JP2015013920A - ACID-MODIFIED α-OLEFIN POLYMER, AND TACKY ADHESIVE COMPOSITION AND ADHESIVE TAPE USING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tacky adhesive composition having high adhesive force using a polyolefin-based polymer and an adhesive tape using the same.SOLUTION: There are provided: an acid-modified α-olefin polymer which is obtained by modifying a raw material, α-olefin polymer with an organic acid and satisfies the following (1) and (2); and a tacky adhesive composition and an adhesive tape using the same. (1) A melting endothermic amount ΔH-D measured by a differential scan calorimeter (DSC) is 0 to 10 J/g. (2) The raw material, α-olefin polymer is a propylene homopolymer, a 1-butene homopolymer and a propylene-1-butene copolymer.

Description

  The present invention relates to an acid-modified α-olefin polymer, an adhesive composition and a pressure-sensitive adhesive tape using the same.

Conventionally, adhesives based on polyolefin-based materials have been studied in various ways because they are inexpensive. However, since polyolefin has low polarity, there are problems that the coating is easily peeled off and the adhesiveness of the adhesive is lowered. Thus, proposals have been made to use polypropylene or polybutene-1 with lowered crystallinity as a primer or improve paintability by acid modification (see Patent Documents 1 to 3).
Patent Document 4 discloses a hot melt adhesive for artificial turf using amorphous polyolefin or acid-modified products thereof.

Japanese Patent No. 4788102 Japanese Patent No. 4260635 International Publication No. 03/087172 Special table 2008-545909

  However, when the conventional pressure-sensitive adhesive is used for a hot-melt adhesive or a pressure-sensitive adhesive, the pressure-sensitive adhesive force to a polar material is improved, but the pressure-sensitive adhesive force is not sufficient. Moreover, there existed a subject that viscosity was high and workability | operativity was bad. Amorphous polyolefins also have a high softening point and are not sufficient in terms of adhesive strength.

  The problem to be solved by the present invention is to provide an adhesive composition having a high adhesive force using a polyolefin polymer.

According to the present invention, the following inventions are provided.
[1] An acid-modified α-olefin polymer obtained by modifying a raw material α-olefin polymer with an organic acid, which satisfies the following (1) and (2).
(1) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 0 to 10 J / g.
(2) The raw material α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, or propylene-1-butene copolymer.
[2] The acid-modified α-olefin polymer according to [1], wherein the raw material α-olefin polymer is a propylene homopolymer and satisfies the following (3-1).
(3-1) Mesopentad fraction [mmmm] is 20 mol% or less.
[3] The acid-modified α-olefin polymer according to [1], wherein the raw material α-olefin polymer is a 1-butene homopolymer and satisfies the following (3-2).
(3-2) Mesopentad fraction [mmmm] is 50 mol% or less.
[4] The acid-modified α-olefin polymer according to any one of [1] to [3], which further satisfies the following (4) and (5).
(4) The intrinsic viscosity [η] is 0.1 to 2.0 dl / g.
(5) The molecular weight distribution is 1.5 to 4.0.
[5] The acid-modified α-olefin according to any one of [1] to [4], wherein the organic acid is at least one selected from maleic anhydride, (meth) acrylic acid, and (meth) acrylic acid alkyl ester. Polymer.
[6] A first step of obtaining a raw material α-olefin polymer using a metallocene catalyst and a second step of modifying the raw material α-olefin polymer obtained in the first step using a radical initiator and an organic acid. A process for producing an acid-modified α-olefin polymer according to any one of [1] to [5].
[7] The acid-modified α-olefin according to [6], wherein the organic acid used in the second step is one or more selected from maleic anhydride, (meth) acrylic acid, and (meth) acrylic acid alkyl ester. A method for producing a polymer.
[8] An adhesive composition comprising the acid-modified α-olefin polymer according to any one of [1] to [5].
[9] The adhesive composition according to [8], which is a hot melt adhesive.
[10] A pressure-sensitive adhesive tape formed by forming an adhesive layer on the support using the adhesive composition according to [8] or [9].

  The polyolefin polymer and the adhesive composition of the present invention have higher adhesive strength than conventional ones.

<Acid-modified α-olefin polymer>
The acid-modified α-olefin polymer of the present invention is obtained by modifying a raw material α-olefin polymer with an organic acid, and satisfies the following (1) and (2).
(1) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 0 to 10 J / g.
(2) The raw material α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, or propylene-1-butene copolymer.

The acid-modified α-olefin polymer of the present invention has a melting endotherm ΔH-D measured by a differential scanning calorimeter (DSC) of 0 to 10 J / g, preferably 0 to 5 J / g, More preferably, it is 1 J / g. When the melting endotherm ΔH-D of the acid-modified α-olefin polymer exceeds 10 J / g, the crystalline component increases, the fluidity at a relatively low temperature deteriorates, energy saving during construction, and safety environment Problems arise from the viewpoint of
The melting endotherm ΔH-D is determined by DSC measurement. That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co., Ltd.), 10 mg of the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere and then heated at 10 ° C./min. Let the melting endotherm be ΔH−D.
In order to control the melting endotherm ΔH-D to 10 J / g or less, it is necessary to control the mesopentad fraction [mmmm], which is an index of stereoregularity of the raw material α-olefin polymer, to 50 mol% or less, This can be controlled by the structure of the main catalyst and the polymerization conditions. For example, when controlling by the structure of a catalyst, it is necessary to design the space where a monomer coordinates to the central metal of a catalyst to an appropriate size. Depending on the size of the coordination space, the insertion of the monomer hardly occurs and the activity is reduced, or a highly regular polymer is obtained if it is a racemic structure, and the melting endotherm exceeds 10 J / g. If the meso-type structure is used, it is easy to obtain a polymer with low regularity and the melting endotherm may be 10 J / g or less, but it is difficult to synthesize a polymer having a balance between the bonding ratio and the melting endotherm. . For example, by using a double-crosslinking catalyst described later, it is possible to synthesize a polymer having a balance between a bonding ratio and a melting endotherm by controlling the coordination space of the monomer.
In the present specification, the melting endotherm ΔH-D is 0 J / g means that the crystal melting peak cannot be substantially observed because the crystallization rate is extremely slow in the DSC measurement.

  In the acid-modified α-olefin polymer of the present invention, the melting point (Tm) by a differential scanning calorimeter (DSC) is not observed, or the melting point is preferably less than 20 ° C., more preferably 10 ° C. or less. . Details of the DSC measurement are the same as the method for measuring the melting endotherm ΔH-D.

The acid-modified α-olefin polymer of the present invention has an acid modification amount of 0.1 to 20% by mass, preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass. More preferably, it is 0.2-3 mass%.
The acid modification amount of the acid-modified α-olefin polymer of the present invention is determined by the following measuring method.

[Measurement method of acid modification amount]
Prior to modification, a blend of the raw α-olefin polymer and the organic acid is subjected to IR measurement using a 0.1 mm spacer (transmission type microscopic IR measuring instrument: “NICOLET 8700” manufactured by Thermo Fisher Scientific Co., Ltd.) , Microscope: "NICOLET CONTINU μM"), creating a calibration curve from the absorption amount of characteristic carbonyl (1900 to 1600 cm ^-1 ) and the charged amount of organic acid, and performing IR measurement of the acid-modified product per unit mass The amount of modification of the (anhydrous) carboxylic acid residue was determined. The modification amount defined in the present specification was calculated in terms of (anhydrous) carboxylic acid residue even when the organic acid was other than (anhydrous) carboxylic acid. In order to correct the thickness of the sample, the carbonyl absorption was corrected by the following formula.
(Absorption amount of 1900-1600 cm ^-1 ) / (Absorption amount of 4480-3950 ^-1 )
Moreover, IR measurement was performed on condition of the following.
<Measurement conditions>
Measurement area: 4500 cm ^{−1 to} 650 cm ⁻¹
Fraction dependency of measurement depth: Uncorrected Detector: MCT
Resolution: 4cm ^-1
Integration count: 100 times

The raw material α-olefin polymer is not particularly limited, but is preferably an α-olefin polymer having 2 to 12 carbon atoms, more preferably an α-olefin polymer having 3 to 12 carbon atoms, and still more preferably. Is at least one selected from the group consisting of 1-butene homopolymer, propylene homopolymer and 1-butene-propylene copolymer.
From the viewpoint of improving the adhesive strength at low temperatures, it is preferable to use a 1-butene homopolymer having a glass transition temperature Tg lower than that of the propylene homopolymer.

