JP2016164233A - FUNCTIONALIZED α-OLEFIN POLYMER AND RESIN COMPOSITION CONTAINING THE SAME - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a functionalized α-olefin polymer having improved hardness and low temperature property of a cured article and a resin composition.SOLUTION: There are provided a functionalized α-olefin polymer satisfying following (1) to (4) and having an alkoxysilyl group and a resin composition. (1) Melting endotherm (ΔH-D) obtained from a melting endothermic curve obtained by using a differential scan type calorimeter (DSC) and increasing temperature at 10°C/min. after holding a sample at -10°C under nitrogen atmosphere for 5 minutes is 0 J/g or more and 10 J/g or less. (2) Weight average molecular weight (Mw) is 1,000 to 500,000. (3) Silyl element concentration is 0.05 mass% to 5 mass%. (4) 50 mol% or more and 100 mol% or less of an α-olefin monomer constituting a polymer is one or more kinds selected from C6 to C10 α-olefin and 0 mol% or more and 50 mol% or less of the α-olefin monomer constituting the polymer is one or more kinds selected from C3 to C5 α-olefin and C11 to C30 α-olefin.SELECTED DRAWING: None

Description

  The present invention relates to a functionalized α-olefin polymer and a resin composition containing the same.

  In recent years, global environmental issues, workers' working environments, safety and health awareness are increasing. Under such circumstances, for example, in the field of hot-melt adhesives, conventional hot-melt adhesives have a melting point of 150 ° C. or higher and need to be heated, so a substance capable of low-temperature coating is required. . If low temperature coating is possible with hot melt adhesives, 1) it can be used even on substrates that are sensitive to heat, 2) the work environment of workers will be improved, and safety and health will be maintained. 3) Adhesion It is expected that the agent is less likely to be thermally deteriorated, and 4) it can enjoy advantages such as less change in viscosity. However, in the field of hot melt adhesives, there are actually few resin compositions that can be applied at a low temperature.

  For example, in Patent Document 1, a specific catalyst is used as a polyolefin-based composition that controls the crystallinity (stereoregularity) of polyolefin, has a uniform composition, has high fluidity, and can be applied at low temperature. The modified α-olefin polymer obtained by reacting a polymer obtained in this manner with a radical initiator, a monomer having a silane group and an ethylenically unsaturated group, or a silane coupling agent is described. It is described that the modified polymer is used as a reactive hot melt adhesive.

JP 2006-348153 A

  In conventional adhesives and pressure-sensitive adhesives, even when the melting point of the base polymer is high or low, the glass transition temperature Tg is high and the low temperature characteristics are not sufficient. In addition, it is not easy to increase the amount of silane modification in order to increase the reactivity. And also about the intensity | strength and hardness after hardening, it will move large by adjustment of melting | fusing point and Tg of a base polymer. In addition, when the molecular weight is increased in order to increase the adhesive strength, there is a problem that fluidity is deteriorated and applicability is deteriorated.

  Accordingly, an object of the present invention is to provide a functionalized α-olefin polymer and a resin composition in which the hardness of the cured product and its low-temperature characteristics are improved.

The present invention relates to the following [1] to [11].
[1] A functionalized α-olefin polymer satisfying the following (1) to (4) and having an alkoxysilyl group.
(1) Using a differential scanning calorimeter (DSC), a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Amount of heat (ΔH-D) is 0 J / g or more and 10 J / g or less (2) Weight average molecular weight (Mw) is 1,000 to 500,000
(3) The silyl element concentration is 0.05 mass% to 5 mass%.
(4) 50 mol% or more and 100 mol% or less of the α-olefin monomer constituting the polymer is at least one selected from C6 to C10 α-olefin, and 0 of the α-olefin monomer constituting the polymer. Mol% or more and 50 mol% or less is at least one selected from C3-C5 α-olefins and C11-C30 α-olefins [2] The functionalized α- described in [1], which satisfies the following (5) Olefin polymer.
(5) Mesopentad fraction [mmmm] of 20 mol% to 80 mol%
[3] The functionalized α-olefin polymer according to [1] or [2], which satisfies the following (6).
(6) Using a differential scanning calorimeter (DSC), defined as the peak top of the melting endothermic curve obtained by holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The observed melting point (Tm-D) is not observed in the range of -10 ° C to 100 ° C.
[4] The functionalized α-olefin polymer according to any one of [1] to [3], which satisfies the following (7).
(7) Alkoxysilyl group concentration in terms of triethoxysilyl group is 0.01 to 30% by mass
[5] A resin composition comprising 1 to 99% by mass of the following A component and 99 to 1% by mass of the following B component with respect to the total of the following A component and the following B component.
Component A: Functionalized α-olefin polymer according to any one of [1] to [4] Component B: Olefin polymer satisfying the following (a) to (c) (a) Differential scanning calorimeter (DSC) was used, and the sample was held at −10 ° C. for 5 minutes under a nitrogen atmosphere and then heated at 10 ° C./min. No defined melting point (Tm-D) is observed or 0-100 ° C
(B) The weight average molecular weight (Mw) is 1,000 to 500,000.
(C) Semi-crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or a crystallization peak measured with a differential scanning calorimeter (DSC) is not observed. [6] The olefin weight The resin composition according to [5], wherein the coalescence satisfies the following (e).
(D) The silyl element concentration is 0.05 mass% to 5 mass%.
[7] The resin composition according to [5] or [6], wherein the olefin polymer satisfies the following (e).
(E) Mesopentad fraction [mmmm] of 20 mol% to 80 mol%
[8] The functionalized α-olefin polymer according to any one of [1] to [4] or the resin composition according to any one of [5] to [7] and a curing accelerator catalyst. Resin composition.
[9] The resin composition according to [8], wherein the composition contains at least one of a tackifier and a diluent.
[10] A cured product obtained by curing the resin composition according to [8] or [9].
[11] The resin composition as described in [8] or [9], which is used for an adhesive, a sealing agent, a pressure-sensitive adhesive, or a modifier.

  According to the present invention, it is possible to provide a functionalized α-olefin polymer and a resin composition having improved cured product hardness and low-temperature characteristics.

  The present invention is described below. In addition, in this specification, the term "-" regarding description of a numerical value is a term which shows more than the lower limit and below an upper limit.

The functionalized α-olefin polymer of the present invention satisfies the following (1) to (4) and has an alkoxysilyl group. The functionalized α-olefin polymer preferably further satisfies the following (5), more preferably further satisfies the following (6), and further preferably satisfies the following (7).
(1) Using a differential scanning calorimeter (DSC), a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Amount of heat (ΔH-D) is 0 J / g or more and 10 J / g or less (2) Weight average molecular weight (Mw) is 1,000 to 500,000
(3) The silyl element concentration is 0.05 mass% to 5 mass%.
(4) 50 mol% or more and 100 mol% or less of the α-olefin monomer constituting the polymer is at least one selected from C6 to C10 α-olefin, and 0 of the α-olefin monomer constituting the polymer. The mol% or more and 50 mol% or less is at least one selected from C3-C5 α-olefins and C11-C30 α-olefins. (5) Mesopentad fraction [mmmm] is 20 mol% -80 mol%
(6) Using a differential scanning calorimeter (DSC), defined as the peak top of the melting endothermic curve obtained by holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. Melting point (Tm-D) is not observed in the range of −10 ° C. to 100 ° C. (7) Alkoxysilyl group concentration in terms of triethoxysilyl group is 0.01 to 30% by mass
According to the functionalized α-olefin polymer, the hardness of the cured product and its low temperature characteristics are improved.
The “functionalized α-olefin polymer” in the present specification means a product in which an alkoxysilyl group is introduced into the α-olefin polymer.

