JP2007262631A - Fiber formed from propylene-based copolymer or composition thereof, and textile product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-based fiber material and textile products thereof, which are excellent in dyeability and hydrophilicity, causes no degradation of inherent performance of polypropylene, such as rigidity and heat resistance. <P>SOLUTION: The fiber formed from a propylene-based copolymer or composition thereof, is compounded with 100-30 wt.% polar group-containing propylene copolymer (A) which includes 94.9-99.99 mol% propylene unit represented by structural formula (I), 0.01-0.1 mol% polar unit represented by structural formula (II) and 0-5 mol% nonpolar unit represented by structural formula (III), and has 20,000-1,000,000 weight-average molecular weight, 0-50 wt.% propylene-based polymer (B) and 0-20 wt.% thermoplastic resin (C) other than the polypropylene-based polymer, wherein MFR of the mixture of the ingredient (A), the ingredient (B) and the ingredient(C) is 1-3,000 g/10 min (wherein, R<SP>1</SP>is a 1-20C hydrocarbon containing a polar group; and R<SP>2</SP>is H or a 2-20C hydrocarbon). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fiber molded from a propylene-based copolymer or a composition thereof and a fiber product thereof. More specifically, the present invention relates to a novel propylene having a small proportion of polar groups in a side chain and high stereoregularity of a propylene chain portion. The present invention relates to a fiber molded from a copolymer or a composition thereof and excellent in dyeability and hydrophilicity, and a fiber product using the same.

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.
Among the many technical fields, there is a field of use in fiber materials, which are used as woven fabrics and non-woven fabrics as fabrics, such as clothing, daily necessities, medical supplies, and electrical materials.
Polypropylene-based materials are chemically stable as an excellent performance, but on the other hand, the resin material is nonpolar, and therefore has disadvantages inferior in adhesiveness, dyeability and hydrophilicity. The lack of dyeability should be improved when used in general clothing that requires colorful dyeing and design, even though it is suitable for carpets and medical fabric materials because of its good stain resistance. It is a drawback, and hydrophilicity is generally an important property in garment materials, and the lack of hydrophilicity has been desired to be improved.
In particular, the dyeability is a required performance that is essential for fiber materials for applications such as apparel and daily necessities, as well as visibility in fishing lines. Therefore, there is a strong demand for improving the dyeability of polypropylene fiber materials.

For this reason, many improvements have been proposed so far in order to improve the dyeability of polypropylene-based materials. In the method of improving dyeability, at present, as a method of coloring a fiber spun with polypropylene, a method of adding a pigment in the melt spinning process is mainly used, but the clear coloring property obtained with a dye is used. Is difficult to respond to multi-color development (color variations) adapted to various needs, and the polypropylene fibers colored with pigments become hard and the flexibility is impaired, and further, Problems such as adverse effects on the processability of colored pigments and poor dispersion have been pointed out.
As another method, a dyeing method using a surface modification method for a polymer material is disclosed (see, for example, Patent Document 1). In order to modify the surface of a polyolefin material such as polypropylene or polyethylene, ozone treatment or ultraviolet light is used. The dyeing property is improved by combining the steps of graft copolymerization of vinyl compound by styrene and grafting Hoffmann rearrangement having an amide group. However, although this method improves the dyeability, it requires a plurality of steps, and it takes a long time only for the ozone treatment or ultraviolet treatment steps, and is expensive even commercially, and is not a practical method.
In addition, many methods have been proposed for adding a specific substance during processing, such as a method of adding an alkyl sulfonate Na salt, a method of causing an aromatic ring-polybrominated olefin compound to act during thermal processing, and exhibiting dyeability. However, it is difficult to say that it is appropriate because it leads to a decrease in physical properties, a problem of workability, a risk of using chemicals and an increase in cost.
Furthermore, as a method of adding a polymer having other polar groups, for example, a method of adding a hydrogenated diene polymer, a method of adding an alkyl acrylate-ethylene copolymer, and the like have been proposed (for example, patents). (Refer to Literatures 4 and 5), and it is difficult to say that it is suitable for practical use, such as deterioration of physical properties due to poor dispersion and difficulty in workability due to viscosity change.
Furthermore, there is a method of adding a polymer additive to a specific polypropylene resin (see Patent Document 6), but even a polymer additive causes bleed and the like, resulting in insufficient improvement in dyeability. Color loss due to dry cleaning may occur.

