WO2013183600A1 - Pressure-sensitive adhesive composition and pressure-sensitive adhesive tape using same - Google Patents

Abstract

A pressure-sensitive adhesive composition containing a butene-based polymer, said butene-based polymer consisting of a 1-butene homopolymer that satisfies conditions (1) and (2) given below and/or a 1-butene-propylene copolymer that satisfies conditions (1') and (2) given below, and a pressure-sensitive adhesive tape using said pressure-sensitive adhesive composition in a pressure-sensitive adhesive layer make it possible to provide a highly adhesive pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape using same. (1) The meso pentad fraction (mmmm) is between 3 and 80 mol%, inclusive. (1') The meso dyad fraction (m) is between 30 and 95 mol%, inclusive. (2) The latent heat of fusion (ΔHd) is less than or equal to 40 J/g.

Description

Adhesive composition and pressure-sensitive adhesive tape using the same

The present invention relates to an adhesive composition containing a butene polymer and a pressure-sensitive adhesive tape using the same.

Conventionally, protective films and adhesives based on polyolefin-based materials have been studied in various ways because they are inexpensive. For example, Patent Document 1 discloses a protective film produced by mixing an ethylene-based polymer with liquid polybutene or polyisobutylene as a tackifier. Patent Document 2 discloses an adhesive tape made of an olefin polymer and an adhesive resin.
However, there are few examples of using a polybutene-based material as an adhesive substrate. Moreover, when a polybutene-based material is used as a base material, the viscosity is too low, or conversely, it is too high, which is difficult to use. Further, the tackiness was not controlled by the polybutene material itself, and the tackiness was adjusted by the blending amount.

JP 6-4729 Special table 2011-519989

An object of the present invention is to provide a pressure-sensitive adhesive composition having an excellent adhesive force and a pressure-sensitive adhesive tape using the same, using a butene polymer.

According to the present invention, the following inventions are provided.
[1] An adhesive composition containing a butene polymer, wherein the butene polymer satisfies the following (1) and (2) and / or the following (1 ′ ) And (2), an adhesive composition which is a 1-butene-propylene copolymer.
(1) Mesopentad fraction [mmmm] is 3 to 80 mol%.
(1 ′) Mesodyad fraction [m] is 30 to 95 mol%.
(2) The melting endotherm ΔHD is 40 J / g or less.
[2] The adhesive composition according to [1], including 10% by mass or more of the butene polymer and 10% by mass or more of the tackifier.
[3] The adhesive composition according to [1] or [2], wherein the 1-butene homopolymer or 1-butene-propylene copolymer satisfies the following (3) to (5).
(3) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the peak observed is not observed or is 0-100 ° C.
(4) The molecular weight distribution (Mw / Mn) measured by the gel permeation chromatograph (GPC) method is 4.0 or less.
(5) The weight average molecular weight (Mw) measured by GPC method is 5,000 to 1,000,000.
[4] In the butene monomer chain portion of the butene polymer, the 1,4-bond fraction observed by ¹³ C-NMR is 0.5 mol% or less, and the 2,1-bond fraction is The adhesive composition according to any one of the above [1] to [3], which is 0.5 mol% or less.
[5] The adhesive composition according to any one of [1] to [4], wherein the butene polymer satisfies the following (6).
(6) After being melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, left at room temperature for 1 hour, and then analyzed by X-ray diffraction, the type II crystal fraction (CII) is 50% or less It is.
[6] A pressure-sensitive adhesive tape using the adhesive composition according to any one of [1] to [5] as an adhesive layer.

According to the present invention, it is possible to provide a pressure-sensitive adhesive composition having excellent adhesive strength and a pressure-sensitive adhesive tape using the same, using a butene polymer.

<Adhesive composition>
The adhesive composition of the present invention is characterized by containing a butene-based polymer described later.
The adhesive composition of the present invention preferably contains 10 to 100% by mass, more preferably 40 to 100% by mass of the butene polymer based on the solid content excluding the solvent. More preferably, the content is 70% by mass. When the ratio of the butene polymer is 10% by mass or more, the cohesive force is improved.
Further, the adhesive composition of the present invention may further contain a tackifier, and the ratio thereof is preferably 10% by mass or more, more preferably based on the solid content excluding the solvent. Is 10 to 60% by mass, more preferably 30 to 60% by mass. When the ratio of the tackifier is within the above range, the cohesive force is improved.

[Butene polymer]
The butene polymer is a 1-butene homopolymer satisfying the following (1) and (2) and / or a 1-butene-propylene copolymer satisfying the following (1 ′) and (2).
(1) Mesopentad fraction [mmmm] is 3 to 80 mol%.
(1 ′) Mesodyad fraction [m] is 30 to 95 mol%.
(2) The melting endotherm ΔHD is 40 J / g or less.

In addition, the butene polymer in the present invention preferably satisfies the following (3) to (6).
(3) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the peak observed is not observed or is 0-100 ° C.
(4) The molecular weight distribution (Mw / Mn) measured by the gel permeation chromatograph (GPC) method is 4.0 or less.
(5) The weight average molecular weight (Mw) measured by GPC method is 5,000 to 1,000,000.
(6) After being melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, left at room temperature for 1 hour, and then analyzed by X-ray diffraction, the type II crystal fraction (CII) is 50% or less It is.

