JPWO2012124345A1 - Reactive polyolefin, process for producing the same, and composition containing the same - Google Patents

Abstract

A structure derived from a specific vinylalkoxysilane (A), and a structure in which one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms are polymerized, except for a polyethylene chain (B (1) The mesopentad fraction [mmmm] representing the average stereoregularity is 25 to 85 mol%, (2) the content of the structure (A) is 0.1 to 20 wt%, (3) Molecular weight distribution (Mw / Mn) = 1.5 to 10 and (4) Reactive polyolefin satisfying a melt viscosity of 2000 to 80000 mPas measured at 190 ° C.

Description

  The present invention relates to a reactive polyolefin, a method for producing the same, and a composition containing the reactive polyolefin.

Since polyolefin (especially polypropylene) has excellent physical properties and is chemically stable, demand for industrial fields such as automobiles and construction materials has been increasing in recent years.
The adhesive in the industrial field is required to have adhesion with metal, resin other than polyolefin or polyolefin resin, and paintability. However, when the polyolefin resin is bonded with an adhesive, a pretreatment step such as surface modification of the polyolefin resin or a plummer treatment is required.

Currently, urethane-based adhesives are mainly used. However, urethane-based adhesives have a problem that they have poor adhesion to the polyolefin interface and have a large environmental load without pretreatment.
In view of the above problems, an adhesive that does not depend on an isocyanate compound is desired, and a polyolefin-based adhesive has been actively studied. However, polyolefin adhesives have problems of poor workability due to poor low temperature coatability and short open time. In addition, in the polyolefin adhesive, the coating property and the heat resistance after curing, which is important as an adhesive, are in inverse proportion to each other, and it has been a problem to achieve both coating property and heat resistance.

Patent Document 1 discloses a composition based on a low stereoregular polyolefin, which contains polypropylene modified with alkoxysilicon and an acrylic monomer.
Patent Document 2 discloses a polypropylene obtained by modifying a low stereoregular polypropylene with maleic anhydride or the like.

JP 2006-348153 A JP 2003-201322 A

Although the composition of Patent Document 1 has improved low-temperature coating properties, the heat resistance is low in a test assuming an actually used environment.
Moreover, the polypropylene of patent document 2 is not disclosed about the heat resistant expression effect important as an adhesive, and moisture hardening.
An object of the present invention is to provide a reactive polyolefin having a long open time, a low melting temperature, which can be applied at a low temperature, and excellent in heat resistance after moisture curing. It is another object of the present invention to provide a reactive polyolefin and / or a method for producing a reactive polyolefin capable of controlling the curing rate and improving the low temperature characteristics.

According to the present invention, the following reactive polyolefin and the like are provided.
1. A structure (A) derived from a vinylalkoxysilane represented by the following formula (I), and a chain obtained by polymerizing at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms, It has a structure (B) except in some cases,
Reactive polyolefin satisfying the following (1) to (4).
[Vinylalkoxysilane]
^{_{CH 2 = CR 1 -Si (OR}} 2) 3-n R 3 n (I)
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms.
n is an integer of 0, 1 or 2. )
[Physical properties of reactive polyolefin]
(1) Mesopentad fraction [mmmm] representing average stereoregularity is 25 to 85 mol%
(2) Content of structure (A) is 0.1 to 20% by weight
(3) Molecular weight distribution (Mw / Mn) = 1.5-10
(4) Melt viscosity measured at 190 ° C. is 2000 to 80000 mPas
2. 2. The reactive polyolefin according to 1, having 1 to 35% by weight of a structure (C) derived from a vinyl monomer represented by the following formula (II).
X ¹ -CR ³ = CR ⁴ -X ² formula (II)
(Wherein X ¹ and X ² are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X ¹ and X ² are bonded to each other to form a ring. Provided that when ^one of X ¹ and X ² is a hydrogen atom, the other is a functional group containing an oxygen, nitrogen, or sulfur atom.
R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
3. 1 or 2 in which the structure (B) is any one of a homopolypropylene chain, a chain composed of a copolymer of propylene and ethylene, and a chain composed of a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms. Reactive polyolefin.
4). The reactive polyolefin according to any one of 1 to 3, wherein the structure (B) is a polyolefin chain having 0.5 to 1.0 terminal unsaturated groups per molecule.
5. The reactive polyolefin in any one of 1-4 satisfy | filling one or more of following (5)-(7).
(5) Heat-resistant creep temperature after moisture curing is 65 to 130 ° C
(6) Open time is 15 seconds to 5 minutes (7) Acetone dissolution amount at 25 ° C. is the following formulas (7-1) and (7-2), or the following formulas (7-3) and (7-4) Meet.
[When the reactive polyolefin has the structure (A) and the structure (B) and does not have the structure (C)]
(7-1) Acetone-soluble amount (% by weight) ≦ 1.1 × [structure (A) content (% by weight)]
(7-2) Acetone soluble amount (% by weight) ≦ 5% by weight
[When the reactive polyolefin has the structure (A), the structure (B), and the structure (C)]
(7-3) Acetone-soluble amount (% by weight) ≦ 0.88 × [structure (A) and (B) content (% by weight)]
(7-4) Acetone soluble amount (% by weight) ≦ 20% by weight
6). The reactive polyolefin in any one of 1-5 in which a vinyl alkoxysilane residue exists in the "sea" component observed based on the form observation by an electron microscope.
7). Mesopentad fraction [mmmm] is in the range of 20 to 80 mol%, weight average molecular weight (Mw) is in the range of 10,000 to 500,000, and molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4.0. A polyolefin obtained by polymerizing one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms, excluding the case where it is a homopolyethylene (1) 100 parts by weight,
A vinyl alkoxysilane represented by the following formula (I) 0.5 to 25 parts by weight and an organic peroxide 0.01 to 5 parts by weight in a molten state of the polyolefin (1) at a temperature range of 120 to 260 ° C. A process for producing a reactive polyolefin.
^{_{CH 2 = CR 1 -Si (OR}} 2) 3-n R 3 n (I)
(In the formula, ^{R 1} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms.
n is an integer of 0, 1 or 2. )
8). 8. The method for producing a reactive polyolefin according to 7, wherein the polyolefin (1) is a polyolefin having 0.5 to 1.0 terminal unsaturated groups per molecule.
9. The method for producing a reactive polyolefin according to 7 or 8, further using 1 to 40 parts by weight of a vinyl monomer represented by the following formula (II).
X ¹ -CR ³ = CR ⁴ -X ² formula (II)
(Wherein X ¹ and X ² are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X ¹ and X ² are bonded to each other to form a ring. Provided that when ^one of X ¹ and X ² is a hydrogen atom, the other is a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom.
R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
10. The manufacturing method of the reactive polyolefin in any one of 7-9 which further uses 0.2-30 weight part of crystalline polyolefin (2).
11. 11. The method for producing a reactive polyolefin according to 10, wherein the crystalline polyolefin (2) is an ethylene polymer or a crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80%.
12 The reaction according to 10, wherein the crystalline polyolefin (2) is a homopolyethylene, an ethylene / α-olefin copolymer, an olefin copolymer containing a polar group, or a polypropylene having a mesopentad fraction [mmmm] of more than 80%. For producing functional polyolefin.
13. A composition comprising the reactive polyolefin according to any one of 1 to 6 and at least one of a curing agent and a curing accelerator.
14. An adhesive composition comprising 100 parts by weight of the reactive polyolefin according to any of 1 to 6, 0 to 200 parts by weight of a thermoplastic resin, and 0 to 100 parts by weight of oil.
15. Furthermore, it contains 1 × 10 ^{−6 to} 0.5 part by weight of a curing catalyst,
15. The adhesive composition according to 14, which is moisture curable under an atmosphere substantially containing moisture.
16. 16. The adhesive composition according to 14 or 15, which is a reactive hot melt agent.
An adhesive, a coating agent, a filler treatment agent, a paint, a dispersion, an ink, or a resin modifier containing the reactive polyolefin according to any one of 17.1 to 6, or the composition according to 13.

  According to the present invention, it is possible to provide a reactive polyolefin that has a long open time, a low melting temperature, can be applied at a low temperature, and is excellent in heat resistance after moisture curing.

2 is an electron micrograph of a reactive polyolefin of Example 24. FIG. 4 is an electron micrograph of a silane-modified polypropylene of Comparative Example 6.

[Reactive polyolefin]
The reactive polyolefin of the present invention is a polyolefin that can be moisture-cured by having an alkoxysilicon group that forms a crosslinked structure by a silanol condensation reaction, and is a structure (A) derived from a vinylalkoxysilane represented by the following formula (I) And a structure (B) in which one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms is a polymerized chain (except that the structure (B) is a homopolyethylene chain).
^{_{CH 2 = CR 1 -Si (OR}} 2) 3-n R 3 n (I)
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms.
n is an integer of 0, 1, or 2. )

  In the present specification, “polyolefin” includes a homopolymer and a copolymer, and “homopolyolefin” means a homopolymer.

The structure (A) is a group derived from a vinylalkoxysilane represented by the formula (I), and an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) of R ¹ , R ² and R ^3. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group.

As specific examples of the vinylalkoxysilane represented by the formula (I), OR ² is methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-butoxy group, tert-butyloxy group, Or the vinyl alkoxysilane which is an octoxy group is mentioned, From a viewpoint with easy acquisition as an industrial raw material, Preferably it is a trimethoxy vinyl silane and a triethoxy vinyl silane.

  The structure (B) is a chain formed by polymerizing at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms, excluding the homopolyethylene chain, and the α having 3 to 20 carbon atoms constituting the chain. Examples of olefins include propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 -Pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and the like.

Examples of the chain form of the chain comprising ethylene and / or α-olefin include, for example, a chain composed of one homopolymer or two or more copolymers selected from α-olefins having 3 to 20 carbon atoms; The chain | strand which consists of a copolymer of 90 mass% or more of 1 or more types of monomers chosen from -20 alpha olefins and 10 mass% or less of ethylene is mentioned.
When the structure (B) is a homopolymer chain, the homopolymer chain is preferably a propylene chain or a 1-butene chain, more preferably a propylene chain.

The chain formed by polymerizing at least one selected from ethylene having the structure (B) and an α-olefin having 3 to 20 carbon atoms is preferably 0.5 to 1.0 terminal unsaturated groups (per molecule) ( For example, a polyolefin chain having a terminal vinylidene group).
When the number of terminal unsaturated groups per molecule of the structure (B) is less than 0.5, heat resistance may not be sufficiently imparted by a reaction starting from the terminal unsaturated group. On the other hand, when the number of terminal unsaturated groups per molecule is more than 1.0, the structure (B) having unsaturated groups at both ends increases, and the melt fluidity changes due to high molecular weight due to crosslinking. The applicability may change.

The reactive polyolefin of the present invention satisfies the following (1) to (4).
(1) Mesopentad fraction [mmmm] representing average stereoregularity is 25 to 85 mol%
(2) Content of structure (A) is 0.1 to 20% by weight
(3) Molecular weight distribution (Mw / Mn) = 1.5-10
(4) Melt viscosity measured at 190 ° C. is 2000 to 80000 mPas

(1) Mesopentad fraction [mmmm] representing average stereoregularity
The reactive polyolefin of the present invention has a mesopentad fraction [mmmm] of 25 to 85 mol%, preferably 30 to 75 mol%, more preferably 35 to 70 mol%, particularly preferably 35 to 60 mol%. .
A mesopentad fraction of 25 mol% or more means that the reactive polyolefin is crystalline, and the reactive polyolefin can exhibit excellent mechanical strength. Further, when the mesopentad fraction is 85 mol% or less, the reactive polyolefin becomes moderately soft and melts at a low temperature, so that excellent coating workability can be exhibited.
Even if the α-olefin chain having a high mesopentad fraction and a low α-olefin chain are mixed, the average mesopentad fraction measured for the reactive polyolefin of the present invention is within the above range. Good.

When the structure (B) is polypropylene, stereoregularity can be evaluated by the following method.
The mesopentad fraction [mmmm] of the reactive polyolefin is based on the method proposed in “Macromolecules, 6,925 (1973)” by A. Zambelli et al., And the methyl group signal in the ¹³ C-NMR spectrum. Is the meso fraction in pentad units in the polypropylene molecule as measured by As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
The measurement of ¹³ C-NMR spectrum can be carried out with the following apparatus and conditions in accordance with the attribution of the peak proposed by “Ama Zambelli” 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 method for calculating the mesopentad fraction M is as follows.
M = (m / S) × 100
S = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atoms of all propylene units Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
m: Mesopentad chain: 21.7-22.5 ppm

When the structure (B) is polybutene, stereoregularity can be evaluated by the following method.
Mesopentad fraction [mmmm] is reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It can be measured according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al.
That is, the mesopentad fraction in the poly (1-butene) molecule can be determined by measuring signals of methylene group and methine group using ¹³ C nuclear magnetic resonance spectrum.
^{The 13} C nuclear magnetic resonance spectrum can be measured using the above apparatus and conditions.