[Melting endotherm (ΔH−D)]
The functionalized α-olefin polymer of the present invention is obtained by using a differential scanning calorimeter (DSC) and holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The melting endotherm (ΔH−D) obtained from the melting endotherm curve is 0 J / g or more and 10 J / g or less. By having the melting endotherm (ΔH−D) in this range, the fluidity at room temperature can be maintained, and the flexibility at room temperature can be maintained even after curing.
The melting endotherm (ΔH−D) is preferably 8 J / g or less, more preferably 5 J / g or less, and still more preferably 1 J / g or less.
Melting point defined as the peak top of a melting endotherm curve obtained by using a differential scanning calorimeter (DSC) and holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. It is preferable that (Tm-D) is not observed in the range of −10 ° C. to 100 ° C.
The glass transition point (Tg) is obtained by holding the sample at −80 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The glass transition point (Tg) is preferably −70 to 0 ° C., more preferably −70 to −10 ° C., still more preferably −70 to −20 ° C., and still more preferably −70 from the viewpoint of adhesive strength at low temperatures. ~ -35 ° C.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) is from 1,000 to 500,000, more preferably from 2,000 to 400,000, and still more preferably from 3,000 to 500,000, from the viewpoint of the balance between the low temperature characteristics and the hardness of the cured product. It is 300,000, More preferably, it is 5,000-200,000, More preferably, it is 10,000-200,000.

[Molecular weight distribution (Mw / Mn)]
The functionalized α-olefin polymer of the present invention has a molecular weight distribution (Mw / Mn) of preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3. from the viewpoint of curing speed and fluidity. 2 or less, more preferably 3.0 or less. The molecular weight distribution is preferably 1.0 or more, more preferably 1.2 or more.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined by the Universal Calibration method using the constants K and a of the Mark-Houwink-Sakurada formula in order to convert the polypropylene-converted molecular weight into the molecular weight of the corresponding polymer. it can.
Specifically, it can be determined by the method described in “Size Exclusion Chromatography” by Sadao Mori, P67-69, 1992, Kyoritsu Shuppan. K and α are ““ Polymer Handbook ”John Wiley & Sons, Inc. "It is described in. Moreover, it can also determine by a conventional method from the relationship of the intrinsic viscosity with respect to the newly calculated absolute molecular weight.

The measuring apparatus and measurement conditions of GPC are as follows, for example.
Detector: RI detector for liquid chromatography Waters 150C
Column: TOSO GMHHR-H (S) HT
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 0.3% by mass

[Concentration of silyl element]
The functionalized α-olefin polymer of the present invention has a silyl element concentration of 0.05% by mass to 5% by mass from the viewpoints of reactivity and reaction curability.
The silyl element concentration is preferably 0.10% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more. The silyl element concentration is preferably 5% by mass or less, more preferably 4% by mass or less, and still more preferably 2% by mass or less.
Concentration of silyl element is as follows: 0.1 g of sample is heated overnight in an electric furnace (550 ° C.), then a sample solution is prepared by alkali melting of ash, and ICP emission spectroscopic analysis (Agilent Technology, 720-ES) Then, the concentration of Si element is measured.

The functionalized α-olefin polymer of the present invention has an alkoxysilyl group.
The alkoxysilyl group is not particularly limited, but is preferably a trialkoxysilyl group having an alkoxy group having 1 to 20 carbon atoms, more preferably a trialkoxysilyl group having an alkoxy group having 1 to 10 carbon atoms. The alkoxy group may be linear or branched.
Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, and a tripropyloxysilyl group, and a trimethoxysilyl group or a triethoxysilyl group is preferable.

In the functionalized α-olefin polymer of the present invention, the alkoxysilyl group concentration in terms of triethoxysilyl group is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably. It is 0.5-10 mass%, More preferably, it is 1.0-8 mass%, More preferably, it is 3.0-8 mass%.
In the functionalized α-olefin polymer of the present invention, when the alkoxysilyl group concentration in terms of triethoxysilyl group is 0.01% by mass or more, the crosslinking performance can be improved, and a cured product can be easily obtained. On the other hand, when it is 30% by mass or less, a cured product having an appropriate hardness can be obtained, and the intended adhesion and pressure-sensitive adhesive performance can be easily expressed. That is, when the functionalized α-olefin polymer having an alkoxysilyl group concentration within the above range is used to obtain a curable composition, the concentration of the alkoxysilyl group is high, so that the crosslinking rate is moderate. The strength of the cured product after curing is high, and the adhesion to glass is improved.
The above-mentioned alkoxysilyl group concentration in terms of triethoxysilyl group can be determined by the measurement method shown below.
The silyl element concentration is measured by the above method, and the value is defined as a mass%. Use the numerical value to convert according to the following formula.
Triethoxysilyl group equivalent alkoxysilyl group concentration = a × 163.3 / 28.1 (mass%)
It should be noted that the presence of an alkoxysilyl group in the functionalized α-olefin is based on the carbon atom next to the oxygen atom of the alkoxysilyl group appearing in the vicinity of 3.7 to 4.1 ppm using ¹ H-NMR. This can be confirmed by the presence or absence of a peak derived from a hydrogen atom (a silyl group having an alkoxy group of C2 or more) or a singlet peak (in the case of a trimethoxysilyl group) appearing near 3.6 ppm.

[Α-olefin monomer]
The functionalized α-olefin polymer of the present invention is one or more types in which 50 mol% to 100 mol% of the α-olefin monomer constituting the polymer is selected from C6 to C10 α-olefin, and 0 mol. % To 50 mol% is at least one selected from C3-C5 α-olefins and C11-C30 α-olefins. By selecting the α-olefin monomer, it is possible to obtain a functionalized α-olefin polymer having both the hardness and low temperature characteristics of the cured product. The functionalized α-olefin polymer of the present invention has a high molecular weight because 50% by mole or more and 100% by mole or less of the α-olefin monomer constituting the polymer is one or more selected from C6-C10 α-olefins. Even if it makes it, compared with a linear polymer, since a principal chain becomes short and a viscosity falls, fluidity | liquidity will not be impaired. When the linear polymer having the same molecular weight is compared with the functionalized α-olefin polymer (side chain polymer) of the present invention, the side chain polymer can increase the number of silane reaction points. The functionalized α-olefin polymer of the present invention is excellent in coatability and adhesiveness.