On the other hand, many methods for improving dyeability by introducing a polar group during propylene polymerization are also known. For example, propylene and 10-undecene-1 are produced using a titanium trichloride catalyst in which titanium trichloride and diethylaluminum chloride are combined. -Although a hydroxyl group-containing propylene copolymer obtained by copolymerizing ol is disclosed (see Patent Document 7), an amorphous by-product is produced in the hydroxyl group-containing propylene copolymer obtained by this method. However, since the stereoregularity of the main component is low, problems such as increased stickiness and low rigidity are derived.
In addition, although it is known as a copolymer of propylene and a hydroxyl group-containing olefin using a metallocene catalyst as an object of improving paintability (see Patent Document 8), the stereoregularity is not sufficient, so the rigidity is low. The performance as a polypropylene material is an unsatisfactory level. In addition, many copolymers with polar group-containing comonomers mainly composed of ethylene or propylene monomer are known (see, for example, Patent Documents 9 and 10). These are mainly polyethylene-based copolymers. Even if the disclosed highly stereoregular catalyst is used for polypropylene, the polymer obtained is rigid because it requires a certain amount of polar group content to impart adhesion and paintability. Is not sufficient, and it cannot be said that the balance between the properties imparted with a polar group such as a hydroxyl group and the rigidity derived from high stereoregularity is sufficient.
Furthermore, a method of obtaining a hydroxyl group-containing propylene copolymer by an oxidation reaction after obtaining a copolymer of propylene and an alkenyldialkylaluminum has been recently proposed (see Patent Document 11). Other physical properties are not good enough.

  As an example other than the random copolymer of propylene and polar group-containing comonomer as described above, a block copolymer in which a polyolefin block and a functional segment are connected by an ether bond is used as a molded article for medical and hygiene purposes. The use of fibers and non-woven fabrics has been proposed (see Patent Document 12), but this copolymer is produced as a by-product of a homopolymer of functional segments and used in a blend with a propylene polymer. There is a problem that impairs its characteristics.

  In addition to dyeability, hydrophilicity, which is important as the performance of fiber materials, includes daily necessities such as diapers and sanitary products, industrial building materials such as concrete reinforcements, electrical and electronic parts such as battery separators, adhesive bandages and leukocyte removal materials. Even if a method similar to the above-described method for improving dyeability is used as a method for improving it, which is required in various applications across medical supplies, an improved method similar to the improvement in dyeability can be obtained. Although it is difficult, and a method of directly acting a surfactant or other chemicals based on sulfuric acid has been taken (see, for example, Patent Documents 13 and 14), in terms of physical properties such as contamination resistance on the other side. It is pointed out.

JP-A-7-90783 (summary) Japanese Patent Laid-Open No. 5-272006 (summary) JP-A-6-200065 (Summary) JP 9-302098 A (summary) Japanese National Patent Publication No. 10-501309 (Abstract and Claims 1.) JP 2000-8223 (Abstract and paragraph 0003) Japanese Patent Laid-Open No. 55-98209 (claims 1. and 2 on the lower right column) JP-A-8-53516 (claim 2 and paragraph 0001) JP 2002-145944 A (summary) JP 2002-145945 A (summary) JP 2003-246820 A (summary) JP 2001-278932 A (summary) JP 2002-313306 (Abstract) International Publication No. WO99 / 10025 (abstract and claims 1, 8)

  In view of the state of the prior art when using a polypropylene-based resin as a fiber material as described above as the background art, the present invention is excellent in both dyeability and hydrophilicity, as well as the original polypropylene such as rigidity and heat resistance. It is an object of the present invention to develop a polypropylene fiber material and its fiber product that do not deteriorate the performance.

