JP2007262330A - Laminated material comprising propylene copolymer or composition thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based laminated material that exhibits excellent adhesion properties, while retaining properties inherent in polypropylene, such as rigidity and heat resistance. <P>SOLUTION: The laminated material comprises a propylene copolymer or a composition thereof comprised of 100-30 wt.% of a polar group-containing propylene copolymer (A) that comprises 94.9-99.99 mol% of a propylene unit represented by structural formula (I), 0.01-0.1 mol% of a polar unit represented by structural formula (II) and 0-5 mol% of a non-polar unit represented by structural formula (III) and has a weight-average molecular weight Mw of 20,000-1,000,000, 0-50 wt.% of a propylene polymer (B) and 0-20 wt.% of a thermoplastic resin (C) other than a propylene polymer, where a mixture of the components (A), (B) and (C) has an MFR of 0.1-3,000 g/10 min. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a propylene-based copolymer and a bonding material using the composition, and more specifically, a novel propylene-based copolymer having a small amount of polar groups in the side chain and high stereoregularity of the propylene chain portion, or the same The present invention relates to a bonding material using the composition.

Polypropylene-based resin materials have many excellent performances, mainly moldability, various physical properties, economy and adaptability to environmental problems, and as one of the most important plastic materials, many Widely used and widely used in industrial materials in technical fields.
Polypropylene-based materials are chemically stable as an excellent performance, but on the other hand, the resin material is nonpolar, and therefore has disadvantages such as poor adhesion and adhesion. In particular, in the case of using general non-polar polypropylene in films, laminated materials, fiber products, molded products, etc., there is a disadvantage that the adhesion to the same material or other materials is inferior.

  Reflecting the diverse needs and high functionality of plastic materials in recent years, decorative items designed for daily necessities, various containers, industrial products and industrial materials using films, laminated materials, textile products and molded products Other films and laminates in addition to films and laminated materials, textile products and molded products, in order to impart high performance, or to provide high functionality such as gas permeation resistance, scratch resistance, high temperature resistance and sound absorption characteristics A method of bonding materials, textile products, molded articles, and the like is often employed.

For example, a wood grain pattern on a daily lunch box is often made by pasting a printed film on a sheet in a heated state, and an aluminum material around a plastic beverage container. A laminate of films is used, and flooring materials such as flooring are used by laminating a wide variety of films mainly made of polypropylene.
In those cases, when polypropylene material is used as a base material or a bonding material, it is not an exaggeration to say that the adhesiveness with the molded product to be bonded is a problem, and the improvement is strongly requested. Yes.

A variety of methods have been studied as an improved technology to meet the demands. For example, a method of bonding by applying physical treatment such as corona treatment or ozone treatment has been performed for a long time, The process is complicated, the adhesive force does not increase so much, and there are inherent defects such as a decrease in adhesive force over time.
On the other hand, methods using adhesives such as chlorinated polypropylene and anchor coat materials (Patent Documents 1 and 2) have also been used, but dioxins are generated when chlorinated products are incinerated, and anchor coat materials require the use of solvents. However, there are problems such as volatile components from the work environment and products.
On the other hand, a method of thermally bonding a thermoplastic resin in a semi-molten state (for example, Patent Document 3) is generally performed. However, there are restrictions on selection of materials to be bonded and difficulty of processes. Many.

As a method for imparting an adhesive function to a polypropylene resin, a method of improving the adhesion with a polar resin by grafting a polar monomer to polypropylene is widely performed (for example, Patent Document 4). However, it is necessary to add a large amount to polypropylene, and as a result, there is a problem that rigidity is lowered.
A method of introducing a polar monomer during propylene polymerization is also known. For example, a hydroxyl group-containing propylene copolymer obtained by copolymerizing propylene and 10-undecen-1-ol using a titanium catalyst is presented. However, since the hydroxyl group-containing propylene copolymer obtained by this method has a low stickiness and low rigidity due to the low degree of stereoregularity of amorphous by-products and main components.
Although a copolymer of propylene and a hydroxyl group-containing olefin using a metallocene catalyst is also disclosed (Patent Document 6), since the stereoregularity is not sufficient, the rigidity is low and the performance as a polypropylene material is insufficient. It is.

JP-A-6-41488 JP-A-6-134942 Japanese Patent Laid-Open No. 7-254035 JP-A-5-295337 JP 55-98209 A JP-A-8-53516

  In view of the above situation in the polypropylene resin material, the present invention improves the adhesiveness or bondability of the polypropylene material, and in the use of film or molded product, the adhesiveness with other molded products. It is an object to be solved by the present invention to develop a propylene-based resin material that does not deteriorate other properties of polypropylene.

In order to solve the above-mentioned problems of the invention, the present inventors have sought a method for improving adhesiveness or bondability in polypropylene-based materials. In polypropylene materials, resin surface modification methods and modifier addition methods Alternatively, considering various aspects such as composition with other materials, copolymerization with other monomers, and introduction of polar groups into the polypropylene molecule, in order to improve and improve such properties It was assumed that the application of the method for introducing a polar group is preferably appropriate.
By the way, in the past, the present inventors conducted research to improve the adhesion and rigidity of polypropylene in a well-balanced manner as an improvement study of polypropylene materials, and by introducing a small amount of hydroxyl groups as polar groups into the polypropylene polymer molecules, adhesion was achieved. The present inventors have developed a novel invention of a polypropylene copolymer in which both properties and rigidity are improved in a well-balanced manner and have filed it as an earlier invention (Japanese Patent Application No. 2004-274499 relating to the prior application of the present applicant). Applied such a new resin material to a bonding material in polypropylene resin, and improved adhesion to other molded products when used in film and molded product applications. It came to create the invention of the propylene-type resin material which does not reduce a characteristic (rigidity, heat resistance, etc.).

  The present invention is basically characterized in that it is molded using the bonding material of the present invention and adhered to a base material, and the present invention includes a polar group such as a trace amount of hydroxyl groups in a polypropylene polymer molecule. A polar group-containing propylene copolymer that has been introduced and copolymerized with other monomers, and a composition of the copolymer and another propylene polymer are used.

（式中、Ｒ^１は極性基を含有する炭素数１〜２０の炭化水素基を、Ｒ^２は水素或いは炭素数２〜２０の炭化水素基を表す。）
そして、その重量平均分子量Ｍｗが２０，０００〜１，０００，０００である極性基含有プロピレン共重合体（Ａ）１００〜５０重量％に対し、プロピレン系重合体（Ｂ）０〜５０重量％、プロピレン系以外の熱可塑性樹脂（C）０〜３０重量％が配合され、（Ａ）と（Ｂ）及び（Ｃ）の混合物のＭＦＲが０．１〜３，０００ｇ／１０分であると規定される。
本発明における、このような基本的な構成の要件が合理的であり、有意性を有することは、後記する各実施例と各比較例との対照により実証されている。 Specifically, in the present invention, the polar group-containing propylene copolymer is composed of structural units represented by the following structural formulas (I) to (III), and the propylene unit (I) is 94.9. ˜99.99 mol%, polar unit (II) is contained in a small amount of 0.01 to 0.1 mol%, nonpolar unit (II) is contained in an amount of 0 to 5 mol%, and the copolymer has a weight average molecular weight. And the melt flow rate (MFR) of the copolymer or composition thereof is also defined and constitutes a basic requirement in the present invention.

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms containing a polar group, and R ² represents hydrogen or a hydrocarbon group having 2 to 20 carbon atoms.)
And with respect to the polar group-containing propylene copolymer (A) having a weight average molecular weight Mw of 20,000 to 1,000,000 (100) to 50% by weight, the propylene-based polymer (B) is 0 to 50% by weight, A non-propylene thermoplastic resin (C) is blended in an amount of 0 to 30% by weight, and the MFR of the mixture of (A), (B) and (C) is defined as 0.1 to 3,000 g / 10 min. The
It is demonstrated by contrast with each Example and each comparative example which will be described later that the requirement of such a basic configuration in the present invention is reasonable and significant.

  Furthermore, in the present invention, incidentally, triad tacticity (mm fraction) of the monomer 3 chain portion centering on propylene consisting of head-to-tail bonds in the polar group-containing propylene copolymer (A), and its Q value (Mw / Mn), storage elastic modulus (G ′) at a temperature of 25 ° C., content of polar units per molecule of polymer, etc. are also specified, and the usage form and molding method of the bonding material are also specified It becomes.

In the above, the background of the creation of the present invention and the basic configuration and features of the invention have been described generally. Here, when overviewing the overall configuration of the present invention, the present invention has the following invention units. It consists of a group.
The invention in [1] constitutes a basic invention, and [2] each of the following inventions adds ancillary requirements to the basic invention or indicates an embodiment thereof.

（式中、Ｒ^１は極性基を含有する炭素数１〜２０の炭化水素基を、Ｒ^２は水素或いは炭素数２〜２０の炭化水素基を表す。）
［２］極性基含有プロピレン共重合体（Ａ）中の頭−尾結合からなるプロピレンを中心とするモノマー（但し、エチレンは除く）３連鎖部のトリアッドタクティシティー（ｍｍ分率）が９７．０％以上であることを特徴とする、［１］に記載された貼合材料。
［３］極性基含有プロピレン共重合体（Ａ）の重量平均分子量Ｍｗと数平均分子量Ｍｎの関係が、Ｑ値（Ｍｗ／Ｍｎ）として５以下であることを特徴とする、［１］又は［２］に記載された貼合材料。
［４］極性基含有プロピレン共重合体（Ａ）の固体粘弾性測定によって得られた温度２５℃における貯蔵弾性率（Ｇ’）が７３０〜２，０００ＭＰａであることを特徴とする、［１］〜［３］のいずれかに記載された貼合材料。
［５］極性基含有プロピレン共重合体（Ａ）のＲ^１及びＲ^２の炭素数が４〜８であることを特徴とする、［１］〜［４］のいずれかに記載された貼合材料。
［６］極性基含有プロピレン共重合体（Ａ）のＲ^１の極性基が水酸基であることを特徴とする、［１］〜［５］のいずれかに記載された貼合材料。
［７］重合体１分子当りの極性単位の含有量が、重合体の平均値として０．２〜２個であることを特徴とする、［１］〜［６］のいずれかに記載された貼合材料。
［８］［１］〜［７］のいずれかに記載された貼合材料を用いて成形し、成形時又はその後に基材を貼り合わせたことを特徴とする貼合成形品。
［９］押出成形又はブロー成形により成形されたことを特徴とする、［８］に記載された貼合成形品。
［１０］［９］に記載された貼合成形品を２次成形したことを特徴とする貼合成形品。
［１１］射出成形により成形されたことを特徴とする、［８］に記載された貼合成形品。
［１２］[１]に示す構造式（Ｉ）で表されるプロピレン単位９４．９〜９９．９９モル％、構造式（ＩＩ）で表される極性単位０．０１〜０．１モル％及び構造式（ＩＩＩ）で表される非極性単位０〜５モル％を含有し、その重量平均分子量Ｍｗが２０，０００〜１，０００，０００である極性基含有プロピレン共重合体（Ａ）９５〜３０重量％、プロピレン系重合体（Ｂ）１０〜５０重量％、及び／又は、プロピレン系重合体以外の熱可塑性樹脂（C）５〜３０重量％が配合され、成分（Ａ）と成分（Ｂ）及び／又は、成分（C）の混合物のＭＦＲが０．１〜３，０００ｇ／１０分であることを特徴とする、プロピレン系共重合体組成物。
［１３］[１]に示す構造式（Ｉ）で表されるプロピレン単位９４．９〜９９．９９モル％、構造式（ＩＩ）で表される極性単位０．０１〜０．１モル％及び構造式（ＩＩＩ）で表される非極性単位０〜５モル％を含有し、その重量平均分子量Ｍｗが２０，０００〜１，０００，０００である極性基含有プロピレン共重合体（Ａ）９５〜３０重量％、プロピレン系重合体（Ｂ）１０〜５０重量％、及び／又は、プロピレン系重合体以外の熱可塑性樹脂（C）５〜３０重量％が配合され、成分（Ａ）と成分（Ｂ）及び／又は、成分（C）の混合物のＭＦＲが０．１〜３，０００ｇ／１０分であることを特徴とする、プロピレン系共重合体組成物による貼合材料。 [1] 94.9 to 99.99 mol% of propylene units represented by the following structural formula (I), 0.01 to 0.1 mol% of polar units represented by the structural formula (II) and the structural formula ( III) The polar group-containing propylene copolymer (A) containing 0 to 5 mol% of nonpolar units represented by formula (III) and having a weight average molecular weight Mw of 20,000 to 1,000,000. , 0 to 50% by weight of the propylene polymer (B), and 0 to 30% by weight of the thermoplastic resin (C) other than the propylene polymer are blended, and the components (A), (B) and (C) A bonding material comprising a propylene-based copolymer or a composition thereof, wherein the mixture has an MFR of 0.1 to 3,000 g / 10 min.