When the structure (B) is a polymer composed of an α-olefin having 5 or more carbon atoms, stereoregularity can be evaluated by the following method.
The mesopentad fraction is determined by T.W. Asakura, M .; Demura, Y .; It can be determined in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama.
That is, the mesopentad fraction is obtained by utilizing the fact that CH ₂ carbon at the side chain α-position derived from the higher α-olefin is split and observed in the ¹³ CNMR spectrum, reflecting the difference in stereoregularity. Can do.
The ¹³ C nuclear magnetic resonance spectrum measuring apparatus and conditions are the same as described above.

(2) Content of structure (A) is 0.1 to 20% by weight
The content (configuration ratio) in the reactive polyolefin of the structure (A) is preferably 0.25 to 20% by weight, more preferably 0.25 to 18% by weight, and further preferably 0.30 to 30%. It is 15% by weight, particularly preferably 0.50 to 10% by weight, still more preferably 0.50 to 6.0% by weight, and most preferably 0.50 to 5.0%.
When the content of the structure (A) is less than 0.1% by weight, the heat resistance of the reactive polyolefin due to moisture curing may be insufficient. On the other hand, when the content of the structure (A) is more than 20% by weight, the heat resistance of the reactive polyolefin is improved, but the flexibility may be lowered. This is because an alkoxysilane group existing in the structure (A) reacts with an adjacent alkoxysilane group, and a molecular chain extension reaction and a crosslinking reaction proceed. This reaction proceeds if a slight number of alkoxysilane groups are present, but if an excess of alkoxysilane groups are present relative to the α-olefin chain, the crosslinking density is greatly increased and the flexibility is assumed to be lowered.

The content of the structure (A) in the reactive polyolefin can be measured by a known method such as NMR, infrared absorption spectrum, or titration.
For example, when the structure (B) of the reactive polyolefin is polypropylene, the infrared absorption spectrum method uses a sample with a clear composition in advance to obtain characteristic absorption based on Si—O bonds (1130.0 to 1054.0 cm ^−1. ) And a C-H stretch of polyolefin and a combined curve of various peaks in the fingerprint region, 4500.0-3850.0 cm ⁻¹ , and a calibration curve is created based on the thickness corrected (normalized) value, The method of calculating by this is mentioned.
In addition to the above method, the content ratio of the structure (A) can be directly determined by NMR.

  In addition, content (component ratio) of structure (B) becomes like this. Preferably it is 99.9-60 weight%, More preferably, it is 99.5-70 weight%, More preferably, it is 99.0-75 weight%. It is. The content of the structure (B) can be measured by a known method such as NMR, infrared absorption spectrum, or titration.

(3) Molecular weight distribution (Mw / Mn)
The reactive polyolefin of the present invention has a molecular weight distribution (Mw / Mn) of 1.5 to 10.0, preferably 1.5 to 4.5, more preferably 1.5 to 4.3, Especially preferably, it is 1.7-4.3.
If the Mw / Mn of the reactive polyolefin is less than 1.5, the melt fluidity may decrease when compared with the same molecular weight. On the other hand, when Mw / Mn is more than 10.0, low molecular weight substances increase, so that the adhesive strength, heat resistance, etc. may be reduced.

The molecular weight distribution (Mw / Mn) of the reactive polyolefin can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by the GPC method.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by the Universal Calibration method using the constants K and a of the Mark-Houwink-Sakurada formula in order to convert the polystyrene equivalent molecular weight into the molecular weight of the corresponding polymer. Can do. 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. Is described in each. It can also be determined by a standard method from the relationship between the intrinsic viscosity and the newly calculated absolute molecular weight.

The measurement apparatus and measurement conditions for measurement using the GPC method 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

(4) Melt viscosity measured at 190 ° C. The reactive polyolefin of the present invention has a melt viscosity (B viscosity) measured at 190 ° C. of 2000 to 80000 mPas, preferably 2000 to 50000 mPas, more preferably 2200 to 45000 mPas. And particularly preferably 2500 to 40000 mPas.
When the B viscosity of the reactive polyolefin is less than 2000, dripping may occur when applying in a molten state, and workability may be reduced. On the other hand, when the B viscosity is more than 80000, the applicability may decrease due to the high viscosity.

The B viscosity of the reactive polyolefin can be measured by using a Brookfield viscometer based on JISK-6862 and a reactive polyolefin melted at 190 ° C. or a composition containing the reactive polyolefin.
As the viscometer, for example, a TVB-10 type viscometer and M2 rotor (No. 21) manufactured by Toki Sangyo Co., Ltd. may be used, and an H-2 type small sample adapter may be used.

The reactive polyolefin of the present invention preferably satisfies any one of the following (5) to (7) in addition to the above (1) to (4).
(5) Heat-resistant creep temperature after moisture curing is 65 to 130 ° C
(6) Open time is 15 seconds to 5 minutes (7) Acetone dissolution amount at 25 ° C. is the following formulas (7-1) and (7-2), or the following formulas (7-3) and (7-4) Meet.
[When the reactive polyolefin has the structure (A) and the structure (B) and does not have the structure (C)]
(7-1) Acetone-soluble amount (% by weight) ≦ 1.1 × [structure (A) content (% by weight)]
(7-2) Acetone soluble amount (% by weight) ≦ 5% by weight
[When the reactive polyolefin has the structure (A), the structure (B), and the structure (C)]
(7-3) Acetone-soluble amount (% by weight) ≦ 0.88 × [structure (A) and (B) content (% by weight)]
(7-4) Acetone soluble amount (% by weight) ≦ 20% by weight

(5) Heat-resistant creep temperature after moisture curing The heat-resistant creep temperature after moisture curing of the reactive polyolefin of the present invention is preferably 65 to 130 ° C, more preferably 66 to 130 ° C, and still more preferably 67 to 130 ° C. 130 ° C.
When the heat-resistant creep temperature after moisture curing of the reactive polyolefin is less than 65 ° C., the use environment of the reactive polyolefin may be limited. On the other hand, it is technically limited that the heat-resistant creep temperature after moisture curing of the reactive polyolefin exceeds 130 ° C.
The heat-resistant creep temperature can be measured according to JIS K6833.

  Reactive polyolefin is preferably an adhesive having a low melt viscosity and a high heat-resistant creep temperature after curing. For example, when compared with a polyolefin-based reactive hot-melt adhesive base material, the heat-resistant creep is the same B viscosity. An adhesive having a high temperature is preferred, and a lower B viscosity is preferred if the heat resistant creep temperature is the same.

The reactive polyolefin of the present invention preferably has a B viscosity and a heat resistant creep temperature satisfying heat resistant creep temperature ≧ 18.2 log [B] +1.4, and satisfying heat resistant creep temperature ≧ 18.2 log [B] +2.0. More preferably, the heat resistant creep temperature ≧ 18.2 log [B] +2.5 is more preferably satisfied.
[B] is the B viscosity of the reactive polyolefin, and can exhibit excellent heat resistance and low-temperature flow when the reactive polyolefin satisfies the above formula.

It is preferable that the adhesive is easy to apply and has high heat resistance after moisture curing, but in order to obtain such an adhesive, the reactive polyolefin must have a low melt viscosity and a high heat-resistant creep temperature. Is required. The melt viscosity and the heat resistant creep temperature are contradictory properties, and if the reactive polyolefin has a low melt viscosity, the heat resistant creep temperature is generally low.
Since the melt viscosity depends on the molecular weight, a low melt viscosity means a low molecular weight product. On the other hand, since the heat-resistant creep temperature depends on an effective cross-linked structure, the high heat-resistant creep temperature means that the reactive polyolefin sandwiches the structure (B) in which the alkoxysilicon group has a chain length of a certain value or more. It means having.
Therefore, it is presumed that the fact that the reactive polyolefin satisfies the above formula means that the reactive polyolefin is a low molecular weight substance and the concentration of the structure in which the alkoxysilicon group sandwiches the structure (B) is high.

(6) Open time The reactive polyolefin of the present invention preferably has an open time of 15 seconds to 5 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 25 seconds to 4 minutes.
The above-mentioned open time means the time from applying the adhesive containing the reactive polyolefin of the present invention to stretching the adherend, and means the time until the initial adhesive force is maintained. A long open time is preferable because a fine adjustment of the position at the time of bonding and a time margin for large-area bonding are created.
When the open time is less than 15 seconds, it is necessary to finish the bonding operation in a short time, and there is a possibility that a defect is likely to occur due to bonding of a large area. On the other hand, it is technically difficult to make the open time longer than 5 minutes.

(7) Acetone solubility at 25 ° C. The reactive polyolefin of the present invention preferably has an acetone solubility at 25 ° C. of the following formulas (7-1) and (7-2), or (7-3) and Satisfies (7-4). The structure (C) will be described later.
[When the reactive polyolefin has the structure (A) and the structure (B) and does not have the structure (C)]
(7-1) Acetone-soluble amount (% by weight) ≦ 1.1 × [structure (A) content (% by weight)]
(7-2) Acetone soluble amount (% by weight) ≦ 5% by weight
[When the reactive polyolefin has the structure (A), the structure (B), and the structure (C)]
(7-3) Acetone-soluble amount (% by weight) ≦ 0.88 × [structure (A) and (B) content (% by weight)]
(7-4) Acetone soluble amount (% by weight) ≦ 20% by weight

Regarding formulas (7-1) and (7-2), the acetone soluble amount of the reactive polyolefin is an index indicating whether or not the structure (A) is uniformly added regardless of the molecular weight of the reactive polyolefin. . In particular, when the reactive polyolefin has a low molecular weight and a large addition amount of the structure (A), the acetone-soluble amount tends to increase, and the heat-resistant creep performance may decrease as the amount increases.
The above formula (7-1) is preferably acetone soluble amount (% by weight) ≦ 1.0 × [structure (A) content (% by weight)], more preferably acetone soluble amount (% by weight). ≦ 0.95 × [structure (A) content (% by weight)].
Regarding the above formula (7-2), the acetone soluble amount (wt%) of the reactive polyolefin ≦ 5 wt%, the acetone soluble amount (wt%) ≦ 4 wt%, the acetone soluble amount (wt%) ≦ 3. 5 wt%, acetone soluble amount (wt%) ≦ 3 wt%, acetone soluble amount (wt%) ≦ 2.5 wt%, acetone soluble amount (wt%) ≦ 2 wt%, acetone soluble amount ( % By weight) <2% by weight.

For formulas (7-3) and (7-4), the amount of acetone soluble in the reactive polyolefin is whether the structures (A) and (C) are uniformly added regardless of the molecular weight of the reactive polyolefin. It is an index to represent. In particular, when the reactive polyolefin has a low molecular weight and a large amount of addition of the structures (A) and (C), the acetone-soluble amount tends to increase, and the heat-resistant creep performance decreases as this amount increases. There is a fear.
About Formula (7-3), Preferably it is acetone soluble amount (weight%) <= 0.87x [structure (A) and (B) content (weight%)], More preferably, acetone soluble amount ( % By weight) ≦ 0.85 × [content of structures (A) and (B) (% by weight)].
Regarding the formula (7-4), the amount of acetone soluble in the reactive polyolefin (wt%) ≦ 20 wt%, the amount of acetone soluble (wt%) ≦ 19 wt%, the amount of acetone soluble (wt%) ≦ 17 wt% Acetone soluble amount (% by weight) ≦ 15% by weight is preferred.
The reactive polyolefin having the structure (A), the structure (B), and the structure (C) more preferably satisfies the following formula (7-5).
(7-5) Acetone soluble amount (% by weight) ≦ 0.90 × [structure (C) content (% by weight)]

The acetone soluble amount of the reactive polyolefin can be measured as follows.
An evaluation sample (1) is obtained by drying a reactive polyolefin obtained by the production method described later at 150 ° C. for 8 hours under reduced pressure. Moreover, the raw material of the structure (B) used for the production of the reactive polyolefin is also treated in the same manner as the evaluation sample (1) to obtain an evaluation sample (2).

  10 grams of each of the evaluation samples (1) and (2) are swollen or dissolved in 20 ml of toluene, and methanol is added to make finer with stirring. Each of the micronized samples (1) and (2) is put into 1000 ml of methanol, stirred and further miniaturized, and then allowed to stand until solid-liquid separation becomes constant. The solid portion is recovered by filtration and washed twice with methanol. Air dry and then vacuum dry at 40 ° C. for 5 hours.