In order to solve the above-described problems of the present invention, the present inventors have sought a method for improving both the dyeability and hydrophilicity of polypropylene-based materials. In order to improve and improve both of these properties, various considerations have been made regarding the formation of a method or a composition with other materials, a copolymerization with other monomers, and the introduction of polar groups into polypropylene molecules. It was assumed that application of a method for introducing a polar group is preferable and 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). Recognizes that such a new resin material can be applied to the solution of the problems of the present invention, and in order to solve the problems of the present invention, the resin material of the prior invention is further studied and experimentally studied. Was examined.
In the process, it can be found that a specific propylene copolymer having a small amount of polar groups introduced into a polymer molecule and a composition thereof can improve both dyeability and hydrophilicity. I came to create.

As a result, it exhibits the performance that satisfies both the dyeability and the hydrophilicity required for fiber materials and textiles such as fabrics, woven fabrics, and nonwoven fabrics, and further, the rigidity, impact resistance, and heat resistance of polypropylene resins. It has been possible to realize the development of a polypropylene-based material that can maintain the original performance such as stretchability and moldability.
Then, the present invention introduces a polar group-containing propylene copolymer in which a polar group such as a small amount of hydroxyl group is introduced into the polypropylene polymer molecule, and other monomers are copolymerized, and further, the copolymer and other propylene polymers. A fiber material is formed by molding a composition such as a coalescence.

（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）０〜２０重量％が配合され、（Ａ）と（Ｂ）及び（Ｃ）の混合物のＭＦＲが１〜３，０００ｇ／１０分であると規定される。 Specifically, in the present invention, such a polar group-containing propylene copolymer comprises structural units represented by the following structural formulas (I) to (III), and the propylene unit (I) is 94. 9 to 99.99 mol%, the polar unit (II) is contained in a trace amount of 0.01 to 0.1 mol%, and the nonpolar unit (II) is contained in an amount of 0 to 5 mol%. The molecular weight and the melt flow rate (MFR) of the copolymer or its composition are also defined and constitute the 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 thermoplastic resin (C) other than the propylene-based resin (C) is blended in an amount of 0 to 20% by weight, and the MFR of the mixture of (A), (B) and (C) is defined as 1 to 3000 g / 10 min.

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.
In the present invention, a specific small amount of polar group is introduced into the polypropylene molecule, and an optional component but other monomer components are also introduced, a novel polypropylene copolymer or a copolymer thereof and another polymer, With this new composition, both dyeability and hydrophilicity are improved in a balanced manner when used for fiber materials, and other properties of polypropylene-based materials are not deteriorated, and epoch-making features are exhibited. However, the requirements and features of such a configuration are not found in the patent documents of the prior art in the background art described above.

  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 The Q value (Mw / Mn), the storage elastic modulus (G ′) at a temperature of 25 ° C., the content of polar units per molecule of polymer, etc. are also defined. Or it is considered as a nonwoven fabric etc.

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］における繊維。
［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］における繊維。
［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］のいずれかにおける繊維。
［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］のいずれかにおける繊維。
［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］のいずれかにおける繊維。
［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］のいずれかにおける繊維。
［８］［１］〜［７］のいずれかにおける繊維により形成されたことを特徴とする、布帛及び織物又は不織布。
［９］スパンボンド法、メルトブローン法、水流交絡法又はカード法のいずれかの方法により製造されたことを特徴とする、［８］における不織布。 [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 20% by weight of the thermoplastic resin (C) other than the propylene polymer are blended, and the components (A), (B) and (C) A fiber molded from a propylene-based copolymer or a composition thereof, wherein the mixture has an MFR of 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 fiber 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].
[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 fiber in any one of [3].
[5] The fiber 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.
[6] The fiber 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] The fiber according to 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 polymers.
[8] A fabric, a woven fabric, or a non-woven fabric, which is formed of the fiber according to any one of [1] to [7].
[9] The nonwoven fabric according to [8], which is produced by any one of a spun bond method, a melt blown method, a hydroentanglement method, or a card method.