When the raw α-olefin polymer of the acid-modified α-olefin polymer of the present invention is a propylene homopolymer or a 1-butene homopolymer, the mesopentad fraction [mmmm] of the acid-modified α-olefin polymer is 50 mol. % Or less, and more preferably 20 mol% or less. The mesopentad fraction [mmmm] of the acid-modified α-olefin polymer is preferably 1 mol% or more, and more preferably 3 mol% or more.
Moreover, when the raw material α-olefin polymer of the acid-modified α-olefin polymer of the present invention is a propylene-1-butene copolymer, the mesodyad fraction [m] is a viewpoint of a balance between heat resistance and adhesiveness. Therefore, it is preferably 30 to 95 mol%, more preferably 40 to 90 mol%, still more preferably 50 to 85 mol%.

  In the acid-modified α-olefin polymer of the present invention, the total of 1,3-bond fraction and 1,4-bond fraction is preferably less than 0.3 mol%, The bond fraction is preferably less than 0.3 mol%.

In the present invention, the mesopentad fraction [mmmm] and mesodyad fraction [m], 1,3-bond fraction, 1,4-bond fraction, and 2,1-bond fraction were reported by Asakura et al. Polymer Journal, 16, 717 (1984) ", J. Am. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It was determined according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. Namely, signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and mesopentad fraction [mmmm] and mesodyad fraction [m], 1,3-bond fraction, 1, The 4-bond fraction and 2,1-bond fraction were determined.
^{The 13} C-NMR spectrum was measured using the following apparatus and conditions.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The 1,3-bond fraction and 2,1-bond fraction of the propylene homopolymer and the propylene-1-butene copolymer can be calculated by the following formula from the measurement result of the ¹³ C-NMR spectrum described above.
1,3-bond fraction = (D / 2) / (A + B + C + D) × 100 (mol%)
2,1-bond fraction = [(A + B) / 2] / (A + B + C + D) × 100 (mol%)
A: integrated value of 15 to 15.5 ppm B: integrated value of 17 to 18 ppm C: integrated value of 19.5 to 22.5 ppm D: integrated value of 27.6 to 27.8 ppm

The 1,4-bond fraction of the propylene-1-butene copolymer and the 1,4-bond fraction and 2,1-bond fraction of the 1-butene homopolymer are shown in the above-mentioned ¹³ C-NMR spectrum. From the measurement result, it can be calculated by the following formula.
1,4-bond fraction = E / (A + B + C + D + E) × 100 (mol%)
2,1-bond fraction = {(A + B + D) / 3} / (A + B + C + D) × 100 (mol%)
A: Integrated value of 29.0 to 28.2 ppm B: Integrated value of 35.4 to 34.6 ppm C: Integrated value of 38.3 to 36.5 ppm D: Integrated value of 43.6 to 42.8 ppm E: 31.1 ppm integrated value

The propylene-1-butene copolymer in the present specification means that the total of the copolymerization ratio of propylene units and the copolymerization ratio of 1-butene units is 50 mol% or more, preferably 70 mol% or more, more preferably 90 A mol% or more, most preferably 100 mol% is shown. In addition to propylene and 1-butene, ethylene or an α-olefin having 5 or more carbon atoms (preferably an α-olefin having 5 to 20 carbon atoms) may be included as a comonomer. Specific examples of the α-olefin used as a comonomer include pentene-1, heptene-1, hexene-1, heptene-1, octene-1, decene-1, 4-methylpentene-1, 3-methylbutene-1, Examples include dienes such as 1,3-butadiene, hexadiene, pentadiene, heptadiene and octadiene.
The 1-butene-propylene copolymer is preferably a random copolymer.

In the propylene-1-butene copolymer, the structural unit obtained from 1-butene is preferably 15 mol% or more, more preferably 50 mol% or more, and particularly preferably 75 mol% or more. . When 1-butene unit is 15 mol% or more, the low-temperature characteristic of the adhesive containing the polymer improves. From the viewpoint of low temperature characteristics, it is better that the number of structural units obtained from 1-butene is larger.
Each structural unit in the propylene-1-butene copolymer can be calculated as follows from the measurement result of the ¹³ C-NMR spectrum.
[Dyad chain strength]
a (propylene-propylene chain): integrated value of 48.0-46.2 ppm b (propylene-butene chain): integrated value of 44.4-43.0 ppm c (butene-butene chain): 40.8-39. Integral value of 8 ppm [Dyad chain fraction (mol%)]
d (propylene-propylene chain fraction) = a / (a + b + c) × 100 (mol%)
e (propylene-butene chain fraction) = b / (a + b + c) × 100 (mol%)
f (butene-butene chain fraction) = c / (a + b + c) × 100 (mol%)
[Copolymerization ratio (mol%)]
Propylene unit copolymerization ratio = d + e / 2
1-butene unit copolymerization ratio = f + e / 2

Further, from the measurement result of the ¹³ C-NMR spectrum, the mesodyad fraction [m] can be calculated from the following formula.
Meso-dyad fraction [m] = (integrated value of 40.4 to 39.9 ppm) / (integrated value of 40.4-39.9 ppm + integrated value of 40.7 to 40.4 ppm)

  The acid-modified α-olefin polymer of the present invention preferably has a molecular weight distribution (Mw / Mn) measured by GPC method of 4.0 or less, more preferably 3.5 or less, and still more preferably 3.0 or less. When the molecular weight distribution (Mw / Mn) is 4.0 or less, the adhesive residue is reduced when used as an adhesive material.

  The acid-modified α-olefin polymer of the present invention preferably has a weight average molecular weight (Mw) measured by GPC method of 3,000 to 1,000,000, more preferably 5,000 to 200,000, Preferably it is 7,000-150,000. When the weight average molecular weight (Mw) is 3,000 or more, stickiness is reduced. Moreover, fluidity | liquidity improves that Mw is 1,000,000 or less, and coating property becomes favorable.

In addition, the said weight average molecular weight (Mw) and number average molecular weight (Mn) are things of polystyrene conversion measured with the following apparatus and conditions, The said molecular weight distribution (Mw / Mn) is these weight average molecular weights (Mw). ) And the number average molecular weight (Mn).
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

  Moreover, as a raw material alpha-olefin polymer, what has an unsaturated bond at the terminal can also be used from a viewpoint of modification | denaturation efficiency improvement.

In the acid-modified α-olefin polymer of the present invention, the number of terminal (anhydrous) carboxylic acid residue-internal double bond structures is preferably less than 0.5 per molecule.
The number of the terminal (anhydrous) carboxylic acid residue-internal double bond structure is determined as follows.
[Terminal (anhydrous) carboxylic acid residue-number of internal double bond structures]
Terminal (anhydrous) carboxylic acid residue appearing at 4.85 to 5.50 ppm obtained from ¹ H-NMR measurement-hydrogen atom of internal double bond in internal double bond structure, appearing at 0.70 to 1.80 ppm Based on the hydrogen atoms of the α-olefin main chain, the number of terminal (anhydrous) carboxylic acid residue-internal double bonds was calculated as follows.
Terminal (anhydrous) carboxylic acid residue-CH (i) of internal double bond structure: 4.85 to 5.50 ppm integrated value α-olefin main chain hydrogen atom (ii): 0.70 to 1.80 ppm Integral value Average molecular weight of monomer units (Mm) = propylene unit ratio × 42.08 + 1-butene unit ratio × 56.11
Average number of hydrogen of monomer units (Hnum) = propylene unit ratio × 6 + 1-butene unit ratio × 8
Terminal (anhydrous) carboxylic acid residue-internal double bond structure concentration = [(i) / ((ii) / (Hnum))
The terminal (anhydrous) carboxylic acid residue-internal double bond structure concentration (C, mol%) calculated by the above method, the number average molecular weight (Mn) determined from the gel permeation chromatograph (GPC), and the monomer unit From the average molecular weight (Mm), the number of terminal (anhydrous) carboxylic acid-internal double bond structures per molecule was calculated according to the following formula.
Number of terminal (anhydrous) carboxylic acid-internal double bond structures per molecule = (Mn) / (Mm) x [terminal (anhydrous) carboxylic acid residue-internal double bond structure concentration]

  The intrinsic viscosity [η] of the raw material α-olefin polymer of the present invention is preferably from 0.01 to 2.0 deciliter / g, more preferably from the viewpoint of reducing the adhesive residue of the adhesive composition. 1 to 1.0 deciliter / g. Here, the intrinsic viscosity is measured at 135 ° C. in tetralin using an Ubbelohde type viscosity tube.