Extraction processing is performed at 25 ° C. for 8 hours while dispersing 5 g (referred to as W ₀ ) of the micronized sample (1) in 150 ml of acetone and stirring. After the extraction treatment, the solid-liquid level becomes constant by standing or by a centrifuge, and then the solid is separated by filtration. The separated solid is subjected to a second extraction process in the same manner, and the solid components separated for the first time and the second time are all dried under reduced pressure at 100 ° C. for 8 hours, and the weight thereof is measured. The weight is defined as W ₁ . . On the other hand, the entire amount of the filtrate is recovered, the solid component is recovered by evaporation to dryness, dried under reduced pressure at 100 ° C. for 8 hours, and its weight (referred to as W ₂ ) is measured. Measure the soluble amount.
Acetone soluble part (% by weight) = 100 × W ₂ / (W ₁ + W ₂ )
(However, (W ₁ + W ₂ ) / W ₀ ≧ 0.98.)
The same operation is performed for the evaluation sample (2), and the acetone-soluble amount is measured. In addition, the acetone soluble amount of the normal evaluation sample (2) is in the range of 0.01 to 0.1% by weight.
The value obtained by subtracting the acetone soluble amount (% by weight) of the evaluation sample (2) from the acetone soluble amount (% by weight) of the evaluation sample (1) obtained from the above formula is defined as the acetone soluble amount of the reactive polyolefin. .

The reactive polyolefin of the present invention preferably satisfies the following (8) in addition to the above (1) to (4).
(8) A vinylalkoxysilane residue is present in the “sea” component observed based on morphological observation with an electron microscope.

The presence of a vinylalkoxysilane residue in the “sea” component indicates that the structure (A) is uniformly added.
Whether or not the structure (A) is uniformly added (hereinafter also referred to as “uniformity”) can be evaluated by measuring the acetone-soluble amount, but whether or not the requirement (8) is satisfied. It can also be evaluated by measuring.
As described in the evaluation of the acetone-soluble amount, in order for the reactive polyolefin to be excellent in heat resistance, the reactive polyolefin is required to be uniformly crosslinked. For this purpose, it is preferable that an alkoxysilane group serving as a crosslinking point is present in the sea (matrix) of the reactive polyolefin. The reactive polyolefin of the present invention is a uniform reactive polyolefin obtained by uniformly reacting vinyl alkoxysilane with the polyolefin (1) forming the structure (B). Since it is a uniform reactive polyolefin, heat resistance is presumed to be exhibited.

Whether or not a vinylalkoxysilane residue is present in the “sea” component can be evaluated by the following measurement method.
The cross section of the reactive polyolefin is subjected to elemental analysis by an electron microscope, and the dispersion state of silicon atoms derived from vinylalkoxysilane is measured.
When the uniformity is low, a sea (matrix) / island (domain) structure is formed, and the amount of silicon elements existing in the sea island is different, and a large amount of silicon atoms exist on the island. In this case, the heat resistance improvement by the crosslinking reaction is limited to the island portion, and the sea portion of the main component has a small degree of crosslinking reaction and does not improve the heat resistance. Therefore, there is almost no improvement in heat resistance of the entire sea island.
When the uniformity is high, the sea-island structure does not exist clearly and a uniform sea is formed. Since the distribution of silicon atoms and the like is uniformly present in the sea, the crosslinking reaction proceeds easily and the heat resistance is improved.
In addition, when a reactive polyolefin is produced by using crystalline polyolefin (2) in combination, or when a vinyl monomer represented by formula (II) is used in combination, a sea-island structure is formed. Alkoxysilane must be present.

The specific measurement method is as follows.
Sea-island structure and elemental analysis method by transmission electron microscope (TEM) a) TEM observation: device, sample pretreatment, measurement conditions Device: JEM-2100 (HR) manufactured by JEOL Ltd.
Sample pretreatment: An ultrathin section was prepared under freezing (−100 ° C.) using an ultramicrotome ULTRACUT R manufactured by Leica Microsystems, and after placing on a Cu grid, 0.5% RuO ₄ aqueous solution was used. Vapor stained.
Measurement conditions: Observation was performed at an acceleration voltage of 200 kV (imaging magnification of 50,000 times (when elemental analysis was performed, the imaging magnification was 200,000 times in STEM mode).
b) Elemental analysis: Equipment, sample pretreatment, measurement conditions
Detector: EX-24063JGT manufactured by JEOL Ltd.
Accelerating voltage: 200kV
Sample: An ultrathin section (on a Cu grid) prepared for TEM observation was used.

Here, as a preferable form when the island component does not exist, the form is observed with a transmission electron microscope to confirm that the island component does not exist, and the vinylalkoxysilane content is 0.1 to 20% by weight. It is in the range.
Here, “the island component does not exist” is more specifically described as follows.
As a result of observation with a transmission electron microscope, there is no island component of 50 nm or more in a field of view with a photographing magnification of 50,000 to 200,000 times. If there is a defect or the like on the observation surface, it may be recognized as an island component. In this case, the presence of silicon atoms and oxygen atoms derived from vinylalkoxysilane by elemental analysis Confirm that there is no difference.
Moreover, as a preferable form when the island component exists, when the form is observed with a transmission electron microscope and it is confirmed that the sea island exists, at least the silicon element derived from vinylalkoxysilane can be detected in the sea component.

The reactive polyolefin of the present invention preferably has 1 to 35% by weight of a structure (C) derived from a vinyl monomer represented by the following formula (II).
X ¹ -CR ³ = CR ⁴ -X ² formula (II)
(Wherein X ¹ and X ² are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X ¹ and X ² are bonded to each other to form a ring. Provided that when ^one of X ¹ and X ² is a hydrogen atom, the other is a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom.
R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

Examples of the vinyl monomer represented by the above formula (II) include the following compounds [i] to [vii].
[I] Acrylic acid and its derivatives [ii] α-alkyl-substituted products of methacrylic acid and acrylic acid [iii] Vinyl esters and derivatives thereof, and alkoxyvinylsilanes [iv] Styrene and derivatives thereof [v] Maleic anhydride and its Substitute [vi] maleic acid and its ester [vii] maleimide and its substitute

[I] Acrylic acid and its derivatives Examples of acrylic acid and its derivatives represented by the formula (II) include the following (1) to (6).
(1) Acrylic acid (2) Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, normal octyl acrylate, 2-ethylhexyl acrylate; polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol acrylate, poly ( (Ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monoacrylate, polypropylene glycol monoacrylate, etc., long-chain polyalkylene glycols having a molecular weight of 30,000 or less (3) sodium acrylate, potassium acrylate, acrylic acid Acrylic acid salt composed of acrylic acid and typical metallic elements such as magnesium and calcium acrylate (4) Ester residue, oxygen atom, Acrylic acid esters containing at least one atom selected from elementary atom, sulfur atom and silicon atom (for example, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate) Acrylates having functional groups such as 4-hydroxybutyl acrylate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane; polyethylene glycol monoacrylate, Polyethylene glycol polypropylene glycol acrylate, poly (ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polymer Butylene glycol monoacrylate, the molecular weight of 30,000 or less of the long chain polyalkylene glycols having a hydroxyl group such as polypropylene glycol monoacrylate)
(5) Acrylamide (6) N-substituted acrylamide containing at least one atom selected from oxygen atom, nitrogen atom, sulfur atom and silicon atom in the substituent (for example, N-methylacrylamide, N-ethylacrylamide, N- Isopropylacrylamide, N-cyclohexylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dibutylacrylamide, N, N-dicyclohexylacrylamide, N- (2-hydroxyethyl) -acrylamide N-substituted acrylamides such as N- (2-hydroxypropyl) -acrylamide, N, N-dimethylaminoethylacrylamide, N-methylolacrylamide)
(7) Acrylonitrile

[Ii] α-Alkyl Substitution of Methacrylic Acid and Acrylic Acid As the α-alkyl substitution product of methacrylic acid and acrylic acid represented by the formula (II), α of the vinyl alkoxysilane represented by the above formula (I) And a compound having an alkyl group such as a methyl group (preferably an alkyl group having 6 or less carbon atoms) at the position.

[Iii] Vinyl ester and derivatives thereof, and alkoxy vinyl silane The vinyl ester represented by the formula (II) and derivatives thereof and alkoxy vinyl silane include vinyl acetate, vinyl propionate, vinyl isolacrate, vinyl pivalate, vinyl caproate, and capryl. Vinyl esters such as vinyl acrylate, vinyl octylate, vinyl caprate, vinyl undecanoate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, etc .; alkoxy vinyl silanes such as trimethoxy vinyl silane and triethoxy vinyl silane Is mentioned.

[Iv] Styrene and its derivatives Styrene and its derivatives represented by formula (II) include α-methyl styrene, p-methyl styrene, p-ethyl styrene, p-propyl styrene, p-isopropyl styrene, p-butyl styrene. P-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m- Alkyl styrenes such as butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,5-dimethyl styrene; alkoxy such as p-methoxy styrene, o-methoxy styrene, m-methoxy styrene Styrenes; p-chlorostyrene, m-k Halogenated styrenes such as chlorostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene; trimethylsilylstyrene, vinylbenzoic acid and the like.

[V] Maleic anhydride and its substitutes Maleic anhydride represented by formula (II) and its substitutes include maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride And maleic anhydrides such as these and substituted products thereof.

[Vi] Maleic acid and its ester Maleic acid represented by the formula (II) and its ester include maleic acid, methyl maleic acid, dimethyl maleate, diethyl maleate, dibutyl maleate, monomethyl maleate, maleic acid and the like These esters are mentioned.

[Vii] Maleimide and its Substitutes Maleimides represented by formula (II) and their substitutes include maleimides such as maleimide, N-alkyl-substituted maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and the like The substitution body of this is mentioned.

The vinyl monomer represented by the formula (II) is preferably a vinyl monomer having a glass transition temperature (Tg) of 20 ° C. or lower from the viewpoint of increasing the open time.
As the vinyl monomer represented by the formula (II) having a glass transition temperature of 20 ° C. or lower as the polymer, [i] acrylic acid and its derivatives are acrylic acid having a long-chain alkyl ester group and its derivatives. Specific examples include acrylate esters containing long-chain alkyls such as butyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate,
[Ii] The α-alkyl substituted methacrylic acid and acrylic acid are α-alkyl substituted methacrylic acid having a long-chain alkyl ester group, specifically, acrylic acid having the long-chain alkyl ester group and A compound having a methyl group as an α-alkyl group of the derivative;
[Iii] Vinyl esters and derivatives thereof include vinyl caprylate having a long-chain alkyl ester group, vinyl octylate, vinyl caprate, vinyl undecanoate, vinyl myristate, vinyl palmitate, and vinyl stearate,
[Iv] Examples of styrene and its derivatives include p-propylstyrene and p-butylstyrene.
Among these, as a preferable vinyl monomer represented by the formula (II), butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, and the like can be effectively provided with low-temperature flexibility. It is an acrylate ester containing a long chain (for example, 6 to 18 carbon atoms) alkyl.

The content in the reactive polyolefin of the structure (C) derived from the vinyl monomer represented by the formula (II) is 1 to 35% by weight, preferably 1 to 30% by weight, more preferably 2 to 25% by weight.
When the content of the structure (C) is 1% by weight or more, the open time can be extended. On the other hand, when the content of the structure (C) is 35% by weight or less, the mechanical strength of the reactive polyolefin is not lowered, which is preferable.

The content of the structure (C) in the reactive polyolefin can be measured by a known method such as NMR, infrared absorption spectrum, or titration.
For example, when the structure (B) of the reactive polyolefin is polypropylene, the infrared absorption spectrum method uses a sample with a clear composition in advance, for example, characteristic absorption based on C═O bonds (1780.0 to 1700.0 cm ^{− 1} ) Create a calibration curve based on the numerical values corrected (thickened) using the characteristic absorption of 4500.0-3850.0cm ^-1 , which is the combined sound of C-H stretch of polyolefin and various peaks in the fingerprint region. The method of calculating by this is mentioned.
In addition, when the reactive polyolefin has a structure (C) derived from two or more kinds of vinyl monomers, a calibration curve may be prepared in advance based on the respective characteristic absorption bands. When the characteristic absorption band overlaps with two types of vinyl monomers, first determine the monomer (*) content from the different absorption bands derived from one monomer (*), and subtract the monomer (*) from the overlapping characteristic absorption The remainder can also be determined as the content of other monomers.
In addition to the above method, the content ratio of the structure (C) can be directly determined by NMR.

  The reactive polyolefin of the present invention can have a structure (D) derived from the crystalline polyolefin (2). The crystalline polyolefin (2) will be described later.

  Content in the reactive polyolefin of the structure (D) is 0.1 to 30% by weight, preferably 0.1 to 25% by weight, and more preferably 0.1 to 20% by weight. Content of structure (D) can be measured similarly to structure (C).

The reactive polyolefin of the present invention may have the structures (A) and (B), and optionally the structures (C) and (D). The structures (A) and (B) and the arbitrary structures (C) The total content of the structure (D) is, for example, 75% or more, 80% or more, 90% or more, 92% or more, 95% or more, 96% or more, 98% or more, or 99% by weight. % Or more and 100% by weight.
In addition to the structures (A, (B), (C), (D), the reactive polyolefin of the present invention may contain an antioxidant, an ultraviolet absorber, a pigment and the like.