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms containing a polar group, and R ² represents hydrogen or a hydrocarbon group having 2 to 20 carbon atoms.)
[2] Triad tacticity (mm fraction) of 3 chain portions of propylene-based monomer (however, excluding ethylene) consisting of a head-to-tail bond in the polar group-containing propylene copolymer (A) is 97. The bonding material according to [1], which is 0% or more.
[3] The relationship between the weight average molecular weight Mw and the number average molecular weight Mn of the polar group-containing propylene copolymer (A) is 5 or less as a Q value (Mw / Mn), [1] or [ 2] The bonding material described in.
[4] The storage elastic modulus (G ′) at a temperature of 25 ° C. obtained by solid viscoelasticity measurement of the polar group-containing propylene copolymer (A) is 730 to 2,000 MPa, [1] The bonding material described in any of [3].
[5] The bonding according to any one of [1] to [4], wherein R ¹ and R ² of the polar group-containing propylene copolymer (A) have 4 to 8 carbon atoms. material.
[6] The bonding material according to any one of [1] to [5], wherein the polar group of R ¹ of the polar group-containing propylene copolymer (A) is a hydroxyl group.
[7] It is described in any one of [1] to [6], wherein the content of polar units per molecule of the polymer is 0.2 to 2 as an average value of the polymer Pasting material.
[8] A pasted composite article, characterized in that it is molded using the pasting material described in any one of [1] to [7] and a base material is pasted at the time of molding or thereafter.
[9] The bonded composite article according to [8], which is formed by extrusion molding or blow molding.
[10] A pasted composite molded product obtained by secondary molding of the pasted synthetic molded product described in [9].
[11] The bonded composite article according to [8], which is formed by injection molding.
[12] 94.9 to 99.99 mol% of propylene units represented by the structural formula (I) shown in [1], 0.01 to 0.1 mol% of polar units represented by the structural formula (II), and Polar group-containing propylene copolymer (A) 95 to 95 containing non-polar units represented by structural formula (III) and having a weight average molecular weight Mw of 20,000 to 1,000,000 30% by weight, 10% to 50% by weight of the propylene polymer (B), and / or 5% to 30% by weight of the thermoplastic resin (C) other than the propylene polymer are blended, and the component (A) and the component (B ) And / or the mixture of component (C) has a MFR of 0.1 to 3,000 g / 10 min, a propylene-based copolymer composition.
[13] 94.9 to 99.99 mol% of propylene units represented by the structural formula (I) shown in [1], 0.01 to 0.1 mol% of polar units represented by the structural formula (II), and Polar group-containing propylene copolymer (A) 95 to 95 containing non-polar units represented by structural formula (III) and having a weight average molecular weight Mw of 20,000 to 1,000,000 30% by weight, 10% to 50% by weight of the propylene polymer (B), and / or 5% to 30% by weight of the thermoplastic resin (C) other than the propylene polymer are blended, and the component (A) and the component (B ) And / or the MFR of the mixture of the component (C) is 0.1 to 3,000 g / 10 min. A bonding material using a propylene-based copolymer composition.

  The bonding material of the present invention improves the adhesiveness required for molding applications compared to general polypropylene resins by using a polypropylene copolymer containing a specific trace amount of polar groups and a composition thereof. In addition, it is possible to control the rigidity and heat resistance of the performance, which are the original characteristics of the polypropylene resin, in a well-balanced manner.

  The outline of the present invention and the basic configuration and features of the present invention have been described above. In the following, the embodiments of the present invention are carried out in order to explain the entire invention group of the present invention in detail. Detailed description will be given in detail as the best mode for the above.

1. Propylene-based copolymer or composition thereof (1) Basic configuration The present invention basically includes (i) a polar group-containing propylene copolymer (A) having the following properties (paragraph 0019) or (ii) the (A) ), A propylene polymer (B), and a thermoplastic resin (C) other than the propylene polymer in a specific ratio is MFR 0.1 to 3,000, (i) It is the bonding material shape | molded by the composition which consists of a polar group containing propylene copolymer (A) or (ii) the (A) and (B) and (C).

（式中、Ｒ^１は極性基を含有する炭素数１〜２０の炭化水素基を、Ｒ^２は水素或いは炭素数２〜２０の炭化水素基を表す。）
ここで、構造式（Ｉ）で表されるプロピレン単位９４．９〜９９．９９モル％、構造式（ＩＩ）で表される極性単位０．０１〜０．１モル％及び構造式（ＩＩＩ）で表される非極性単位０〜５モル％を含有する。その重量平均分子量Ｍｗは２０，０００〜１，０００，０００とされる。 (2) Propylene-based copolymer (2-1) Basic rules The polar group-containing propylene copolymer (A) as a raw material for the bonding material of the present invention has the following structural formulas (I) to (III). The unit represented is contained in a specific ratio.

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms containing a polar group, and R ² represents hydrogen or a hydrocarbon group having 2 to 20 carbon atoms.)
Here, 94.9 to 99.99 mol% of propylene units represented by structural formula (I), 0.01 to 0.1 mol% of polar units represented by structural formula (II), and structural formula (III) 0-5 mol% of nonpolar units represented by The weight average molecular weight Mw is 20,000 to 1,000,000.

The polar group-containing propylene copolymer (A) of the present invention is essentially close to a propylene homopolymer because both of the units (II) and (III) are in trace amounts, and contains a trace amount of polar group units. There is a special feature.
If the content of the propylene unit represented by the structural formula (I) (the fraction of the unit in the total unit) is less than 94.9 mol%, the crystallinity is lowered and the elastic modulus and heat resistance are adversely affected. When it exceeds 99.99 mol%, it is difficult to introduce a desired amount of units represented by the structural formula (II) and the structural formula (III). Therefore, the preferable propylene unit content is selected from the range of 97.91 to 99.99 mol%, more preferably 99.82 to 99.97 mol%.

  The polar unit represented by the structural formula (II) is a unit mainly composed of a hydrocarbon group having a polar group in the side chain, and the content thereof is 0.01 to 0.00 with respect to all units of the polymer. It is selected from a very narrow range of 1 mol%. When this content exceeds 0.1 mol%, the effect of improving the adhesiveness is saturated, and adversely affects the excellent elastic modulus and heat resistance of the propylene copolymer. On the other hand, if it is less than 0.01 mol%, the effect of improving adhesiveness cannot be obtained. Therefore, the content of the preferred polar unit is selected from the range of 0.01 to 0.09 mol%, more preferably 0.02 to 0.08 mol%.

(2-2) R ¹ in Structural Formula (II)
R ¹ in the structural formula (II) is a C 1-20 aliphatic, alicyclic or aromatic hydrocarbon group having a polar group, which may have a branch, on the aromatic ring It may have a substituent and may have an unsaturated bond inside.
R ¹ is preferably an aliphatic hydrocarbon group. More preferably, it is a linear saturated hydrocarbon group. The polar group may be bonded to the primary carbon, or may be bonded to the secondary or tertiary carbon. Preferably, it is a polar group present at the side chain end position bonded to the primary carbon. The carbon number of R ¹ is preferably 2 to 10, more preferably 4 to 8.

Specific examples of R ¹ are shown below as chemical structural formulas. In the formula, P represents the main chain of the propylene copolymer and is represented as R ¹ bonded thereto, and the polar group is represented by a hydroxyl group as an example.

Polar group content In the propylene copolymer (A), the distribution of the polar unit represented by the structural formula (II) is arbitrary and is not particularly limited, and a polar group is mainly formed at the side chain position of the polymer. It becomes. However, when the polar unit represented by the structural formula (II) is bonded to the terminal position of the polymer, a polar group is formed at the terminal position, which is naturally included in the present invention.
The number of polar groups in the polar group-containing propylene copolymer depends on the molecular weight of the copolymer, but is usually 0.2 to 2, preferably 0.3 as an average value per polymer molecule. Selected from a range of ~ 1.5. At least one polar group is not required for all polymer molecules, and if the average value per polymer molecule is 0.2 to 2, the effect of the present invention can be sufficiently achieved.
The “average number of polar groups per molecule of polymer” (N) here is calculated by the following formula.
N = (Molar concentration of polar unit) * (Number average molecular weight of the polymer determined by GPC) / 42

The polar group of R ¹ in the structural formula (II) is selected from a hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an amino group, an amide group, an epoxy group, and a mercapto group. Among these, a hydroxyl group, a carboxylic acid group, and an amino group are preferable, and a hydroxyl group is particularly preferable.

(2-3) Unit represented by Structural Formula (III) The unit represented by Structural Formula (III) is a nonpolar unit having only a hydrocarbon group in the side chain, and its content is 0 to 5%. Preferably it is 0-2 mol%, Most preferably, it is 0.01-0.1 mol%. The content of the unit represented by the structural formula (III) may be zero, but conversely, if it exceeds 5 mol%, the polar group content is selected from the above range because it decreases the elastic modulus and heat resistance of the propylene copolymer. Is done.