The fiber of the present invention and the fiber product thereof use a polypropylene-based copolymer containing a specific trace amount of polar groups, so that the dyeability required for the fiber and the fiber product is higher than that of a general polypropylene-based resin. And hydrophilicity are both improved.
Compared to the conventional improved technology, it is relatively easy to control the dyeability and hydrophilic performance as well as the inherent characteristics of polypropylene resin such as rigidity and heat resistance. Is.

  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 1 to 3,000, and (i) a polar group A propylene copolymer (A) or (ii) is a fiber material molded from a composition comprising (A), (B) and (C).
That is, the basic invention of the present invention (the invention of [1] in paragraph 0015) is a fiber material molded from the raw material of either aspect (i) or (ii).

（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 fiber and the fiber product of the present invention has the following structures (I) to (III): The unit represented by the formula is contained at 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 dyeability 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 dyeability 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%. In applications in which rigidity is important, it is preferably 0 to 2 mol%, particularly preferably 0.01 to 0.1 mol%. On the other hand, in applications requiring flexibility, it is preferably 1 to 5 mol%, more preferably 2 to 4 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 in the range of 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
An example of the baseline and section of the obtained chromatogram is shown in FIG.

(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, cyclopentadiene, indene, fluorene, or azulene having a carbon bridge or a silicon or germane bridge group and substituted or unsubstituted is used. A Group 4 transition metal compound as a ligand is 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)
(Wherein R represents an optionally branched divalent hydrocarbon group having 1 to 20 carbon atoms, and 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, there is a device such as controlling each to 0.1 mol% or less. is necessary. 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 Since the amount of the propylene polymer (component (B)) used is too large, the dyeability and hydrophilicity become insufficient, so that it is 50% by weight or less, preferably 40% by weight or less, more preferably. 30% by weight or less.

6). Thermoplastic resin (component (C))
The thermoplastic resin component (C) is an optional component in the composition of the present invention, and, if necessary, polyethylene, elastomers such as polyolefin elastomers, SEBS, SBR, EPR, maleic acid modified polyolefins, acid modified polyolefins. Other modifiers such as polystyrene, ABS, PET, and nylon are used as modifiers.
You may add the usage-amount in the range which does not impair a physical property, ie, the range of 0-20 weight%, Preferably it is 0-10 weight%.

7). Propylene-based copolymer composition (1) blending amount and mixing In the present invention, polar group-containing propylene copolymer (component (A)) 100 to 30% by weight, propylene-based polymer (component (B)) 0 to 0 50% by weight and 0 to 20% by weight of a thermoplastic resin (component (C)) other than propylene are blended. Component (A) is blended in an amount of 100 to 30% by weight, preferably 100 to 50% by weight, more preferably 100 to 70% by weight. If it is less than 30% by weight, the dyeability and hydrophilicity are poor.
Component (B) is blended in an amount of 0 to 50% by weight, preferably 0 to 40% by weight, more preferably 0 to 30% by weight. If it exceeds 50% by weight, the dyeability and hydrophilicity are also inferior. Component (C) is blended in an amount of 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0 to 5% by weight. It will adversely affect mechanical properties.
The mixing adjustment method of the components (A), (B), and (C) can be performed by any known blending method. For example, each material is supplied to the hopper of the melt spinning apparatus after dry blending. Examples thereof include a method, or a method of supplying the melt spinning apparatus after dry blending by melt kneading with a single screw extruder, a twin screw extruder, a kneader, a ruder or the like.