[Method for producing reactive polyolefin]
The reactive polyolefin of the present invention has a mesopentad fraction [mmmm] in the range of 20 to 80 mol%, a weight average molecular weight (Mw) in the range of 10,000 to 500,000, and a molecular weight distribution (Mw / Mn) of 1. 100 parts by weight of a polyolefin (1) obtained by polymerizing at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms in the range of 5 to 4.0; vinyl alkoxysilane represented by the following formula (I) It can be produced by reacting 0.5 to 25 parts by weight; and 0.01 to 5 parts by weight of an organic peroxide in a temperature range of 120 to 260 ° C. under the molten state of the polyolefin (1). However, polyolefin (1) is not homopolyethylene.
^{_{CH 2 = CR 1 -Si (OR}} 2) 3-n R 3 n (I)
(In the formula, ^{R 1} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms.
n is an integer of 0, 1 or 2. )

The polyolefin (1) corresponds to the structure (B) of the reactive polyolefin, and specific examples, combinations, and the like are the same as those of the structure (B).
Mesopentad fraction [mmmm] is in the range of 20 to 80 mol%, weight average molecular weight (Mw) is in the range of 10,000 to 500,000, and molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4.0. A certain polyolefin (1) is obtained by polymerizing one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms using hydrogen as a molecular weight regulator in the presence of a main catalyst, a co-catalyst and organoaluminum described later. Can be manufactured.

As the main catalyst used for the production of the polyolefin (1), a metallocene catalyst can be used. The metallocene catalyst is preferably a double bridged metallocene catalyst or a C ₁ symmetric ansa metallocene compound, more preferably a double bridged metallocene catalyst.

Examples of the double bridged metallocene catalyst include bibridged complexes represented by the following formula (I ′).

In the above 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 terminal vinylidene group 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) is shown, and a crosslinked structure is formed through A ¹ and A ² . E ¹ and E ² may be the same as 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;
X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of X 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 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group 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 a divalent bridging group that binds two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they may be the same as each other 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. Examples of such a crosslinking group include those represented by the formula (a), and specific examples thereof include a methylene group, an ethylene group, an ethylidene group, a propylidene group, an isopropylidene group, a cyclohexylidene group, 1 , 2-cyclohexylene group, vinylidene group (CH ₂ = C =), dimethylsilylene group, diphenylsilylene group, methylphenylsilylene group, dimethylgermylene group, dimethylstannylene group, tetramethyldisiylene group, diphenyldisiylene group Etc. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.

(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 formula (I ′) include specific examples described in WO2008 / 066168 and WO2008 / 047860.
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 above formula (I ′), the compounds represented by the formula (II ′) are preferable.

In the above formula (II ′), M represents a metal element of Groups 3 to 10 of the periodic table, and A ^1a and A ^2a each represent a bridging group represented by the formula (a) in the above formula (I ′). _{shows, CH 2, CH 2 CH 2} , (CH 3) 2 C, (CH 3) 2 C (CH 3) 2 C, the _{(CH 3)} 2 Si, and _{(C 6 H 5)} 2 Si 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. Among these, as R ⁴ and R ⁵ , a group containing a hetero atom such as halogen, oxygen, or silicon is preferable because of high polymerization activity. As R < ⁶ > -R < ¹³ >, a hydrogen atom or a C1-C20 hydrocarbon group is preferable. X and Y are the same as those in formula (I ′). q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.

Among the transition metal compounds represented by the above formula (II ′), when both indenyl groups are the same, examples of the transition metal compounds in Group 4 of the periodic table include those described in WO2008 / 066168 and WO2008 / 047860. An example is given.
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 formula (II ′), when R ⁵ is a hydrogen atom and R ⁴ is not a hydrogen atom, examples of the transition metal compound belonging to Group 4 of the periodic table include WO2008 / 066168 and Specific examples described in WO2008 / 047860 can be 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.

The C ₁ symmetric ansa metallocene compound is a transition metal compound represented by the following formula (I ″).

In formula (I ″), A ¹ and A ² are each a conjugated 5-membered ring ligand, and at least one of A ¹ and A ² is an adjacent substituent on the conjugated 5-membered ring ligand. Have a 7 to 10 membered condensed ring formed including two atoms of a 5-membered ring, and Q is a bonding group that bridges two conjugated 5-membered ring ligands at an arbitrary position, M represents a transition metal atom selected from Group 4 of the periodic table, and X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkylamide group, or a halogenated carbon atom bonded to M. A hydrogen group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a silicon-containing hydrocarbon group, and a sulfur-containing group are shown.

Specific examples of the conjugated 5-membered ring ligand include a cyclopentadienyl group which may have a substituent.
Specific examples of the substituent include hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, phenyl group, naphthyl group, Examples include butenyl, butadienyl, and triphenylcarbyl groups.
Examples of the substituent other than the hydrocarbon group include hydrocarbon residues containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Specific examples thereof include methoxy group, ethoxy group, phenoxy group, furyl group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, carbazolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group. , Dimethoxyboron group, thienyl group and the like.
Examples of other substituents include a halogen atom or a halogen-containing hydrocarbon group. Specific examples thereof include chlorine, bromine, iodine, fluorine, trichloromethyl group, chlorophenyl group, chlorobiphenyl group, chloronaphthyl group, trifluoromethyl group, fluorophenyl group, fluorobiphenyl group, fluoronaphthyl group, pentafluorophenyl group. Etc.

At least one of A ¹ and A ² is bonded to an adjacent substituent on the conjugated 5-membered ring ligand to form a 7-10 membered condensed ring including 2 atoms of the 5-membered ring. Specific examples thereof include compounds such as azulene and derivatives thereof. More specifically, hydroazurenyl group, methylhydroazurenyl group, ethylhydroazurenyl group, dimethylhydroazurenyl group, methylethylhydroazurenyl group, methylisopropylhydroazurenyl group, methylphenylisopropylhydroazurenyl group, various types Hydrogenated azulenyl group, bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -undecanyl group, ethyl-bicyclo- [6.3.0] -undecanyl group, Phenyl-bicyclo- [6.3.0] -undecanyl group, methylphenyl-bicyclo- [6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -undecanyl group, methyldiphenyl- Bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -u Decadienyl group, methylphenyl-bicyclo- [6.3.0] -undecadienyl group, ethylphenyl-bicyclo- [6.3.0] -undecadienyl group, methylisopropyl-bicyclo- [6.3.0] -undecadienyl group Bicyclo- [7.3.0] -dodecanyl group and derivatives thereof, bicyclo- [7.3.0] -dodecadienyl group and derivatives thereof, bicyclo- [8.3.0] -tridecanyl group and derivatives thereof, bicyclo -[8.3.0] -Tridecadienyl group and derivatives thereof are exemplified.

Examples of the substituent for each group include the hydrocarbon groups described above, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur, halogen atoms, or halogen-containing hydrocarbon groups. Q represents a binding group that bridges two conjugated 5-membered ring ligands at an arbitrary position. That is, Q is a divalent linking group and crosslinks A ¹ and A ² . There is no particular limitation on the type of Q. Specific examples thereof include (a) a divalent hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically, An unsaturated hydrocarbon group such as an alkylene group, a cycloalkylene group, and an arylene, a haloalkylene group, a halocycloalkylene group, (b) a silylene group or an oligosilylene group, and (c) a carbon number of usually 1 to 20, preferably 1 to A silylene group or an oligosilylene group having 12 hydrocarbon groups or halogenated hydrocarbon groups as a substituent, (d) germylene group, (e) a hydrocarbon group or halogenated hydrocarbon group usually having 1 to 20 carbon atoms. Examples thereof include a germylene group as a substituent. In these, the silylene group or germylene group which has an alkylene group, a cycloalkylene group, an arylene group, and a hydrocarbon group as a substituent is preferable.

M represents a transition metal atom selected from Group 4 of the periodic table, and is preferably zirconium or hafnium.
X and Y are each independently a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an alkylamide group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a phosphorus-containing hydrocarbon. Group, silicon-containing hydrocarbon group, sulfur-containing group. Carbon number in each said hydrocarbon group is 1-20 normally, Preferably it is 1-12. Among these, a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamide group, a diethylamide group, and a sulfinate group are preferable.

Specific examples of the C ₁ symmetric ansa metallocene compound include specific examples described in JP-A-2003-231714.

  The co-catalyst of the polyolefin (1) is a compound that can react with the transition metal compound as the main catalyst to form an ionic complex, and examples thereof include aluminoxane, borate compounds and clay minerals, and borate compounds are preferable.

Examples of the aluminoxane as a promoter include a chain aluminoxane represented by the following formula (V) and a cyclic aluminoxane represented by the following formula (IV).
(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, or an arylalkyl group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms) or a halogen atom.
w represents an average degree of polymerization and is usually an integer of 2 to 50, preferably 2 to 40.
R ¹⁵ may be the same or different from each other. )

These aluminoxanes may be used alone or in combination of two or more.
The aluminoxane may be insoluble in toluene.

The aluminoxane can be produced by a known method, for example, a method in which an alkylaluminum is brought into contact with a condensing agent such as water.
Specifically, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water; a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later; There are a method of reacting crystallization water, water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound; a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting with water.

  Specific examples of the borate compound that is a co-catalyst are described in WO2008 / 047860. These can be used individually by 1 type or in combination of 2 or more types. When the molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate and tetrakis (per Fluorophenyl) methylanilinium borate and the like are preferred.

  The clay minerals that are co-catalysts include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, serpentine such as chrysotile, lizardite and antigolite. Tribes, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. , Gyrome clay, hysingelite, pyrophyllite, ryokdee stone group and the like. These may form a mixed layer.

As an organoaluminum compound used for manufacture of polyolefin (1), the specific example as described in WO2008 / 047860 is mentioned. 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 preferred, and triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum are more preferred. preferable.

In producing the polyolefin (1), the amount of the main catalyst 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 to} 1.2 × 10 ⁻⁵ mol / L, particularly preferably 0.3 × 10 ^{−6 to} 1.0 × 10 ⁻⁵ mol / L It is. When the amount of the main catalyst used is 0.1 × 10 ⁻⁶ mol / L or more, the catalyst activity is sufficiently expressed, and when it is 1.5 × 10 ⁻⁵ mol / L or less, the heat of polymerization is easily removed. can do.
The main catalyst / promoter, which is the ratio of the main catalyst to the cocatalyst, is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in terms of molar ratio. When the main catalyst / co-catalyst 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 polyolefin (1).
The main catalyst / organoaluminum compound, which is the ratio of the main catalyst to the organoaluminum compound used, is preferably 1/1 to 1/10000, more preferably 1/5 to 1/2000, and even more preferably 1/10 in molar ratio. ~ 1/1000. By using the organoaluminum compound, the polymerization activity per transition metal can be improved. When the main catalyst / organoaluminum compound is in the range of 1/1 to 1/10000, the balance between the addition effect of the organoaluminum compound and the economy is good, and a large amount of aluminum is present in the polyolefin (1). There is no fear.

  In the production of the polyolefin (1), preliminary contact can be carried out using the main catalyst and promoter described above or the main catalyst, promoter and organoaluminum compound. The preliminary contact can be performed by bringing the main catalyst into contact with, for example, a cocatalyst, but 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 catalyst activity and reducing the proportion of the cocatalyst used.

  There are no particular restrictions on the polymerization temperature, polymerization pressure, and polymerization time when producing the polyolefin (1), but in general, optimum settings can be made in consideration of productivity and process capability from the following ranges. . That is, the polymerization temperature is usually −20 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., the polymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 10 MPa, more preferably 0.5 MPa to 4 MPa, polymerization time. Can be selected from the range of 0.1 to 10 hours, preferably 0.3 to 7 hours, more preferably 0.5 to 6 hours.

The polyolefin (1) is preferably a polyolefin having 0.5 to 1.0 terminal unsaturated groups (for example, terminal vinylidene groups) per molecule, and when the polyolefin is produced, the main catalyst is preferably double. It is a bridged metallocene compound, and the polymerization reaction may be carried out in the presence of a trace amount of hydrogen (hydrogen / main catalyst molar ratio is 10,000 or less). By carrying out the polymerization reaction in the presence of a small amount of hydrogen, a significant improvement in terminal vinylidene group selectivity can be obtained.
Although there is no restriction | limiting in particular about the polymerization method at the time of manufacturing the polyolefin which has 0.5-1.0 terminal unsaturated group per molecule, Solution polymerization and bulk polymerization are preferable. In addition, either a batch method or a continuous polymerization method can be applied. Solvents used for solution polymerization include saturated hydrocarbon solutions such as hexane, heptane, butane, octane and isobutane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. A solvent is mentioned.

It is preferable that the terminal of the polyolefin (1) has an unsaturated group (for example, vinylidene group), since the unsaturated group is easily subjected to radical attack, so that the reaction with vinylalkoxysilane proceeds easily.
Moreover, since copolymerization with a vinyl monomer (C) and a vinylidene unsaturated group advances and a uniformity improves, it is preferable.