R ² in Structural Formula (III) is hydrogen or an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may have a branch, and has a substituent on the aromatic ring. And may have an unsaturated bond inside. R ² is preferably hydrogen or an aliphatic hydrocarbon group, more preferably hydrogen or a linear saturated hydrocarbon group. When R ² is a hydrocarbon group, the number of carbon atoms is 2 to 20, preferably 2 to 10, and more preferably 4 to 8.

Specific examples of R ² are shown below. In the formula, P represents the main chain of the propylene copolymer.

(2-4) Analysis of ratio of each unit The existence ratio of each unit represented by the structural formulas (I), (II), and (III) is an analysis method such as ¹³ C-NMR, ¹ H-NMR, or FTIR. Can be determined. ^When determining using ¹³ C-NMR, for example, when R ² and R ³ in (II) and (III) are linear saturated hydrocarbon structures and a hydroxyl group is present at the end of the side chain of R ² , By referring to the relationship between the chemical shift value and the structure described in the document “Macromolecules 2002, 35 卷, p. 6760”, peak assignment can be performed and the abundance ratio of each unit can be calculated.

Specific measurement conditions are as follows.
Equipment used: GSX-400 manufactured by JEOL Ltd. Measurement temperature: 130 ° C. Solvent type: 80% by volume of o-dichlorobenzene + 20% by volume of deuterated benzene Decoupling: Proton complete decoupling Sample amount: 375 mg Integration number: 10 1,000 times Pulse angle: 90 ° Pulse interval: 10 seconds Sample tube: 10 mmφ Amount of solvent used: 2.5 ml

Peak assignments can be made according to various literature. For example, when R ^{1 of the} unit represented by the structural formula (II) is an n-butanol group (4-hydroxybutyl group) or an n-nonanol group (9-hydroxynonyl group), “Journal of Polymer Science: Part A Polymer Chemistry, 37, 2457 (1999) ”, and in the case of n-hexanol group (6-hydroxyhexyl group), structural unit (II) with reference to“ Macromolecules, 35, 6760 (2002) ” The peak derived from can be attributed.
As for the peak derived from the structural formula (III), when R ¹ is hydrogen, “Macromolecules, 10 773 (1977)”, “Polymer, 30 1350 (1989)”, ethyl group , N-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-butyl group, “Macromolecular Chemistry and Physics”, 204, page 1738 (2003) ” That's fine.

  The abundance ratio of the polar unit represented by Structural Formula (II) is obtained by using the sum of the peak intensities of methylene carbon in the main chain portion of the polymer as the denominator and the intensity of the characteristic peak derived from Structural Formula Unit (II) as the numerator. The obtained value is further divided by the number of moles of carbon that produce the characteristic peak used in the calculation contained in 1 mole of structural unit (II). Here, in many cases, the peak derived from the carbon atom adjacent to the polar group in the side chain portion of the structural formula unit (II) may be used as the characteristic peak used for the analysis.

The abundance ratio of the nonpolar unit represented by the structural formula (III) is based on the sum of the peak intensities of methylene carbons in the main chain portion of the polymer as the denominator, except when R ¹ in the structural formula (III) is hydrogen Then, the value obtained as a molecule of the intensity of the characteristic peak derived from the structural formula unit (III) is further divided by the number of moles of carbon producing the characteristic peak used in the calculation contained in 1 mol of the structural formula unit (III). Ask. Here, in many cases, the peak of the terminal methyl carbon of the side chain portion may be used as the characteristic peak used for the analysis.
When R ¹ in structural formula (III) is hydrogen, that is, when structural formula (III) is an ethylene monomer unit, for example, the method of “Macromolecules, Vol. 15, 1150 (1982)” is used. Then, the existence ratio may be calculated.

Further, as a more specific example below, when R ¹ is an n-hexanol group (6-hydroxyhexyl group) and R ² is an n-hexyl group, the following calculation formula is obtained.
Ratio of n-hexanol group = [o ¹ ] / [S _p + S _po + S _oo ]
Ratio of n-hexyl group = [h ¹ ] / [S _p + S _po + S _oo ]
An example of the partial chemical structure of the polymer in this case is shown below. Here, the meaning of each symbol is as follows.
o ¹ : represents carbon adjacent to the hydroxyl group in the hexanol group.
h ¹ : represents the terminal methyl carbon of the hexyl group.
T _p : represents a methine carbon adjacent to a methyl group derived from propylene in the main chain.
T _o: it represents a methine carbon adjacent to a hexyl group or hexanol group derived from a comonomer in the backbone.
S _p : represents a methylene carbon having a methine carbon T _p adjacent to a methyl group derived from propylene in the main chain at both ends.
S _po: a methylene carbon bearing across a methine carbon T _o adjacent hexyl group or hexanol group derived from methine carbon T _p and a comonomer which is adjacent to the methyl group derived from the main chain in the propylene.
S _oo: a methylene carbon bearing across a methine carbon T _o adjacent hexyl group or hexanol group derived from a comonomer in the backbone.
[] Represents the peak intensity, and the peak assignment was in accordance with the method described in “Macromolecules 2002, 35 卷, p. 6760”.

(2-5) Molecular Weight The polar group-containing propylene copolymer of the present invention needs to have a weight average molecular weight Mw of 20,000 to 1,000,000. If it is less than the lower limit, mechanical properties such as impact strength and tensile strength are lowered. On the other hand, when the upper limit is exceeded, the flowability at the time of molding deteriorates and is not practical. Mw is preferably 60,000 to 500,000.
The ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn is an index representing the extent of the molecular weight distribution of the polymer, and is also called the Q value. In the polar group-containing propylene copolymer of the present invention, the Q value is preferably 5 or less, preferably 2 to 5, and more preferably 3 to 5. If this upper limit is exceeded, the storage elastic modulus described later cannot be improved due to the presence of the units represented by the structural formulas (I) and (II), and therefore the rigidity cannot be improved. Also, in the process operation, when slurry polymerization or bulk polymerization is performed, low molecular weight components and low stereoregular components are eluted, or when gas phase polymerization is performed, the particles are aggregated to each other. There is an inconvenience that stable operation is impossible due to adhesion to the wall surface and blockage of the extraction pipe. On the other hand, if the molecular weight distribution is too narrow, the rigidity improving effect may not be exhibited. Therefore, the Q value is more preferably in the range of more than 3.0 and 4.8 or less. If it is 3.0 or less, orientation crystallization is less likely to occur, so the orientation of the polar group is also reduced, and the effect of improving the rigidity is reduced and the effect of the polar group such as adhesiveness is also reduced.

In the present invention, Mw and Mn are determined by gel permeation column chromatography (GPC). The specific measurement conditions are as follows.
Model used: Waters 150C Measurement temperature: 140 ° C Solvent: Orthodichlorobenzene (ODCB) Column: Showa Denko Shodex 80M / S 2 Flow rate: 1.0mL / min Injection volume: 0.2mL
Sample preparation: A sample was prepared as a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)), Dissolve in 1 hour.
Calculation of molecular weight: Standard polystyrene method

Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. The standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
The viscosity equation [η] = K × M ^α used for conversion to molecular weight uses the following numerical values.
PS: K = 1.38 × 10−4, α = 0.7
PE: K = 3.92 × 10−4, α = 0.733
PP: K = 1.03 × 10−4, α = 0.78
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm) Column: AD806M / S (three) manufactured by Showa Denko KK

(2-6) Triad tacticity (mm fraction)
The polar group-containing propylene copolymer (A) of the present invention has a triad tacticity (mm fraction) of a monomer 3 chain portion (provided that ethylene is excluded) mainly consisting of a head-to-tail bond. It is 0% or more, preferably 98.0% or more, more preferably 99% or more. If the mm fraction is less than the above, the crystallinity of the propylene portion is insufficient, and there is a concern that problems such as elastic modulus and heat resistance may occur.

但し、Ｘ、及びYはメチル基、構造式（ＩＩ）のR¹、構造式（ＩＩＩ）のR²の何れかであり、かつ水素を除くものである。
本発明に用いる極性基含有プロピレン共重合体が上記の部分構造のみを有する場合には、
ｍｍ分率＝ ｍｍ領域のピーク面積／（ｍｍ領域のピーク面積＋ｍｒ領域のピーク面積＋ｒｒ領域の目ピーク面積）×１００ ［％］として求められる。 The mm fraction is measured using a ¹³ C-NMR spectrum measured under the above conditions. In addition to the above-mentioned literature, spectrum assignment was performed with reference to “Macromolecules, 8 卷, pp. 67. A more specific method for determining the mm fraction is described below.
Peaks derived from the methyl group of the three-chain central propylene bonded head-to-tail around the propylene unit are generated in three regions depending on the configuration.
mm: about 22.5 to about 21.2 ppm
mr: about 21.2 to about 20.5 ppm
rr: about 20.5 to about 19.5 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight and copolymer composition, but the above three regions can be easily identified. The standard of chemical shift is that the peak of isotactic propylene 5-chain (mmmm) is 21.8 ppm. Here, mm, mr, and rr are each represented by the following structure.

However, X and Y are any of a methyl group, R < ¹ > of Structural formula (II), R < ² > of Structural formula (III), and exclude hydrogen.
When the polar group-containing propylene copolymer used in the present invention has only the above partial structure,
mm fraction = mm area peak area / (mm area peak area + mr area peak area + rr area eye peak area) × 100 [%].

部分構造PPEの中心プロピレン単位のメチル基（PPE−メチル基）は20.9 ppm付近のｍｒ領域で共鳴し、部分構造EPEの中心プロピレン単位のメチル基（EPE−メチル基）は20.2 ppm付近のrr領域で共鳴するため、このような部分構造を有する場合にはｍｒ、ｒｒ両領域のピーク面積から、PPE−メチル基及びEPE−メチル基に基づくピーク面積を減ずる必要がある。PPE−メチル基に基づくピーク面積は、対応するメチン基（31.0 ppm付近で共鳴）のピーク面積により評価でき、EPE−メチル基に基づくピーク面積は、対応するメチン基（33.3 ppm付近で共鳴）のピーク面積により評価できる。 When R ^{2 in} the structural formula (III) of the polar group-containing propylene copolymer used in the present invention is hydrogen (that is, includes an ethylene unit), it can have the following partial structure.

The methyl group (PPE-methyl group) of the central propylene unit of the partial structure PPE resonates in the mr region near 20.9 ppm, and the methyl group (EPE-methyl group) of the central propylene unit of the partial structure EPE is the rr region near 20.2 ppm. In the case of having such a partial structure, it is necessary to subtract the peak areas based on the PPE-methyl group and the EPE-methyl group from the peak areas of both the mr and rr regions. The peak area based on the PPE-methyl group can be evaluated by the peak area of the corresponding methine group (resonance around 31.0 ppm), and the peak area based on the EPE-methyl group is the resonance of the corresponding methine group (resonance around 33.3 ppm). It can be evaluated by the peak area.