In the present invention, the mesopentad fraction [mmmm], 1,4-bond fraction, and 2,1-bond fraction are reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “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. Specifically, signals of methylene group and methine group were measured using ¹³ C nuclear magnetic resonance spectrum, and mesopentad fraction [mmmm] 1,4-bond fraction and 2,1-bond in poly (1-butene) chain The fraction was determined.
^{The 13} C-NMR spectrum was measured with 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 butene polymer preferably has a 1,4-bond fraction in the butene monomer (1-butene) chain portion of 0.5 mol% or less, more preferably 0.3 mol% or less, More preferably, it is 1 mol% or less.
In the butene polymer, the 2,1-bond fraction in the butene monomer (1-butene) chain is preferably 0.5 mol% or less, more preferably 0.3 mol% or less. More preferably, it is 0.1 mol% or less.
When these are within the above range, the fluidity at low temperature is good, the low-temperature adhesiveness is improved, and the compatibility with the tackifier is good.

The 1,4-bond fraction and 2,1-bond fraction can be calculated by the following formula from the measurement result of the ¹³ C-NMR spectrum.
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: Integration value of 29.0 to 28.2 ppm B: Integration value of 35.4 to 34.6 ppm C: Integration value of 38.3 to 36.5 ppm D: Integration value of 43.6 to 42.8 ppm E: 31.1 ppm integrated value

The butene polymer requires a melting endotherm ΔHD as measured by DSC of 40 J / g or less, and a melting endotherm ΔHD is preferably 36 J / g, preferably 25 J / g or less. It is more preferable. If the melting endotherm ΔHD is more than 40 J / g, the adhesive performance changes greatly during the crystallization process, which may make it difficult to use as an adhesive substrate. The lower limit of the melting endotherm ΔHD is 0 J / g (not observed).
Here, the melting point (ΔHD) is 0 J / g because the crystallization speed is extremely slow or does not crystallize in the DSC measurement, so that the crystal melting peak cannot be substantially observed, and the melting endotherm is It means that it cannot be observed.
The melting endotherm ΔH-D was increased at 10 ° C./min after holding a 10 mg sample at −10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (Perkin Elmer, DSC-7). It was obtained by heating.

The butene polymer is preferably a crystalline resin in which the Tm-D is not observed or the Tm-D is 0 to 100 ° C., preferably 0 to 80 ° C. Tm-D is determined by DSC measurement. That is, a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7) was used to hold a 10 mg sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raise the temperature at 10 ° C./min. The peak top of the peak observed on the highest temperature side of the melting endotherm curve is the melting point: Tm-D.
In the present invention, the fact that the melting point (Tm−D) is not observed with a differential scanning calorimeter (DSC) means that the crystal melting peak cannot be substantially observed because the crystallization rate is very slow in the DSC measurement.

The butene polymer preferably has a molecular weight distribution (Mw / Mn) measured by GPC method of 4 or less, more preferably 3.5 or less, and particularly preferably 3.0 or less. When the molecular weight distribution (Mw / Mn) is 4 or less, when used as an adhesive material, the remainder is reduced.
The butene polymer preferably has a weight average molecular weight (Mw) measured by GPC method of 5,000 to 1,000,000, more preferably 9,000 to 200,000, still more preferably 20,000. ~ 100,000. If Mw is 5,000 or more, stickiness is reduced. Moreover, fluidity | liquidity improves that Mw is 1,000,000 or less, and a moldability becomes favorable.
In addition, the said molecular weight distribution (Mw / Mn) is the value computed from the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion measured with the following apparatus and conditions by GPC method.
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)

The butene-based polymer was melted at 190 ° C. for 5 minutes, quenched and solidified with ice water, allowed to stand at room temperature for 1 hour, and then analyzed by X-ray diffraction to obtain a type II crystal fraction. (CII) is preferably 50% or less, more preferably 20% or less, and still more preferably 0%.
In the present invention, the type II crystal fraction (CII) It was determined according to the method proposed in “Polymer, 7, 23 (1966)” reported by Turner Jones et al. That is, the peak of the type I crystal state and the peak of the type II crystal state were measured by X-ray diffraction analysis, and the type II crystal fraction (CII) in the butene polymer crystal was determined. X-ray diffraction analysis (WAXD) was performed using a counter cathode type rotor flex RU-200 manufactured by Rigaku Corporation under the following conditions.
Sample state: Melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, then left at room temperature for 1 hour Output: 30 kV, 200 mA
Detector: PSPC (position sensitive proportional counter)
Total time: 200 seconds

The above-mentioned butene-based polymer preferably has a tensile elastic modulus measured by a tensile test according to JIS K-7113 of 500 MPa or less, and more preferably 300 MPa or less. It is because sufficient softness may not be obtained when it exceeds 500 MPa.

[A] 1-Butene Homopolymer The 1-butene homopolymer satisfies the following (1) and (2).
(1) Mesopentad fraction [mmmm] is 3 to 80 mol%.
(2) The melting endotherm ΔHD is 0 to 40 J / g.
The 1-butene homopolymer needs to have a mesopentad fraction [mmmm] of 3 to 80 mol%, preferably 30 to 85 mol%, and more preferably 30 to 80 mol%. When the mesopentad fraction is less than 3 mol%, stickiness of the surface of the molded body and a decrease in transparency may occur. On the other hand, when it exceeds 80 mol%, the flexibility and the adhesiveness may be lowered.
On the other hand, the adhesive composition of the present invention has a mesopentad fraction [mmmm] of preferably 3 to 40 mol%, more preferably 3 to 25 mol% from the viewpoint of repeated adhesive bonding. It is particularly preferred to be ˜10 mol%.