(Method for producing raw material α-olefin polymer)
As a method for producing the raw material α-olefin polymer, a method of producing a propylene homopolymer or 1-butene homopolymer by homopolymerizing propylene or 1-butene using a metallocene catalyst, or 1-butene and propylene Further, a method of producing a 1-butene-propylene copolymer by copolymerizing with (alpha-olefin having 5 to 20 carbon atoms, which is used as necessary) can be mentioned.
Examples of the metallocene catalyst include JP-A-58-19309, JP-A-61-130314, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, and special tables. Transition metal compounds having one or two ligands such as a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and the like, as described in JP-A-1-502036 Examples thereof include a catalyst obtained by combining a transition metal compound whose ligand is geometrically controlled and a promoter.

In the present invention, among metallocene catalysts, the ligand is preferably composed of a transition metal compound that forms a crosslinked structure via a crosslinking group, and in particular, the crosslinked structure is formed via two crosslinking groups. A method using a metallocene catalyst obtained by combining the formed transition metal compound and the promoter is further preferred.
Specifically, (A) the transition metal compound represented by the general formula (I), and (B) (B-1) the ion reacting with the transition metal compound of the component (A) or a derivative thereof In the presence of a polymerization catalyst containing a compound capable of forming a functional complex and (B-2) an aluminoxane, or a method of homopolymerizing propylene or 1-butene, or 1-butene and propylene (further necessary And a method of copolymerizing with an α-olefin having 5 to 20 carbon atoms used accordingly.

[In the formula, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series. E ¹ and E ² are substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group, phosphide group, hydrocarbon group and silicon-containing group, respectively. A ligand selected from the above, which forms a crosslinked structure via A ¹ and A ² , and they may be the same or different from each other. X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different and may be cross-linked with other Y, E ¹ , E ² or X. A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, germanium containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 -Or -AlR ^1- , wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different from each other. Also good. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]

  In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. And lanthanoid metals. Among these, from the viewpoint of olefin polymerization activity, a metal element belonging to Group 4 of the periodic table is preferable, and titanium, zirconium and hafnium are particularly preferable.

E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable. Examples of the substituent include a hydrocarbon group having 1 to 20 carbon atoms and a silicon-containing group.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. . Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

  Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, cyclohexyl groups, octyl groups and other alkyl groups; vinyl groups, propenyl groups, cyclohexenyl groups, etc. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

Examples of the alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, a phenylmethoxy group, and a phenylethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, and a dimethylphenoxy group. Examples of the amide group having 1 to 20 carbon atoms include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, a dicyclohexylamide group, and a methylethylamide group, a divinylamide group, and a dipropenylamide group. Alkenylamide groups such as dicyclohexenylamide group; arylalkylamide groups such as dibenzylamide group, phenylethylamide group and phenylpropylamide group; arylamide groups such as diphenylamide group and dinaphthylamide group.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group, Trihydrocarbon-substituted silyl groups such as tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tolylsilylsilyl group and trinaphthylsilyl group; hydrocarbons such as trimethylsilyl ether group A substituted silyl ether group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group; Of these, a trimethylsilylmethyl group, a phenyldimethylsilylethyl group, and the like are preferable.

  Examples of the phosphide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.

Examples of the sulfide group having 1 to 20 carbon atoms include alkyl sulfide groups such as methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, hexyl sulfide group, cyclohexyl sulfide group, octyl sulfide group; vinyl sulfide group, propenyl sulfide Group, alkenyl sulfide group such as cyclohexenyl sulfide group; arylalkyl sulfide group such as benzyl sulfide group, phenylethyl sulfide group, phenylpropyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethylphenyl sulfide group, trimethylphenyl sulfide group, Ethyl phenyl sulfide group, propyl phenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide group, Tiger Se Nils sulfide group, an aryl sulfide groups such as a phenanthridine Nils sulfide group.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, palmitoyl group, thearoyl group, oleoyl group and other alkyl acyl groups, benzoyl group, toluoyl group, salicyloyl group, Examples thereof include arylacyl groups such as cinnamoyl group, naphthoyl group and phthaloyl group, and oxalyl group, malonyl group and succinyl group respectively derived from dicarboxylic acid such as oxalic acid, malonic acid and succinic acid.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
Examples of the amine include amines having 1 to 20 carbon atoms, specifically, methylamine, ethylamine, propylamine, butylamine, cyclohexylamine, methylethylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dicyclohexylamine. Alkylamines such as methylethylamine; alkenylamines such as vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine; arylalkylamines such as phenylamine, phenylethylamine, phenylpropylamine; An arylamine such as naphthylamine can be mentioned.

  Examples of ethers include aliphatic single ether compounds such as methyl ether, ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, and isoamyl ether; methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, Aliphatic hybrid ether compounds such as methyl-n-amyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl-n-amyl ether, ethyl isoamyl ether; vinyl ether, allyl ether, methyl Aliphatic unsaturated ether compounds such as vinyl ether, methyl allyl ether, ethyl vinyl ether, ethyl allyl ether; anisole Aromatic ether compounds such as phenetol, phenyl ether, benzyl ether, phenyl benzyl ether, α-naphthyl ether, β-naphthyl ether, and cyclic ether compounds such as ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran, and dioxane. Can be mentioned.

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specific examples include monohydrocarbon-substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, and octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkyl phosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine; vinyl Monoalkenes such as phosphine, propenylphosphine, cyclohexenylphosphine, etc. Dialkenylphosphine in which two alkenyls are substituted for phosphine and phosphine hydrogen atoms; Trialkenylphosphine in which three alkenyls are substituted for phosphine hydrogens; Arylalkylphosphine such as benzylphosphine, phenylethylphosphine, phenylpropylphosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, anthracenyl phosphine, phenanthenyl phosphine; phosphine water Atom alkyl aryl two substituted di (alkylaryl) phosphine; arylphosphine such as a hydrogen atom of phosphine alkylaryl three substituted with tri (alkylaryl) phosphine. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they are identical to each other. But it can be different. Examples of such a crosslinking group include those represented by the following general formula.

（Ｄは炭素、ケイ素又はスズ、Ｒ²及びＲ³はそれぞれ水素原子又は炭素数１〜２０の炭化水素基で、それらはたがいに同一でも異なっていてもよく、またたがいに結合して環構造を形成していてもよい。ｅは１〜４の整数を示す。）

(D is carbon, silicon or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)

Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ ═C =), dimethylsilylene group, diphenyl. Examples thereof include a silylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

  q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the general formula (I), a transition metal compound having a double-bridged biscyclopentadienyl derivative represented by the following general formula (II) as a ligand is preferable. .

In the above general formula (II), M, A ¹ , A ² , q and r are the same as described above.
X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I). R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same or different, and adjacent groups may be bonded to each other to form a ring. Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring. As R ⁴ and R ⁵ , a group containing a heteroatom such as oxygen, halogen, or silicon is preferable because of high polymerization activity. In another preferred embodiment, R ⁴ and R ⁶ or R ⁶ and R ⁷ preferably form a ring, and R ⁵ and R ⁸ or R ⁸ and R ⁹ preferably form a ring. As the substituent in the case where R ^4, R ⁵ , R ⁷ and R ⁹ do not form a ring, a group containing a heteroatom such as oxygen, halogen or silicon is preferable from the viewpoint of polymerization activity.
The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.

As specific examples of the transition metal compound represented by the general formula (I), specific examples described in WO02 / 16450 are also preferable examples in the present invention.
More preferable specific examples include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-methylphenylsilylene) (2 , 1′-methylphenylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride (Sym.), (1,1′-ethylene) (2,2′-tetramethyldisylylene) bisindenylzirconium dichloride, etc. Can be mentioned.

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). Although it can be used, what is represented by the following general formula (III), (IV) can be used conveniently.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R ¹⁴ M ^3.)