Examples of the C6-C10 α-olefin include octene-1, hexene-1, heptene-1, decene-1, 4-methylpentene-1.
Examples of the C3-C5 α-olefin include propylene, butene-1, and pentene-1.
Examples of the C11 to C30 α-olefin include undecene-1, dodecene-1, pentadecene-1, eicosene-1, and triacontene-1.

The amount of the C6-C10 α-olefin is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, more preferably 100 mol in the α-olefin monomer constituting the polymer. %. And the said quantity is 100 mol% or less in the alpha olefin monomer which comprises a polymer, Preferably it is 99 mol% or less, More preferably, it is 95 mol% or less, More preferably, it is 90 mol% or less.
The amount of the C3-C5 α-olefin and the C11-C30 α-olefin is preferably 0 mol% or more, more preferably 1 mol% or more, still more preferably 5 mol in the α-olefin monomer constituting the polymer. % Or more, more preferably 10 mol% or more. The amount is preferably 40 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, still more preferably 0 mol% in the α-olefin monomer constituting the polymer.

[Stereoregularity]
The functionalized α-olefin polymer preferably has a mesopentad fraction [mmmm] of 20 mol% to 80 mol%.
The functionalized α-olefin polymer of the present invention has a mesopentad fraction [mmmm] of 20 mol% to 80 mol%, preferably 30 mol% to 70 mol%, more preferably 40 mol% to 60 mol%. It is.
The mesopentad fraction [mmmm] is controlled by the structure of the main catalyst and the polymerization conditions.

Mesopentad fraction [mmmm], racemic pentad fraction [rrrr], and racemic meso racemic meso fraction [rmrm], meso meso racemic fraction [mmrr] and racemic meso meso racemic fraction [ rmmr] is a meso fraction of pentad units in a polyolefin molecule measured by a methyl group signal of ¹³ C-NMR spectrum based on the method proposed by Asakura et al. in “Macromolecules, 24, 2334 (1991)”. , Racemic fraction and racemic meso racemic meso fraction. As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The measurement of the ¹³ C-NMR spectrum can be carried out with the following apparatus and conditions in accordance with the attribution of the peak proposed by A. Zambelli et al. In “Macromolecules, 8, 687 (1975)”. it can.

Apparatus: JNM-EX400 type ¹³ C-NMR apparatus manufactured by JEOL Ltd. Method: Proton complete decoupling method Concentration: 220 mg / ml
Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds Integration: 10,000 times

The stereoregularity index {(mmmm) / (mmrr + rmmr)} of the functionalized α-olefin polymer can be calculated from the values obtained by measuring (mmmm), (mmrr) and (rmmr) by the above method. The racemic triad fraction (rr) can also be calculated by the above method.
The functionalized α-olefin polymer has a stereoregularity index {(mmmm) / (mmrr + rmmr)} of, for example, 20 or less, preferably 18 or less, and more preferably 15 or less.
When the stereoregularity index exceeds 20, there is a possibility that the flexibility is lowered.

[Intrinsic viscosity [η]]
The functionalized α-olefin polymer of the present invention has an intrinsic viscosity [η] measured at 135 ° C. in tetralin of 0.01 to 2.5 dl / g, preferably 0.1 to 2.0 dl / g. More preferably, it is 0.1-1.5 dl / g, More preferably, it is 0.15-1.8 dl / g, More preferably, it is 0.50-1.8 dl / g.

The intrinsic viscosity [η] is calculated by measuring the reduced viscosity (ηSP / c) in tetralin at 135 ° C. with an Ubbelohde viscometer, and using the following equation (Haggins equation).
ηSP / c = [η] + K [η] ² c
ηSP / c (dl / g): Reduced viscosity [η] (dl / g): Intrinsic viscosity c (g / dl): Polymer viscosity K = 0.35 (Haggins constant)

〔Production method〕
The functionalized α-olefin polymer of the present invention may be abbreviated as, for example, an α-olefin polymer, a radical initiator, a monomer having an alkoxysilyl group and an ethylenically unsaturated group (hereinafter, a silane-modified monomer). .) Can be made to react.

The α-olefin polymer can be produced, for example, by using a metallocene catalyst comprising a combination of the following components (A), (B) and (C) and using hydrogen as a molecular weight regulator.
(A) Transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group. (B) Reacts with a transition metal compound. Compound capable of forming an ionic complex (C) Organoaluminum compound Specifically, it can be produced by the method disclosed in WO2008 / 047860.

The transition metal compound containing a metal element belonging to Groups 3 to 10 of the periodic table having a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group as the component (A) is represented by the following general formula (I ) Is represented.

In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table. Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. Metal etc. are mentioned. Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of yield of the α-olefin polymer and catalytic 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 from each other. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E ¹ and E ² is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
The substituent of the substituted cyclopentadienyl group, substituted indenyl group, or substituted heterocyclopentadienyl group has 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms). A substituent such as a hydrocarbon group, a silicon-containing group or a heteroatom-containing group is shown.
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. 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, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 40 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 phenanthryl 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 40 carbon atoms include dialkyl phosphide groups, diethyl phosphide groups, dipropyl phosphide groups, dibutyl phosphide groups, dihexyl phosphide groups, dicyclohexyl phosphide groups, and dioctyl phosphide groups. Fido group; dialkenyl phosphide group such as divinyl phosphide group, dipropenyl phosphide group, dicyclohexenyl phosphide group; bis such as dibenzyl phosphide group, bisphenylethyl phosphide group, bisphenylpropyl phosphide group Arylalkyl phosphide group; diphenyl phosphide group, ditolyl phosphide group, bisdimethylphenyl phosphide group, bistrimethylphenyl phosphide group, bisethylphenyl phosphide group, bispropylphenyl phosphide group, bisbiphenyl phosphide group I de group, bisnaphthyl phosphide group, bis methyl naphthyl phosphide group, bis anthracenyl phosphide group, and a diarylamino phosphide group such as bis phenanthryl phosphide 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 phenanthryl 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, stearoyl 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 vinylamine, propenylamine, cyclohexenylamine, divinylamine, dipropenylamine, dicyclohexenylamine, etc .; arylalkylamines such as phenylethylamine, phenylpropylamine; phenylamine, diphenylamine, dinaphthylamine, etc. Arylamine is 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, anthracenylphosphine, phenanthrylphosphine; 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, May be different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms or a silicon-containing group. Examples of such a bridging group include those represented by the following general formula (a), and specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, and a cyclohexylidene group. , 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisilylene group, diphenyldi A silylene group etc. can be mentioned. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

（Ｄは周期律表第１４族元素であり、例えば炭素，ケイ素，ゲルマニウム及びスズが挙げられる。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、それらは互いに同一でも異なっていてもよく、また互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 a group 14 element of the periodic table, and examples thereof include carbon, silicon, germanium and tin. R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other, and may be bonded to each other to form a ring structure.