(2) Additives The propylene-based copolymer composition for fibers and textiles of the present invention includes auxiliary additive components generally used for polyolefins as required, such as antioxidants, neutralizers, and heat. Stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, antifogging agents, slip agents, antiblocking agents, antibacterial agents, colorants, flame retardants, conductive materials, antistatic materials, and the like can be blended.

(3) MFR value The resin composition finally adjusted is melt flow rate at 230 ° C. and 21.18 N according to JIS-K6921 as a physical property after addition in order to maintain the moldability of subsequent melt spinning. (MFR) needs to satisfy the relationship of 1 to 3000 g / 10 min, preferably 5 to 100 g / 10 min, more preferably 10 to 90 g / 10 min, and more preferably 15 ~ 80 g / 10 min. In that case, if the MFR is less than 1 g / 10 minutes, the spinning pressure becomes too high, drawing at high magnification becomes difficult, and problems such as uneven fiber diameters occur. On the other hand, if it exceeds 3,000 g / 10 minutes, the melt viscosity is low, so that the yarn sway becomes noticeable at the time of spinning, and the adjacent yarns are fused together and yarn breakage frequently occurs. The same applies when a propylene-based copolymer alone is formed into a fiber.

8). Forming Method for Fiber and Textile Product The polypropylene fiber of the present invention is fiberized by a known melt spinning method using a propylene copolymer or a composition thereof.
The shape of the fiber may be a single, core-sheath type composite fiber, or side-by-side type composite fiber. In the case of a composite fiber, the fiber from the propylene resin composition is included as one component of either fiber. It only has to be. The fineness of the polypropylene fiber is not particularly specified, but is preferably 0.01 to 1000 dtex, more preferably 0.1 to 100 dtex. In addition, the fabric, woven fabric, and nonwoven fabric of the present invention are produced using the polypropylene fiber, or are produced directly from the polypropylene resin composition. In particular, the nonwoven fabric is preferably produced by a method such as a spunbond method, a melt blown method, a hydroentanglement method, or a card method. The basis weight of the nonwoven fabric is preferably 5 to 200 g / m ² . Further, the nonwoven fabric can be suitably used not only as a single layer but also as, for example, a laminate of a nonwoven fabric obtained by a spunbond method and a nonwoven fabric obtained by a melt blown method, or a laminate of a nonwoven fabric and a film.

9. Field of Use As an application for the purpose of improving dyeability and hydrophilicity in the present invention, as an example, a fiber material, and further, a fabric, a woven fabric, a nonwoven fabric and the like using the fiber material are finished.
Applications that require improved functions using these include textiles such as clothing and daily necessities that need to be dyed, fishing lines, etc. Daily necessities such as supplies, cleaning tools, wet towels, synthetic cloth, medical materials such as adhesive bandages, pads, leukocyte removal agents, electronic and electrical parts such as battery separators, civil engineering and building materials such as concrete reinforcements, and other food packaging materials A wide range of applications can be expected.

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 0076.

[Production Example 1]
(Method for producing copolymer sample 1)
Production of metallocene compound: Dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl} zirconium dichloride was synthesized by the method described in Example 1 of JP-A-11-240909.
Production of octenyl diisobutylaluminum: To a 2,000 ml glass reactor equipped with a stirrer, 1,7-octadiene (800 ml; 5.6 mol) and diisobutylaluminum hydride (100 ml; 0.56 mol) were added and the mixture was heated 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 of 27 μm) manufactured by Mizusawa Chemical Co., Ltd., which is an ion-exchange layered silicate (montmorillonite). 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 139 g of chemically treated montmorillonite. The composition of the chemically treated smectite was Al: 4.5% 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 aluminum After adding 50 mmol 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), 87 ml of heptane containing 3% toluene was added to dimethylsilylenebis {2-methyl-4- (p-chlorophenyl) -4H-azurenyl} zirconium dichloride (218 mg; 0.3 mmol). 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 stirred at room temperature for 60 minutes to be reacted. 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 66.4 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.32.