In the general formulas (III) and (IV), L ¹ represents a Lewis base, and [Z] ⁻ represents a non-coordinating anion [Z1] ⁻ and [Z ² ] ⁻ .
[Z ¹ ] ⁻ represents an anion having a plurality of groups bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ . Here, M ¹ represents a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms , An organic metalloid group, or a C2-C20 heteroatom-containing hydrocarbon group. Two or more of G ^{1 to} G ^f may form a ring. f represents an integer of [(valence of central metal M ¹ ) +1].
[Z ² ] ⁻ is defined as a Bronsted acid alone having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base of a combination of Bronsted acid and Lewis acid, or generally a super strong acid. Indicates a conjugate base of an acid. In addition, a Lewis base may be coordinated.
R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, or an arylalkyl group.
R ¹¹ and R ¹² each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group.
R ¹³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like. Specific examples of R ¹³ include a phenyl group, p-tolyl group, p-methoxyphenyl group, and the like. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, I _{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn. Etc.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al are Can be mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include a dimethylamino group and a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group as an alkoxy group or an aryloxy group, and the like. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Oromechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

The non-coordinating anion i.e. pKa of -10 or less Bronsted acid alone or Bronsted acid and the conjugate base of a combination of a Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion (CF ₃ SO Specific examples of ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ^- , trifluoroacetate anion (CF ₃ CO ₂ ) ^- , Hexafluoroantimony anion (SbF ₆ ) ^- , fluorosulfonate anion (FSO ₃ ) ^- , chlorosulfonate anion (ClSO ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , Fluorosulfonate anion / 5 Fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

Specific examples of such an ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the component compound (B-1), include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) tetraethylammonium borate, benzyl (tri-n-butyl) ammonium borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluoro) Phenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate, Dimethylanilinium trakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methyl borate (4-cyanopyridinium), tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis [ Bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, tetrapheni Silver ruborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) ) Decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) trityl borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Teoraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, tri Examples thereof include silver fluoromethanesulfonate.
(B-1) may be used alone or in combination of two or more.

（式中、Ｒ¹⁵は炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基などの炭化水素基あるいはハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。なお、各Ｒ¹⁵は同じでも異なっていてもよい。）
で示される鎖状アルミノキサン、及び一般式（ＶＩ）

（式中、Ｒ¹⁵及びｗは前記一般式（Ｖ）におけるものと同じである。）
で示される環状アルミノキサンを挙げることができる。 On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.

Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method. For example, (i) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (ii) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (iii) a metal There are a method of reacting water adsorbed on a salt or the like with water adsorbed on an inorganic or organic substance with an organoaluminum compound, and (iv) a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water. . The aluminoxane may be insoluble in toluene.
These aluminoxanes may be used alone or in combination of two or more.

  The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical. Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).

The catalyst for polymerization in the above production method can use an organoaluminum compound as the component (C) in addition to the components (A) and (B).
Here, as the organoaluminum compound of the component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. It is an integer. ]
The compound shown by these is used.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

In the said manufacturing method, a preliminary contact can also be performed using (A) component, (B) component, and (C) component mentioned above. The preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (B), but the method is not particularly limited, and a known method can be used. These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the (B) component that is the promoter. Further, by bringing the component (A) and the component (B-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above effect. The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.
The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, as a carrier other than the above, a magnesium compound represented by the general formula MgR ¹⁷ _X X ¹ _y typified by MgCl ₂ , Mg (OC ₂ H ₅ ) ₂ or the like, or a complex salt thereof can be used. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, poly 1-butene, substituted polystyrene, and polyarylate, starch, and carbon.
As the carrier used in the above production method, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) ₂ , SiO ₂ , Al ₂ O _{3 and the} like are preferable. The properties of the carrier vary depending on the type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm.
If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there.
When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume can be determined from the volume of nitrogen gas adsorbed according to the BET method, for example.
Further, when the carrier is an inorganic oxide carrier, it is usually desirable to use it after baking at 150 to 1000 ° C, preferably 200 to 800 ° C.

When at least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .
The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (i) at least one of the component (A) and the component (B) is mixed with the carrier. A method, (ii) a method in which a support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (iii) the support and (A) A method of reacting the component and / or the component (B) with the organoaluminum compound or the halogen-containing silicon compound, (iv) after the component (A) or the component (B) is supported on the carrier, the component (B) or (A ) A method of mixing with the component, (v) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, and (vi) a carrier during the contact reaction of the component (A) with the component (B). Coexist Or the like can be used that way.
In the above reactions (iv), (v) and (vi), an organoaluminum compound (C) can also be added.

In the present invention, when contacting the (A), (B), and (C), the catalyst may be prepared by irradiating elastic waves. Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for polymerization after removing the solvent once and taking out as a solid, or may be used for polymerization as it is.
Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within a polymerization system. For example, at least one of the component (A) and the component (B), a carrier, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa (gauge), and -20 to 200 A method of preliminarily polymerizing at about 1 minute to 2 hours to form catalyst particles can be used.
In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio. When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio. In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.
If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g. , Preferably it is 50-500 m < ² > / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. When the specific surface area is less than 20 m ² / g, the activity may decrease, and when it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. If the amount of transition metal is outside the above range, the activity may be lowered.
In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.

As the raw material α-olefin polymer, propylene or 1-butene is homopolymerized to produce a propylene homopolymer or 1-butene homopolymer using the polymerization catalyst described above, or 1-butene and propylene Can be copolymerized to produce a propylene-1-butene copolymer.
In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a suspension polymerization method may be used. A polymerization method is particularly preferred.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably 10 ⁵ to 10 ⁸ , particularly preferably 10 ⁶ to 10 ^7, with respect to the raw material monomer / the component (A) (molar ratio). Furthermore, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 3 MPa (gauge), more preferably normal pressure to 2 MPa (gauge).
Examples of the method for adjusting the molecular weight of the polymer include selection of the type, amount used, and polymerization temperature of each catalyst component, and further polymerization in the presence of hydrogen.

When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. Depending on the polymerization method, it can be carried out without solvent.
In the polymerization, prepolymerization can be performed using the polymerization catalyst. The prepolymerization can be performed, for example, by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and examples thereof include ethylene, an α-olefin having 3 to 20 carbon atoms, or a mixture thereof. It is advantageous to use the same olefin as that used in the polymerization. It is.
Moreover, prepolymerization temperature is -20-200 degreeC normally, Preferably it is -10-130 degreeC, More preferably, it is 0-80 degreeC. In the prepolymerization, an aliphatic hydrocarbon, aromatic hydrocarbon, monomer or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Moreover, you may perform prepolymerization without a solvent.
In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, particularly 0.5 deciliter / g or more, per 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10000 g, particularly 10 to 1000 g.

(Method for producing acid-modified α-olefin polymer)
The acid-modified α-olefin polymer of the present invention can be produced by modifying the α-olefin polymer with a radical initiator and an organic acid.
As the organic acid used for the modification treatment, an unsaturated carboxylic acid or a derivative thereof can be used.
Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid and the like.
Examples of unsaturated carboxylic acid derivatives include acid water, esters, amides, imides, metal salts, and the like, such as maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, Examples thereof include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Among these, those selected from maleic anhydride, (meth) acrylic acid and alkyl (meth) acrylate are particularly preferable, and maleic anhydride or (meth) acrylic acid is more preferable.
Moreover, these organic acids may be used independently and may be used in combination of 2 or more type.

  There is no restriction | limiting in particular as the usage-amount of an organic acid, Although it selects suitably according to the desired physical property of the target acid-modified alpha-olefin polymer, Usually 0 with respect to 100 mass parts of raw material alpha-olefin polymers to be used. .1 to 50 parts by mass, preferably 0.1 to 30 parts by mass.

On the other hand, the radical initiator is not particularly limited, and is appropriately selected from conventionally known radical initiators such as various organic peroxides, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Among these, organic peroxides are preferable.
Examples of the organic peroxide include dibenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t- Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Α, α′bis (t-butylperoxy) diisopropylbenzene Oxides, peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxyoct , Alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di Examples include peroxycarbonates such as -sec-butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate.
Of these, dialkyl peroxides are preferred.
Moreover, these may be used individually by 1 type and may be used in combination of 2 or more types.
Specific examples of commercially available organic oxides include Perhexin 25B, Perbutyl D, Perbutyl C, Perhexa 25B, Park Mill D, Perbutyl P, Perbutyl H, Perhexyl H, Park Mill H, manufactured by NOF Corporation. Perocta H, Parkmill P, Permenta H, Perbutyl SM, Permec N, Peromer AC, Perhexa V, Perhexa 22, Perhexa CD, Perhexa A, Perhexa C, Perhexa 3M, Perhexa HC, Perhexa TMH, Perbutyl IF, Perbutyl Z, Perbutyl A Perhexyl Z, Perhexa 25Z, Perbutyl E, Perbutyl L, Perhexa 25MT, Perbutyl I, Perbutyl 355, Perbutyl MA, Perhexyl I, Perbutyl IB, Perbutyl O, Perhexyl O, Persic O, Perhexa 250, Perocta O, Perbutyl PV, Perhexyl PV, Perbutyl ND, Perhexyl ND, Percyclo ND, Perocta ND, Park Mill ND, Dyper ND, Parroyl SOP, Parroyl OPP, Parroyl MBP, Parroyl EEP, Parroyl IPP, Parroyl NPP, Examples include Parroyl TCP, Parroyl IB, Parroyl SA, Parroyl S, Parroyl O, Parroyl L, Parroyl 355, Nyper BW, Nyper BMT, and Nyper CS.