[A ′] 1-butene-propylene copolymer The 1-butene-propylene copolymer satisfies the following (1 ′) and (2).
(1 ′) Mesodyad fraction [m] is 30 to 95 mol%.
(2) The melting endotherm ΔHD is 0 to 40 J / g.
The 1-butene-propylene copolymer requires a meso-dyad fraction [m] of 30 to 95 mol%, preferably 40 to 90 mol%, and more preferably 50 to 85 mol%. When the meso-dyad fraction is less than 30 mol%, the syndiotactic property becomes strong and the heat resistance may be deteriorated. On the other hand, when it exceeds 95 mol%, the flexibility and the adhesiveness may be lowered.
The 1-butene-propylene copolymer is preferably a random copolymer.
It is also preferable to use a 1-butene-propylene copolymer from the viewpoint of repeated adhesive bonding of the above-mentioned adhesive composition of the present invention.

In the 1-butene-propylene 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 the 1-butene unit is 15 mol% or more, the low temperature characteristics of the pressure-sensitive adhesive containing the same polymer are improved. From the viewpoint of low temperature characteristics, it is better that the number of structural units obtained from 1-butene is larger.
The above mesopentad and mesodyad are both indicators of the structural stereoregularity of the polymer. In the case of a 1-butene homopolymer, the methyl group signal in the polymer chain is measured and the 1-butene-propylene copolymer is measured. In the case of a polymer, even if the signal of the methyl group in the polymer chain is the same stereoregularity, the structure stereoregularity is different according to the following measurement method because it differs in the case of butene-1 only and butene-1 / propylene Is shown.
Each structural unit in the 1-butene-propylene copolymer can be calculated as follows from the measurement result of the ¹³ C-NMR spectrum.
[Dyad chain strength]
a (propylene-propylene chain): integral value of 48.0 to 46.2 ppm b (propylene-butene chain): integral value of 44.4 to 43.0 ppm c (butene-butene chain): 40.8 to 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 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)

[Butene polymer production method]
As a method for producing a butene polymer, a method for producing the 1-butene homopolymer by homopolymerizing 1-butene using a metallocene catalyst, 1-butene and propylene (further used if necessary) And a method of producing the 1-butene-propylene copolymer by copolymerizing an α-olefin having 5 to 20 carbon atoms.
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, and a substituted indenyl group as described in JP-A-1-503636 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 general formula (I)

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² And they may be the same or different, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different, and other X, E1, It may be cross-linked with E2 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, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a 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 - 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, which may be the same or different. q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. ]
And (B) (B-1) a compound capable of reacting with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B-2) an aluminoxane. A method of homopolymerizing 1-butene in the presence of a polymerization catalyst containing a component selected from 1 or a copolymer of 1-butene and propylene (and an α-olefin having 5 to 20 carbon atoms if necessary) The method of letting it be mentioned.

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. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity.
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 silicon-containing groups having 1 to 20 carbon atoms, phosphide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, and acyl groups having 1 to 20 carbon atoms.

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. Next, A ¹ and A ² are divalent bridging groups for linking two ligands, including a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and silicon-containing groups. 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, which may be the same May be different. Examples of such a bridging group include a general formula

(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 =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisilylene group, a diphenyldisilylene group, and the like. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable. q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these 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 from each other, 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 from the viewpoint of increasing the 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 a 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 in view of increasing the 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 / 16450A1 International Publication are also preferable examples in the present invention.
Among them, in order to provide a 1-butene homopolymer that satisfies the above-mentioned requirement (1) or a 1-butene-propylene copolymer that satisfies the above-mentioned requirement (1 ′), the ligand is a crosslinking group. A transition metal compound (single bridge) that forms a cross-linked structure via a transition metal compound that forms a cross-linked structure via two cross-linking groups, a transition metal compound having a meso-type structure, It is preferable to select a transition metal compound having a substituent in the ligand or bridging group.
Further, in order to provide a 1-butene homopolymer or 1-butene-propylene copolymer satisfying the requirement of (2), a transition metal compound in which a ligand exists without a crosslinking group (non-crosslinked), It is preferable to select a transition metal compound which forms a cross-linked structure via a half metallocene complex or two cross-linking groups and has a substituent on the ligand or the cross-linking group.
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. By selecting the preferred specific examples, the 1-butene homopolymer satisfying the above (1) and (2) and / or the 1-butene-propylene copolymer satisfying the following (1 ′) and (2) A polymer can be provided.

Next, the component (B-1) in the component (B) is any compound that can react with the transition metal compound of the component (A) to form an ionic complex. The following general formulas (III) and (IV)
([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 formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z1] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of groups Is an anion bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where 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 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, and an aryl having 6 to 20 carbon atoms, respectively. Group, 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, and 1 to 20 carbon atoms Acyloxy group, organic metalloid group, or C2-C20 heteroatom-containing charcoal Two or more of .G ¹ ~ G ^f represents a hydrogen group may form a ring.
f represents an integer of [(valence of central metal M ¹ ) +1]. ), [Z ^{2] -} is the logarithm of the reciprocal of the acid dissociation constant (pKa) -10 below Bronsted acid alone or Bronsted acid and Lewis acid combination of conjugate base, or a general superacid defined The conjugate base of the acid to be produced is shown. 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 in groups 7 to 12 of the periodic table. ]
What is represented by these can be used conveniently.

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 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, and I _3. Specific examples of M ³ include Mn, Fe, Co, Ni, and Zn. And so on.
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 namely the combination of a conjugate base with a pKa of -10 or less Bronsted acid alone or Bronsted acid and Lewis acid [Z ^{2] -} trifluoromethanesulfonic acid anion Specific examples of (CF ₃ SO 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 ) ^- , fluorosulfonic acid anion (FSO ₃ ) ^- , chlorosulfonic acid anion (ClSO ₃ ) ^- , fluorosulfonic acid anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^-, fluoro sulfonic acid anion / - 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, that is, the (B-1) component compound, include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzylammonium tetraphenylborate (tri-n-butyl) ammonium 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, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) benzyl benzyl (tri-n-butyl) 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), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) 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 singly or in combination of two or more.