  Copolymerization with propylene: 5L of fully dehydrated and deoxygenated n-heptane, 6.06mmol of triisobutylaluminum, diluted with n-heptane in a 15L stainless steel autoclave with stirring and temperature controller Tenenyldiisobutylaluminum was introduced in an amount of 0.33 mol, followed by propylene, and the internal pressure was adjusted to 0.5 MPa at 60 ° 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 60 ° C. for 5 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 aqueous layer was allowed to stand and then separated, and the slurry was separated from heptane by 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, 1.39 kg of a propylene copolymer was obtained. When the polymer was analyzed and evaluated, the content of the unit of the structural formula (I) was 99.84 mol%, the content of the unit of the structural formula (II) was 0.08 mol%, and the structural formula (III) The content of the unit was 0.08 mol%, and the weight average molecular weight was 251,000. The results are shown in Table 1 together with other results.

[Production Example 2]
In Production Example 1, the amount of octenyl diisobutylaluminum used for copolymerization with propylene was changed from 0.33 mol to 0.09 mol, the polymerization temperature was changed from 65 ° C to 70 ° C, and the polymerization time was changed from 5 hours to 3 hours. Except that, the copolymerization was carried out in the same manner as in Production Example 1, and the post-treatment of the obtained copolymer was also carried out in the same manner. 1.54 kg of propylene copolymer (sample 2) was obtained. The results are shown in Table 1.
[Production Example 3]
In Production Example 1, polymerization was carried out in the same manner as in Production Example 2 except that the comonomer octenyldiisobutylaluminum was not used and the polymerization time was changed from 5 hours to 3 hours. 1.59 kg of propylene polymer (sample 3) was obtained. The results are shown in Table 1.
[Production Example 4]
In Production Example 1, copolymerization was carried out in the same manner as in Example 1 except that the amount of octenyl diisobutylaluminum used in the copolymerization with propylene was changed from 0.33 mol to 1.32 mol. Polymer post-treatment was performed in the same manner. 1.00 kg of propylene polymer (sample 4) was obtained. The results are shown in Table 1.

[Production Example 5]
(OH group masking and propylene copolymerization)
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. Ten minutes later, propylene was introduced, and the internal pressure was adjusted to 70 MPa at 70 ° 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 70 ° C. for 5 hours.
(Post-processing of copolymer sample 5)
After the polymerization, the remaining propylene monomer was purged, and 1,000 ml of butanol was added and treated 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 aqueous layer was allowed to stand and separated, and the slurry was separated from heptane by 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, 1.46 kg of a propylene copolymer was obtained. The results are shown in Table 1 together with other results.

[Production Example 6]
(Manufacture of solid catalyst)
200 ml of dehydrated and deoxygenated n-heptane was introduced into a fully nitrogen-substituted flask, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. The reaction was carried out 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)
In a 15 L stainless steel autoclave with stirring and temperature control, 5 L of dehydrated and deoxygenated 5 L, 6.06 mmol of triethylaluminum, 0.62 mol of octenyldiisobutylaluminum diluted with n-heptane Subsequently, propylene was introduced, and the internal pressure was adjusted to 0.5 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 6)
After the polymerization was completed, 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 aqueous layer was allowed to stand and separated, and the slurry was separated from heptane by 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 7]
In an oil bath, 7 L of xylene, 1015 g of homopolypropylene (manufactured by Nippon Polypro Co., Ltd., product name: Novatec PP, FY4) was dissolved at 140 ° C. in a glass of 10 L 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 (Sample 7) are shown in Table 1.

[Production Example 8]
Into a 15 L stainless steel autoclave with stirring and temperature control, 5 L of fully dehydrated and deoxygenated n-heptane and 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 8]
After the polymerization, the remaining propylene monomer was purged, and 1,000 ml of butanol was added and treated 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 aqueous layer was allowed to stand and separated, and the slurry was separated from heptane by 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 ethylene copolymer (sample 8) was obtained. The results are shown in Table 1 together with other results.