このうち、炭素Ａ、Ａ’、Ａ”ピークはｍｒ領域に、炭素Ｂ、Ｂ’ピークはｒｒ領域に現れる。さらに炭素Ｃ、Ｃ’ピークは１６．８〜１７．８ｐｐｍに現れる。従って、頭−尾結合した３連鎖に基づかないピークでmr及びｒｒ領域に現れる炭素Ａ、Ａ’、Ａ”、Ｂ、Ｂ’に基づくピーク面積を減ずる必要がある。 Moreover, as a partial structure containing a position irregular unit, it may have the following structure (i), structure (ii), structure (iii), and structure (iv).

Among them, the carbon A, A ′, A ″ peaks appear in the mr region, and the carbon B, B ′ peaks appear in the rr region. Further, the carbon C, C ′ peaks appear in 16.8 to 17.8 ppm. -It is necessary to reduce the peak areas based on carbon A, A ', A ", B, B' appearing in the mr and rr regions with peaks that are not based on the tail-linked three linkages.

The peak areas based on carbon A are carbon D (resonance around 42.4 ppm), carbon E and G (resonance around 36.0 ppm), and carbon F (38.7 ppm) in the position irregular substructure [structure (i)]. It can be evaluated from 1/4 of the sum of the peak areas of resonance in the vicinity.
The peak areas based on carbon A ′ are carbon H and I (resonance around 34.7 ppm and around 35.0 ppm) and carbon J (34.1 ppm) in the position irregular substructure [structure (ii) and structure (iii)]. It can be evaluated by 2/5 of the sum of the peak areas of resonance in the vicinity and the sum of the peak areas of carbon K (resonance in the vicinity of 33.7 ppm).
The peak area based on the carbon A ″ can be evaluated by 1/2 of the carbon L (resonance at around 27.7 ppm).
The peak area based on carbon B can be evaluated by carbon J. The peak area based on carbon B ′ can be evaluated by carbon K.
Note that the positions of the carbon c peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.
Since the peak areas of mm, mr, and rr can be evaluated as described above, the mm fraction of the triple chain portion composed of the head-to-tail bond with the propylene unit as the center can be obtained according to the above formula.

3. Method for producing polar group-containing propylene copolymer (A)
The method for producing the polar group-containing propylene copolymer in the present invention is not particularly limited as long as it contains a predetermined amount of the above-described structural units and has a predetermined weight average molecular weight.
In the present invention, the method for producing a polar group-containing propylene copolymer (A) uses an alkenyl capable of introducing a specific polar group-containing monomer using a specific stereoregular catalyst, or introducing a polar group by post-treatment. Manufacture is possible by copolymerizing a dialkylaluminum monomer with propylene and converting the resulting polymer to a polar group by post-treatment.
Details of the available catalyst, specific copolymerization monomer, its production method and copolymerization method will be described below.

(1) Polymerization catalyst The polar group-containing propylene copolymer used in the present invention can be produced using a specific Ziegler catalyst known as a highly stereoregular catalyst, but preferably a metallocene catalyst is used. It can also be manufactured.
Examples of such highly stereoregular catalysts include solid components (component A) and organoaluminum compounds (component B) that require titanium, magnesium, halogen, and specific electron donating compounds, and electron donating compounds as optional components. From a so-called Ziegler-based catalyst such as a catalyst comprising (C component), or a metallocene complex (A ′ component), and a promoter component (B ′ component) such as an organoaluminum oxy compound, Lewis acid, anionic compound, and clay mineral The so-called metallocene catalyst is used.

(1-1) Ziegler-based catalyst As a titanium compound that constitutes a titanium source constituting a solid component (component A) essentially comprising titanium, magnesium, halogen, and a specific electron donating compound, a general formula Ti (OR) _4-n X _n (wherein R represents a hydrocarbon residue having 1 to 10 carbon atoms, X represents a halogen, and n is a number from 0 to 4), and titanium tetrachloride is exemplified. Tetraethoxy titanium, tetrabutoxy titanium and the like are preferable.

  Examples of the magnesium compound that serves as the supply source of magnesium include dialkyl magnesium, magnesium dihalide, dialkoxy magnesium, and alkoxy magnesium halide. Among these, magnesium dihalide is preferable.

  Examples of the halogen include fluorine, chlorine, bromine, and iodine. Among them, chlorine is preferable, and these are usually supplied from the titanium compound or the magnesium compound, but are aluminum halide, silicon halide, tungsten It may be supplied from other halogen sources such as halides.

As the organoaluminum compound (component B) in the Ziegler-based catalyst, the general formula R _m AlX _3-m (wherein R represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen, and m represents 1 to 3). It is possible to use a compound represented by: Examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, alkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and ethylaluminum sesquichloride, and alkylaluminum hydrides such as diethylaluminum hydride. Alumoxanes such as methylalumoxane and butylalumoxane can also be used.

Examples of electron donating compounds include alcohols, phenols, ketones, ethers, aldehydes, carboxylic acids, oxygen-containing compounds such as organic acids or inorganic acids and their derivatives, ammonia, amines, nitriles, isocyanates, etc. Organic silicon compounds and organic phosphorus compounds such as nitrogen-containing compounds are preferred. Among them, ethers, inorganic acid esters, organic acid esters, organic acid halides, and organic silicon compounds are preferred. Silicate esters, substituted succinic acid esters, and phthalic acids Polycarboxylic acid esters such as esters, acetic acid cellosolve esters, phthalic acid halides, diethers, and organic alkoxysilicon compounds are more preferred.
For example, the general formula RR ¹ _3-p Si such as t-butyl-methyl-dimethoxysilane, t-butyl-methyl-diethoxysilane, cyclohexyl-methyl-dimethoxysilane, cyclohexyl-methyl-diethoxysilane, dicyclopentyldimethoxysilane, etc. (OR ² ) _p (wherein R is a branched aliphatic hydrocarbon group having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms, preferably 6 to 10 carbon atoms. R ¹ represents a branched or straight-chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and R ² is an aliphatic carbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. Represents a hydrogen residue, and p is a number of 1 to 3.), 2,2-diisopropyl-1,3-diether, 2,2-diisobutyl-1,3-diete 1,3-diethers having 2,2-substituents such as ruthenium, polyvalent carboxylic acid esters such as butyl phthalate, octyl phthalate and dibutyl 1,2-diisopropyl succinate, and phthalic halides such as phthalic chloride Is preferred. It is also possible to use a plurality of these in combination.
Particularly preferred are 1,3-diethers, coexistence of 1,3-diethers, combined use of 1,3-diethers and organosilicon compounds represented by the above general formula, or phthalic acid esters and phthalic acid chlorides. A combination of a phthalic acid derivative such as the above and an organosilicon compound represented by the above general formula is particularly preferred.
In addition, these preferable electron donors can be used in the same manner as the electron donating compound (C component) not only during the production of the solid catalyst component but also during the polymerization in contact with the organoaluminum. And since the structure of the formula (II) is introduced, it is possible to keep practical practical properties without causing deterioration of physical properties such as rigidity even when good copolymerization or some different monomers are introduced. A Ziegler catalyst having excellent stereoregularity is preferred.

  In the propylene copolymer of the present invention, the amount of the catalyst component (A), the catalyst component (B) and the catalyst component (C) used may be arbitrary as long as the effect of the present invention is recognized. The following range is preferable. Component (A) contains 0.01 to 10,000 mol. Of titanium in component (A) with respect to propylene supplied to the reactor. The amount of component (B) used is 0.1 to 10,000 mol. per propylene fed to the reactor. ppm, preferably 1 to 1,000 mol. ppm, more preferably 10 to 300 mol. Within the ppm range. Moreover, the usage-amount of a component (C) is 0-100 mol. With respect to the propylene supplied to a reactor. ppm, preferably 0 to 50 mol. ppm, particularly preferably 0 to 20 mol. Within the ppm range.

(1-2) Metallocene-based catalyst As the metallocene compound (A ′ component) in the metallocene-based catalyst, it has a carbon bridge, or a silicon or germane bridge, and is substituted or unsubstituted cyclopentadiene, indene, fluorene, azulene, etc. Group 4 transition metal compounds having a ligand as a ligand are preferably used.

  Non-limiting specific examples include (i) carbon bridging systems such as ethylene bis (2,4-dimethylindenyl) zirconium chloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, isopropylidene. (3-methylindenyl) (fluorenyl) zirconium chloride, isopropylidene (2-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride and the like can be mentioned.

  (Ii) Examples of the silicon crosslinking system include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene bis (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis {2-isopropyl. -4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis {2-propyl-4- (9-phenanthryl) indenyl} zirconium dichloride, (9-silafluorenyl) bis {2-ethyl-4- ( 4-t-butylphenyl) indenyl} zirconium dichloride, dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl} zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (4-chloro) Phenyl) -4H-azurenyl} zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (4-tert-butyl-3-chlorophenyl) -4H-azurenyl} zirconium dichloride, dimethylsilylenebis {2-ethyl-4- ( 3-fluorobiphenylyl) -4H-azurenyl} zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl} zirconium dichloride, and the like.

(Iii) As the germane cross-linking system, a compound in which the silicon cross-linked silylene of (ii) above is replaced with germylene is used.
A compound in which zirconium is replaced with hafnium is exemplified as a suitable compound as it is. Furthermore, the dichloride of the exemplified compound may be exemplified by other halides, compounds substituted with a methyl group, an isobutyl group, a phenyl group, a hydride group, a dimethylamide, a diethylamide group, and the like as suitable compounds.

As the promoter (B ′ component) used for the metallocene catalyst, an organoaluminum oxy compound, a Lewis acid, an ionic compound, and a clay mineral can be used.
(I) Examples of organoaluminum oxy compounds include methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum tetraisobutyl butylboronate, methylaluminum bispentafluorophenoxide, diethylaluminum pentafluorophenoxide and the like.

(Ii) As the Lewis acid, a compound represented by BR ₃ (wherein R is a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group or a fluorine atom). For example, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) Examples include borane, tris (p-tolyl) borane, tris (o-tolyl) borane, tris (3,5-dimethylphenyl) borane, and inorganic compounds such as magnesium chloride and aluminum oxide.

  (Iii) Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetra (phenyl) borate, and tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate. Is mentioned. Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetra (phenyl) borate. Examples of ionic compounds other than ammonium salts include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, and ferrocenium tetra (pentafluorophenyl) borate.

(Iv) Examples of the clay mineral include montmorillonite, mica, teniolite, hectorite, modified products obtained by acid / salt treatment thereof, and composites with other inorganic oxides.
Of these, in the promoter system using clay minerals, the effect of the composition of the present invention is particularly remarkable.
Specifically, it is selected from the group consisting of an ion-exchange layered compound or an inorganic silicate, and the ion-exchange layered compound occupies most of the clay mineral, preferably an ion-exchange layered silicate. is there.
The ion-exchange layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other and having exchangeable ions.
Various known silicates can be used. Specifically, the following layered silicates described in “Clay Mineralogy” by Asakura Shoten (1995) by Haruo Shiramizu are given as typical examples.

