polymer (B) having a melting point measured by DSC of 100 ° C or higher. The composition (X) is 100 to 40 parts by weight of the propylene polymer (A), and 0 to 60 parts by weight of the propylene polymer (B) [the sum of (A) and (B). 100 parts by weight. The interlayer film for laminated glass according to claim 1, wherein the interlayer film is a composition to be contained. The composition (X) is 99 to 40 parts by weight of the propylene polymer (A), and 1 to 60 parts by weight of the propylene polymer (B) [the sum of (A) and (B). 100 parts by weight. The interlayer film for laminated glass according to any one of claims 1 to 3, which is a composition to be contained. The propylene polymer (A) contains 1 to 40 mol% of a structural unit derived from an α-olefin having 4 to 20 carbon atoms (here, a structural unit derived from a structural unit derived from propylene and an α-olefin having 4 to 20 carbon atoms). The laminated glass according to any one of claims 1 to 4, wherein the laminated glass is a propylene / α-olefin copolymer (A1) having 4 to 20 carbon atoms contained in a total of 100 mol%. Interlayer film. The propylene-based polymer (A) contains 1 to 25 mol% of structural units derived from ethylene and 1 to 35 mol% of structural units derived from an α-olefin having 4 to 20 carbon atoms (herein, the structural units derived from propylene and Propylene / ethylene / C4-20 α-olefin copolymer (A2) containing ethylene as a structural unit derived from ethylene and a C4-20 α-olefin-derived structural unit as 100 mol%) The interlayer film for laminated glass according to any one of claims 1 to 5, wherein The propylene-based polymer (A) has an MFR measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K-6721 in the range of 0.01 to 100 g / 10 minutes, and the following requirements (a- The interlayer film for laminated glass according to any one of claims 1 to 6, wherein 2) is satisfied.
(A-2): The intrinsic viscosity [η] (dL / g) measured in 135 ° C. decalin and the MFR (g / 10 minutes, 230 ° C., 2.16 kg load) satisfy the following relational expression:
1.50 × MFR ^(−0.20) ≦ [η] ≦ 2.65 × MFR ^(−0.20) The propylene-based polymer (B) is a syndiotactic polypropylene (B2) having a syndiotactic pentad fraction of 0.50 or more. Interlayer film for laminated glass . The composition (X) is an ethylene / α-olefin copolymer (C) with respect to a total of 100 parts by weight of the propylene polymer (A) and the propylene polymer (B) as an optional component. The interlayer film for laminated glass according to any one of claims 1 to 8, wherein the interlayer film is a composition containing 1 to 500 parts by weight. The composition (X) is an ethylene / polar monomer copolymer (D) with respect to a total of 100 parts by weight of the propylene polymer (A) and the propylene polymer (B) as an optional component. The interlayer film for laminated glass according to any one of claims 1 to 9, which is a composition containing 1 to 500 parts by weight. One or more compounds selected from the group consisting of a silane compound, a titanium compound, an unsaturated carboxylic acid and an anhydride of an unsaturated carboxylic acid, at least a part of the composition (X) containing the propylene polymer (A) The interlayer film for laminated glass according to any one of claims 1 to 10, wherein the interlayer film is laminated with a graft. The composition (X) comprises a radical generator (G), the propylene polymer (A), the propylene polymer (B) as an optional component, and the ethylene / α-olefin copolymer as an optional component. 2. The composition containing 0.001 to 10 parts by weight with respect to 100 parts by weight as a total of the union (C) and the ethylene / polar monomer copolymer (D) as an optional component. The interlayer film for laminated glass according to any one of to 11 . The composition (X) comprises the propylene polymer (A), the propylene polymer (B) as an optional component, the ethylene / α-olefin copolymer (C) as an optional component, and an optional component. A component containing the ethylene / polar monomer copolymer (D) is 0.001 to 10 parts by weight of a radical generator with respect to 100 parts by weight in total of (A) + (B) + (C) + (D). The interlayer film for laminated glass according to claim 12, which is obtained by heat treatment in the presence of (G). The interlayer film for laminated glass according to any one of claims 1 to 13, wherein a layer made of plasticized polyvinyl butyral is laminated. A laminated glass comprising the interlayer film for laminated glass according to any one of claims 1 to 14 .