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 terms of molar ratio when (B-1) compound is used as (B) catalyst component. 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 becomes high, 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. Further, as the catalyst component (B), (B-1) and (B-2) may be used alone or in combination of two or more.

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. Furthermore, when the component (A) and the component (B-2) are brought 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. Of these, particularly preferred 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, 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 firing 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 as component (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 in which prepolymerization is performed at a temperature of 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 in mass ratio is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500.
If the proportion of the component (B) [component (B-1) or component (B-2)] and the carrier, or the proportion of component (A) and the carrier used deviates from the above ranges, 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. It is preferably 50 to 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 usually 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 butene polymer used in the present invention, the above-mentioned polymerization catalyst is used to homopolymerize 1-butene to produce the 1-butene homopolymer, or by copolymerizing 1-butene and propylene. The 1-butene-propylene copolymer can be produced.
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.
Regarding the polymerization conditions, the polymerization temperature is usually −100 to 250 ° C., preferably −50 to 200 ° C., more preferably 0 to 130 ° C. The ratio of the catalyst to the reaction raw material is preferably 10 ⁵ to 10 ⁸ , particularly 10 ⁶ to 10 ⁷ , preferably from raw material monomer / component (A) (molar ratio). Further, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is preferably from atmospheric pressure to 3 MPa (gauge), more preferably from atmospheric 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. A monomer such as α-olefin may be used 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 in the prepolymerization is not particularly limited, and examples thereof include ethylene, 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.
The prepolymerization temperature is usually −20 to 200 ° C., preferably −10 to 130 ° C., more preferably 0 to 80 ° C. 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.

[Tackifier]
As tackifying resins [II], Idemitsu Petrochemical's Imabu P-125, Imabu P-100, Imabu P-90, Sanyo Chemical Industries Umex 1001, Mitsui Chemicals Highlets T1115, Yashara Chemicals Clearon K100, Tonex Examples include ECR227 manufactured by the same company, Escoretz 2101, Alcon P100 manufactured by Arakawa Chemical, and Regalrez 1078 manufactured by Hercules.
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.

[Butene polymer functionalized product]
In addition to the butene polymer, the adhesive composition of the present invention is a butene modified with 5 mol% or more (more preferably 10 mol% or more) of the terminal vinylidene group of the butene polymer as a functional group. It may contain a functionalized polymer.
The functional group is preferably one or more functional groups selected from a hydroxyl group, an epoxy group, an alkoxysilicon group, an alkylsilicon group, a carboxyl group, an amino group, and an isocyanate group.
Moreover, the butene polymer functionalized product may have an acid anhydride structure. An acid anhydride structure is a structure in which one molecule of water is lost from two carboxyls of a carboxylic acid and two acyl groups share one oxygen atom. Generally indicated by R ¹ COOCOR ² . For example, maleic anhydride, succinic anhydride, phthalic anhydride and the like can be mentioned.

The functionalized butene polymer has a functional group, thereby improving compatibility and dispersibility with polar compounds, making it easy to obtain compositions with various polymers, and polarities such as water. Solubility and dispersibility in a solvent can be improved.

Examples of functional group introduction methods include maleic anhydride ene addition reaction; introduction of hydroxyl group with formic acid / hydrogen peroxide; epoxidation with peracetic acid; trimethoxysilane, triethoxysilane, triisopropoxysilane, methyldimethoxysilane, Introduction of an alkoxysilicon group by reaction with an alkoxysilane such as ethyldiethoxysilane, phenyldimethoxysilane, phenyldiethoxysilane; introduction of an alkylsilicon group by reaction with an alkylsilane such as tri-hexylsilane, tri-normal octylsilane; Carboxylation with copper bromide / tertiary butyl peroxyacetate; introduction of amino group by reaction of anhydrous maleate and diamine compound; introduction of isocyanate group by reaction of anhydrous maleate and diisocyanate compound It is.

In addition to the above, the functional group is introduced by hydroboration with BH ₃ .THF; boronation with 9-boranebicyclo [3,3,1] nonane; metalation with isobutylaluminum hydride or the like; halogen with dibromo or hydrogen bromide Hydroformylation with formic acid / cobalt catalyst; aldehyde formation with carbon monoxide / dicobalt octacarbonyl catalyst; sulfonation with acetic anhydride / sulfuric acid, etc. can be used.

[solvent]
The adhesive composition of the present invention may contain a solvent, and specific examples thereof 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 cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, benzene, toluene, xylene, ethylbenzene, methoxybenzene, 1, Examples thereof include organic solvents such as aromatic hydrocarbons such as 2-dimethoxybenzene, hexane, cyclohexane, heptane, and pentane.
The ratio of the solvent in the adhesive composition of the present invention is 70% by mass or less based on the total amount of the adhesive composition, except for the case of preparing a solution for the purpose of preparing the composition. It is preferably 50% by mass or less, and more preferably 30% by mass or less.

[Additive]
An additive may be added to the adhesive composition of the present invention, and as the additive, a conventionally known additive can be blended, for example, a foaming agent, an anti-wrinkle stabilizer, an ultraviolet absorber, light Stabilizer, heat stabilizer, antistatic agent, flame retardant, synthetic oil, wax, electrical property improver, oil, viscosity modifier, anti-coloring agent, antifogging agent, pigment, dye, plasticizer, softener, aging Additives such as an inhibitor, a hydrochloric acid absorbent, a chlorine scavenger, and an antioxidant can be mentioned.