[Example 1]
(Nonwoven fabric manufacturing method)
100 parts by weight of the copolymer sample 1 obtained above is 0.10 parts by weight of a 3-methylbutene polymer masterbatch as a crystal nucleating agent and 1,3,5-tris [( 4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (product name: Cyanox 1790, manufactured by Cytec) ) 0.04 parts by weight, Tris- (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, trade name: Irgafos 168), and steer as a neutralizing agent After adding 0.05 parts by weight of calcium phosphate (product name: Ca-St, manufactured by Nitto Kasei Kogyo), high speed mixing at 500 rpm for 3 minutes with a Henschel mixer, Using the on-plastic Co.), it melted in the conditions of an extrusion temperature of 230 ° C., kneaded, cooled, was prepared by cutting pelletized propylene resin composition (A) (a composition structure shown in Table 1.). The MFR of the prepared pellet was measured according to the following method. (The results are shown in Table 3)
Next, melt spinning was performed using the obtained composition (A) as a spinning raw material using a core-sheath type spinneret having 24 holes. Melt spinning was performed at a spinning temperature of 230 ° C., a discharge rate of 0.8 g / min / hole, and then drawn by air soccer to obtain a single fiber having a fineness of 2.2 dtex. Using this fiber, hydrophilicity and the like were evaluated by the following method. After this single fiber was accumulated on the conveyor under the air soccer, the fibers were fused together by an embossing roll set at 120 ° C. to obtain a nonwoven fabric having a basis weight of 20 g / m ² .

Evaluation of spinnability: Extrusion temperature 230 ° C., discharge rate 0.8 g / min, extrusion using a core-sheath type spinneret with 24 holes and holes, spinning for 1 hour under the condition of a take-up speed of 600 m / min The number of yarn breaks was measured to determine the spinnability.
○: No thread breakage ×: Evaluation of thread breakage hydrophilicity more than once: Create a fiber bundle so that the length is 10 cm and the weight is 6 g, and apply 4 twists to make a small drop of red aqueous ink on the surface The ink was allowed to adhere, and the permeability of the ink into the fiber bundle was visually confirmed according to the following criteria.
◎: Penetration quickly ○: Penetration within 3 seconds Δ: Penetration after taking 3 seconds or more X: Dyeing method not penetrating: Acetic acid 2% owf (weight per fiber) and dyeing assistant (Takemoto Yushi Co., Ltd.) Therion NW-403 (alkyl ether-ternonion) 1% owf and dyeing assistant Electrostripper K (Kao Atlas Co., Ltd., alkyl phosphate potassium salt) 2% owf Dissolve Irgaran Red 2GL 200% as a dye in 1% owf and warm to 50 ° C. 3 g of the nonwoven fabric fiber sample is immersed, heated at a temperature of 1 ° C./min while stirring up and down, and after reaching 100 ° C. in 50 minutes, dyeing is continued for 30 minutes. A dyed fiber sample is taken out, washed with water, and a bath ratio containing just (made by Kao Corporation, surfactant (49%), higher alcohol (anion, non-ion) fluorescent agent) 2 g / water 1 L The soap was soaped for 3 minutes in a 1:60 soap bath, further washed with water and dried. The dyeability (dye colorability) and wash fastness of this fiber sample were measured, and the results were judged from the values of dye colorability evaluation: dye consumption% shown in Table 3 according to the following criteria.
Dye consumption%: Given that the absorbance at the intrinsic absorption wavelength of the bath solution after dyeing at 90 ° C. for 30 minutes is B and the concentration of the first dye solution is A, (AB) / A × 100 The value obtained was defined as dye consumption rate%.
A: Dye consumption rate% exceeds 80% B: Dye consumption rate% is 70% to less than 80% B: Dye consumption rate% is 60% to less than 70% X: Dye consumption rate% is less than 60% Degree evaluation: The dyed fiber is taken out, washed with water, and a bath ratio containing 2 g / L of detergent (just (Kao), higher alcohol (anion, cation), surfactant (49%), fluorescent agent)) 1:60 soaping was performed, followed by washing with water and drying, and judgment was made according to the following criteria.
5th grade: Dye with no color fading 4th grade: Slightly fading 3rd grade: Slightly fading 2nd grade: Slightly fading 1st grade: Completely fading