2: 1 type minerals Montmorillonite, Sauconite, Beidellite, Nontronite, Saponite, Hectorite, Stevensite and other smectite groups; Vermiculite and other vermiculite groups; Pyrophyllite such as phyllite and talc-talc group; Chlorite group such as magnesium chlorite.
2: 1 Ribbon-type minerals such as sepiolite and palygorskite.

The amount of the catalyst component used is such that component (A ′) and component (B ′) are 0.001 to 100 mol. As for the usage-amount of ppm and a component (B '), 1-10,000 (weight ratio) are common with respect to a component (A').
In order to introduce the units (II) and (III) without deteriorating the performance such as catalytic activity and stereoregularity, it is preferable that the copolymerization is excellent, and among them, the metallocene catalyst Is preferably used.

(2) Production of copolymer There are various methods for producing the polar group-containing propylene-based copolymer (A), and typical examples are illustrated below.
(2-1) Propylene-alkenyldialkylaluminum copolymer intermediate intermediate method Propylene-based copolymer in which hydroxyl groups are introduced by oxygen decomposition after copolymerization of propylene and alkenyldialkylaluminum by the method described in JP-A-2003-246820. A polymer can be produced.
Although the alkenyldialkylaluminum used is a special monomer, its production method is known and disclosed in, for example, JP-A-2003-246820.
As the alkenyldialkylaluminum used in the present invention, the following general formula (1)
CH ₂ = CH—R—AlR ¹ R ² (1)
(In the formula, R represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a branch, and is an aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 20 carbon atoms. Yes, it may have a substituent on the aromatic ring and may have an unsaturated bond inside, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms. Can be used. Particularly preferably, the following general formula (2)
_{CH 2 = CH- (CH 2)} n -AlR 1 R 2 ····· (2)
(Wherein R ¹ and R ² are alkyl groups having 1 to 20 carbon atoms, and n is an integer of 1 to 20). Specifically, R ¹ and R ² are an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. N is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 4 or 6.
In addition, the alkenyl dialkyl aluminum whose dialkyl is diisobutyl (iBu) was illustrated below.

Method for producing alkenyldialkylaluminum compound:
The alkenyldialkylaluminum used in the present invention can be obtained by a number of known methods. For example, there are hydroalumination reaction of non-conjugated dienes, cross-coupling reaction of alkenyl halide and organoaluminum compound, transmetalation reaction of organometallic compound such as alkenyl lithium and alkenyl magnesium and organoaluminum compound.
Among these, a preferred method is a hydroalumination reaction of a nonconjugated diene, and an alkenyldialkylaluminum can be produced by reacting a nonconjugated diene and a dialkylaluminum hydride under mild conditions.

Copolymerization method of propylene and alkenyldialkylaluminum:
Since a catalyst for obtaining a copolymer of propylene and alkenyldialkylaluminum requires high stereoregularity (high mm) and high copolymerization performance, it is preferable to use a so-called metallocene catalyst. Moreover, it is necessary to employ | adopt appropriate polymerization conditions according to the ligand structure of a metallocene complex.

Below, the general manufacture example of the copolymer which introduce | transduced the hydroxyl group by the alkenyl aluminum copolymerization method is shown as an example of the polar group containing propylene copolymer (A) used by this invention.
Production of hydroxyl-containing propylene copolymer:
The hydroxyl group-containing propylene copolymer used in the present invention can be produced by reacting a propylene-alkenyldialkylaluminum copolymer with various decomposition agents. That is, it can be obtained by converting a dialkylaluminum group (carbon-aluminum bond) in the copolymer into a carbon-hydroxyl bond. The reaction with the decomposing agent can be carried out according to a known method relating to the reaction between a low molecular weight organoaluminum compound and an inorganic compound (example: R. Rienacker and G. Ohloff, Angew.chem., 1961, 73 卷, 240, P. Tesseire and M. Plattier, Recherches, 1963, 13 卷, 34 [Chem. Abstr., 1964, 60 卷, 15915]).
Examples of the decomposing agent include oxygen and peroxide. Moreover, it is possible to introduce | transduce a carboxylic acid group similarly by using a carbon dioxide instead of oxygen.

(2-2) Masking method Polar group of polar group-containing olefin monomer such as 5-hexen-1-ol, 5-hexenoic acid, 7-octen-1-ol, 10-undecenoic acid, 10-undecenoic acid methyl ester Is masked with organoaluminum, copolymerized with propylene, and finally the masking is removed. Here, the masking means that the polar group does not act as a catalyst poison during the polymerization reaction by bringing the polar group-containing olefin monomer into contact with the organic aluminum. Moreover, the polar group masked during the polymerization can be returned to the original polar group while removing the aluminum atom by contacting with a compound containing active hydrogen after the polymerization. Examples of the compound containing active hydrogen include alcohols such as methanol and ethanol, and water. For this method, reference can be made to JP-A-55-98209 and JP-A-8-53516.

Copolymerization of propylene and masked polar group-containing olefin monomer:
Since a copolymer of propylene and a masked polar group-containing olefin monomer requires high stereoregularity (high mm) and high copolymerization performance, it is preferable to use a so-called metallocene catalyst. Moreover, it is necessary to employ | adopt appropriate polymerization conditions according to the ligand structure of a metallocene complex. Moreover, the part of (III) can be introduce | transduced by making a C4-C22 alpha olefin coexist in the case of copolymerization.

Specific polymerization method / mode:
This is a common matter between the above-described (2-1) propylene-alkenyldialkylaluminum copolymer intermediate method and (2-2) masking method.
In the production method described above, any polymerization method can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a bulk method using propylene as a solvent without using an inert solvent, a solution polymerization method, or a gas phase method using substantially no liquid solvent can be employed. . Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene or the like is used alone or as a polymerization solvent.
The polymerization temperature is −50 to 200 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure can be carried out in the range of greater than 0 to 5 MPa, but as described above, it is important to employ appropriate polymerization conditions depending on the metallocene complex used.

(2-3) Introduction of unit represented by structural formula (III) In the polar group-containing propylene copolymer used in the present invention, the unit represented by structural formula (III) is introduced into the copolymer. As a method, in addition to alkenyldialkylaluminum as a comonomer, it can be produced by coexisting ethylene or an α-olefin having 4 or more carbon atoms. However, as another method, the ratio of converting a dialkylaluminum group to a hydroxyl group is 100%. There are techniques that are not allowed to occur. That is, in the decomposition reaction, when oxygen and the propylene-alkenyldialkylaluminum copolymer are brought into contact with each other, alcohol or water is mixed, oxygen is brought into contact with the content of alkenyldialkylaluminum or less (equivalent or less), or the reaction. By changing the temperature, time, etc. of time, the carbon-aluminum bond of the dialkylaluminum group that is not converted to a hydroxyl group is simply hydrolyzed (converted to a carbon-hydrogen bond) and converted to the unit of structural formula (III) It is possible. In this way, the propylene copolymer of the present invention can be produced by partial decomposition without adding an α-olefin having 4 or more carbon atoms during the copolymerization reaction.

4). Various characteristic values (1) Storage elastic modulus G '
The storage elastic modulus G ′ is assumed to be at a temperature of 25 ° C. obtained by solid viscoelasticity measurement. Specifically, the solid viscoelasticity measurement is performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress, the strain, and the phase difference between the stresses. Here, the frequency is 1 Hz, and the measurement temperature is raised in a step shape from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus G ′ is obtained as a component having the same phase as the strain by a known method.
The storage elastic modulus of the polypropylene homopolymer not containing the structural unit (II) (III) is about 730 MPa, as is clear from the comparative examples described later, but the structural unit (III) is 0.01 to 0.1. According to the present invention in the case of mol%, this can be improved to a level exceeding 800 MPa.

(2) Control of mm fraction and storage elastic modulus G ′ (2-1) Change in stereoregularity / isotactic triad tacticity (mm fraction) The mm fraction is the stereoregular performance of the catalyst used. In the case of Ziegler-based catalysts, titanium-containing solid catalyst components such as phthalates and 1,3-diethers that improve steric regulation are treated with an internal donor, and a silicon compound that further enhances stereoregularity is used as an external donor. The catalyst used as is preferably used.
Moreover, when using a metallocene catalyst system, mm fraction can be raised and G 'can be improved by using a metallocene complex with high isotactic stereoregular performance. Specifically, a transition metal compound having a specific ligand structure described later is used. It is more preferable to use a racemate in the form of a crosslinked complex. As a preferred ligand structure, a bridging group bisindenyl type or bridged bisazulenyl type ligand is used. By introducing a specific bulky substituent such as a phenyl group or a substituted phenyl group at the 4-position having a methyl group, an ethyl group or an isopropyl group at the 2-position, the mm fraction has a high value of about 99%. Then, by controlling the polymerization temperature and the polymerization pressure, the mm fraction value can be controlled to a desired value between 97% and 100%.
Further, the storage elastic modulus G ′ is also affected by the quantity ratio of the structural units (II) and (III), and in order to achieve 730 MPa or more, the device is controlled to 0.1 mol% or less. is required. Particularly preferably, the structural unit (III) is zero.

(2-2) Number of branches in the polymer The branch in the polymer means a side chain portion based on the structural unit (II) or (III). In the region where the total number of branches is 0.2 mol% or less, the degree of crystallinity is higher than that of polypropylene having no branch, and G ′ is improved. When the number exceeds 0.2 mol%, the degree of crystallinity is reversed. By decreasing, G ′ becomes smaller. This phenomenon is influenced by the molecular weight distribution of polypropylene, and is a phenomenon particularly noticeable when the molecular weight distribution (Q value) is lower than 5. The number of branches can be controlled by the comonomer concentration, temperature and pressure during copolymerization.

5). Propylene polymer (component (B))
(1) Type of polymer The propylene polymer (B) used in the propylene resin composition of the present invention can be any propylene polymer other than the polar group-containing propylene copolymer (A). Specifically, a propylene homopolymer, a random copolymer of propylene and ethylene or / and an α-olefin having 4 or more carbon atoms, a propylene / ethylene block copolymer, and the like can be given. These propylene polymers (B) can be selected according to the purpose. For example, when adjusting the MFR of the entire propylene resin composition, the propylene homopolymer, propylene and ethylene or / and 4 carbon atoms. Use any of the above-mentioned random copolymers with α-olefins and propylene / ethylene block copolymers, taking into consideration the MFR and amount of the polar group-containing propylene copolymer (A), and an appropriate amount of MFR The propylene polymer (B) is selected and used. When the molecular weight distribution and the moldability are adjusted, the same concept can be used. Also, depending on the application, a propylene homopolymer is used when improvement in rigidity is required, and a random combination of propylene and ethylene or / and an α-olefin having 4 or more carbon atoms when transparency or flexibility is required. When it is necessary to improve the low temperature impact resistance, a propylene / ethylene block copolymer can be selected and added to the copolymer. If necessary, these propylene polymers (B) can be used in a plurality of types.