  Specific examples of the transition metal compound represented by the general formula (I) include specific examples described in WO2008 / 066168. Moreover, the analogous compound of the metal element of another group may be sufficient. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

Among the transition metal compounds represented by the general formula (I), compounds represented by the following general formula (II) are preferable.

In the above general formula (II), M represents a metal element belonging to Groups 3 to 10 of the periodic table, and A ^1a and A ^2a each represent a bridging group represented by the general formula (a) in the above general formula (I). CH ₂ , CH ₂ CH ₂ , (CH ₃ ) ₂ C, (CH ₃ ) ₂ C (CH ₃ ) ₂ C, (CH ₃ ) ₂ Si and (C ₆ H _{5) 2} Si are preferred. A ^1a and A ^2a may be the same as or different from each other. R ^{4 to} R ¹³ 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. Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the silicon-containing group are the same as those described in the general formula (I). Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include p-fluorophenyl group, 3,5-difluorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis ( (Trifluoro) phenyl group, fluorobutyl group and the like. Examples of the heteroatom-containing group include C1-C20 heteroatom-containing groups. Specifically, nitrogen-containing groups such as a dimethylamino group, a diethylamino group, and a diphenylamino group; a phenylsulfide group, a methylsulfide group, and the like Sulfur-containing groups of: phosphorus-containing groups such as dimethylphosphino groups and diphenylphosphino groups; oxygen-containing groups such as methoxy groups, ethoxy groups, and phenoxy groups. Among these, as R ⁴ and R ⁵ , a group containing a hetero atom such as a halogen atom, oxygen, or silicon, or a hydrocarbon group having 1 to 20 carbon atoms is preferable because of high polymerization activity. R ^{6 to} R ¹³ are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. X and Y are the same as in general formula (I). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

  Of the transition metal compounds represented by the above general formula (II), when both indenyl groups are the same, examples of the transition metal compounds belonging to Group 4 of the periodic table include specific examples described in WO2008 / 066168. . Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

On the other hand, among the transition metal compounds represented by the above general formula (II), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, the transition metal compound of Group 4 of the periodic table is disclosed in WO2008 / 066168. Specific examples of the description are given. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.

  As a compound capable of reacting with the transition metal compound (B) constituting the catalyst used in the present invention to form an ionic complex, a high purity terminal unsaturated olefin polymer having a relatively low molecular weight can be obtained, and A borate compound is preferable in terms of high catalyst activity. Specific examples of the borate compound include those described in WO2008 / 066168. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen and transition metal compound (hydrogen / transition metal compound) described later is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, and tetrakis (Perfluorophenyl) methylanilinium borate and the like are preferable.

The catalyst used in the method for producing an α-olefin polymer may be a combination of the component (A) and the component (B), and an organoaluminum compound as the component (C) in addition to the component (A) and the component (B). May be used.
As the organoaluminum compound (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride. Dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.
Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum is preferable, and triisobutylaluminum, trinormalhexylaluminum, and trinormaloctylaluminum are more preferable. preferable.

The amount of component (A) used is usually 0.1 × 10 ^{−6 to} 1.5 × 10 ⁻⁵ mol / L, preferably 0.15 × 10 ^{−6 to} 1.3 × 10 ⁻⁵ mol / L, more preferably ^{0.2 × 10 -6 ~1.2 × 10 -5} mol / L, particularly preferably ^{0.3 × 10 -6 ~1.0 × 10 -5} mol / L. When the amount of component (A) used is 0.1 × 10 ⁻⁶ mol / L or more, the catalytic activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the heat of polymerization is easy. Can be removed.
The use ratio (A) / (B) of the component (A) and the component (B) is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio. When (A) / (B) is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Further, there is no fear that a large amount of boron is present in the target α-olefin polymer.
The use ratio (A) / (C) of the component (A) and the component (C) is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, still more preferably 1 in terms of molar ratio. / 10 to 1/1000. By using the component (C), the polymerization activity per transition metal can be improved. When (A) / (C) is in the range of 1/1 to 1/10000, the balance between the effect of addition of component (C) and economy is good, and the desired α-olefin polymer There is no fear of a large amount of aluminum.
In the method for producing an α-olefin polymer, preliminary contact may be performed using the above-described component (A) and component (B), or component (A), component (B) and component (C). The preliminary contact can be performed by bringing the component (A) into contact with, for example, the component (B). However, the method is not particularly limited, and a known method can be used. Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component used as the promoter.

(Radical initiator)
The radical initiator used in the reaction between the α-olefin polymer and the silane-modified monomer is not particularly limited, and conventionally known radical initiators such as various organic peroxides, azobisisobutyronitrile, azobisiso Of these, azo compounds such as valeronitrile can be appropriately selected and used, and among these, organic peroxides are preferred.
Examples of the organic peroxide used as the radical initiator include dibenzoyl peroxide, di-3,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, di (2,4- Diacyl peroxides such as dichlorobenzoyl) peroxide, 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) ) Hexin-3, α, α 'bis (t-butylperoxy) diisopro Dialkyl peroxides such as rubenzene, peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t Alkyl peresters such as butyl peroxy octoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxy Examples thereof include peroxycarbonates such as oxydicarbonate, di-sec-butyl peroxydicarbonate, and t-butyl peroxyisopropyl 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.
Although there is no restriction | limiting in particular as the usage-amount of a radical initiator, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of alpha-olefin polymers to be used, More preferably, in the range of 0.01-5 mass parts. Used.

(Silane modified monomer)
Specific examples of the silane-modified monomer to be reacted with the α-olefin polymer include those represented by the following general formula (i).
(RO) ₃ -Si-Y (i)
(In the formula, Y is an ethylenically unsaturated group, R is an alkyl group, and three Rs may be the same or different from each other.)
The ethylenically unsaturated group has reactivity with free radical sites generated in the α-olefin polymer. Examples of the ethylenically unsaturated group include vinyl group, allyl group, butenyl group, cyclohexenyl group, cyclopentadienyl group, (meth) acryloxyalkyl group, etc., preferably vinyl group, methacryloxyalkyl group. And at least one selected from a group and an acryloxyalkyl group.
The alkyl group may be linear or branched, preferably has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, various decanyl groups, etc. Among these, at least one selected from a methyl group and an ethyl group is preferable.
Specific examples of the silane-modified monomer include vinyltriethoxysilane, vinyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, and the like.

  The usage-amount of a silane modification monomer becomes like this. Preferably it is 0.1-50 mass parts with respect to 100 mass parts of alpha olefin polymers, More preferably, it is 0.5-10 mass parts.

As a method of reacting the above-mentioned α-olefin polymer with a radical initiator and a silane-modified monomer, a method of reacting by melting and kneading at a temperature of about 100 to 300 ° C. using a roll mill, a Banbury mixer, an extruder, or the like. Or hydrocarbon solvents such as butane, pentane, hexane, heptane, cyclohexane, toluene, xylene, decahydronaphthalene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, and liquefied α-olefins In an organic solvent, a method of reacting by solution modification at a temperature of about −50 to 300 ° C. can be used.
In order to keep the silyl element concentration within a predetermined range, it is preferable to carry out the reaction at a high temperature of about 120 to 200 ° C. under solvent-free conditions from the viewpoint of increasing the concentration of radicals and silane-modified monomers. On the other hand, in order to set the silyl element concentration to 5% by mass or less, the α-olefin polymer is diluted in the above-mentioned organic solvent until the concentration becomes about 10 to 50% by mass, and the low temperature of about 80 to 120 ° C. It is preferable to make it react under.