<Adhesive tape>
The pressure-sensitive adhesive tape of the present invention uses the above adhesive composition for an adhesive layer, and the adhesive composition may be applied directly on a support or on an auxiliary support. And then transferred onto the final support. The material of the support is not particularly limited, and for example, woven fabric, knit, scrim, non-woven fabric, laminate, net, film, paper, tissue, foam, foam film, etc. can be used. Examples of the film include polypropylene, polyethylene, polybutene, oriented polyester, hard PVC and soft PVC, polyolefin foam, polyurethane foam, EPDM, and chloroprene foam.
The support can be prepared chemically by priming or by physical pretreatment such as corona prior to abutting the adhesive composition. The back side of the support can be provided with an anti-adhesive physical treatment or coating.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical property measuring method and measuring apparatus are shown below.

Synthesis Example 1 [Synthesis of Complex A ((1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride)]
A Schlenk bottle was charged with 0.83 g (2.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 50 mL of ether. After cooling to −78 ° C. and adding 3.1 mL (5.0 mmol) of n-BuLi (hexane solution 1.6 M), the mixture was stirred at room temperature for 12 hours. The solid obtained by distilling off the solvent was washed with 20 mL of hexane to obtain 1.1 g (2.3 mmol) of a lithium salt as an ether adduct. This lithium salt was dissolved in 50 mL of THF and cooled to -78 ° C. 0.57 mL (5.3 mmol) of n-butyl bromide was slowly added dropwise and stirred at room temperature for 12 hours. After the solvent was distilled off and extraction was performed with 50 mL of hexane, the solvent was removed and 0.81 g (1. 1'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-n-butylindene) was added. 77 mmol). (Yield 74%)
Next, 0.81 g (1.77 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. ) And 100 mL of ether. After cooling to −78 ° C. and adding 2.7 mL (4.15 mmol) of n-BuLi (hexane solution 1.54 M), the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the resulting solid was washed with hexane to obtain 0.28 g (1.43 mmol) of a lithium salt as an ether adduct.
The lithium salt obtained above was dissolved in 50 mL of toluene under a nitrogen stream. The solution was cooled to −78 ° C., and a suspension of 0.33 g (1.42 mmol) of zirconium tetrachloride previously cooled to −78 ° C. in toluene (50 mL) was added dropwise thereto, followed by stirring at room temperature for 6 hours. Thereafter, the mixture was filtered, and the solvent of the filtrate was distilled off. Recrystallization from dichloromethane yielded 0.2 g (0.32 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride. (Yield 22%)
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are: δ 0.88, 0.99 (12H, dimethylsilylene), 0.7-1.0, 1.1-1.5 (18H, n -Bu), 7.0-7.6 (8H, benzene ring proton).

Synthesis Example 2 [Production of Complex B ((1,2′-Methylphenylsilylene) (2,1′-Methylphenylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium Dichloride (Cis))]
(Synthesis of 2-methylphenylsilylindene)
After putting magnesium (20.0 g, 833 mmol) and THF (250 ml) into a 2 L three-necked flask, 1,2-dibromoethane (1.0 ml) was added and stirred at room temperature for 15 minutes to activate the magnesium surface. It was. A solution of 2-bromoindene (78.3 g, 401 mmol) in THF (250 ml) was added dropwise thereto using the same pressure dropping funnel, and the mixture was stirred at room temperature for 30 minutes after completion of the addition. The obtained Grignard solution was cooled using an ice bath, dichloromethylphenylsilane (65.0 ml, 400 mmol) was added thereto, and the mixture was returned to room temperature and stirred for 30 minutes. The reaction mixture was evaporated, sufficiently dried under vacuum, extracted with hexane (1 L), and the hexane solution was evaporated to give 2-methylphenylsilylindene as a pale yellow oil (66. 3 g, 245 mmol, 66%).
¹ H-NMR (CDCl ₃ ): δ 0.920 (s, 3H, SiMe), δ 3.60 (2H, IndH ₂ ), δ 7.3 to 7.7 (5H, aromatics)

The 2-methylphenylsilylindene was dissolved in THF (180 ml), cooled in an ice bath, and then LDA (245 mmol) was added dropwise using the same pressure dropping funnel. After raising the temperature to room temperature, the solvent was distilled off under vacuum, and the resulting foam solid was extracted with hexane (500 ml × 2) to obtain (1,2′-methylphenylsilylene) (2,1′- Methylphenylsilylene) bisindene was obtained as a white foamy solid (40.0 g, 85.5 mmol, 70%).
The above (1,2'-methylphenylsilylene) (2,1'-methylphenylsilylene) bisindene was dissolved in diethyl ether (220 ml), and cooled with an ice bath while being cooled with an n-butyllithium hexane solution (67.0 ml, 181 mmol). ) Was dropped, and the mixture was warmed to room temperature and stirred for 15 minutes. The solid obtained from the supernatant of the reaction mixture was washed with hexane to obtain a lithium salt of (1,2'-methylphenylsilylene) (2,1'-methylphenylsilylene) bisindene (cis isomer rich) as a white solid. . (31.5 g, 51.2 mmol, 63%, cis isomer: trans isomer = 74: 26)
¹ H-NMR (THF-d ₈ ): δ 0.742 (s, 6H, SiMe-trans isomer), δ 0.844 (s, 6H, SiMe-cis isomer), δ 6.54 (s, 2H, IndH-trans ), Δ 6.61 (s, 2H, IndH-cis isomer), δ 6.4 to 7.8 (8H, aromatics)