  There is no restriction | limiting in particular as the usage-amount of a radical initiator, Although it selects suitably according to the desired physical property of the target acid-modified alpha-olefin polymer, It is normal with respect to 100 mass parts of raw material alpha-olefin polymers to be used. It is used in the range of 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass.

  The modification treatment method is not particularly limited. For example, the raw material α-olefin polymer, the organic acid and the radical initiator described above are preferably used at 150 to 300 ° C. using a roll mill, a Banbury mixer, an extruder, or the like. Is reacted at a temperature of about 140 to 250 ° C. for 0.01 to 0.5 hours by melting and kneading, or a hydrocarbon solvent such as butane, pentane, hexane, cyclohexane or toluene, chlorobenzene, dichlorobenzene, or trichlorobenzene. In a suitable organic solvent such as a halogenated hydrocarbon solvent such as liquefied α-olefin or in the absence of solvent, a temperature of about −50 to 300 ° C., preferably about 40 to 180 ° C. The raw material α-olefin polymer can be modified by reacting for ˜2 hours.

Moreover, in this invention, this modification process can be performed in presence of a styrene-type compound.
Examples of the styrenic compound include styrene and α-methylstyrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene, 2 Alkyl styrenes such as 4-dimethyl styrene, 2.5-dimethyl styrene and 3.5-dimethyl styrene; alkoxy styrenes such as p-methoxy styrene, o-methoxy styrene and m-methoxy styrene; m-chlorostyrene, o-bromo Styrene, p- fluoro styrene, m- fluorostyrene, o- fluorostyrene, o- halogenated styrenes methyl -p- fluorostyrene and the like; further trimethylsilyl styrene, vinyl benzoate, divinylbenzene, and the like.
These styrenic compounds may be used singly or in combination of two or more.
Moreover, the usage-amount of a styrene-type compound is 0.1-10.0 mass parts normally with respect to 100 mass parts of raw material alpha olefin polymers, Preferably it is the range of 0.1-5.0 mass parts.
By using a styrenic compound, the modification treatment can be performed more efficiently.

Furthermore, in the present invention, the modification treatment can be performed in the presence of a vinylsilane compound.
Examples of the vinylsilane compound include vinyltriethoxysilane, vinyldiethoxysilane, vinylmonoethoxysilane, vinyltrimethoxysilane, vinyldimethoxysilane, vinylmonomethoxysilane, and vinyltriphenoxysilane.
These vinyl silane compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
Moreover, the usage-amount of a vinylsilane compound is 0.1-10.0 mass parts normally with respect to 100 mass parts of raw material alpha olefin polymers, Preferably it is the range of 0.1-5.0 mass parts.
By using a vinylsilane compound, a moisture curing function can be imparted to the acid-modified α-olefin polymer of the present invention.

The acid-modified α-olefin polymer of the present invention thus produced can impart high adhesion, high strength, softness, etc. to polyolefin, etc., hot melt adhesive, pressure-sensitive adhesive component, polyolefin-based It is useful as an adhesive for molded articles, a primer for coating, an adhesive component, an ink modifier, a compatibilizing agent and the like.
Further, the acid-modified α-olefin polymer of the present invention can be used as a modifier by adding to an adhesive, a pressure-sensitive adhesive, rubber or the like.
Specific examples of the adhesive include urethane type, epoxy type, alkoxysilane type and the like.
Specific examples of the pressure-sensitive adhesive include acrylics, rubbers, and silicons.

<Adhesive composition>
The adhesive composition of the present invention is characterized by containing the acid-modified α-olefin polymer.
The adhesive composition of the present invention is one or more adhesives selected from urethane-based, epoxy-based, alkoxysilane-type, acrylic-based, rubber-based, and silicon-based, together with the acid-modified α-olefin polymer. An agent may also be contained.
By containing the acid-modified α-olefin polymer of the present invention and the above adhesive, the polarity of the adhesive can be controlled, so that it adheres to a low-polarity material such as polyethylene or polypropylene. It can be used as a modifier for controlling properties.
The adhesive composition of the present invention may contain a tackifier or a solvent as necessary.
The content of the acid-modified α-olefin polymer in the adhesive composition is from 5 to 95% by mass, more preferably from 10 to 95% from the viewpoint of the balance between adhesive strength and tackiness, holding power and low adhesive residue. 80 mass%, More preferably, it is 20-70 mass%, Most preferably, it is 30-60 mass%.

As one aspect, the adhesive composition of the present invention may be a hot melt adhesive containing the acid-modified α-olefin polymer.
The hot melt adhesive may contain various additives such as oils, plasticizers, waxes, inorganic fillers, and antioxidants as necessary.

(Urethane adhesive)
Examples of the urethane-based adhesive that may be included in the adhesive composition of the present invention include (1) polyol composition and (2) described in JP-A-2008-63425 and JP-A-2011-231317. ) Adhesives containing isocyanate group-containing compounds.
Although it does not specifically limit as a method of making the acid-modified alpha-olefin polymer of this invention contain in a urethane type adhesive agent, (1) After mixing a polyol composition and (2) isocyanate group containing compound of this invention. An acid-modified α-olefin polymer may be added, or after (1) the polyol composition and the acid-modified α-olefin polymer of the present invention are mixed, (2) an isocyanate group-containing compound may be mixed.
In the adhesive composition of the present invention, the content of the acid-modified α-olefin polymer of the present invention relative to the urethane-based adhesive is based on 100 parts by mass of the urethane-based adhesive. It is preferable that it is 5-50 mass parts of olefin polymers, More preferably, it is 5-30 mass parts.

(Tackifier)
Examples of the tackifier include solid, semi-solid or liquid materials at room temperature made of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin and the like. You may use these individually or in combination of 2 or more types. In the present invention, it is preferable to use a hydrogenated product in consideration of compatibility with a butene polymer. Among them, a hydride of petroleum resin having excellent thermal stability is more preferable.
Commercially available tackifiers include Imabe P-125, P-100, P-90 (above, manufactured by Idemitsu Kosan Co., Ltd.), Umex 1001 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), Hilets T1115 (Mitsui Chemicals, Inc.) ), Clearon K100 (manufactured by Yasuhara Chemical Co., Ltd.), ECR227, Escorez 2101 (manufactured by Tonex Co., Ltd.), Alcon P100 (manufactured by Arakawa Chemical Co., Ltd.), Regalrez 1078 (manufactured by Hercules) Yes (both are trade names).
The content of the tackifier in the adhesive composition of the present invention is preferably from 5 to 95% by mass, more preferably from 10 to 80% by mass, and more preferably from 10 to 80% by mass, from the viewpoint of the balance between improvement in adhesiveness and adhesive residue. Preferably it is 20-70 mass%, Most preferably, it is 30-60 mass%.

(solvent)
Solvents include ethyl acetate, acetone, tert-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether acetate, ethyl cellosolve, ethyl cell Such as sorb acetate, butyl cell sorb, butyl cell sorb acetate, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, methoxybenzene, 1,2-dimethoxybenzene, hexane, cyclohexane, heptane, pentane, etc. Mention may be made of organic solvents.

(Α-olefin polymer)
The adhesive composition of the present invention may further contain an α-olefin polymer in addition to the acid-modified α-olefin polymer.
By including the α-olefin polymer, the adhesive composition of the present invention can easily control the polarity in the adhesive composition and control the adhesiveness.
Details of the α-olefin polymer are basically the same as those of the raw material α-olefin polymer. When the adhesive composition requires hardness, the mesopentad fraction [mmmm] is 20 to 80 mol%, preferably 40 to 80 mol%, more preferably 50 to 80 mol%. It is preferable.
The content of the α-olefin polymer in the adhesive composition of the present invention is preferably 5 to 50% by mass, more preferably 5 to 30% by mass.

(Additive)
The adhesive composition of the present invention may contain an additive.
As the additive, conventionally known additives can be blended within a range that does not impair the effects of the present invention. For example, foaming agents, anti-fogging stabilizers, ultraviolet absorbers, light stabilizers, heat stabilizers, antistatic agents. , Flame retardants, synthetic oils, waxes, electrical property improvers, oils (process oils), viscosity modifiers, anti-coloring agents, anti-fogging agents, pigments, dyes, plasticizers, softeners, anti-aging agents, hydrochloric acid absorbers , Chlorine scavengers, antioxidants and the like.
The content of the additive in the adhesive composition of the present invention is preferably 0.01 to 1.00% by mass, more preferably 0.05 to 0.50% by mass.