When the terminal unsaturated group is a terminal vinylidene group, the number of terminal vinylidene groups per molecule can be determined by ¹ H-NMR measurement. Based on the terminal vinylidene group appearing in δ 4.8 to 4.6 (2H) obtained from ¹ H-NMR measurement, the content (C) (mol%) of the terminal vinylidene group can be calculated. Furthermore, the number per terminal vinylidene group per molecule can be calculated from the number average molecular weight (Mn) and monomer molecular weight (M) determined from gel permeation chromatography (GPC) by the following formula.
Number of terminal vinylidene groups per molecule (pieces) = (Mn / M) × (C / 100)

In addition to the above method, the number of terminal vinylidene groups can also be determined using ¹³ C-NMR. In this method, all end group species are determined, and their abundance is measured.
The number of terminal vinylidene groups per molecule can be determined from the proportion of terminal vinylidene groups relative to the total amount of terminal groups, and the selectivity of terminal vinylidene groups can be determined from the proportion of terminal vinylidene groups relative to all unsaturated groups.
The measurement of the number of terminal vinylidene groups using ¹ H-NMR and ¹³ C-NMR will be described below using a propylene polymer as an example.

[Measurement of the number of terminal vinylidene groups using ¹ H-NMR]
In the propylene polymer, a methylene group (4.8 to 4.6 ppm) of <2> terminal vinylidene group and a methylene group (5.10 to 4.90 ppm) of <1> terminal vinyl group were observed, and the ratio to the total propylene Can be calculated by the following equation. <3> corresponds to the peak intensity corresponding to the methine, methylene, and methyl groups of the propylene chain (0.6 to 2.3 ppm).
Terminal vinylidene group amount (A) = (<2> / 2) / [(<3> + 4 × <1> / 2 + 3 × <2> / 2) / 6] × 100 Unit: mol%
Terminal vinyl group amount (B) = (<1> / 2) / [(<3> + 4 × <1> / 2 + 3 × <2> / 2) / 6] × 100 Unit: mol%

[Measurement of the number of terminal vinylidene groups using ¹³ C-NMR]
In the propylene polymer, <5> terminal methyl group (near 14.5 ppm) of n-propyl terminal, <6> terminal methyl group (near 14.0 ppm) of n-butyl group, <4> iso-butyl terminal A methine group (near 25.9 ppm) and a <7> terminal vinylidene group methylene group (near 111.7 ppm) are observed.

The peak intensity of the amount of terminal vinyl groups in ¹³ C-NMR is calculated as follows using (A) and (B) obtained by ¹ H-NMR spectrum.
¹³ C-NMR terminal vinyl group content peak intensity = (B) / (A) × <7>
Here, the total concentration (T) of the end groups is expressed as follows.
T = (B) / (A) × <7> + <4> + <5> + <6> + <7>
Therefore, the ratio of each terminal is as follows.
(C) Terminal vinylidene group = <7> / T × 100 Unit: mol%
(D) Terminal vinyl group = (B) / (A) × <7> × 100
(E) n-propyl terminal = <5> / T × 100
(F) n-butyl group terminal = <6> / T × 100
(G) iso-butyl end = <4> / T × 100
The number of terminal vinylidene groups per molecule is 2 × (C) / 100 units: pieces / molecule.

  The vinyl alkoxysilane represented by the formula (I) used for the production of the reactive polyolefin of the present invention corresponds to the structure (A) of the reactive polyolefin, and specific examples thereof are the same as those of the structure (A).

The addition amount of the vinylalkoxysilane represented by the formula (I) is 0.5 to 25 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 100 parts by weight of the polyolefin (1). 5 to 15 parts by weight.
When the addition amount of vinyl alkoxysilane is less than 0.5 part by weight, the effect of developing the heat resistance of the reactive polyolefin may be reduced. On the other hand, when the amount of vinyl alkoxysilane added exceeds 25 parts by weight, the heat resistance is improved, but the reactive polyolefin becomes hard and the elasticity may be lowered.

From the viewpoint of the uniformity of the reactive polyolefin, it is preferable to select and use a vinyl alkoxysilane having poor homopolymerization. More preferably, the vinyl alkoxysilane has low homopolymerization and high radical addition reactivity.
When the homopolymerizability of vinyl alkoxysilane is high, a long alkoxysilane chain may be locally formed in any part of the polyolefin (1) chain. In addition, a polymer consisting only of vinylalkoxysilane without being added to the polyolefin (1) may be produced as a by-product, and a highly uniform polymer reaction product may not be provided. Furthermore, since there is no alkoxy group so as to sandwich a chain of polyolefin (1) effective for crosslinking, heat resistance may not be exhibited. Such reactivity differences appear in the solid state form of the reactive polyolefin. Specifically, the sea-island structure is generated, and only the island portion having a high vinylalkoxysilane content is cross-linked, and the cross-linking density of the sea portion is low.
Similarly, acetone-soluble parts that do not have an effect on crosslinking increase.
From the above, trialkoxysilanes such as trimethoxyvinylsilane are suitable, and polar vinyl monomer types, such as methacryloxypropyltrimethoxysilane, have high homopolymerizability and are presumed to cause the above problems.

  The organic peroxide used for the production of the reactive polyolefin is not particularly limited, but is preferably an organic peroxide that decomposes at a temperature at which the polyolefin (1) and the crystalline polyolefin (2) to be described later melt, more preferably 1 Organic peroxide having a minute half-life temperature of 140 to 270 ° C.

Specific examples of the organic peroxide that can be used include diisobutyryl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, and di-sec-butyl peroxydicarbonate. 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxy Neodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilaurylper Oxide, 1,1,3,3-tetramethylbutyl Oxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methyl) Benzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, 1,1-di (t-butylperoxy) -2-methylcyclohexane 1,1-di (t-hexylpropylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) Cyclohexasan, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxy Propyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 3,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-di- (t -Butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valate, di (2-t-butylperoxyisopropyl) benzoate, dicumyl peroxide, Di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-Menthans hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and the like.
Of these organic peroxides, dicumyl peroxide or 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, di (2- t-butylperoxyisopropyl) benzoate.

The addition amount of the organic peroxide is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the polyolefin (1).
When the amount of the organic peroxide added is less than 0.01 parts by weight, the radical reaction may not proceed sufficiently. On the other hand, when the addition amount of the organic peroxide is more than 5 parts by weight, there is a risk that the odor of the decomposition product or the like may become strong, and yellowing may easily occur.

  The organic peroxide is water, an inert solvent, in order to improve its quantitative supply, reduce the risk, improve the adhesion to the polyolefin (1) and / or the crystalline polyolefin (2), and improve the impregnation. Or you may use in combination with an inorganic compound. Also, a master batch of polyolefin (1) containing organic peroxide (1), crystalline polyolefin (2) containing organic peroxide, or polyolefin (1) and (2) containing organic peroxide was prepared. It may be used.

In the method for producing a reactive polyolefin of the present invention, a vinyl monomer represented by the following formula (II) is preferably further used.
X ¹ -CR ³ = CR ⁴ -X ² formula (II)
(Wherein X ¹ and X ² are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X ¹ and X ² are bonded to each other to form a ring. Provided that when ^one of X ¹ and X ² is a hydrogen atom, the other is a functional group containing an oxygen, nitrogen, or sulfur atom.
R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

  The vinyl monomer represented by the formula (II) used for the production of the reactive polyolefin of the present invention corresponds to the structure (C) of the reactive polyolefin, and specific examples thereof are the same as those of the structure (C).

The addition amount of the vinyl monomer represented by the formula (II) is preferably 1 to 40 parts by weight, more preferably 2 to 35 parts by weight, still more preferably 100 parts by weight of the polyolefin (1). 4 to 30 parts by weight.
When the added amount of the vinyl monomer represented by the formula (II) is less than 1 part by weight, the effect of improving the open time may be lowered. On the other hand, when the addition amount of the vinyl monomer represented by the formula (II) exceeds 40 parts by weight, the mechanical strength of the reactive polyolefin may be lowered.

In the method for producing a reactive polyolefin of the present invention, it is preferable to use the crystalline polyolefin (2) from the viewpoint of further improving the heat resistance.
Examples of the crystalline polyolefin (2) include high-density polyethylene; polypropylene resin and polybutene-based homopolypropylene, random polypropylene, block polypropylene, homopolybutene-1; linear low-density polyethylene, ethylene / 1- Butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / decene copolymer, ethylene / α-olefin copolymer such as ethylene / eicocene copolymer, ethylene vinyl acetate copolymer Saponified polymer, ethylene acrylic acid copolymer, ethylene methyl acrylate copolymer, ethylene copolymer in which (meth) acrylic acid methyl ester portion is changed to butyl, hexyl, octyl, 2-ethylhexyl, decyl group, etc. An olefin copolymer containing a polar group such as Low-density polyethylene made of ethylene alone, which is a low-density polyethylene produced by the pressure radical method, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer and its metal neutralized product (so-called ionomer), ethylene / methyl methacrylate And copolymers such as copolymers and ethylene / ethyl acrylate copolymers. The “crystallinity” of the crystalline polyolefin (2) indicates that a melting point exists between 20 and 170 ° C. in DSC measurement.

  The crystalline polyolefin (2) is preferably an ethylene polymer such as high density polyethylene or polyethylene having an ethylene content of 90% by weight or more, or a crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80 mol%. . The crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80 mol% is preferably a polypropylene-based resin or a polybutene-based resin, more preferably a homopolypropylene, a random polypropylene, or a block polypropylene.

The crystalline polyolefin (2) preferably has a polypropylene average weight average molecular weight (Mw) measured by GPC in the range of 3000 to 400,000.
The crystalline polyolefin (2) preferably has a crystal melting peak temperature measured by DSC in the range of 80 to 168 ° C.

The addition amount of the crystalline polyolefin (2) is 0.2-30 parts by weight, preferably 0.2-25 parts by weight, more preferably 0.2-0.2 parts by weight with respect to 100 parts by weight of the polyolefin (1). 20 parts by weight.
The addition of the crystalline polyolefin (2) is aimed at imparting heat resistance, but when the addition amount exceeds 30 parts by weight, the open time may be lowered and the low temperature coating property may be lowered.

As another form, in the manufacturing method of the reactive polyolefin of this invention, it is preferable that crystalline polyolefin (2) satisfy | fills the following physical property from a viewpoint which can provide low temperature flexibility.
-Glass transition temperature (Tg) is -20 degrees C or less-Weight average molecular weight (Mw) is 3000-400000.

  Specific examples of the crystalline polyolefin (2) capable of imparting low-temperature flexibility include high-density polyethylene, low-density polyethylene by high pressure method, polybutene, polyhexene, polyoctene, polydecene, polyecene, and other α-olefin polymers such as ethylene. Butene copolymer, ethylene hexene copolymer, ethylene octene copolymer, ethylene / decene copolymer, ethylene / α-olefin copolymer such as ethylene / eicosene copolymer, ethylene vinyl acetate copolymer, ethylene acetate Saponified vinyl copolymer, ethylene (meth) acrylic acid copolymer, ethylene (meth) methyl acrylate copolymer, (meth) acrylic acid methyl ester moiety ethyl, butyl. Examples thereof include olefin copolymers containing polar groups such as ethylene copolymers changed to hexyl, octyl, 2-ethylhexyl, decyl groups, and the like. Preferably, an ethylene / α olefin copolymer, a low density polyethylene, an ethylene vinyl acetate copolymer, and the like are used.

  A preferable composition ratio is 0.2 to 30 parts by weight, more preferably 1 to 30 parts by weight, 2 to 30 parts by weight, and 2.5 to 25 parts by weight with respect to 100 parts by weight of the polyolefin (1). is there. If the amount is less than 0.2 parts by weight, the low-temperature flexibility may not be sufficiently imparted. If the amount exceeds 30 parts by weight, the compatibility is deteriorated and separated, so that the heat resistance performance may not be exhibited.

Moreover, as another form, in the manufacturing method of the reactive polyolefin of this invention, it is preferable that crystalline polyolefin (2) satisfy | fills the following physical property from a viewpoint that a cure rate can be controlled.
-Weight average molecular weight (Mw) is 3000-200000
・ Glass transition temperature (Tg) is −10 ° C. or lower. ・ When polar group is contained, the content of polar group is 1 to 50% by weight
Specific examples of the crystalline polyolefin (2) capable of controlling the curing rate are the same as the specific examples of the crystalline polyolefin (2) capable of imparting the low-temperature flexibility. Preferably, ethylene alpha olefin copolymer, low density polyethylene, etc. are mentioned.