As described above, the functionalized α-olefin polymer of the present invention obtained by reacting an α-olefin polymer with a radical initiator and a silane-modified monomer is a double bond remaining at the end of the main chain of the raw material α-olefin. In addition, a group derived from a silane-modified monomer (for example, alkoxysilylethyl group) is bonded to the other main chain. In this case, in ¹³ C-NMR measurement, a peak derived from a quaternary carbon atom in the polymer chain to which the alkoxysilylethyl group is bonded is observed at 36 to 40 ppm.
Adjusting (accelerating) the curing rate by mixing the functionalized α-olefin polymer of the present invention with silicone-based materials such as silicone-based adhesives, silicone-based sealants, modified silicone-based adhesives, and modified silicone-based sealants. Can do.
In addition, the silicone-based materials listed above include low molecular weight silicone-based materials in the manufacturing process and cause stickiness of the cured product and surface contamination. Since the low molecular weight silicone material can be captured (curing reaction) and cured by mixing the coalescence, it is possible to reduce the inclusion of the low molecular weight silicone material in the cured product, and the resulting cured product Stickiness and surface contamination can be suppressed.

[Resin composition]
The resin composition of this invention contains 1-99 mass% of following A component and 99-1 mass% of following B component with respect to the sum total of the following A component and the following B component.
Component A: Functionalized α-olefin polymer Component B: Olefin polymer satisfying the following (a) to (c) The resin composition preferably further contains a curing accelerating catalyst, and more preferably imparts tackiness. It may contain at least one selected from an agent and a diluent.

(Component A)
The content of the A component is preferably 10 to 95% by mass, more preferably 20 to 95% by mass, still more preferably 30 to 90% by mass, and still more preferably 40 to 80% with respect to the total of the A component and the B component. % By mass.

(B component)
The component B satisfies the following (a) to (c), preferably further satisfies the following (d), more preferably further satisfies the following (e), and more preferably further satisfies the following (f). It is.
(A) 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 observed peak is not observed or 0-100 ° C
(B) The weight average molecular weight (Mw) is 1,000 to 500,000.
(C) Semi-crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or no crystallization peak measured with a differential scanning calorimeter (DSC) is observed. 0.05% to 5% by mass
(E) Mesopentad fraction [mmmm] of 20 mol% to 80 mol%
(F) Alkoxysilyl group concentration in terms of triethoxysilyl group is 0.01 to 30% by mass

[Melting point (Tm-D)]
The olefin polymer is the most of the melting endotherm curve obtained by using a differential scanning calorimeter (DSC) and holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The melting point (Tm-D) defined as the peak top of the peak observed on the high temperature side is not observed or is 0 to 100 ° C.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) of the olefin polymer is preferably 1,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000.

[Semi-crystallization time]
It is preferable that the half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed.
The differential scanning calorimeter (DSC) is measured by the following method using a differential scanning calorimeter (DSC) (manufactured by Perkin Elmer, trade name: “DSC-7”).
(1) 10 mg of a sample is held at 25 ° C. for 5 minutes, heated to 220 ° C. at 320 ° C./second and held for 5 minutes. By cooling to 25 ° C. at 320 ° C./second and holding for 60 minutes, the time change of the calorific value in the isothermal crystallization process is measured.
(2) When the integrated value of the calorific value from the start of isothermal crystallization to the completion of crystallization is 100%, the time from the start of isothermal crystallization until the integrated value of the calorific value becomes 50% is semi-crystallized. Define as time.

[Concentration of silyl element]
The silyl element concentration of the olefin polymer is preferably 0.05% by mass to 5% by mass, more preferably 0.10% by mass to 3% by mass, and still more preferably 0.30% by mass to 1.0% by mass. is there.
The alkoxysilyl group is preferably a trialkoxysilyl group having an alkoxy group having 1 to 20 carbon atoms, more preferably a trialkoxysilyl group having an alkoxy group having 1 to 10 carbon atoms.
Examples of the alkoxysilyl group include a trimethoxysilyl group, a triethoxysilyl group, and a tripropyloxysilyl group, and a trimethoxysilyl group or a triethoxysilyl group is preferable.
The alkoxysilyl group concentration in terms of triethoxysilyl group is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 10% by mass, and still more preferably 1 It is 0-5 mass%, More preferably, it is 1.5-5 mass%.
The conversion method of the alkoxysilyl group concentration from the silyl element concentration and the confirmation method of the alkoxysilyl group are as described above.

[Α-olefin monomer]
The olefin polymer is a polymer containing 50 mol% or more of a C3 to C30 α-olefin structural unit with respect to the α-olefin monomer constituting the polymer.
The α-olefin is preferably C3 to C10, more preferably C3 to C8, and still more preferably C3 to C5.
The amount of the C3-C30 α-olefin structural unit is preferably at least 70 mol%, more preferably at least 80 mol%, based on the α-olefin monomer constituting the polymer.
C3-C30 α-olefins include propylene, butene-1, isobutene, pentene-1, octene-1, hexene-1, heptene-1, decene-1, 4-methylpentene-1, 3-methylbutene-1 , Undecene-1, dodecene-1, pentadecene-1, eicosene-1, triacontene-1, and the like.

[Mesopentad fraction [mmmm]]
The mesopentad fraction [mmmm] of the olefin polymer is preferably 20 to 80 mol%, more preferably 30 to 80 mol%, still more preferably 40 to 80 mol%, still more preferably 50 to 80 mol%, still more preferably. Is 60 to 80 mol%.

  The B component olefin polymer can be produced by the method disclosed in WO2008 / 047860, WO2008 / 066168, and WO2013 / 118841.

The content of component B is preferably 90 to 10% by mass, more preferably 80 to 20% by mass, still more preferably 70 to 30% by mass, and still more preferably 60 to 40%, based on the total of component A and component B. % By mass.
In addition, the total content of the component A and the component B is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 60% by mass or more with respect to the entire resin composition. The total content of the A component and the B component is 100% by mass or less, preferably 98% by mass or less, more preferably 90% by mass or less.

(Curing acceleration catalyst)
Examples of the curing accelerating catalyst include organometallic catalysts and tertiary amines.
Examples of the organic metals include organic tin metal compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate and tin octenoate, lead octenoate and lead naphthenate.
Tertiary amines include N-triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethyl Examples include aminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl-N′-dimethylaminoethylpiperazine, and imidazole compounds in which the secondary amine functional group of the imidazole ring is substituted with a cyanoethyl group. it can.
These may be used alone or in combination of two or more. Of the above catalysts, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin dioctate are particularly preferable.
The content of the curing accelerating catalyst in the resin composition of the present invention is preferably 0.005 to 2.0% by mass, more preferably 0.01 to 0.5% by mass in the resin composition of the present invention. is there.