(Use)
The adhesive composition of this invention can be used conveniently for an adhesive tape, a protective film, and an adhesive agent.

<Adhesive tape>
The pressure-sensitive adhesive tape of the present invention is obtained by forming a pressure-sensitive adhesive layer on a support using the above-mentioned pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition may be applied directly on the support. Alternatively, it may be applied on an auxiliary support and then transferred onto the final support. The material of the support is not particularly limited. For example, woven fabric, knit, scrim, non-woven fabric, laminate, net, film, paper, tissue, foam, foamed film, etc. can be used. , Polybutene, oriented polyester, rigid PVC and soft PVC, polyolefin foam, polyurethane foam, EPDM, chloroprene foam and the like.
The support can be prepared chemically by undercoating or by physical pretreatment such as corona before forming the adhesive layer. The back side of the support can be provided with an anti-adhesive physical treatment or coating.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Synthesis example 1
[Production of Complex A ((1,1′-Ethylene) (2,2′-Tetramethyldisilylene) bisindenylzirconium Dichloride)]
Magnesium (12 grams, 500 mmol) and tetrahydrofuran (30 ml) were charged into a 500 ml two-necked flask, and magnesium was activated by dropwise addition of 1,2-dibromoethane (0.2 ml). To this was added dropwise 2-bromoindene (20 grams, 103 mmol) dissolved in tetrahydrofuran (150 milliliters), and the mixture was stirred at room temperature for 1 hour. Thereafter, 1,2-dichlorotetramethyldisilane (9.4 ml, 5.1 mmol) was added dropwise at 0 ° C. After the reaction mixture was stirred at room temperature for 1 hour, the solvent was distilled off, the residue was extracted with hexane (150 ml × 2 times), and 1,2-di (1H-inden-2-yl) -1,1, 2,2-Tetramethyldisilane was obtained as a white solid (15.4 grams, 44.4 mmol, 86% yield).
This was dissolved in diethyl ether (100 ml), n-butyllithium (2.6 mol / l, 38 ml, 98 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 1 hour to precipitate a white powder. The supernatant was removed and the solid was washed with hexane (80 ml) to give the lithium salt as a white powdery solid (14.6 grams, 33.8 mmol, 76%).
This was dissolved in tetrahydrofuran (120 ml), and 1,2-dibromoethane (2.88 ml, 33.8 mmol) was added dropwise at -30 ° C. The reaction mixture was stirred at room temperature for 1 hour and then evaporated to dryness, and the residue was extracted with hexane (150 milliliters) to give the bibridged ligand as a colorless oily liquid (14.2 grams, 37.9 millimoles). ).
This was dissolved in diethyl ether (120 ml), n-butyllithium (2.6 mol / liter, 32 ml, 84 mmol) was added dropwise at 0 ° C., and the mixture was stirred at room temperature for 1 hour to precipitate a white powder. The supernatant was removed, and the solid was washed with hexane (70 ml) to give a lithium salt of the bi-bridged ligand as a white powder (14.0 grams, 31 mmol, 81% yield).
To a suspension of the obtained lithium salt of the bi-bridged ligand (3.00 g, 6.54 mmol) in toluene (30 mL) at −78 ° C., zirconium tetrachloride (1.52 g, 6.54 mmol). ) In toluene (30 ml) was added dropwise with a cannula. After the reaction mixture was stirred at room temperature for 2 hours, the supernatant was separated and the residue was extracted with toluene.
Under reduced pressure, the solvent of the supernatant and the extract was distilled off to dryness to give (1,1′-ethylene) (2,2′-tetramethyldisilene) bis represented by the following formula (1) as a yellow solid. Indenyl zirconium dichloride was obtained (2.5 grams, 4.7 mmol, 72% yield).

The measurement result of ¹ H-NMR is shown below.
¹ H-NMR (CDCl ₃ ): δ 0.617 (s, 6H, —SiMe ₂ —), 0.623 (s, 6H, —SiMe ₂ —), 3.65-3.74, 4.05-4 _{.15 (m, 4H, CH 2} CH 2), 6.79 (s, 2H, CpH), 7.0-7.5 (m, 8H, Aromatic-H)

Synthesis example 2
[Complex B ((1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride)]
(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride) was synthesized according to the description in Reference Example 1 of Japanese Patent No. 4053993.

Synthesis example 3
[Complex C ((1,2′-dimethylsilylene) (2 ′, 1-dimethylsilylene) bis (3-neopentylindenyl) zirconium dichloride)]
A Schlenk bottle was charged with 5.0 g (14.5 mmol) of (1,2′-dimethylsilylene) (2 ′, 1-dimethylsilylene) bis (indene) and 40 mL of ether, and n-BuLi (hexane solution, 2 at 0 ° C.). .69M) After 12.0 mL was added dropwise, the mixture was allowed to rise to room temperature and stirred for 8 hours. The precipitate was separated by filtration, washed with 30 mL of hexane, and dried under reduced pressure to obtain a lithium salt white solid. This was dissolved in 40 mL of THF, 4.9 mL (36.6 mmol) of 1-iodo-2,2-dimethylpropane was added dropwise, and the mixture was heated to reflux for 4 hours. After hydrolysis with 20 mL of water, liquid separation is performed, the organic layer is dried, and the solvent is distilled off to clarify (1,2′-dimethylsilylene) (2 ′, 1-dimethylsilylene) bis (3-neopentylindene). 7.1 g (14.7 mmol) was obtained as an orange oil.
Next, under a nitrogen stream, 7.1 g (14.7 mmol) of (1,2′-dimethylsilylene) (2 ′, 1-dimethylsilylene) bis (3-neopentylindene) and 40 mL of ether are added to the Schlenk bottle. did. After cooling to 0 ° C. and adding 12.0 mL (32.3 mmol) of n-BuLi (hexane solution, 2.69 M), the mixture was stirred at room temperature for 2 hours. The supernatant was filtered off, and the resulting solid was washed with 40 mL of hexane and dried to obtain a lithium salt.
To this lithium salt, 50 mL of toluene is added and cooled to −78 ° C., and a toluene suspension of 3.4 g (14.7 mmol) of zirconium tetrachloride which has been cooled to −78 ° C. in advance is added thereto. After stirring at room temperature for 8 hours, the supernatant was filtered off and the yellow precipitate was extracted with 65 mL of dichloromethane, filtered and evaporated to remove (1,2'-dimethylsilylene) (2 ', 1-dimethylsilylene) bis ( 0.7 g (1.1 mmol) of 3-neopentylindenyl) zirconium dichloride was obtained.
¹ H NMR (CDCl ₃ ): δ0.99 (6H, SiMe ₂ ), 1.06 (6H, SiMe ₂ ), 0.85 (18H, C (CH ₃ ) ₃ ), 2.50, 3.02 ( _{4H, CH 2), 7.1-7.5 (} 8H, Aromatic-H)

Production Example 1
(Production of amorphous 1-butene homopolymer)
In a heat-dried 1 liter autoclave, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), heptane slurry of complex A (10 μmol / mL, 0.20 mL, 2.0 μmol) and MAO (2000 μmol) manufactured by Tosoh Finechem Co. were added, and 0.1 MPa of hydrogen was further introduced. The temperature was raised to 70 ° C. while stirring, and then polymerization was performed for 30 minutes. After completion of the polymerization reaction, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 82 g of amorphous 1-butene homopolymer (polymer a).