All lithium salts of (1,2′-methylphenylsilylene) (2,1′-methylphenylsilylene) bisindene (cis isomer excess) were dissolved in THF (200 ml) and cooled using an ice bath. Iodomethyltrimethylsilane (16.0 ml, 108 mmol) was added dropwise thereto, and after completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and then quenched with water. From the organic layer, (1,2'-methylphenylsilylene) (2, 1′-methylphenylsilylene) (bis-3-trimethylsilylmethylindene) was obtained as a yellow-brown viscous solid (32.4 g, 50.6 mmol, 99%).
The above (1,2′-methylphenylsilylene) (2,1′-methylphenylsilylene) (bis-3-trimethylsilylmethylindene) was dissolved in diethyl ether, cooled in an ice bath, and then n-butyllithium ( (40.0 ml, 106 mmol) was added dropwise, and the pale yellow powder precipitated was separated from the supernatant and washed with hexane to obtain (1,2'-methylphenylsilylene) (2,1'-methylphenylsilylene) (bis -3-trimethylsilylmethylindene) lithium salt was obtained (19.3 g, 25.3 mmol, 50%)
¹ H-NMR (THF-d ₈ ): δ-0.115 (s, 18H, CH ₂ SiMe ₃ -Asym), δ-0.03 (s, 18H, CH ₂ SiMe ₃ -Sym.), Δ2. 4 to 2.6 (4H, CH ₂ SMe ₃ ), δ 6.3 to 7.7 (aromatics)
Suspend the lithium salt of (1,2'-methylphenylsilylene) (2,1'-methylphenylsilylene) (bis-3-trimethylsilylmethylindene) in hexane, and bring it to -30 ° C with a dry ice-ethanol bath After cooling, a hexane suspension of zirconium tetrachloride (5.9 g, 25 mmol) was added dropwise thereto. After stirring overnight, the precipitated yellow solid was separated from the supernatant, and this yellow solid was extracted with methylene chloride to extract (1,2'-methylphenylsilylene) (2,1'-methylphenylsilylene) (bis-3- Trimethylsilylmethylindenyl) zirconium dichloride (cis isomer) was obtained as a yellow powder (7.35 g, 9.24 mmol, 37%, cis isomer: trans isomer = 100: 0).
¹ H-NMR of L25-Sym. (CDCl ₃ ): δ-0.07 (s, 18H, CH ₂ SiMe ₃ ), δ 0.929 (s, 6H, SiMe), δ 2.26, 2.29 (d, 2H, CH ₂ SiMe ₃ ) δ2.71, 2.75 (d, 2H, CH ₂ SiMe ₃ ) δ6.9-7.5 (8H, aromatics)

Synthesis Example 3 [Production of Complex C ((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 stirring the reaction mixture at room temperature for 1 hour, the solvent was distilled off, the residue was extracted with hexane (150 ml × 2), 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 ml) to give a bi-bridged ligand as a colorless oily liquid (14.2 grams, 37.9 mmol). ).
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 4 [Complex D (Dimethylsilylenebis (2-methylbenzoindenyl) zirconium dichloride)]
The following (dimethylsilylene bis (2-methylbenzoindenyl) zirconium dichloride) was synthesized according to the description in the literature (Organometallics 1994, 13, 954).

Production Example 1 (Production of 1-butene homopolymer)
To a heat-dried 1 liter autoclave, heptane (200 mL), triisobutylaluminium (2M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), complex A heptane slurry (10 μmol / mL, 0.04 mL, 0.4 μmol), heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate (10 μmol / mL, 0.12 mL, 1.2 μmol) was added, and 0.1 MPa of hydrogen was further introduced. While stirring, the temperature was raised to 52 ° C. and polymerization was carried out 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 83 g of 1-butene homopolymer (Polymer A).

[ ¹³ C-NMR measurement]
The polymer a was measured for ¹³ C-NMR spectrum using the following apparatus and conditions, and mesopentad fraction [mmmm], mesodyad fraction [m], 1,4-bond fraction, and 2,1-bond. The fraction was 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

[DSC measurement]
Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer Co.), a 10 mg sample is held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. The melting endotherm obtained by the above step was defined as ΔHD, and the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained at this time was determined as the melting point Tm-D. 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. The following apparatus and conditions were used for the measurement, 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)

[Type II crystal fraction (CII)]
About the said polymer a, the peak of the I type crystal state and the peak of the II type crystal state were measured by X-ray diffraction analysis, and the II type crystal fraction (CII) in a crystal | crystallization was calculated | required. X-ray diffraction analysis (WAXD) was performed using a counter cathode type rotor flex RU-200 manufactured by Rigaku Corporation under the following conditions. The results are shown in Table 1.
Sample state: Melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, then left at room temperature for 1 hour Output: 30 kV, 200 mA
Detector: PSPC (position sensitive proportional counter)
Total time: 200 seconds

[Intrinsic viscosity [η]]
With respect to the polymer a, a viscometer (manufactured by Kogai Co., Ltd., trade name: “VMR-053U-PC • F01”), Ubbelohde type viscosity tube (time volume of bulb: 2-3 ml, capillary diameter: 0.44) And a solution of 0.02 to 0.16 g / dL was measured at 145 ° C. using 1,2,4-trichlorobenzene as a solvent. The results are shown in Table 1.