(Tackifier)
Examples of tackifiers (tackifier resins) include rosin and derivatives thereof, terpene resins and hydrogenated resins thereof, styrene resins, coumarone-indene resins, dicyclopentadiene (DCPD) resins and hydrogenated resins thereof. Resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and C5-C9 copolymerized petroleum resin and its hydrogenated type Among many commonly used tackifiers such as resins, those having good compatibility with the functionalized α-olefin polymer are selected. One of these tackifiers may be used alone, or two or more thereof may be used as a mixture.
Preferred tackifiers include terpene resins and their hydrogenated resins, styrene resins, and dicyclopentadiene (DCPD) resins from the viewpoint of the balance between removability and adhesion to curved and uneven surfaces. And its hydrogenated resin, aliphatic (C5) petroleum resin and its hydrogenated resin, aromatic (C9) petroleum resin and its hydrogenated resin, and C5 -C9 copolymer petroleum resin It is preferable to use one kind of resin or a mixture of two or more kinds selected from the group of hydrogenated resins.
The content of the tackifier in the resin composition of the present invention is preferably 1 to 50% by mass, more preferably 2 to 45% by mass in the resin composition of the present invention.

(Diluent)
Examples of the diluent include oils such as naphthenic oils, paraffinic oils and aroma oils, oils obtained by mixing these oils, and liquid rubbers such as liquid polybutene and liquid isopolybutylene. You may use these individually by 1 type or in mixture of 2 or more types.
The content of the diluent in the resin composition of the present invention is preferably 1 to 50% by mass, more preferably 2 to 40% by mass in the resin composition of the present invention.

(Other ingredients)
The resin composition of the present invention may contain additives such as fillers, pigments or antioxidants as long as the effects of the present invention are not impaired.

The filler includes an inorganic filler and an organic filler.
Inorganic fillers include silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, Calcium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, sericite, glass fiber, glass beads, silica series Examples include balun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fiber, carbon balun, zinc borate, and various magnetic powders.
As an inorganic filler, you may surface-treat with various coupling agents, such as a silane type and a titanate type. As this treatment method, a method of directly treating an inorganic filler with various coupling agents such as a dry method, a slurry method or a spray method, an integral blend method such as a direct method or a masterbatch method, or a dry concentrate method, etc. The method is mentioned.
Organic fillers include starch (for example, powdered starch), fibrous leather, natural organic fibers (for example, those made of cellulose such as cotton and hemp), and synthetic fibers made of synthetic polymers such as nylon, polyester, and polyolefin. Can be mentioned.

Examples of the pigment include inorganic pigments and organic pigments (for example, azo pigments and polycyclic pigments).
Inorganic pigments include oxides (titanium dioxide, zinc white (zinc oxide), iron oxide, chromium oxide, iron black, cobalt blue, etc., hydroxides: alumina white, iron oxide yellow, viridian, etc.), sulfides ( Zinc sulfide, lithopone, cadmium yellow, vermilion, cadmium red, etc.), chromate (yellow lead, molybdate orange, zinc chromate, strontium chromate, etc.), silicate (white carbon, clay, talc, ultramarine blue, etc.), sulfate (Precipitated barium sulfate, barite powder, etc., as carbonates: calcium carbonate, lead white, etc.), ferrocyanide (bitumen), phosphate (manganese violet), carbon (carbon black), etc. are also used be able to.
Examples of azo pigments that are organic pigments include soluble azo (carmine 6B, lake red C, etc.), insoluble azo (disazo yellow, lake red 4R, etc.), condensed azo (chromophthal yellow 3G, chromophthalscarlet RN, etc.), azo Examples thereof include complex salts (such as nickel azo yellow) and benzimidazolone azo (such as permanent orange HL). Examples of polycyclic pigments that are organic pigments include isoindolinone, isoindoline, quinophthalone, pyrazolone, flavantron, anthraquinone, diketo-pyrrolo-pyrrole, pyrrole, pyranthrone, perinone, perylene, quinacridone, indigoid, oxazine, imidazolone, Xanthene, carbonium, violanthrone, phthalocyanine, nitroso and the like can be mentioned.

The resin composition of this invention can be manufactured by mixing the said component by arbitrary methods.
The curing accelerating catalyst is preferably mixed and used. As a method for adding the curing accelerating catalyst, it is preferable to prepare a catalyst master batch in which the curing accelerating catalyst is in a high concentration in advance, blend the catalyst master batch and other components, and knead or melt.
Moreover, the resin composition of this invention can also be manufactured using a solvent.

The resin composition of the present invention can be dissolved in a solvent and used as a solvent-type adhesive, and can be applied and sprayed to form a film on the surface of an adhesive substrate and adhere to an adherend.
Furthermore, the polymerizable composition of the present invention can also be used as an adhesive by dispersing it in a polar solvent such as water or forming an emulsion. In addition, the resin composition of the present invention can be formed into a sheet shape or a film shape, sandwiched between adhesive substrates, heated and bonded to a temperature higher than the temperature at which the resin composition flows, and bonded by cooling and solidification.

The present invention also provides a cured product obtained by curing the resin composition.
The resin composition of this invention can implement hardening reaction at low temperature. Specifically, a cured product can be obtained by curing reaction of the resin composition of the present invention at 100 ° C. or lower. In the curing reaction, curing can be carried out by bringing it into contact with moisture or moisture and curing it under heat treatment or at room temperature. In order to bring moisture or moisture into contact, for example, the curable adhesive composition of the present invention may be left in the air, or may be immersed in a water tank or steam. Moreover, although room temperature (25 degreeC) may be sufficient as temperature, it can bridge | crosslink in a short time if it makes high temperature.

The resin composition of the present invention comprises a resin compatibilizer, a polyolefin emulsion, a reactive adhesive, a reactive hot melt adhesive, other adhesives, an adhesive, a sealing material, a sealing material, a potting material, and a reactive plastic. It can be used for applications such as agents and modifiers.
The cured product of the present invention is used for reactive adhesives, reactive hot melt adhesives, other adhesives, adhesives, adhesive tapes, sealing materials, sealing materials, potting materials, reactive plasticizers, modifiers, etc. Can be used. Moreover, since the hardened | cured material obtained by the said hardening method has heat resistance, it can be used also in the environment of high temperature.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these. Various physical properties were measured as described above and as follows.