(2) Amount used It is 10% to 45% by weight, more preferably 15% to 40% by weight of the propylene polymer (component (B)).

6). Thermoplastic resin (component (C))
The thermoplastic resin component (C) is an optional component in the composition of the present invention. If necessary, an elastomer such as polyethylene, polyolefin-based elastomer, SEBS, SBR, EPR, maleic acid-modified polyolefin, acid-modified polyolefin, etc. Other polymers such as a modified material, polystyrene, ABS, PET, and nylon may be added in a range that does not impair the physical properties, that is, in the range of 0 to 30% by weight, preferably 10 to 30% by weight.

7). Preparation method of polypropylene resin composition (1) Mixing ratio In the present invention, polar group-containing propylene copolymer (component (A)) is 100 to 30% by weight, propylene polymer (component (B)) is 0 to 50% by weight. In addition, 0 to 20% by weight of a thermoplastic resin (component (C)) other than propylene is blended. The component (A) is blended in an amount of 100 to 30% by weight, preferably 95 to 30% by weight, more preferably 90 to 50% by weight. Component (B) is blended in an amount of 0 to 50% by weight, preferably 10 to 45% by weight, and more preferably 15 to 40% by weight. If it is 50% by weight or more, the adhesiveness is still poor. Component (C) is 0 to 30% by weight, preferably 5 to 30% by weight, and more preferably 10 to 20% by weight. When 30% by weight or more is blended, the dispersion with polypropylene deteriorates, and the workability and mechanical properties are reduced. It will adversely affect physical properties.

(2) Mixing The mixing method of components (A), (B), and (C) can be performed by any known blending method. For example, after dry blending each material, it is used as a hopper of a molding apparatus. A method of supplying, or a method of supplying to a molding device after dry blending and then melt-kneading with a single-screw extruder, a twin-screw extruder, a kneader, a ruder or the like can be raised.

(3) Additives In the propylene-based resin composition of the present invention, auxiliary additive components generally used for polyolefins as necessary, for example, antioxidants, neutralizers, heat stabilizers, light stabilizers, ultraviolet rays, are used. Absorbent, antistatic agent, antifogging agent, foaming agent, slip agent, antiblocking agent, antibacterial agent, colorant, flame retardant, conductive material, antistatic material, etc., talc, carbon black, glass fiber, oxidation Inorganic and organic fillers such as titanium, calcium carbonate, carbon fiber, carbon nanotube, fullerene, mica, non-organically modified or organically modified clay, glass beads, acrylic polymer beads, silica gel, etc. Can do.

(4) MFR
The resin composition finally adjusted has a melt flow rate (MFR) of 0.2 at 230 ° C. and 21.18 N according to JIS-K6921 as a physical property after addition in order to maintain the workability of the molding to be performed next. It is necessary to satisfy the relationship of 1 to 3,000 g / 10 min. In the case of extrusion molding and blow molding, it is preferably 0.1 to 50 g / 10 min, more preferably 0.5 to 30 g / 10. Minutes. In the case of the injection molding method, preferably, it is 1 to 300 g / 10 minutes, more preferably 5 to 250 g / 10 minutes. When the MFR is less than 0.1 g / 10 minutes, the extrusion pressure becomes high in extrusion molding and the like, and the extrusion becomes unstable, and in injection molding and the like, the resin does not turn to the corner of the mold. On the other hand, if it exceeds 300 g / 10 minutes, dripping after extrusion occurs, it does not adhere to the cooling roll, the blowdown is too large in blow molding, and blow cannot be performed, and the injection molding causes defective extrusion. is there.

8). Molding method The polypropylene-based bonding material of the present invention is molded by a known method using the above mixture. In extrusion molding, when classified by shape, it is classified into a film shape, a cylindrical shape, an irregular shape, a fiber shape, and the like, and in addition to being subjected to secondary processing as required, it is directly processed into a form such as a molded product. Extrusion molding and calender molding methods that extrude into a plate shape from a die or the like are generally used for the plate shape. After forming into a plate shape, secondary molding is performed by methods such as vacuum forming, pressure forming, vacuum / pressure forming, plug forming, and press forming. It can also be processed into a molded product.
Extrusion conditions are not particularly limited, and the extruder is selected from a single screw and a twin screw. There is no particular restriction on the cooling after extrusion, too, narrow pressure cooling with a polishing roll, winding with a single-sided chill roll, cooling one side with an air knife, water cooling, single-sided or double-sided endless steel belt. There are methods. In addition to mirror finish, the roll may be textured. After cooling, it is possible to perform a uniaxial or biaxial stretching process, and simultaneous biaxial and sequential biaxial stretching methods can be used. There are no particular limitations on post-treatment such as flame treatment after cooling and solidification, corona treatment, and coating.

Examples of the cylindrical shape include an inflation molding method, a water-cooled inflation molding method, and a round die molding method. For the irregular shape, the die after the extruder is extruded using an irregular shape, and is nipped and wound by a roll or a conveyor.
Examples of methods for directly processing into molded products include blow molding, rotational molding, and injection molding. In a general blow molding method, a parison is extruded from the tip of an extruder, clamped with a mold, and then blown with air to finish a hollow molded product. Otherwise, cold stretch blow can also be used. This is done by molding a precursor molded body in advance by an injection molding method, etc., heating the precursor molded body and then blowing it in a clamped mold. It is a method to process. A general method can be used for injection molding and rotational molding.
In each molding method, for example, at the time of melt extrusion, a chemical foaming agent such as sodium bicarbonate or citric acid, or a physical foaming agent such as carbon dioxide, butane, or nitrogen can be added for foaming.

9. Bonding composite article When the bonding material of the present invention is used for molding and bonding to a substrate, it can have an adhesion step immediately after molding or after molding.
The base material can be selected from molded products of general materials, but it is preferable to bond with the propylene resin on the molding line, so paper, paperboard, aluminum, iron, copper, etc. Polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polybutylene terephthalate, polyester such as polyethylene naphthalate, EVOH, ABS, polycarbonate, EVA, nylon 6, nylon 12, nylon MXD6, Non-stretched or stretched films, sheets, rayon, cotton cloth, woven fabrics, and other materials having a polar group, such as polyamides such as nylon 6/66 and nylon 66, and polylactic acid, are preferable, such as polypropylene, polyethylene, and polystyrene. Non-polar group plastic , Etc. when subjected to printing in the lamination surface, the general propylene resin when the material having an adhesive hardly polar group is present at the bonding surface are preferred.
The target form of bonding is preferably a sheet form such as a film, a sheet, a nonwoven fabric, a cloth, or a woven fabric. For example, in the case of blow molding, injection molding, etc., when insert molding is performed, it is extended to the shape of the mold. Therefore, a sheet-like material composed of a thermoplastic resin is preferable among the above materials, and even if it is not a thermoplastic resin, it is preliminarily formed into a shape suitable for the die as a part of the die shape. It must be processed.
The structure of the molded article can be either a single layer or multiple layers, but it is necessary to dispose the resin composition of the present invention in the layer on the side to be bonded in order to improve the adhesion to the substrate.

Hereinafter, the bonding method in each molding will be described. In the case of extrusion molding, generally, there is a thermal lamination method, an extrusion lamination method, etc., in which the base material is fed out to the molten resin portion at the die outlet and cooled and solidified simultaneously at the cooling roll portion after the molten resin and the base material contact. To be elected. In the case of extrusion lamination, the propylene-based resin of the present invention has improved affinity with adhesives such as anchor coating agents having other polar groups. However, there is a problem such as volatilization of the solvent, and it is preferable not to use it. In addition, for non-woven fabrics, sheets, etc., after the sheet or non-woven fabric is once cooled and solidified, it is heated with a dielectric heating roll or the like, and the substrates are bonded together to be bonded.
Moreover, in the case of a laminated product, this resin composition is preferably used for the outer layer on the side to be bonded. In addition to the layers necessary for the actual adhesion, a foamed layer, a gas barrier layer, a filler layer, a conductive layer, a recycled layer, and the like can be multilayered in order to provide performance and functions according to each application.
On the other hand, in the case of blow molding, rotational molding, and injection molding, the base film, sheet, or preformed shaped body is inserted into the mold cavity, the mold is closed, and the molten resin is injected. In the case of filling and blow molding, a pasted composite product can be obtained by blow-up.

10. Preferred fields of application For the purpose of improving the adhesiveness in the present invention, as an example, food containers, food packaging materials, daily necessities such as stationery, industrial materials, industrial parts such as automobile parts, etc. Suitable for applications that require functionality.

In the following, in order to describe the present invention more specifically and clearly, the present invention will be described in contrast to Examples and Comparative Examples, and the rationality and significance of the requirements of the constitution of the present invention will be demonstrated. In addition, the measuring method of the physical property in a following example is as follows.
(1) Content of units represented by structural formulas (I), (II), and (III) (mol%)
According to the NMR method detailed in paragraphs 0028-0033.
(2) Average molecular weight (Mw and Mn) and molecular weight distribution (Q value)
According to the GPC method described in detail in paragraphs 0034 to 0036.
(3) Storage elastic modulus (G ')
The sample used was a hot-press molded sheet of 2 mm thickness cut into a strip shape of 10 mm width × 18 mm length × 2 mm thickness. The apparatus uses ARES manufactured by Rheometric Scientific, and the frequency is 1 Hz. The measurement temperature was raised from −60 ° C. in a stepwise manner until the sample melted and became impossible to measure, and the strain was in the range of 0.1 to 0.5%.
(4) Measurement of melting peak temperature (Tm) Using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.), a sample piece made into a sheet is packed in a 5 mg aluminum pan, and the heating rate from room temperature to 200 ° C is 100 ° C. The maximum melting temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min after being crystallized by lowering to 40 ° C. at 10 ° C./min. ).
(5) MFR value According to the method described in paragraph 0077.

[Production Example 1]
[Method for Producing Copolymer Sample 1]
[Production of Metallocene Compound] Dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl} zirconium dichloride was synthesized by the method described in Example 1 of JP-A-11-240909.
[Production of octenyl diisobutylaluminum] 1,7-octadiene (800 ml; 5.6 mol) and diisobutylaluminum hydride (100 ml; 0.56 mol) were added to a 2,000 ml glass reactor equipped with a stirrer at 60 ° C. for 6 hours. Reacted. Thereafter, the remaining 1,7-octadiene was removed under reduced pressure to obtain a reaction product. This reaction product was analyzed by gas chromatography (GC) and NMR. In the GC analysis, 0.5 ml of the reaction product was diluted with 2 ml of metaxylene (internal standard), and then decomposed by adding distilled water and hydrochloric acid and used for the analysis. As a result, it was confirmed that octenyl diisobutylaluminum was quantitatively produced.