Production Example 2 (Production of 1-butene homopolymer)
In Production Example 1, complex B (10 μmol / mL, 0.12 mL, 1.2 μmol) was used instead of complex A, and the amount of heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate used was 3.6 μmol ( 10 μmol / mL, 0.36 mL) and 40 g of 1-butene homopolymer was obtained in the same manner as in Production Example 1 except that the polymerization temperature was 50 ° C. (Polymer B). The physical properties of the polymer B are shown in Table 1.

Production Example 3 (Production of 1-butene homopolymer)
In Production Example 1, instead of Complex A, Complex C (10 μmol / mL, 0.20 mL, 2.0 μmol) was used, and instead of dimethylanilinium tetrakis (pentafluorophenyl) borate, MAO manufactured by Tosoh Finechem Corporation (2000 μmol) Was used in the same manner as in Production Example 1 except that the polymerization temperature was changed to 70 ° C., to obtain 82 g of a 1-butene homopolymer (Polymer C). The physical properties of the polymer C are shown in Table 1.

Production Example 4 (Production of 1-butene-propylene copolymer)
To a heat-dried 1 liter autoclave, heptane (300 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (60 mL), complex A heptane slurry (10 μmol / mL, 0.02 mL, 0.2 μmol) and heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate (10 μmol / mL, 0.06 mL, 0.6 μmol) were 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 20 minutes of polymerization, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 57 g of 1-butene-propylene copolymer (Polymer D). The physical properties of the polymer D are shown in Table 1.

Production Example 5 (Production of 1-butene-propylene copolymer)
To a heat-dried 1 liter autoclave, heptane (180 mL), triisobutylaluminum (2 M, 0.2 mL, 0.4 mmol), butene-1 (180 mL), complex A heptane slurry (10 μmol / mL, 0.02 mL, 0.2 μmol), heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate (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 0.6 MPa by introducing propylene at the same time as the temperature was 60 ° C. while stirring. Then, after 20 minutes of polymerization, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 45 g of 1-butene-propylene copolymer (Polymer E). The physical properties of the polymer E are shown in Table 1.

Comparative Production Example 1 (Production of 1-butene homopolymer)
In Production Example 1, complex D (10 μmol / mL, 0.30 mL, 0.6 μmol) was used instead of complex A, and the amount of heptane slurry of dimethylanilinium tetrakis (pentafluorophenyl) borate used was 1.8 μmol ( 10 μmol / mL, 0.18 mL), and the same procedure as in Production Example 1 except that the polymerization temperature was 70 ° C., yielded 68 g of 1-butene homopolymer (Polymer F). The physical properties of the polymer F are shown in Table 1.

Production Example 6
In Production Example 5, a polymer was produced in the same manner as Polymer G except that the total pressure when propylene was applied was 0.55 MPa. Table 2 shows the physical properties of the polymer G.

Example 1 (Preparation of adhesive composition and pressure-sensitive adhesive tape)
1.35 g of polymer A produced in Production Example 1, 1.35 g of hydrogenated petroleum resin Imabe (P-100) manufactured by Idemitsu Kosan Co., Ltd., 0.3 g of Diana Process Oil (PW-90) manufactured by Idemitsu Kosan Co., Ltd. 20 mL of toluene was mixed and dissolved in a 50 mL sample bottle to prepare a solution-like adhesive composition.
In addition, since Diana process oil may be added to an adhesion layer as a viscosity modifier, it is added also in the present Example, and does not make addition essential.
Apply and dry the adhesive composition on the 10 mm width of 80 mm x 25 mm 50 μm thick PET film (Toray Industries, Lumirror T60) so that the pressure-sensitive adhesive layer after drying is 18-20 μm. Thus, a test piece of an adhesive tape was obtained.

(Adhesive strength evaluation)
Then, using two test pieces, at the end of the 25 mm width where the adhesive layer is formed, the adhesive layers are pasted together so that the adhesive layers are in contact with each other, and the pasted part is rolled twice with a force of 2.0 kg / 25 mm. The pressure was applied to make it stick. Using a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph AG-I), the initial length L ₀ was set to 120 mm, the sample was pulled at a speed of 300 mm / min, and a T-shaped peel test was performed. The average load at the time of the peel test was taken at five points, and the average was taken as the adhesive strength. Further, when slip sticking or zipping occurred during the peeling test, the stress value varied, and the average value of the fourth value for the maximum value and the minimum value was taken as the adhesive strength. The results are shown in Table 3.
Moreover, the two test pieces peeled once in the above test were pasted together again, and the adhesive strength was evaluated in the same manner as described above. The results are shown in Table 4.

Example 2 (Preparation of adhesive composition and adhesive tape)
An adhesive composition and a pressure-sensitive adhesive tape test piece were obtained by the same operation as in Example 1 except that the polymer B was used instead of the polymer A in Example 1. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 3 (Production of adhesive composition and pressure-sensitive adhesive tape)
An adhesive composition and a pressure-sensitive adhesive tape test piece were obtained by the same operation as in Example 1 except that the polymer C was used instead of the polymer A in Example 1. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 4 (Preparation of adhesive composition and adhesive tape)
An adhesive composition and a pressure-sensitive adhesive tape test piece were obtained by the same operation as in Example 1 except that the polymer D was used instead of the polymer A in Example 1. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 5 (Preparation of adhesive composition and adhesive tape)
Except having used the polymer E instead of the polymer A in Example 1, it carried out similarly to Example 1 and obtained the adhesive composition and the adhesive tape test piece. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 6 (Production of adhesive composition and pressure-sensitive adhesive tape)
An adhesive composition and a pressure-sensitive adhesive tape test piece were obtained by the same operation as in Example 1 except that the polymer G was used instead of the polymer A in Example 1. The evaluation results of the test pieces are shown in Tables 3 and 4.