[Measurement of solid viscoelasticity]
Using a viscoelasticity measuring device (trade name: DMS 6100 (EXSTAR6000) manufactured by SII Nano Technology Co., Ltd.), measurement was performed under the following conditions under a nitrogen atmosphere.
<Measurement conditions>
Measurement mode: Tensile mode Measurement temperature: Among −150 ° C. to 230 ° C., three points of −50 ° C., 25 ° C. and 150 ° C. were observed.
Temperature increase rate: 5 ° C / min
Measurement frequency: 1Hz
Sample size: length 10mm, width 4mm, thickness 1mm (press molded product)

Synthesis Example 1 [Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride (complex A)]
Under a nitrogen stream, 2.5 g (7.2 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) and 100 ml of ether were added to a 200 ml Schlenk bottle.
After cooling to −78 ° C. and adding 9.0 ml (14.8 mmol) of a hexane solution (1.6 mol / liter) of n-butyllithium (n-BuLi), the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 20 ml of hexane and dried under reduced pressure to quantitatively obtain a lithium salt as a white solid.
In a Schlenk bottle, lithium salt (6.97 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) was dissolved in 50 ml of THF (tetrahydrofuran), and iodomethyl at room temperature. Trimethylsilane 2.1 ml (14.2 mmol) was slowly added dropwise and stirred for 12 hours.
The solvent was distilled off, and 50 ml of ether was added, followed by washing with a saturated ammonium chloride solution.
After liquid separation, the organic phase is dried, and the solvent is removed to remove 3.04 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) (complex A) ( 5.9 mmol). (Yield 84%)

Next, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. ) And 50 ml of ether. After cooling to −78 ° C., 7.4 ml (11.8 mmol) of a hexane solution (1.6 mol / liter) of n-butyllithium (n-BuLi) was added, and the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the resulting solid was washed with 40 ml of hexane to obtain 3.06 g of a lithium salt as an ether adduct.
Under a nitrogen stream, 3.06 g of the lithium salt obtained above was suspended in 50 ml of toluene. This was cooled to −78 ° C., and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to −78 ° C. in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. After the solvent of the reaction solution was distilled off, the resulting residue was recrystallized from dichloromethane to obtain (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl). 0.9 g (1.33 mmol) of yellow fine crystals of zirconium dichloride (complex A) was obtained. (Yield 26%)
When ¹ H-NMR of this product was determined, the following results were obtained.
¹ H-NMR (90 MHz, CDCl ₃ ): δ0.0 (s, -SiMe _3- , 18H), 1.02, 1.12 (s, -Me ₂ Si-, 12H), 2.51 (dd, _{-CH 2 -, 4H), 7.1-7.6} (m, Ar-H, 8H)

Synthesis Example 2 [Production of (1,1′-ethylene) (2,2′-tetramethyldisilene) bisindenylzirconium dichloride (complex B)]
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 was extracted. , 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 further extracted with toluene.
Under reduced pressure, the solvent of the supernatant and the extract was evaporated to dryness to give (1,1′-ethylene) (2,2′-tetramethyldisylylene) bisindenylzirconium dichloride (complex B) as a yellow solid. (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)

Production Example 1 [Polyoctene-1 Polymerization (A)]
To a heat-dried 1 liter autoclave, 400 ml of octene-1, 0.4 mmol of triisobutylaluminum, 2 μmol of complex A obtained in Synthesis Example 1, and 6 μmol of dimethylanilinium tetrakispentafluorophenylborate are added. Further, 0.05 MPa of hydrogen was introduced. Polymerization was carried out at 50 ° C. for 120 minutes. After completion of the polymerization reaction, 5 ml of ethanol was added to stop the reaction, and the reaction product was dried at 110 ° C. under reduced pressure to obtain 190 g of polyoctene-1.
Polyoctene-1 obtained had an intrinsic viscosity [η] of 0.93 deciliter / g, a polypropylene-converted weight average molecular weight (Mw) measured by GPC method of 177,000, a molecular weight distribution (Mw / Mn) of 2.1, The stereoregularity (mesopentad fraction: mmmm) was 46.4 mol%, and the melting point (Tm-D) as measured by DSC was not observed, so the melting endotherm (ΔHD) was 0 J / g.

Production Example 2 [Production of Silane Modified Low Crystalline Polybutene-1]
In a heat-dried 2 liter autoclave, 600 ml of heptane, 0.6 mmol of triisobutylaluminum, 3.0 μmol of complex A obtained in Production Example 1, and 9.0 μmol of dimethylanilinium tetrakispentafluorophenylborate were added. In addition, the pressure was reduced to −0.01 MPaG at 20 ° C. Further, 0.02 MPa of hydrogen (-0.03 MPa by gauge) was introduced. While increasing the polymerization temperature to 48 ° C., butene-1 was introduced and the total pressure was increased to 0.17 MPa, and polymerization was performed for 90 minutes. After completion of the polymerization reaction, 120 g of polybutene-1 was obtained by drying the reaction product under reduced pressure.
The resulting polybutene-1 had an intrinsic viscosity [η] of 0.99 deciliter / g, a weight average molecular weight (Mw) of 133,000, a molecular weight distribution (Mw / Mn) of 1.9, and stereoregularity (mesopentad fraction). : Mmmm) was 73.6 mol%, and the melting point (Tm) was 72.0 ° C.
60 g of the polybutene-1 obtained above was charged into a 0.5 liter Separa flask equipped with a nitrogen introduction tube, a Dimroth tube, and a stirrer, and heated to 130 ° C. using a bath temperature in a nitrogen atmosphere. 5 g of triethoxyvinylsilane was added and stirred for 5 minutes, and then 0.5 g of Perhexa 25B (manufactured by NOF Corporation) was added, heated to 160 ° C. and stirred for 1 hour. The obtained reaction product was dried under heating and reduced pressure to obtain the desired product.
The resulting silane-modified polymer has an intrinsic viscosity [η] of 0.57 deciliter / g, a weight average molecular weight (Mw) of 72,000, a molecular weight distribution (Mw / Mn) of 2.1, and stereoregularity (mesopentad content). (Rate: mmmm) was 72.1 mol%, melting point (Tm) was 70.5 ° C., ΔH-D was 37 J / g, Tg was −35 ° C., and the half-crystallization time was 65 minutes. In the polymer, the silyl element concentration was 0.66% by mass.

Production Example 3 [Production of Liquid Silane-Modified Polybutene-1]
In a heat-dried 1 liter autoclave, heptane (200 mL), triisobutylaluminum (2M, 0.2 mL, 0.4 mmol), butene-1 (200 mL), complex B (10 μmol / mL, 0.20 mL, 2.0 μmol) Then, MAO (2000 μmol) manufactured by Tosoh Finechem Co. was 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 polymer (B).
With respect to the obtained polymer (B), the melting endotherm ΔH-D was 0 J / g, the glass transition temperature Tg was −30 ° C., the melting point Tm could not be detected, and the mesopentad fraction [mmmm] was 5.8 mol%, The weight average molecular weight (Mw) was 34,500, and the molecular weight distribution (Mw / Mn) was 2.0.