  As a preferable composition ratio, a blending amount is determined and used so as to obtain a desired curing rate between 0.2 and 30 parts by weight with respect to 100 parts by weight of the polyolefin (1). If it is less than 0.2 parts by weight, the curing rate is small, and it may take a long time to reach the desired heat-resistant adhesive strength. When it exceeds 30 parts by weight, the stability is lowered, and thus the viscosity increases during long-term storage and storage, and the storage stability may be lowered.

  In the method for producing a reactive polyolefin of the present invention, the polyolefin (1) is melted and the polyolefin (1), the vinylalkoxysilane represented by the formula (I) and the organic peroxide are melt-reacted at a temperature of 120 to 260 ° C. . The melt reaction can be performed by, for example, a melt batch method, a melt extrusion method, or the like.

  When at least one of the vinyl monomer represented by the formula (II) and the crystalline polyolefin (2) is used, at least one of the vinyl monomer and the crystalline polyolefin (2) is used in the melt reaction stage. Polyolefin (1), vinyl alkoxysilane represented by the formula (I), and organic peroxide may be present together.

For example, specifically, polyolefin (1) 100 parts by weight, vinylalkoxysilane represented by formula (I) 0.5-25 parts by weight, crystalline polyolefin (2) 0.2-30 parts by weight, and organic peroxide A process for producing a reactive polyolefin, in which 0.01 to 5 parts by weight of an oxide are reacted in a temperature range of 120 to 260 ° C. under the molten state of the polyolefin (1), or
100 parts by weight of polyolefin (1), 0.5 to 25 parts by weight of vinylalkoxysilane represented by formula (I), 1 to 40 parts by weight of vinyl monomer represented by formula (II), and organic peroxide A process for producing a reactive polyolefin in which 01 to 5 parts by weight are reacted in a temperature range of 120 to 260 ° C. under the molten state of the polyolefin (1), or
100 parts by weight of polyolefin (1), 0.5 to 25 parts by weight of vinylalkoxysilane represented by formula (I), 1 to 40 parts by weight of vinyl monomer represented by formula (II), crystalline polyolefin (2) 0 There is a method for producing a reactive polyolefin in which 2 to 30 parts by weight and 0.01 to 5 parts by weight of an organic peroxide are reacted in a temperature range of 120 to 260 ° C. in a molten state of the polyolefin (1).

For example, when crystalline polyolefin (2) is used, the polyolefin (1) and the crystalline polyolefin (2) are melt-reacted in the presence of the organic peroxide and vinyl alkoxysilane, so that the crystalline polyolefin is added to the reactive polyolefin. Compared with the case where (2) is added after manufacture, the dispersibility is high, and the mechanical properties, heat resistance, and adhesion performance are excellent.
In addition, the polyolefin (1) and the crystalline polyolefin (2) are melt-reacted in the presence of the organic peroxide and vinyl alkoxysilane, thereby improving the uniformity of the reactive polyolefin and improving the performance such as low-temperature characteristics. Can be preferable.

  Moreover, when using a vinyl monomer, it is thought that a vinyl monomer copolymerizes with the terminal unsaturated group produced | generated by decomposition | disassembly of polyolefin (1), and one part or all. The copolymer of decomposed polyolefin (1) and vinyl monomer contained in the reactive polyolefin increases the uniformity of the reactive polyolefin. As a result, not only the mechanical properties are improved, but also the controllability of the curing rate, the heat resistance performance and the adhesion performance are improved. In particular, when the vinyl monomer is a long-chain alkyl ester such as 2-ethylhexyl acrylate, the glass transition temperature can be lowered to improve the low temperature characteristics.

Factors that can control the primary structure of the reactive polyolefin of the present invention include the following (a) to (g), and the conditions are as described above or below.
a) Stereoregularity of polyolefin (1),
b) Structure and amount of vinylalkoxysilane c) Organic peroxide species and amount used,
d) melting reaction temperature,
e) Residence time or reaction time,
f) Stirring strength g) Terminal structure of polyolefin (1)

The viscosity of the reactive polyolefin can be controlled to a desired viscosity (B viscosity = 2000 to 80000 mPas) by reducing the molecular weight of the polyolefin (1). The most effective method is a method of changing the organic peroxide concentration in the presence of a certain amount of vinylalkoxysilane, and then a method of controlling by changing the temperature.
Specifically, the organic peroxide is added in an amount of 0.01 to 5 parts by weight in a temperature range where polyolefin radicals are sufficiently generated at a temperature of 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. or higher. Depending on how to change in range. Or, it is based on a method of changing the temperature while keeping the organic peroxide constant.

Moreover, content of vinyl alkoxysilane can be controlled by changing vinyl alkoxysilane in the range of 0.5-25 weight part as above-mentioned.
A reactive polyolefin having a desired viscosity and alkoxysilane content can be produced by first setting conditions for controlling the viscosity to a desired value and then changing the amount of vinylalkoxysilane charged. Although the amount of vinylalkoxysilane added is somewhat affected by the concentration of organic peroxide, the fluctuation is slight, so that the production conditions can be determined by repeating the above operation once or twice.

The uniformity of the reactive polyolefin can be controlled by performing the melting reaction in a uniform reaction field.
For example, since the polyolefin (1) has low stereoregularity and a low melting point, it does not require a high temperature to be in a molten state, and further a vinyl alkoxysilane such as trimethoxyvinylsilane is uniformly dissolved in the molten state, The melting reaction can be performed in a uniform reaction field.
On the other hand, polar vinyl monomer types such as methacryloxypropyltrimethoxysilane are separated in the molten state and the reaction field becomes non-uniform. Thus, since it is a uniform state in a low-temperature melted state, a uniform reaction is possible, and as a result, a uniform reactive polyolefin can be produced.
In addition, polyolefin (1) absorbs vinylalkoxysilane in a solid state like a pellet, has no wetness on the surface, and becomes a highly fluid pellet. Therefore, it is very easy to handle as an impregnated pellet.

  Moreover, since the main component is polyolefin (1) that does not contain homopolyethylene, such as propylene base or 1-butene base, cross-linking between polyolefins that normally occurs in homopolyethylene is suppressed. Therefore, it is easy to reduce the viscosity, and it is possible to produce a reactive polyolefin excellent in coatability.

When the melt reaction is carried out by a melt batch method, it is preferably carried out in an inert gas atmosphere such as nitrogen, argon or helium. For example, the polyolefin (1) or the polyolefin (1) and the crystalline polyolefin (2) are stirred. The melt reaction can be carried out by continuously or intermittently adding the organic peroxide and the vinylalkoxysilane after being heated and melted.
When at least one of the vinyl monomer represented by the formula (II) and the crystalline polyolefin (2) is used in the molten batch method, it may be added together with the organic peroxide and the vinyl alkoxysilane. Each addition may be performed independently. Moreover, you may mix arbitrary 2 or more types of components, and may add from one or more insertion ports.
The addition time of the above components is usually in the range of 1 minute to 10 hours, and the reaction may be continued for 1 minute to 5 hours after the dropwise addition.

The stirring state affects the molecular weight of the reactive polyolefin and the amount of vinylalkoxysilane added.
When stirring and mixing is insufficient, the decrease in molecular weight is small, and the addition amount of vinylalkoxysilane may also decrease. If a sufficiently mixed state is maintained, the molecular weight and the alkoxysilane addition amount do not vary greatly depending on the stirring speed. It is preferable to react in such a stable state. Usually, the rotation speed is in the range of 50 to 800 rpm, preferably 100 to 800 rpm, more preferably 120 to 700 rpm.

When the melt reaction is carried out by a melt extrusion method, a single-screw or twin-screw melt extruder can be used, preferably an extruder having an inlet in the middle of the barrel and capable of degassing under reduced pressure, It is an extruder with L / D = 10 or more.
In the melt extrusion method, the polyolefin (1), the vinyl alkoxysilane represented by the formula (I), and the organic peroxide are brought into contact in a molten state, and only the vinyl monomer and the organic peroxide are in the reaction temperature range. A method that excludes the case of contact can be adopted.
The reaction time in the above case is an average residence time of, for example, 20 seconds to 10 minutes.

Specifically, the melt reaction is carried out by a melt extrusion method in which the polyolefin (1) or the polyolefin (1) and the crystalline polyolefin (2) are preliminarily represented by the formula (I), a vinyl alkoxysilane, an organic peroxide. In addition, the vinyl monomer represented by the arbitrary formula (II) may be impregnated in whole or in part and used as impregnated pellets that have no wetness or adhesion on the polyolefin pellet surface or have reduced adhesion.
In addition to the above, all the raw materials may be supplied all at once from the upstream hopper and melt extrusion may be carried out. From the upstream hopper, polyolefin (1) or polyolefin (1) and crystalline polyolefin (2 ) And by supplying vinylalkoxysilane, vinyl monomer, and organic peroxide downstream, the melt extrusion can be carried out. Alternatively, polyolefin (1) or polyolefin (1) and crystalline polyolefin (2) and vinylalkoxysilane may be introduced from an upstream hopper, and an organic peroxide may be supplied downstream.

Most preferably, the melting reaction is carried out under conditions that can maintain uniformity in the molten state.
In addition, by using an organic peroxide in the melt reaction, the decomposition of the polyolefin (1) is accompanied, and the molecular weight of the resulting reactive polyolefin is reduced. The ratio of the molecular weight reduction is the weight average molecular weight of the polyolefin (1). (Mw) or a range of 90 to 20% of the average weight average molecular weight (Mw) of the polyolefin (1) and the crystalline polyolefin (2).

The reaction temperature of the melt reaction is 120 to 260 ° C, preferably 130 to 250 ° C, more preferably 140 to 240 ° C.
When the reaction temperature is less than 120 ° C., the reaction does not proceed sufficiently, and the heat resistance performance of the resulting reactive polyolefin may not be exhibited. On the other hand, when the reaction temperature exceeds 260 ° C., the decomposition of vinylalkoxysilane may be accelerated.

  For example, taking the case of production by melt extrusion as an example, the polyolefin (1) supply port is on the uppermost stream side, the supply port for vinylalkoxysilane and organic peroxide is downstream, and the downstream portion is the reaction zone. A vent for removing volatile components exists on the downstream side of the reaction zone, and a discharge port such as a die is provided on the most downstream side. The reaction temperature refers to the temperature of the reaction zone. In the case of Labo Plast Mill (manufactured by Toyo Seiki Co., Ltd.) shown in the examples, it corresponds to the C2 to C5 zones. The temperature in the other region can be appropriately set so as to be normally performed from the viewpoint of setting the supply stability of the polyolefin (1) pellets and the temperature of the discharged resin.

The primary structure of the reactive polyolefin can be controlled by reacting at a temperature and peroxide conditions at which polyolefin radicals are sufficiently generated. The reaction proceeds by a mechanism in which vinylsilane is added under the condition that the polyolefin (1) has a low molecular weight. That is, a radical is generated in the polyolefin (1) chain, which becomes a reaction point, and alkoxysilane is added. On the other hand, radicals generated in the polyolefin (1) chain are cleaved into an unsaturated terminal polyolefin and a radical terminal polyolefin with a certain probability. The radical-terminated polyolefin undergoes an addition reaction with vinylalkoxysilane, and the unsaturated-terminated polyolefin is easily radical-reactive and therefore easily reacts with alkoxysilane. From this, it is important for the addition reaction of alkoxysilane to generate radicals of polyolefin chain, and it reacts while lowering the molecular weight.
The reaction proceeds according to the above reaction mechanism, and the molecular weight of the produced reactive polyolefin is lower than that of the raw material polyolefin (1).
Radicals that cleave at low temperatures are not active enough to generate the tertiary carbon radical of polyolefin (1), and in order to proceed with this reaction, temperatures of 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. A temperature of ℃ or higher is required.
Accordingly, the organic peroxide is preferably one that decomposes in this temperature range to generate radicals, and one that has a one-minute half-life temperature in the range of 140 to 270 ° C.

  From the viewpoint of controlling the primary structure of the reactive polyolefin, it is preferably a reaction time or residence time at which the decomposition of 40% or more of the organic peroxide is completed. The decomposition time is represented by a value calculated using the Arrhenius equation, using the activation energy and frequency factor specific to each organic peroxide.

[Reactive Polyolefin Composition]
The composition containing the reactive polyolefin of the present invention can be suitably used as an adhesive, a coating agent, a filler treatment agent, a paint, a dispersion, an ink, or a resin modifier. Among these, the composition containing the reactive polyolefin of the present invention can be particularly suitably used as an adhesive (hereinafter also referred to as “adhesive composition”).

The adhesive composition of the present invention comprises 100 parts by weight of the reactive polyolefin of the present invention, 0 to 200 parts by weight of a thermoplastic resin, and 0 to 100 parts by weight of oil.
In addition, the said thermoplastic resin is a thermoplastic composition except the reactive polyolefin of this invention, for example, is resin which provides adhesiveness to adhesive composition.

  The tackifying resin is not particularly limited as long as it is a resin generally used in the related field of hot melt adhesives. For example, an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, an aromatic carbonization is used. Examples thereof include hydrogen resins, polyterpene resins, rosin resins, styrene resins, and coumarone indene resins.