[ ¹³ C-NMR measurement]
About the said polymer a, a ¹³ C-NMR spectrum is measured with the following apparatus and conditions, a meso pentad fraction (mmmm), a meso dyad fraction (m), a 1, 3- bond fraction, a 1, 4- bond The fraction and 2,1-bond fraction were determined. The results are shown in Table 1.
Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 230 mg / ml Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

Each structural unit in the 1-butene-propylene copolymer was calculated as follows from the measurement result of the ¹³ C-NMR spectrum described above.
[Dyad chain strength]
a (propylene-propylene chain): integrated value of 48.0-46.2 ppm b (propylene-butene chain): integrated value of 44.4-43.0 ppm c (butene-butene chain): 40.8-39. Integral value of 8 ppm [Dyad chain fraction (mol%)]
d (propylene-propylene chain fraction) = a / (a + b + c) × 100 (mol%)
e (propylene-butene chain fraction) = b / (a + b + c) × 100 (mol%)
f (butene-butene chain fraction) = c / (a + b + c) × 100 (mol%)
[Copolymerization ratio (mol%)]
Propylene unit copolymerization ratio = d + e / 2
1-butene unit copolymerization ratio = f + e / 2

Further, from the measurement result of the ¹³ C-NMR spectrum, the mesodyad fraction (m) was calculated by the following formula.
Mesodyad fraction (m) = (integrated value of 40.4 to 39.9 ppm) / (integrated value of 40.4-39.9 ppm + integrated value of 40.7 to 40.4 ppm)

Furthermore, from the measurement result of the ¹³ C-NMR spectrum, a 1,3-bond fraction, a 1,4-bond fraction, and a 2,1-bond fraction were calculated by the following formulas.
<In case of propylene polymer>
1,3-bond fraction = (D / 2) / (A + B + C + D) × 100 (mol%)
2,1-bond fraction = [(A + B) / 2] / (A + B + C + D) × 100 (mol%)
A: integrated value of 15 to 15.5 ppm B: integrated value of 17 to 18 ppm C: integrated value of 19.5 to 22.5 ppm D: integrated value of 27.6 to 27.8 ppm <1-butene polymer Case>
1,4-bond fraction = E / (A + B + C + D + E) × 100 (mol%)
2,1-bond fraction = {(A + B + D) / 3} / (A + B + C + D) × 100 (mol%)
A: Integrated value of 29.0 to 28.2 ppm B: Integrated value of 35.4 to 34.6 ppm C: Integrated value of 38.3 to 36.5 ppm D: Integrated value of 43.6 to 42.8 ppm E: 31.1 ppm integrated value

[DSC measurement]
For the polymer a, a differential scanning calorimeter (manufactured by Perkin Elmer, trade name: DSC-7) was used, and 10 mg of a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, then 10 ° C./min. Was obtained as ΔH-D (J / g). Further, the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained at this time was determined as the melting point Tm (° C.). The results are shown in Table 1.

[GPC measurement]
About the said polymer a, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were calculated | required by the gel permeation chromatography (GPC) method. For the measurement, the following apparatus and conditions were used, and a weight average molecular weight in terms of polystyrene was obtained. The results are shown in Table 1.
<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

[Intrinsic viscosity (η)]
About the said polymer a, a viscometer (Corporation | KK Co., Ltd. make, brand name: "VMR-053U-PC * F01"), an Ubbelohde-type viscosity tube (time volume of a bulb: 2-3 ml, capillary diameter: 0.44) 0.04 to 0.18 g), a solution of 0.02 to 0.16 g / dL was measured at 135 ° C. using tetralin as a solvent. The results are shown in Table 1.

Production Example 2
(Production of amorphous 1-butene-propylene copolymer)
In a heat-dried 1 liter autoclave, heptane (300 mL), triisobutylaluminum (2 M, 0.2 mL, 0.4 mmol), butene-1 (60 mL), heptane slurry of complex B (10 μmol / mL, 0.02 mL, 0 0.2 μmol), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate heptane slurry (10 μmol / mL, 0.06 mL, 0.6 μmol) was added, and 0.05 MPa of hydrogen was further introduced. The total pressure was set to 0.8 MPa by bringing propylene into the temperature at 60 ° C. while stirring. Then, after superposing | polymerizing for 20 minutes, superposition | polymerization was stopped with 5 mL ethanol, 57 g of amorphous 1-butene-propylene copolymers were obtained by drying a reaction material under reduced pressure (polymer b). The physical properties of the polymer b were measured in the same manner as in Production Example 1. The results are shown in Table 1.

Production Example 3
(Production of amorphous propylene homopolymer)
To a heat-dried 1 liter autoclave, heptane (400 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), complex A (10 μmol / mL, 0.20 mL, 2.0 μmol), MAO manufactured by Tosoh Finechem Co., Ltd. 2000 μmol) and 0.1 MPa of hydrogen were further introduced. While stirring, propylene was charged, the total pressure was increased to 0.7 MPa, and polymerization was performed at a temperature of 50 ° C. for 60 minutes. After completion of the polymerization reaction, propylene and hydrogen were depressurized, and the polymerization solution was heated and dried under reduced pressure to obtain 105 g of an amorphous propylene homopolymer (polymer c). The physical properties of the polymer c were measured in the same manner as in Production Example 1. The results are shown in Table 1.

Production Example 4
To a heat-dried 2 liter autoclave, add heptane (600 mL), complex A (10 μmol / mL, 0.60 mL, 6.0 μmol), MAO (2000 μmol) manufactured by Tosoh Finechem Co., Ltd. at 20 ° C., to −0.09 MPa. The pressure was reduced. And after charging hydrogen to −0.08 MPa (hydrogen partial pressure 0.01 MPa), butene-1 was pressurized to 0.16 MPa (butene-1 partial pressure 0.24 MPa), and the temperature was raised to 40 ° C., Polymerization was carried out at 40 ° C. for 2 hours. After completion of the polymerization reaction, butene-1 and hydrogen were depressurized, and the polymerization solution was heated and dried under reduced pressure to obtain 223 g of an amorphous butene-1 homopolymer (polymer d). The physical properties of the polymer d were measured in the same manner as in Production Example 1. The results are shown in Table 1.

Production Example 5
(Production of crystalline 1-butene homopolymer)
In Production Example 1, Complex B (10 μmol / mL, 0.04 mL, 0.4 μmol) was used instead of Complex A, and N, N-dimethylanilinium tetrakis (pentafluoro) was used instead of MAO (2000 μmol) manufactured by Tosoh Finechem. Phenyl) borate heptane slurry (10 μmol / mL, 0.12 mL, 1.2 μmol) was used in the same manner as in Production Example 1 except that the polymerization temperature was 52 ° C. Obtained (polymer e). The physical properties of the polymer e were measured in the same manner as in Production Example 1. The results are shown in Table 1.

Production Example 6
In a heat-dried 1 liter autoclave, heptane (400 mL), triisobutylaluminum (0.5 mmol), N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (0.8 μmol), and complex C (0.2 μmol) were added. In addition, hydrogen was further introduced at 0.05 MPa, propylene was introduced, the total pressure was 0.8 MPa, and polymerization was carried out at 70 ° C. for 30 minutes. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 90 g of a crystalline propylene homopolymer (polymer f). The physical properties of the polymer f were measured in the same manner as in Production Example 1. The results are shown in Table 1.

Example 1
[Synthesis of acid-modified α-olefin polymer]
Into a 1 liter eggplant flask equipped with a Dimroth tube, 50.0 g of the polymer a obtained in Production Example 1 and 400 mL of trichlorobenzene were added, and stirred at 120 ° C. for 1 hour.
Thereafter, 0.1 g of organic peroxide 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne-3 (“Perhexin 25B” manufactured by NOF Corporation), 1.0 g of maleic anhydride, Was added and stirred at 180 ° C. for 30 minutes.
After heating, the mixture was allowed to stand until it reached room temperature, and then poured into 2 L of methanol, and the precipitate was filtered and dried to obtain acid-modified α-olefin polymer A.
For the acid-modified α-olefin polymer A, the amount of acid modification was measured as follows.

<Measurement method of acid modification amount>
A blend of raw material α-olefin polymer and organic acid before modification is pressed using a 0.1 mm spacer, IR is measured, and the characteristic carbonyl (1600-1900 cm ⁻¹ ) absorption and organic acid are measured. A calibration curve was prepared from the charged amount of the product, IR measurement was performed on the acid-modified press plate, and the amount of modification of (anhydrous) carboxylic acid residue per unit weight was determined. The modification amount defined in the present specification was calculated in terms of (anhydrous) carboxylic acid residue even when the organic acid was other than (anhydrous) carboxylic acid.
IR measuring instrument: “FT / IR-5300” manufactured by JASCO Corporation

[Manufacture of adhesive composition]
4.5 g of acid-modified α-olefin polymer A obtained as described above, 4.5 g of hydrogenated petroleum resin Imabe (P-100) manufactured by Idemitsu Kosan Co., Ltd., and Diana Process Oil (PW-) manufactured by Idemitsu Kosan Co., Ltd. 90) 1.0 g was put into a 50 mL sample bottle, heated and melted at 180 ° C. for 30 minutes, and then sufficiently mixed and stirred with a metal spoon to produce an adhesive composition.

[Manufacture of adhesive tape]
The obtained adhesive composition was sandwiched between a PET film for base material (trade name: Lumirror S10, thickness 50 μm, manufactured by Toray Industries, Inc.) and a PET film for mold release, and was heated to 110 ° C. Then, after coating so that the thickness of the pressure-sensitive adhesive layer was about 30 μm, the release PET film was peeled off and stabilized at room temperature for one day to obtain a test piece of pressure-sensitive adhesive tape.