60 g of butene-1 obtained above was charged into a 0.5 liter Separa flask equipped with a nitrogen introduction tube, a Dimroth tube, and a stirrer, and heated to 130 ° C. using a bath temperature in a nitrogen atmosphere. 5 g of triethoxyvinylsilane was added and stirred for 5 minutes, and then 0.5 g of Perhexa 25B (manufactured by NOF Corporation) was added, heated to 160 ° C. and stirred for 1 hour. The obtained reaction product was dried under heating and reduced pressure to obtain the desired product.
The resulting silane-modified polymer has an intrinsic viscosity [η] of 0.35 deciliter / g, a weight average molecular weight (Mw) of 34,500, a molecular weight distribution (Mw / Mn) of 1.9, and stereoregularity (mesopentad content). (Rate: mmmm) was 6 mol%, no melting point (Tm) was observed, ΔH-D was 0 J / g, and Tg was −30 ° C. In the polymer, the silyl element concentration was 0.50% by mass.

Example 1 [Silane modification of polyoctene-1 polymer]
120 g of the polyoctene produced in Production Example 1 was introduced into a 0.5 liter Separa flask equipped with a nitrogen introduction tube, a Dimroth tube, and a stirrer, and heated to 130 ° C. using a bath temperature in a nitrogen atmosphere. 10 g of triethoxyvinylsilane was added and stirred for 5 minutes, and then 1.0 g of Perhexa 25B (manufactured by NOF Corporation) was added, heated to 160 ° C. and stirred for 1 hour. The obtained reaction product was dried under heating and reduced pressure to obtain the desired product.
The resulting silane-modified polymer has an intrinsic viscosity [η] of 0.74 deciliter / g, a weight average molecular weight (Mw) of 174,000, a molecular weight distribution (Mw / Mn) of 2.8, and stereoregularity (mesopentad content). (Rate: mmmm) is 46.5 mol%, Tg is −61 ° C., and no melting point (Tm-D) as measured by DSC was observed, so the melting endotherm (ΔH-D) is 0 J / g. In the polymer, the silyl element concentration was 0.88% by mass.

Example 2 [Curing of Silane Modified Polyoctene-1 Polymer]
15 mg of dibutyltin dilaurate was added to 10 g of the liquid silane-modified polyoctene-1 obtained in Example 1 at room temperature (25 ° C.) and stirred until uniform. Thereafter, the mixture was poured into a 10 × 10 × 0.5 cm ³ container and allowed to stand. When the obtained composition was allowed to stand in an atmosphere of 23 ° C. and 50% humidity for 1 hour, it was confirmed that tack was eliminated and the curing reaction proceeded. The obtained cured product was heated on a hot plate controlled at 120 ° C. for 10 minutes, and its shape change was observed. As a result, it was confirmed that it was a cured product that retained its shape in a heated state and exhibited rubber elasticity. The solid viscoelasticity was E ′ = 2.6 MPa (−50 ° C.), E ′ = 0.6 MPa (25 ° C.), E ′ = 0.8 MPa (150 ° C.).

Example 3 [Curing 1/1 Blend of Silane Modified Polyoctene-1 Polymer and Silane Modified Low Crystalline Polybutene-1]
5 g of the liquid silane-modified polyoctene-1 obtained in Example 1 and 5 g of the silane-modified low crystalline polybutene-1 obtained in Production Example 2 were stirred at 100 ° C. until uniform. After cooling to 50 ° C., 15 mg of dibutyltin dilaurate was added and stirred until uniform. Thereafter, the mixture was poured into a 10 × 10 × 0.5 cm ³ container and allowed to stand. When the obtained composition was allowed to stand in an atmosphere of 23 ° C. and 50% humidity for 1 hour, it was confirmed that tack was eliminated and the curing reaction proceeded. The obtained cured product was heated on a hot plate controlled at 120 ° C. for 10 minutes, and its shape change was observed. As a result, it was confirmed that it was a cured product that retained its shape in a heated state and exhibited rubber elasticity. The solid viscoelasticity was E ′ = 531 MPa (−50 ° C.), E ′ = 32 MPa (25 ° C.), E ′ = 0.9 MPa (150 ° C.).

Comparative Example 1 [Curing of liquid silane-modified polybutene-1]
In place of 10 g of the liquid silane-modified polyoctene-1 in Example 2, 10 g of the liquid silane-modified polybutene-1 obtained in Production Example 3 was used except that 10 g was used. It could not be confirmed, and it took more than 100 hours for the tack to disappear.

  According to the present invention, it is possible to provide a functionalized α-olefin polymer having improved hardness and low temperature properties of a cured product, and can be applied as a reactive adhesive or the like.

Claims (11)

A functionalized α-olefin polymer satisfying the following (1) to (4) and having an alkoxysilyl group.
(1) Using a differential scanning calorimeter (DSC), a sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. Amount of heat (ΔH-D) is 0 J / g or more and 10 J / g or less (2) Weight average molecular weight (Mw) is 1,000 to 500,000
(3) The silyl element concentration is 0.05 mass% to 5 mass%.
(4) 50 mol% or more and 100 mol% or less of the α-olefin monomer constituting the polymer is at least one selected from C6 to C10 α-olefin, and 0 of the α-olefin monomer constituting the polymer. The mol% or more and 50 mol% or less is at least one selected from C3 to C5 α-olefins and C11 to C30 α-olefins. The functionalized alpha-olefin polymer of Claim 1 which satisfy | fills following (5).
(5) Mesopentad fraction [mmmm] of 20 mol% to 80 mol% The functionalized α-olefin polymer according to claim 1 or 2, which satisfies the following (6).
(6) Using a differential scanning calorimeter (DSC), defined as the peak top of the melting endothermic curve obtained by holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. The observed melting point (Tm-D) is not observed in the range of -10 ° C to 100 ° C. The functionalized alpha-olefin polymer as described in any one of Claims 1-3 which satisfy | fills following (7).
(7) Alkoxysilyl group concentration in terms of triethoxysilyl group is 0.01 to 30% by mass The resin composition containing 1-99 mass% of following A component with respect to the sum total of the following A component and the following B component, and 99-1 mass% of the following B component.
Component A: Functionalized α-olefin polymer according to any one of claims 1 to 4 Component B: Olefin polymer satisfying the following (a) to (c) (a) Differential scanning calorimeter (DSC) ), And holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min is defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve. Melting point (Tm-D) is not observed or 0-100 ° C
(B) The weight average molecular weight (Mw) is 1,000 to 500,000.
(C) The half crystallization time measured with a differential scanning calorimeter (DSC) is 3 minutes or more, or the crystallization peak measured with a differential scanning calorimeter (DSC) is not observed. The resin composition according to claim 5, wherein the olefin polymer satisfies the following (d).
(D) The silyl element concentration is 0.05 mass% to 5 mass%. The resin composition according to claim 5 or 6, wherein the olefin polymer satisfies the following (e).
(E) Mesopentad fraction [mmmm] of 20 mol% to 80 mol%   A resin composition comprising the functionalized α-olefin polymer according to any one of claims 1 to 4 or the resin composition according to any one of claims 5 to 7 and a curing accelerator catalyst.   The resin composition according to claim 8, wherein the composition contains at least one selected from a tackifier and a diluent.   A cured product obtained by curing the resin composition according to claim 8 or 9.   The resin composition according to claim 8 or 9, which is used for an adhesive, a sealing agent, a pressure-sensitive adhesive, or a modifier.