[Production of Clay-Supported Catalyst] 96% sulfuric acid (750 g) was added to 1,130 g of distilled water in a separable flask, and then Benclay SL (average particle size) manufactured by Mizusawa Chemical Co., Ltd., which is an ion-exchange layered silicate (montmorillonite). 27 μm, 300 g) was added and reacted at 90 ° C. for 390 minutes. Thereafter, it was washed with distilled water to pH 3. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed and further dried under a nitrogen stream at 200 ° C. to obtain 141 g of chemically treated montmorillonite. The composition of the chemically treated smectite was Al: 4.6% by weight, Si: 41.4% by weight, Mg: 0.59% by weight, Fe: 0.9% by weight, and Na <0.2% by weight.

[Preparation of catalyst / preliminary polymerization catalyst] The inside of a 1 L three-necked flask was replaced with dry nitrogen, 20 g of the chemically treated montmorillonite obtained above was added, and 116 mL of heptane was further added to form a slurry, which was tri-normal octyl. After adding 50 mmol of aluminum and stirring for 1 hour, it was washed with heptane (washing rate: 1/100), and heptane was added so that the total volume became 200 mL.
In another flask (volume: 200 mL), dimethylsilylenebis {2-methyl-4- (p-chlorophenyl) -4H-azurenyl} zirconium dichloride (218 mg; 0.3 mmol) was added to heptane containing 3% toluene. After making the slurry, triisobutylaluminum (3 mmol: 4.26 mL of a heptane solution having a concentration of 145 mg / mL) was added, and the mixture was reacted by stirring at room temperature for 60 minutes. This solution was placed in a 1 L flask containing a slurry of chemically treated montmorillonite reacted with the above-described tri-normal octyl aluminum and stirred for 1 hour. To the flask containing the pre-prepolymerization catalyst slurry, 213 mL of 3% toluene-containing heptane was added, and this slurry was introduced into a 1 L autoclave.
Propylene was fed to the autoclave at a rate of 10 g / hour for 4 hours, and prepolymerization was performed while maintaining 40 ° C. Thereafter, the propylene feed was stopped, the internal temperature was raised to 50 ° C. in 5 minutes, and the remaining polymerization was further performed for 2 hours. The supernatant of the obtained catalyst slurry was removed by decantation, and triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added to the remaining portion, followed by stirring for 10 minutes. This solid was dried under reduced pressure at 40 ° C. for 3 hours to obtain 67.3 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.24.

[Copolymerization with propylene] In a 15 L stainless steel autoclave with stirring and temperature control, 5 L of dehydrated and deoxygenated n-heptane, 6.06 mmol of triisobutylaluminum, and n-heptane were diluted. Octenyl diisobutylaluminum (0.33 mol) and then propylene were introduced, and the internal pressure was adjusted to 65 MPa at 65 ° C. Thereafter, 5 g of the prepolymerized catalyst obtained above was introduced as a solid catalyst component, polymerization was started, and polymerization was carried out at 65 ° C. for 4 hours.

[Post-treatment of copolymer sample 1] After the completion of polymerization, the remaining propylene monomer was purged and then treated by blowing 600 L of dry oxygen over 2 hours at 30 ° C., and further 400 ml of butanol was added, followed by treatment at 70 ° C. for 1 hour. . Next, the slurry was transferred to another tank with a stirrer, 5 L of pure water in which 5 g of sodium hydroxide was dissolved was added, and the mixture was treated at 80 ° C. for 1 hour. Thereafter, the water tank was allowed to stand and then separated, and the slurry separated the heptane with a centrifugal separator to recover the polymer. The obtained polymer was dried at 100 ° C. for 5 hours under a nitrogen stream. As a result, 1.45 kg of a propylene copolymer was obtained. When this polymer was analyzed and evaluated, the content of the unit of structural formula (I) was 99.85 mol%, the content of the unit of structural formula (II) was 0.08 mol%, and structural formula (III) The content of the unit was 0.07 mol%, and the weight average molecular weight was 214,000. The results are shown in Table 1 together with other results.

[Production Example 2]
[Production of solid catalyst] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a sufficiently nitrogen-substituted flask, and then 0.4 mol of MgCl ₂ and 0 of Ti (On-C ₄ H ₉ ) ₄ were added. .8 moles were introduced and reacted at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane. Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.006 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Then, 2.5 mol of TiCl ₄ was introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the mixture was thoroughly washed with n-heptane, and 2.5 mol of TiCl _{4 was} further introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the solid component (A1) for producing the component (A) was thoroughly washed with n-heptane. The titanium content of this product was 2.6% by weight.
Further, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 5 g of the solid component synthesized above was introduced, and (t-C ₄ H ₉ ) Si (CH ₃ ) ( 1.2 ml of OCH ₃ ) _{2 and} 1.7 grams of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. The titanium content of this product was 2.3% by weight.

[Propylene copolymerization] 5 L of dehydrated and deoxygenated n-heptane, 6.06 mmol of triethylaluminum, and octenyldiisobutyl diluted with n-heptane in a 15 L stainless steel autoclave with stirring and temperature control device 0.62 mol of aluminum was introduced, followed by propylene, and the internal pressure was adjusted to 70 MPa at 70 ° C. Thereafter, 0.25 g of the prepolymerized catalyst obtained above was introduced as a solid catalyst component, polymerization was started, and polymerization was carried out at 70 ° C. for 2 hours.

[Post-treatment of copolymer sample 2] After the completion of polymerization, the remaining propylene monomer was purged, and then treated by blowing 600 L of dry oxygen over 2 hours at 30 ° C., and further 400 ml of butanol was added, followed by treatment at 70 ° C. for 1 hour. . Next, the slurry was transferred to another tank with a stirrer, 5 L of pure water in which 5 g of sodium hydroxide was dissolved was added, and the mixture was treated at 80 ° C. for 1 hour. Thereafter, the water tank was allowed to stand and then separated, and the slurry separated the heptane with a centrifugal separator to recover the polymer. The obtained polymer was dried at 100 ° C. for 5 hours under a nitrogen stream. As a result, 1.29 kg of a propylene copolymer was obtained. The results are shown in Table 1 together with other results.

[Production Example 3]
In Production Example 1, the same procedure as in Production Example 1 was conducted, except that the comonomer octenyl diisobutylaluminum was not used, the polymerization temperature was changed from 65 ° C. to 60 ° C., and the polymerization time was changed from 5 hours to 3 hours. Polymerization was performed. 1.59 kg of propylene polymer was obtained. The results are shown in Table 1.

[Production Example 4]
Into a 15 L stainless steel autoclave with stirring and temperature control device, 5 L of fully dehydrated and deoxygenated n-heptane, 46.8 ml of 7-octen-1-ol (8-hydroxy-1-octene) ( 0.31 mol) and 0.341 mol of triisobutylaluminum were introduced. After 10 minutes, a mixed gas of propylene / ethylene (weight ratio) = 40/1 was introduced, and adjusted to 0.4 MPa at 60 ° C. Thereafter, 2 g of the prepolymerized catalyst synthesized in Production Example 1 was introduced to initiate polymerization. In order not to lower the pressure due to the polymerization, the pressure was maintained with a mixed gas having the same weight ratio, and the polymerization was carried out for 3 hours.

[Post-treatment of copolymer sample 4] After the completion of polymerization, the remaining propylene monomer was purged, and 1,000 ml of butanol was added, followed by treatment at 70 ° C for 1 hour. Next, the slurry was transferred to another tank with a stirrer, 5 L of pure water in which 5 g of sodium hydroxide was dissolved was added, and the mixture was treated at 80 ° C. for 1 hour. Thereafter, the water tank was allowed to stand and then separated, and the slurry separated the heptane with a centrifugal separator to recover the polymer. The obtained polymer was dried at 100 ° C. for 5 hours under a nitrogen stream. As a result, 1.23 kg of a propylene copolymer was obtained. The results are shown in Table 1 together with other results.

[Production Example 5]
[OH group masking and propylene copolymerization / post-treatment] Into a 15 L stainless steel autoclave with stirring and temperature control, 5 L, 7-octen-1-ol (8 46.8 ml (0.31 mol) of 3-hydroxy-1-octene) and 0.341 mol of triisobutylaluminum were introduced. Ten minutes later, propylene was introduced, and the internal pressure was adjusted to 65 MPa at 65 ° C. Thereafter, 3 g of the prepolymerized catalyst obtained above was introduced as a solid catalyst component, polymerization was started, and polymerization was carried out at 65 ° C. for 5 hours. The post-treatment after completion of the polymerization was carried out in the same manner as in Production Example 4. As a result, 1.3 kg of a propylene copolymer was obtained. The results are shown in Table 1 together with other results.

[Production Example 6]
In an oil bath, 7 L of xylene, 1015 g of homopolypropylene (manufactured by Nippon Polypro Co., Ltd., product name: Novatec PP, MA3) was dissolved at 140 ° C. in a 10 L glass flask equipped with a stirrer. Next, the xylene solution of maleic anhydride (0.58 g / 300 ml) and the dicumyl peroxide (DPC) xylene solution (0.048 g / 60 ml) were gradually fed to the xylene solution from separate conduits over 4 hours. . After the feed yield, the reaction was continued for another 30 minutes and then cooled to room temperature to precipitate the polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. overnight to obtain a modified propylene polymer. This modified propylene homopolymer was subjected to elemental analysis and the amount of maleic anhydride grafted was measured. As a result, maleic anhydride corresponding to 0.1 mol% was graft polymerized. The results for the modified propylene homopolymer are shown in Table 1.

[Example 1]
[Film production method]
100 parts by weight of the copolymer sample 1 obtained above, 0.1 parts by weight of IR1010 manufactured by Ciba Specialty Chemicals as an antioxidant, and calcium stearate (made by Nitto Kasei Kogyo, trade name Ca-St as a neutralizer) ) Is mixed at a high speed of 500 rpm for 3 minutes with a Henschel mixer, and then melted, kneaded, cooled and cut under the conditions of an extrusion temperature of 230 ° C. using a φ30 mm single screw extruder (manufactured by Union Plastics). Thus, a propylene resin composition in the form of pellets was prepared (composition composition is shown in Table 1).
The obtained composition was melt-extruded from a die having a width of 350 mm and a lip opening of 0.5 mm to an extrusion temperature of 250 ° C. using an extrusion laminator of a 30 mm single-screw extruder, and the surface temperature of the cooling roll was 25 ° C. The amount of extrusion was adjusted so that the coating thickness was 30 μm at 20 m / min, and laminating was performed on kraft paper having a width of 370 mm and a basis weight of 75 g / m ² .
Evaluation of adhesive strength of the obtained sample was performed by the following method. Adhesive evaluation method: The sample prepared by the above method was cut into 1 cm × 7 cm, and the interface was peeled off by about 1 cm using a cutter. Using the sample thus prepared, it was attached to the chuck of a tensile tester (Shimadzu Corporation, Autograph AG1000A), and the maximum load when it was peeled off at a speed of 50 mm / min in the 180 ° direction was recorded.