[Adhesive strength evaluation]
The adhesive strength of the adhesive tape obtained as described above was evaluated according to JIS Z 0237. The pressure-sensitive adhesive tape on which the pressure-sensitive adhesive layer is formed is bonded to an adherend PET film (manufactured by Toray Industries, Inc., trade name: Lumirror S10, thickness 50 μm) and stainless steel (SUS304), 25 mm wide and 200 mm long. After cutting to a size of 2 mm, the bonded portion was applied with a rubber roller twice with a force of 2.0 kg / 25 mm to be adhered. At a measurement temperature of 23 ° C., using a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph AG-I), the initial length L ₀ is set to 120 mm, the sample is pulled at a speed of 300 mm / min, and the 180 ° peel test is performed. Went. The average load at the time of the peel test was taken at five points, and the average value was taken as the adhesive strength. In addition, when slip sticking or zipping occurred during the peeling test, the stress value varies greatly. Therefore, the average value of the fourth value of the maximum value and the minimum value was determined as the adhesive strength. The results are shown in Table 2.

Example 2
[Synthesis of acid-modified α-olefin polymer]
An acid-modified α-olefin polymer B was produced in the same manner as in Example 1 except that 50.0 g of the polymer b obtained in Production Example 2 was used in place of the polymer a.
Further, using the acid-modified α-olefin polymer B, an adhesive composition and a pressure-sensitive adhesive tape were produced in the same manner as in Example 1, and the adhesive strength was evaluated. The results are shown in Table 2.

Example 3
[Synthesis of acid-modified α-olefin polymer]
50.0 g of the polymer c obtained in Production Example 3 and 400 mL of trichlorobenzene were charged into a 1 liter eggplant flask equipped with a Dimroth tube, and the mixture was stirred at 120 ° C. for 1 hour.
Then, 0.1 g of organic peroxide 2,5-dimethyl-2,5 di (t-butylperoxy) hexyne-3 (“Perhexin 25B” manufactured by NOF Corporation), 1.0 g of maleic anhydride, and Acrylic acid 0.5g was added and heated and stirred at 180 ° C. for 30 minutes.
After heating, the mixture was allowed to stand until it reached room temperature, and then poured into 2 L of methanol, and the precipitate was filtered and dried to obtain an acid-modified α-olefin polymer C.
Moreover, using the acid-modified α-olefin polymer C, an adhesive composition and a pressure-sensitive adhesive tape were produced in the same manner as in Example 1, and the adhesive strength was evaluated. The results are shown in Table 2.

Example 4
[Synthesis of acid-modified α-olefin polymer]
An acid-modified α-olefin polymer D was produced in the same manner as in Example 1 except that 50.0 g of the polymer c obtained in Production Example 3 was used in place of the polymer a.
Moreover, using the acid-modified α-olefin polymer D, an adhesive composition and a pressure-sensitive adhesive tape were produced in the same manner as in Example 1, and the adhesive strength was evaluated. The results are shown in Table 2.

Comparative Example 1
An acid-modified α-olefin polymer E was produced in the same manner as in Example 1 except that 50.0 g of the polymer e obtained in Production Example 5 was used in place of the polymer a.
Moreover, using the acid-modified α-olefin polymer E, an adhesive composition and a pressure-sensitive adhesive tape were produced in the same manner as in Example 1, and the adhesive strength was evaluated. The results are shown in Table 2.

Comparative Example 2
An acid-modified α-olefin polymer F was produced in the same manner as in Example 1 except that 50.0 g of the polymer f obtained in Production Example 6 was used in place of the polymer a.
Moreover, using the acid-modified α-olefin polymer F, an adhesive composition and a pressure-sensitive adhesive tape were produced in the same manner as in Example 1, and the adhesive strength was evaluated. The results are shown in Table 2.

Comparative Example 3
Using the polymer a as it was without acid modification, an adhesive composition and a pressure-sensitive adhesive tape were produced in the same manner as in Example 1, and the adhesive strength was evaluated. The results are shown in Table 2.

Example 5
100 g of polybutadiene (Epol, hydroxyl group content = 0.84 meq / g, number average molecular weight = 2590, viscosity = 5.1 Pa · s / 30 ° C.) manufactured by Idemitsu Kosan Co., Ltd. in a 300 mL polyethylene cup Combined A (20 g) was added and heated to about 50 ° C. in an oven and mixed well. Furthermore, at about 20 ° C., 9.8 g of isophorodiisocyanate and 0.05 g of dibutyltin dilaurate were added and mixed well to obtain an adhesive composition (isocyanate / hydroxyl group = about 1).
About the obtained adhesive composition, the tensile shear strength was measured as follows.

[Measurement of tensile shear strength]
In accordance with JIS-K6850, different materials of polycarbonate and polypropylene were used as adherends, and the tensile shear strength was measured. The test piece manufacturing method and measurement conditions are shown below, and the maximum stress (average value of five test pieces) obtained by the measurement is shown in Table 3.

(Test piece manufacturing method)
Adhesive obtained in Example 5 or Comparative Example 4 with a thickness of 1 mm to 2 mm on the entire surface of 12.5 mm from the end of a rigid adherend made of polycarbonate having a width of 25.0 mm, a length of 100 mm, and a thickness of 1.5 mm The composition was applied. The coated surface and the entire surface of 12.5 mm from the end of the polypropylene rigid adherend were superposed and left to stand at room temperature for 3 days while being pressed with a force of about 20 N. Furthermore, after being left at 70 ° C. for 1 hour, it was left at room temperature for 4 days.

(Measurement condition)
Test speed: 50 mm / min
Testing machine: Tensile testing machine AUTOGRAPH AG-X manufactured by Shimadzu Corporation
Temperature: 20 ° C and 80 ° C

Comparative Example 4
100 g of polybutadiene (epol, hydroxyl group content = 0.84 meq / g, number average molecular weight = 2590, viscosity = 5.1 Pa · s / 30 ° C.) manufactured by Idemitsu Kosan Co., Ltd. was obtained in Production Example 1 in a 300 mL polyethylene cup. Polymer a (20 g) was placed and heated to about 50 ° C. in an oven and mixed well. Furthermore, at about 20 ° C., 9.8 g of isophorodiisocyanate and 0.05 g of dibutyltin dilaurate were added and mixed well to obtain an adhesive composition (isocyanate / hydroxyl group = about 1).
The obtained adhesive composition was measured for tensile shear strength in the same manner as in Example 5.

  The adhesive composition of the present invention can be used in the fields of pressure-sensitive adhesive tapes and adhesives.

Claims (10)

An acid-modified α-olefin polymer obtained by modifying a raw material α-olefin polymer with an organic acid, which satisfies the following (1) and (2).
(1) The melting endotherm ΔH-D measured with a differential scanning calorimeter (DSC) is 0 to 10 J / g.
(2) The raw material α-olefin polymer is a propylene homopolymer, 1-butene homopolymer, or propylene-1-butene copolymer. The acid-modified α-olefin polymer according to claim 1, wherein the raw material α-olefin polymer is a propylene homopolymer and satisfies the following (3-1).
(3-1) Mesopentad fraction [mmmm] is 20 mol% or less. The acid-modified α-olefin polymer according to claim 1, wherein the raw material α-olefin polymer is a 1-butene homopolymer and satisfies the following (3-2).
(3-2) Mesopentad fraction [mmmm] is 50 mol% or less. Furthermore, the acid-modified alpha-olefin polymer in any one of Claims 1-3 which satisfy | fills following (4) and (5).
(4) The intrinsic viscosity [η] is 0.1 to 2.0 dl / g.
(5) The molecular weight distribution is 1.5 to 4.0.   The acid-modified α-olefin polymer according to any one of claims 1 to 4, wherein the organic acid is one or more selected from maleic anhydride, (meth) acrylic acid, and (meth) acrylic acid alkyl ester.   A first step of obtaining a raw material α-olefin polymer using a metallocene catalyst, and a second step of modifying the raw material α-olefin polymer obtained in the first step using a radical initiator and an organic acid. The method for producing an acid-modified α-olefin polymer according to any one of claims 1 to 5.   The acid-modified α-olefin polymer according to claim 6, wherein the organic acid used in the second step is at least one selected from maleic anhydride, (meth) acrylic acid, and (meth) acrylic acid alkyl ester. Production method.   An adhesive composition comprising the acid-modified α-olefin polymer according to any one of claims 1 to 5.   The adhesive composition according to claim 8, which is a hot melt adhesive.   A pressure-sensitive adhesive tape obtained by forming a pressure-sensitive adhesive layer on the support using the pressure-sensitive adhesive composition according to claim 8 or 9.