Examples of the tackifying aliphatic hydrocarbon resin include polymers having a main component of a mono- or diolefin having 4 to 5 carbon atoms such as 1-butene, isobutylene, butadiene, 1,3-pentadiene, isoprene, and piperidine. Can be mentioned.
As the tackifying alicyclic hydrocarbon resin, a resin obtained by polymerizing a diene component in a petroleum fraction having 4 to 5 carbon atoms after cyclization and dimerization, a resin obtained by polymerizing a cyclization monomer such as cyclopentadiene, Examples thereof include resins obtained by hydrogenating aromatic hydrocarbon resins.
Examples of the tackifying aromatic hydrocarbon resin include resins mainly composed of a vinyl aromatic hydrocarbon having 9 to 10 carbon atoms such as vinyl toluene, indene, and α-methylstyrene.
Examples of the tackifying polyterpene resin include α-pinene polymers, diterpene polymers, terpene phenol copolymers, α-pinene-phenol copolymers, and the like.
The tackifying rosin resin is a rosin such as gum rosin, wood rosin, tall oil or a modified product thereof, and the modified product is a resin subjected to modification means such as hydrogenation, disproportionation, dimerization, esterification, etc. Can be illustrated.
Examples of the tackifying rosin ester include esters such as ethylene glycol, diethylene glycol, glycerin and pentaerythritol.
Examples of the tackifying styrene resin include polymers such as styrene, methylstyrene, α-methylstyrene, and isopropenyltoluene.
Examples of tackifying resins that have been marketed include Idemitsu Petrochemical's Imabu P-125, Imabu P-100, Imabu P-90, Mitsui Chemicals Highlets T1115, Yashara Chemicals Clearon K100, Tonex's Escolez 5300, and Escolez 2101, Alcon P100 manufactured by Arakawa Chemical, Regalrez 1078 manufactured by Hercules, and the like.
Among these, in the adhesive composition of the present invention, it is preferable to use an alicyclic hydrocarbon resin in consideration of compatibility with the modified soft polypropylene and thermal stability.

The content of the tackifying resin in the adhesive composition is 0 to 200 parts by weight of the tackifying resin with respect to 100 parts by weight of the reactive polyolefin, preferably 1 to 150 parts by weight, more preferably 2 to 100 parts. Parts by weight.
When the compounding amount of the tackifying resin is more than 200 parts by weight with respect to 100 parts by weight of the reactive polyolefin, the adhesive composition may become brittle and the adhesive strength may be reduced.

The oil contained in the adhesive composition of the present invention includes a wax, and the oil and the wax are not particularly limited as long as they are oils generally used in related fields of hot melt adhesives. can do. By containing oil, the adhesive composition can achieve both good coatability and high heat resistance due to low viscosity.
Examples of the oil include paraffinic process oil, glycols, and naphthenic oil. Examples of the wax include synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax and atactic polypropylene, petroleum waxes such as paraffin wax and microcrystalline wax, and natural waxes such as wood wax, carnauba wax and beeswax. It is done.

Content of the oil in an adhesive composition is 0-100 weight part with respect to 100 weight part of reactive polyolefin, Preferably it is 0-50 weight part, More preferably, it is 0-20 weight part.
When the oil content is more than 100 parts by weight with respect to 100 parts by weight of the reactive polyolefin, the cohesive strength, heat resistance, creep resistance, etc. of the adhesive composition are greatly reduced, and the appearance is impaired by bleeding. The adhesive may become sticky and cause rash.

The adhesive composition of the present invention is preferably an adhesive composition that further contains 1 × 10 ^{−6 to} 0.5 parts by weight of a curing catalyst and is moisture curable in an atmosphere substantially containing moisture.
The atmosphere in which moisture substantially exists is, for example, a normal room temperature atmosphere, and when the curing rate is managed, the humidity is preferably controlled in the range of 30 to 90%. Moisture curing can also be performed by immersion in water.

  The curing catalyst can impart high heat resistance to the adhesive, such as dibutyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctoate, lead naphthenate, zinc caprylate, cobalt naphthenate, titanium And organic metal compounds such as acid tetrabutyl ester, lead stearate, zinc stearate, cadmium stearate, barium stearate and calcium stearate.

The content of the curing catalyst in the adhesive composition is preferably 1 × 10 ^{−6 to} 0.5 part by weight, more preferably 1 × 10 ^{−4 to} 0.4 part by weight based on 100 parts by weight of the reactive polyolefin. Part, more preferably 1 × 10 ^{−3 to} 0.35 part by weight, and particularly preferably 0.015 to 0.3 part by weight.
When the content of the curing catalyst is less than 1 × 10 ⁻⁶ parts by weight with respect to 100 parts by weight of the reactive polyolefin, there is a possibility that sufficient crosslinking reaction does not proceed and heat resistance cannot be expressed. On the other hand, when the content of the curing catalyst is more than 0.5 parts by weight, the crosslinking reaction may proceed non-uniformly and the surface may be roughened.

The adhesive composition of the present invention preferably further contains a curing accelerator.
As the curing accelerator, specifically, additives such as amines shown below can be used.

(1) Acidic substances, hydrogen halides such as hydrochloric acid, hydrogen peroxide, carbonic acid,
・ Carboxylic acid such as formic acid and acetic acid ・ Sulphonic acid such as benzene sulfonic acid ・ Phosphoric acid ・ Heteropoly acid ・ Inorganic solid acid (2) Basic substance ・ Ammonia base such as ammonia water ・ Amines

Amines are aliphatic or cycloaliphatic, saturated or unsaturated hydrocarbon groups; aromatic hydrocarbon groups: oxygen-containing, sulfur-containing and / or selenium-containing hydrocarbon groups, etc. bonded to one or more nitrogen atoms. A compound.
In the case of a secondary or tertiary amine, each substituent for N may be the same or different, or one or more may be different.

  Primary amines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monobenthylamine, monohexylamine, monohexylamine, octylamine, nonylamine, 1-aminododecane, 1-aminoundecane, dodecylamine 1-aminotridecane, hexadecylamine, 1-aminoheptadecane, octadecylamine, 1-aminonanodecane, vinylamine, allylamine, butenylamine, pentenylamine, hexenylamine, bentadienylamine, hexadienylamine, Cyclopentylamine, cyclohexylamine, cyclooctylamine, p-menthylamine, cyclopentenylamine, cyclohexenylamine, cyclohexahexenylamine, aniline, benzylamine, sodium Ethylamine, naphthyl methylamine, toluidine, Rirenjiamin include ethylenediamine, ethylenetriamine, monoethanolamine, Aminochiofuen, glycine, alanine, phenylalanine, amino acetone, and the like.

  Secondary amines include dimethylamine, diethylamine, dibroviramine, dibutylamine, dipentylamine, dihexylamine, methylethylamine, methylbroviramine, methylbutylamine, methylpentylamine, methylhexylamine, ethyl propylamine, ethylbutylamine , Ethylpentylamine, propylbutylamine, propylpentylamine, bububuylhexylamine, butylpentylamine, pentylhexylamine, divinylamine, diallylamine, dibutenylamine, dipentenylamine, dihexenylamine, methylvinylamine, methylallylamine, Methylbutenylamine, methylpentenylamine, methylhexenylamine, ethylvinylamine, ethylallylamine, ethylbutenylamine , Ethyl benzylenyl amine, ethyl hexenyl amine, propyl vinyl amine, propyl allyl amine, propyl butenyl amine, propyl pentenyl amine, butyl hexenyl amine, butyl vinyl amine, butyl allyl amine, butyl butenyl amine, butyl pentenyl amine, Butylhexenylamine, vinylallylamine, vinylbutenylamine, vinylpentenylamine, vinylhexenylamine, allylbutenylamine, allylbenthenylamine, allylhexenylamine, butenylbenthenylamine, butenylhexenylamine, dicyclopentylamine, N-methylamine Phosphorus, N-ethyl aniline, N-provir aniline, N-butyl aniline, N-methyl toluidine, X-ethyl toluidine, N-buccill virului N-butyltoluidine, N-methylbenzylamine, N-ethylbenzylamine, N-butylbenzylamine, N-butylbenzylamine, N-methylnaphthylamine, N-ethylnaphthylamine, N-butylbenzylnaphthylamine, N -Allylaniline, N-vinyltoluidine, N-allyltoluidine, phenylcyclobenzoylamine, phenylcyclohexylamine, phenylcyclooctylamine, phenylcyclopentenylamine, phenylcyclohexenylamine, phenylcyclopentadienylamine, N-methylanisole, virol , Pyrrolidine, imidazole, biveridine, biverazine, methyl pyrrole, methyl pyrrolidine, methyl imidazole, methyl piperidine, methyl piperazine, ethyl pyrrole, ethyl Gin, ethylimidazole, ethylpepyridine, ethylpiperazine, maleimide, caprolactam, pyrrolidone, morpholine, N-methylglycine, N-methylalanine, N-ethylalanine, N-methylaminothiophene, N-ethylaminothiophene, etc. Is mentioned.

Tertiary amines include trimethylamine, triethylamine, tributylamine, tributylamine, tripentylamine, trihexylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamis, dimethylpentylamine, dimethylhexylamine, diethylpropylamine , Diethylbutylamine, diethylpentylamine, diethylhexylamine, dibutyl butylamine, dibromopentylamine, dibutyl hexylamine, dibutylpentylamine, dibutylhexylamine, dipentylhexylamine, methyldiethylamine, methyldibroviramine, Methyldibutylamine, methyldipentylamine, methyldihexylamine, ethyldiproviramine, ethyldibutylamine, ethyldibutylamine Nethylamine, ethyldihexylamine, propyldipentylamine, bromodihexylamine, butyldihexylamine, methylethylpropylamine, methylethylbutylamine, methylethylhexylamine, methylpropylbutylamine N, N-dimethylaniline, N, N-dimethylpenti Ruamine, N, N-dimethylnaphthylamine, N, N-diethylaniline, N, N-diethylbenzylylamine, N, N-diethylnaphthylamines, N-methylpidogrel, N-methylpidociridine, N-methylimidazole, N-methylpiveridine, N-ethylpyrrole, N-methylpyrrolidine, N-ethylimidazole, viridine, viridazine, virazine, quinoline, quinazoline, quinuclidine, N-methylpidocidone, N-methylmorphol Emissions, N- ethyl pyrrolidone, N one-ethylmorpholine, N, N- dimethyl anisole, N, N- diethyl anisole, N, N- dimethylglycine and the like.
In addition, hydrazine such as dimethylhydrazine can be exemplified.

Among these, those compatible with the reactive polyolefin (1) are preferable from the viewpoint of promoting the curing reaction.
Moreover, when manufacturing an adhesive composition, since it does not evaporate by heating, what has a high boiling point is preferable.
As a preferred specific example, an amine having a total carbon number of 8 or more, more preferably an amine having a total carbon number of 9 or more.

  The content of the curing accelerator in the adhesive composition is 0.05 to 5 parts by weight, preferably 0.07 to 4 parts by weight, more preferably 0 with respect to 100 parts by weight of the reactive polyolefin. 0.1 to 3 parts by weight.

  Moreover, the adhesive composition of this invention can contain a hardening | curing agent further. The curing agent is a compound having two or more crosslinking groups (for example, alkoxysilane groups or silanol groups) that can react with the reactive polyolefin.

The following can be illustrated as a hardening | curing agent which has an alkoxysilane group.
a) Phenylalkoxysilanes such as dimethoxymethylphenylsilane, phenyltrimethoxysilane, diethoxymethylphenylsilane, phenyltriethoxysilane, diethoxydiphenylsilane, dimethoxydiphenylsilane

b) benzylalkoxysilanes such as benzyltriethoxysilane

c) methyltripropoxysilane, methyltriisopropoxysilane, n-propyltriethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltriethoxysilane, Linear hydrocarbon alkoxysilanes such as diethoxyethyloctadecylsilane and octadecyltriethoxysilane

d) Tetraalkoxysilanes such as tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraethoxysilane

e) N-2- (aminomethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminomethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Nitrogen-containing alkoxysilanes such as silane and N-phenyl-3-aminopropyltrimethoxysilane

f) 1,3,5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetrapropoxycyclotetra Siloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetraisopropoxycyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetrabutoxycyclo Cyclic alkoxy oligomers such as tetrasiloxane and 1,3,5,7,9-pentaethoxy-1,3,5,7,9-pentamethylcyclopentasiloxane

g) Chain alkoxy oligomer A chain alkoxy oligomer having a viscosity of 5 to 200 mm ² / s (25 ° C.) and an alkoxy group amount of 10 to 70% by weight is preferable. The alkoxy group is preferably a methoxy group or an ethoxy group. A chain alkoxy oligomer containing a silicon atom and having a methyl group or a phenyl group as a substituent bonded to the silicon atom is preferable.