[Example 2]
In Example 1, evaluation was performed in the same manner as in Example except that a biaxially stretched PET film (diafoil manufactured by Diafoil Hoechst) having a width of 370 mm and a thickness of 12 μm was used.
[Example 3]
In Example 1, a width of 370 mm, a thickness of PET 12 μm (diafoil manufactured by Diafoil Hoechst) / aluminum foil 8 μm (manufactured by Toyo Aluminum Co., Ltd.) was dry-laminated with a urethane adhesive in advance, and was used as a base material. Evaluation was performed in the same manner as in the examples. In addition, the aluminum side was used for the bonding surface.
[Example 4]
Evaluation was performed in the same manner as in Example 1 except that the biaxially stretched nylon film (emblem manufactured by Unitika Co., Ltd.) of 12 μm was used.
[Example 5]
In Example 2, with respect to 80 parts by weight of the copolymer sample 1, 20 parts by weight of a metallocene propylene-ethylene random copolymer (Wintech WFX4T manufactured by Nippon Polypro Co., Ltd.) was used, and the evaluation was performed in the same manner.
[Example 6]
In Example 2, 80 parts by weight of copolymer sample 1 was used, and 20 parts by weight of propylene-ethylene block copolymer (Newcon NHF5015A manufactured by Nippon Polypro Co., Ltd.) was used.
[Example 7]
In Example 2, 90 parts by weight of the copolymer sample 1 was used, 10 parts by weight of metallocene polyethylene (kernel KS340 manufactured by Nippon Polyethylene Co., Ltd.) was used, and the following evaluation was performed in the same manner.
[Example 8]
In Example 3, 10 parts by weight of ethylene propylene rubber (EP07P manufactured by JSR) was used for 90 parts by weight of the copolymer sample 1, and the same evaluation was performed in the same manner.
[Example 9]
In Example 2, with respect to 90 parts by weight of copolymer sample 1, 10 parts by weight of hydrogenated styrene-butadiene copolymer (Dynalon 1320P manufactured by JSR) and Newcon NHF5015A manufactured by Nippon Polypro Co., Ltd. were used. Evaluation was performed in the same manner.
[Example 10]
In Example 2, molding evaluation was carried out in the same manner except that 100 parts by weight of Sample 4 was used.

[Example 11]
100 parts by weight of the copolymer sample 2 obtained above, 0.1 parts by weight of IR1010 manufactured by Ciba Specialty Chemicals as an antioxidant, and calcium stearate (made by Nitto Kasei Kogyo, trade name Ca-St as a neutralizer) ) Is mixed at a high speed of 500 rpm for 3 minutes with a Henschel mixer, and then melted, kneaded, cooled and cut under the conditions of an extrusion temperature of 230 ° C. using a φ30 mm single screw extruder (manufactured by Union Plastics). Thus, a propylene resin composition in the form of pellets was prepared (composition composition is shown in Table 1). Using a 30 mm single screw extruder, the obtained composition was melt-extruded from a die having a width of 350 mm and a lip opening of 0.8 mm to an extrusion temperature of 230 ° C., and the take-up speed and extrusion amount were adjusted to a thickness of 500 μm. The PET film used in Example 2 was adjusted and subjected to narrow pressure cooling with three polishing rolls having a cooling roll surface temperature of 40 ° C., and at that time, the portion subjected to narrow pressure cooling with two polishing rolls from the die outlet. Was passed through at the same time and heat lamination was performed. The heat-laminated sheet was wound up to obtain a sheet sample having a width of 330 cm. The adhesive strength of the sample thus obtained was evaluated.
[Example 12]
In Example 11, 90 parts by weight of the copolymer sample 2 and 10 parts by weight of a propylene-ethylene block copolymer (Newcon NHF5015A manufactured by Nippon Polypro Co., Ltd.) were used, and the evaluation was performed in the same manner.

[Example 13]
A laminate sheet section of vertical 100 mm × horizontal 10 mm cut out from the PET / aluminum foil sheet used in Example 3 was injected into an injection mold (vertical 100 mm × horizontal 100 mm, 0.5 mm thickness × 100 mm side film gate, After inserting and fixing the aluminum foil surface on the inner side of the step side of the step side cavity of a cavity thickness of 3.0 mm from the film gate to a distance of 50 mm and a cavity thickness of 1.0 mm from the distance of 50 mm to 100 mm, the gold The mold was closed and injection molding machine (clamping pressure: 170 tons, molding temperature: 210 ° C.), pellets mixed with 100 parts by weight of sample 5 as in Example 1, were melt-kneaded, injected, injected, and lengthened. A 100 mm × 100 mm laminated plate injection molded product was obtained and evaluated.
[Example 14]
In Example 8, a 30φ biaxial structure adjusted to 230 ° C. using 60 parts by weight of sample 5, 30 parts by weight of ethylene-propylene rubber (EPR EP02P manufactured by JSR), 10 parts by weight of talc, and 2 parts by weight of carbon black. Molding evaluation was carried out in the same manner except for melt-kneading with a granulator and pelletizing.

[Comparative Example 1]
In Example 2, molding evaluation was carried out in the same manner except that 100 parts by weight of Sample 3 was used.
[Comparative Example 2]
In Example 5, with respect to 40 parts by weight of the copolymer sample 1, 60 parts by weight of a metallocene propylene-ethylene random copolymer (Wintech WFX4T manufactured by Nippon Polypro Co., Ltd.) was used and evaluated in the same manner.
[Comparative Example 3]
In Example 2, molding evaluation was carried out in the same manner except that 100 parts by weight of Sample 7 was used.
The above evaluation results are shown in Table 2.

[Consideration of results of Examples and Comparative Examples]
By examining and contrasting each Example and Comparative Example according to Tables 1 and 2 above, the bonding material of the present invention satisfies all the constituent requirements in Claim 1 of the claims. It has been shown to be excellent in adhesion. In addition, from the data of melting peak temperature and storage elastic modulus in Table 1, it is shown that the original polypropylene performance such as rigidity and heat resistance is not deteriorated in the polypropylene resin material of the present invention. .
Since the bonding material of each comparative example does not satisfy the constituent requirements in claim 1, it is shown that the adhesiveness is inferior.
Specifically, in Examples 1 to 4, 10, 11, and 13, in the bonding material using the propylene-based copolymer having a polar group, the good results of the improvement in adhesion that the present invention has a problem are shown. In Examples 5 to 9, 12, and 14, similar good results are shown in the composition of the propylene-based copolymer having a polar group and another polymer.
On the other hand, in Comparative Example 1, since the polar group is not present, the adhesiveness is poor, and in Comparative Example 2, since the blending amount of the polar group-containing propylene copolymer is insufficient in the composition, the adhesiveness is poor. In Comparative Example 3, since the polypropylene resin is grafted with a polar group different from that of the present application, the adhesiveness is deteriorated.
From the above, the rationality and significance of the requirements of the configuration in the present invention and the superiority of the present invention over the prior art are clarified.

Claims (13)

Propylene units 94.9 to 99.99 mol% represented by the following structural formula (I), polar units 0.01 to 0.1 mol% represented by the structural formula (II) and structural formula (III) 100 to 30 wt% of a polar group-containing propylene copolymer (A) containing 0 to 5 mol% of the nonpolar units represented and having a weight average molecular weight Mw of 20,000 to 1,000,000, propylene-based MFR of a mixture of component (A), component (B), and component (C) is blended with 0 to 50% by weight of polymer (B) and 0 to 30% by weight of thermoplastic resin (C) other than propylene-based polymer. Is a paste material made of a propylene-based copolymer or a composition thereof, characterized by being 0.1 to 3,000 g / 10 min.

(In the formula, R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms containing a polar group, and R ² represents hydrogen or a hydrocarbon group having 2 to 20 carbon atoms.) Triad tacticity (mm fraction) of 3 chain parts of propylene-based monomer (excluding ethylene) consisting of head-to-tail bond in polar group-containing propylene copolymer (A) is 97.0% or more The bonding material according to claim 1, wherein the bonding material is. The relationship between the weight average molecular weight Mw and the number average molecular weight Mn of the polar group-containing propylene copolymer (A) is 5 or less as a Q value (Mw / Mn), according to claim 1 or 2. Pasting material. The storage elastic modulus (G ′) at a temperature of 25 ° C. obtained by solid viscoelasticity measurement of the polar group-containing propylene copolymer (A) is 730 to 2,000 MPa, The bonding material described in any one. The bonding material according to claim ^1, wherein R ¹ and R ² of the polar group-containing propylene copolymer (A) have 4 to 8 carbon atoms. The bonding material according to claim ¹ , wherein the polar group of R ¹ of the polar group-containing propylene copolymer (A) is a hydroxyl group. The bonding material according to any one of claims 1 to 6, wherein the content of polar units per molecule of the polymer is 0.2 to 2 as an average value of the polymer. A pasted composite article, characterized in that it is molded using the bonding material according to any one of claims 1 to 7, and a base material is pasted at the time of molding or thereafter. The pasted composite article according to claim 8, which is formed by extrusion molding or blow molding. A pasted composite molded product according to claim 9, wherein the pasted synthetic molded product is secondarily molded. The pasted composite article according to claim 8, which is formed by injection molding. From 94.9 to 99.99 mol% of propylene units represented by the structural formula (I), 0.01 to 0.1 mol% of polar units represented by the structural formula (II) and structural formula (III) 95-30 wt% of a polar group-containing propylene copolymer (A) containing 0-5 mol% of the nonpolar units represented and having a weight average molecular weight Mw of 20,000-1,000,000, propylene-based 10 to 50% by weight of the polymer (B) and / or 5 to 30% by weight of the thermoplastic resin (C) other than the propylene-based polymer are blended, and the component (A), the component (B) and / or the component ( A propylene-based copolymer composition, wherein the mixture (C) has an MFR of 0.1 to 3,000 g / 10 min. From 94.9 to 99.99 mol% of the propylene unit represented by the structural formula (I), 0.01 to 0.1 mol% of the polar unit represented by the structural formula (II) and the structural formula (III) 95-30 wt% of a polar group-containing propylene copolymer (A) containing 0-5 mol% of the nonpolar units represented and having a weight average molecular weight Mw of 20,000-1,000,000, propylene-based 10 to 50% by weight of the polymer (B) and / or 5 to 30% by weight of the thermoplastic resin (C) other than the propylene-based polymer are blended, and the component (A), the component (B) and / or the component ( The paste material by the propylene-type copolymer composition characterized by MFR of the mixture of C) being 0.1-3000 g / 10min.