Comparative Example 1 (Preparation of adhesive composition and adhesive tape)
An adhesive composition and a pressure-sensitive adhesive tape test piece were obtained by the same operation as in Example 1 except that the polymer F was used instead of the polymer A in Example 1. Table 3 shows the evaluation results of the test pieces.

Example 7 (Preparation of adhesive composition and adhesive tape)
Except that a polypropylene film (thickness: 0.5 μm) was used instead of the PET film in Example 1, the same procedure as in Example 1 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 8 (Preparation of adhesive composition and pressure-sensitive adhesive tape)
Except that a polypropylene film (thickness: 0.5 μm) was used instead of the PET film in Example 2, the same procedure as in Example 2 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. Table 3 shows the evaluation results of the test pieces.

Example 9 (Production of adhesive composition and pressure-sensitive adhesive tape)
Except that a polypropylene film (thickness: 0.5 μm) was used instead of the PET film in Example 3, the same procedure as in Example 3 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 10 (Preparation of adhesive composition and adhesive tape)
Except that a polypropylene film (thickness: 0.5 μm) was used instead of the PET film in Example 4, the same procedure as in Example 4 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. Table 3 shows the evaluation results of the test pieces.

Example 11 (Preparation of adhesive composition and adhesive tape)
Except that a polypropylene film (thickness: 0.5 μm) was used instead of the PET film in Example 5, the same procedure as in Example 5 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. The evaluation results of the test pieces are shown in Tables 3 and 4.

Example 12 (Preparation of adhesive composition and adhesive tape)
Except that a polypropylene film (thickness: 0.5 μm) was used instead of the PET film in Example 6, the same procedure as in Example 6 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. The evaluation results of the test pieces are shown in Tables 3 and 4.

Comparative Example 2 (Production of adhesive composition and adhesive tape)
Except for using a polypropylene film (thickness: 0.5 μm) instead of the PET film in Comparative Example 1, the same procedure as in Comparative Example 1 was performed to obtain an adhesive composition and a pressure-sensitive adhesive tape test piece. It was. The evaluation results of the test pieces are shown in Tables 3 and 4.

Comparative Production Example 2 (Production of propylene homopolymer)
To a 1 L autoclave, heptane (400 mL) was added at 25 ° C. under a nitrogen stream, and a heptane solution of triisobutylaluminum (2 M, 0.4 mmol, 0.2 mL) was added. After stirring for 1 minute, Complex A (0.1 mL, 0.2 μmol) was added. Next, hydrogen was introduced to 0.04 MPa and propylene to a total pressure of 0.7 MPa, and at the same time, the temperature was raised to 70 ° C. over about 3 minutes while stirring. Thereafter, propylene was continuously introduced for 15 minutes so that the pressure became constant. Thereafter, the polymerization was stopped with 5 mL of ethanol, and the reaction product was dried under reduced pressure to obtain 75 g of a propylene homopolymer (polymer H). Table 5 shows the physical properties of the polymer H.

Comparative Example 3 (Preparation of adhesive composition and adhesive tape)
An adhesive composition and a pressure-sensitive adhesive tape test piece were obtained in the same manner as in Example 1 except that the polymer H was used in place of the polymer A in Example 1.
Thereafter, a thermostatic bath was installed at the test piece mounting portion of the tensile tester, and a tensile test was performed at −20 ° C. to determine the adhesive strength. The results are shown in Table 6.

Example 13 (Preparation of adhesive composition and adhesive tape)
A test piece was produced using the polymer B in the same manner as in Example 2, and a tensile test was performed at −20 ° C. to determine the adhesive strength. The results are shown in Table 6.

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

Claims (6)

1. An adhesive composition comprising a butene polymer, wherein the butene polymer satisfies the following (1) and (2) and / or the following (1 ′) and ( An adhesive composition which is a 1-butene-propylene copolymer satisfying 2).
   (1) Mesopentad fraction [mmmm] is 3 to 80 mol%.
   (1 ′) Mesodyad fraction [m] is 30 to 95 mol%.
   (2) The melting endotherm ΔHD is 40 J / g or less.
2. The adhesive composition according to claim 1, comprising 10% by mass or more of the butene polymer and 10% by mass or more of the tackifier.
3. The adhesive composition according to claim 1 or 2, wherein the 1-butene homopolymer or 1-butene-propylene copolymer satisfies the following (3) to (5).
   (3) Using a differential scanning calorimeter (DSC), hold the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raise the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the peak observed is not observed or is 0-100 ° C.
   (4) The molecular weight distribution (Mw / Mn) measured by the gel permeation chromatograph (GPC) method is 4.0 or less.
   (5) The weight average molecular weight (Mw) measured by GPC method is 5,000 to 1,000,000.
4. In the butene monomer chain portion of the butene polymer, the 1,4-bond fraction observed by ¹³ C-NMR is 0.5 mol% or less, and the 2,1-bond fraction is 0.5 The adhesive composition according to any one of claims 1 to 3, which is not more than mol%.
5. The adhesive composition according to any one of claims 1 to 4, wherein the butene polymer satisfies the following (6).
   (6) After being melted at 190 ° C. for 5 minutes, rapidly cooled and solidified with ice water, left at room temperature for 1 hour, and then analyzed by X-ray diffraction, the type II crystal fraction (CII) is 50% or less It is.
6. 6. An adhesive tape using the adhesive composition according to any one of claims 1 to 5 for an adhesive layer.