[Examples 2 to 8], [Comparative Examples 1 to 6]
Using the materials shown in Table 1, and optionally the materials shown in Table 2, melt-kneading and pelletizing were performed, and MFR was measured by the method described above. Next, a single fiber was obtained by the fiber molding method described above using the prepared pellets, and used as a sample for hydrophilicity evaluation. Next, a nonwoven fabric was prepared from the single fiber by the above method, and the nonwoven fabric was dyed by the above method to evaluate the dye colorability and the fastness to washing. The results are shown in Table 3.

[Example 9]
Similarly to Example 2, after melt-kneading with the formulation shown in Table 3 and making pellets, a nonwoven fabric was prepared under the following meltblown conditions to obtain a nonwoven fabric with a fineness of 0.3 decix and a basis weight of 40 g / m ² It was. Evaluation similar to Example 1 was implemented using the nonwoven fabric.
Melt blow conditions: Die size (20 inches), nozzle holes (720), nozzle diameter (0.3 mm), spinning temperature (300 ° C.), air temperature (200 ° C.), air flow rate (70 Nm 3 / hour), between ejector conveyors (200mm), conveyor speed (3.2m / min)

[Consideration of results of Examples and Comparative Examples]
By examining and contrasting each Example and Comparative Example according to Tables 1 to 3 above, the fiber material of the present invention satisfies all the constituent requirements in Claim 1 of the claims, It is shown that the hydrophilicity, spinnability, dye colorability (dyeability) and wash fastness are excellent in balance. 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 fiber material of each comparative example does not satisfy any or all of the constituent requirements in claim 1, it is inferior to any or all of hydrophilicity, spinnability, dye colorability (dyeability) and wash fastness. It has been shown.
Specifically, in Examples 1, 3, 5 and 6, in the fiber material by the propylene-based copolymer having a polar group, the good results of the dyeability and hydrophilicity improvement which are the problems of the present invention are obtained. In Examples 2, 4 and 4, a composition of a propylene copolymer having a polar group and another polypropylene polymer, and in Example 7, a propylene copolymer having a polar group and another composition Similar good results have been shown in polypropylene polymer and thermoplastic elastomer compositions.
On the other hand, in Comparative Example 1, since there is no polar group, hydrophilicity, dye coloring property and wash fastness are poor, and in Comparative Example 2, since the unit having the polar group is too much as mol%, the spinnability is high. In Comparative Examples 3 and 4, since the blending amount of the propylene copolymer is insufficient in the composition, hydrophilicity, dye coloring property and fastness to washing are poor. In Comparative Example 5, MFR is 1 For the following reasons, the spinnability is deteriorated. In Comparative Example 6, only the unit having a polar group is used, and therefore the spinnability 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.

It is a simple graph figure which shows an example of a baseline and a section in GPC measurement.

Claims (9)

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 20% by weight of thermoplastic resin (C) other than propylene-based polymer. Is a fiber molded from a propylene-based copolymer or a composition thereof, wherein the fiber is 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 fiber according to claim 1, characterized in that 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. Fiber. 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 fiber described in any one. The fiber 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 fiber according to any one of claims 1 to 5, wherein the polar group of R ¹ of the polar group-containing propylene copolymer (A) is a hydroxyl group. The fiber 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 fabric, a woven fabric, or a non-woven fabric, which is formed of the fiber according to any one of claims 1 to 7. The nonwoven fabric according to claim 8, wherein the nonwoven fabric is manufactured by any one of a spun bond method, a melt blown method, a hydroentanglement method, and a card method.

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