  Commercially available products include KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, and X-40-9227 manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the curing agent having a silanol alkoxy group include a partial hydrolyzate or hydrolyzate of the above alkoxysilane.
Preferably, the alkoxy group is a methoxy group, and the boiling point is 200 ° C. or higher.

  The content of the curing agent in the adhesive composition is 0.01 to 5 parts by weight, preferably 0.05 to 4.5 parts by weight, and more preferably 0 to 100 parts by weight of the reactive polyolefin. .1 to 4 parts by weight.

  The adhesive composition can contain an antioxidant, a pigment, an ultraviolet absorber and the like in addition to the above components.

  The adhesive composition can be produced by adding other components to the reactive polyolefin. About a hardening | curing agent and a hardening accelerator, it can also mix at the time of manufacture of reactive polyolefin.

The adhesive composition of the present invention is preferably used as a reactive hot melt adhesive.
The reactive hot melt adhesive can be used, for example, for adhesion of automobile interior and exterior materials, adhesion in the field of construction and building materials, adhesion of furniture, and adhesion of home appliance OA equipment.

In the examples and comparative examples, the following characteristics were measured by the following methods.
(1) Mesopentad fraction [mmmm], weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)
It measured by the method as described in the said embodiment.
(2) Number of terminal unsaturated groups The number of vinylidene groups per molecule as terminal unsaturated groups was measured by the method described in the above embodiment.

[Production of low crystalline polypropylene (polyolefin (1))]
Production Example 1
In a stainless steel reactor with an internal volume of 20 L with a stirrer, n-heptane was 24 L / h, triisobutylaluminum was 15 mmol / h, and dimethylanilinium tetrakispentafluorophenylborate, (1,2′-dimethylsilylene) (2 , 1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride and triisobutylaluminum in a weight ratio of 1: 2: 20, and the catalyst component obtained by contacting with propylene was 6 μmol in terms of zirconium. / H was continuously fed.
The polymerization temperature was set to 67 ° C., and propylene and hydrogen were continuously fed so that the hydrogen concentration in the gas phase part of the reactor was 0.74% and the total pressure in the reactor was maintained at 0.75 MPa · G. A polymerization reaction was performed. To the resulting polymerization solution, Irganox 1010 (manufactured by Ciba Specialty Chemicals), which is a stabilizer, is added so that its content is 500 ppm by mass, and n-heptane, which is a solvent, is removed to reduce the content. Crystalline polypropylene was obtained. This low crystalline polypropylene was made into resin pellets by underwater cutting.

The physical properties of the resulting low crystalline polypropylene were as follows:
Stereoregularity [mmmm]: 46 mol%
Weight average molecular weight (Mw): 131000
Molecular weight distribution (Mw / Mn): 1.9
Number of terminal unsaturated groups: 0.97 / molecule

Production Example 2
The polymerization temperature was set to 75 ° C., propylene and hydrogen were continuously fed so that the hydrogen concentration in the gas phase of the reactor was 2.6 mol% and the total pressure in the reactor was maintained at 0.79 MPa · G. Produced and evaluated resin pellets of low crystalline polypropylene in the same manner as in Production Example 1.
The physical properties of the resulting low crystalline polypropylene were as follows:
Stereoregularity [mmmm]: 46 mol%
Weight average molecular weight (Mw): 74200
Molecular weight distribution (Mw / Mn): 1.9
Number of terminal unsaturated groups: 0.98 per molecule

Production Example 3
After drying a 5 liter stainless steel autoclave having a stirrer, catalyst inlet, and propylene and hydrogen gas input lines, 2500 mL of heptane, 6.25 mmol of triisobutylaluminum, and methylaluminoxane in terms of aluminum atoms were added under a nitrogen atmosphere. 12.5 mmol was added and stirred at 40 ° C. for 10 minutes. To this, 10 μmol of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added, and the temperature was controlled at 60 ° C. After introducing hydrogen gas at a partial pressure of 0.12 MPa, the introduction was stopped. Further, propylene gas was introduced at a partial pressure of 0.5 MPa, and polymerization was carried out at a constant total pressure for 90 minutes.
After completion of the reaction, the pressure was cooled and depressurized, the reaction mixture was poured into a large amount of methanol to precipitate a polymer, and then separated and dried to produce a low crystalline polypropylene (yield 945 g).

The physical properties of the obtained low crystalline polypropylene were as follows. Incidentally, “not observed” of the number of terminal unsaturated groups means that it is at least less than 0.05 per molecule. :
Stereoregularity [mmmm]: 47 mol%
Weight average molecular weight (Mw): 72000
Molecular weight distribution (Mw / Mn): 1.8
Number of terminal unsaturated groups: not observed

[Production of reactive polyolefin]
Example 1
90.0 g of the low crystalline polyolefin synthesized in Production Example 1 was put into a 300 ml separable flask equipped with a stirrer, a thermometer, and an inlet, and dry nitrogen was circulated to sufficiently substitute the nitrogen. The following reactions were all carried out under a nitrogen atmosphere. The separable flask was immersed in a heated oil bath to melt the low crystalline polyolefin, and then the temperature was controlled at 170 ° C. with stirring. A previously prepared uniform solution of 9 g of trimethoxyvinylsilane and 0.9 g of dicumyl peroxide was dropped from the dropping funnel over 45 minutes, and the reaction was further continued for 5 minutes. In order to remove unreacted substances, the supply of nitrogen was stopped, and dried under reduced pressure at about 2 mmHg for 2 hours. Nitrogen was then introduced to atmospheric pressure, stirring was stopped, the oil bath was removed, and the mixture was allowed to cool to room temperature. The recovered reactive polyolefin was 92.7 g.

  The mesopentad fraction, B viscosity, molecular weight distribution, heat resistant creep temperature, open time and adhesive strength of the obtained reactive polyolefin were evaluated. The evaluation method is as follows. The results are shown in Table 1.

(1) B viscosity Based on JISK-6862, the reactive polyolefin melted at 190 ° C was measured by using a Brookfield viscometer. As a viscometer, a TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd. and an M2 rotor (No. 21) were used, and an H-2 type small sample adapter was used.

(2) Heat-resistant creep temperature 35 g of the obtained reactive polyolefin was heated and melted at 180 ° C., 0.07 g of dibutyltin dilaurate (IV) was added as a curing catalyst, and the mixture was sufficiently stirred. 0.5 g of this molten resin is uniformly applied with a stainless steel spatula to 80 mm from the end of a cotton canvas (JIS No. 10) having a width of 25 mm and a length of 200 mm, and a polypropylene having a width of 25 mm, a length of 100 mm, and a thickness of 2 mm. Overlaid on the board. Next, a 2 kg weight was placed on the bonded portion and heat-sealed in an oven at 120 ° C. for 10 minutes, taken out as it was, and cooled to room temperature. The laminated body bonded together was cured for 7 days in an atmosphere of 23 ° C. and 50% RH and moisture-cured to obtain a test piece.
Using this test piece, the heat resistant creep temperature was measured in accordance with JIS K6833. Specifically, the lower part of the test piece was cut off so that the length of the bonded portion was 25 mm, and a 500 g weight was attached to the lower end of the test piece suspended in the thermostat. The temperature of the thermostatic bath was maintained at 38 ° C. for 15 minutes, and then the temperature was increased at a rate of 2 ° C. for 5 minutes. The temperature when the weight dropped was defined as the heat-resistant creep temperature.

(3) Adhesive strength Measured according to JIS K6854-2 using the same specimen as that used for the creep test. For the measurement, an autograph AG-X manufactured by Shimadzu Corporation was used, and the test piece was placed in a thermostat controlled at 80 ° C., and after reaching the constant temperature, a 180 ° peel test was performed at a test speed of 200 mm / min, and an average peel was performed. The load was determined.

(4) Open time After applying the obtained reactive polyolefin melt to the cotton canvas, the time until it is bonded to the polypropylene (PP) plate is increased every 5 or 10 seconds. The longest time during which the initial adhesive strength to such an extent that the PP plate does not easily peel off was expressed as the open time.

Example 2
The same procedure as in Example 1 was repeated except that the low crystalline polyolefin of Production Example 2 was used instead of the low crystalline polyolefin of Production Example 1 and the dropping time of the uniform solution of trimethoxyvinylsilane and dicumyl peroxide was 20 minutes. Reactive polyolefin was prepared (yield 95.1 g) and evaluated. The results are shown in Table 1.

Example 3
Reactive polyolefin in the same manner as in Example 1 except that instead of a uniform solution of trimethoxyvinylsilane and dicumyl peroxide, a solution obtained by adding 4.5 g of 2-ethylhexyl acrylate to the uniform solution was added dropwise over 75 minutes. (Yield 97.3 g) and evaluated. The results are shown in Table 1.

Example 4
Instead of the low crystalline polyolefin of Production Example 1, a mixture of 81.0 g of the low crystalline polyolefin of Production Example 3 and 9.0 g of polypropylene wax was used, and the dropping time of the uniform solution of trimethoxyvinylsilane and dicumyl peroxide was 45. A reactive polyolefin was produced in the same manner as in Example 1 except that the amount was 9% (yield 91.4 g) and evaluated. The results are shown in Table 1.
The polypropylene wax is 330-P (mesopentad fraction: 85.4 mol%) manufactured by Sanyo Chemical Industries, and corresponds to the crystalline polyolefin (2) of the present invention.

Example 5
Under a nitrogen atmosphere in a 2-liter cylindrical container, a homogeneous solution consisting of 90 g of trimethoxyvinylsilane, 44.3 g of 2-ethylhexyl acrylate, and 9.0 g of dicumyl peroxide was added to 900 g of the low crystalline polyolefin of Production Example 1. After sealing, it was spun for mixing. After 3 hours, no residual liquid material or adhesion was observed in the low crystalline polyolefin pellets. Impregnated pellets with good flowability were obtained.
The obtained impregnated pellets were extruded at a barrel temperature of 170 ° C., a die temperature of 170 ° C., a rotation speed of 120 rpm, and a discharge rate of 1200 g / hour using a twin screw lab plast mill (26 mmφ, L / D = 27) manufactured by Toyo Seiki, A reactive polyolefin was obtained. In addition, the discharge thing which is reactive polyolefin was extract | collected under nitrogen stream so that a die | dye and a collection container may not contact air | atmosphere.
The obtained reactive polyolefin was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6
Impregnated pellets and reactive polyolefin were produced and evaluated in the same manner as in Example 5 except that the amount of trimethoxyvinylsilane used was 45 g. The results are shown in Table 1.
The impregnated pellets obtained were free from residual liquid matter and adhesion as in Example 5, had good fluidity, and the discharge amount during melt extrusion was 1480 grams / hour.

Example 7
Impregnated pellets and reactive polyolefin were produced and evaluated in the same manner as in Example 5 except that the amount of trimethoxyvinylsilane used was 45 g and the amount of 2-ethylhexyl acrylate used was 88.6 g. The results are shown in Table 1.
The impregnated pellets obtained were free from residual liquid matter and adhesion as in Example 5, had good fluidity, and had a discharge amount of 1280 grams / hour during melt extrusion.

Example 8
Impregnated pellets and reactive polyolefin were produced and evaluated in the same manner as in Example 5 except that 45 g of trimethoxyvinylsilane was used and 73.6 g of 2-ethylhexyl acrylate was used. The results are shown in Table 1.
The impregnated pellets obtained were free from residual liquid matter and adhesion as in Example 5 and had good fluidity. Further, the melt extrusion was carried out by changing the barrel temperature to 190 ° C. and the die temperature to 190 ° C., and the extrusion was carried out at a discharge amount of 2450 g / hour.

Comparative Example 1
(1) Production of Silane-modified Polypropylene In a 1 liter autoclave, which was dried by heating, 400 ml of heptane, 0.5 mmol of triisobutylaluminum, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3- 0.2 micromol of trimethylsilylmethylindenyl) zirconium dichloride and 0.8 micromol of dimethylanilinium tetrakispentafluorophenylborate are added, 0.2 MPa of hydrogen is further introduced, and 0.6 MPa of propylene is introduced to bring the total pressure to 0. Polymerization was carried out at a polymerization temperature of 70 ° C. for 60 minutes at a pressure of 0.8 MPa. After completion of the polymerization reaction, the reaction product was dried under reduced pressure to obtain 110 g of a propylene polymer.
The physical properties of the resulting propylene polymer were as follows:
Stereoregularity [mmmm]: 43 mol%
Weight average molecular weight (Mw): 32000
Molecular weight distribution (Mw / Mn): 1.8
Number of terminal unsaturated groups: 0.3

  30 g of the obtained propylene polymer and 250 ml of toluene were placed in a 1000 ml separable three-necked flask equipped with a stirring blade, heated to 110 ° C., 0.2 g of di-t-butyl peroxide, methacryloxypropyltrimethoxysilane. 5 g was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 110 ° C. for about 240 minutes, then charged into a beaker, washed with methanol and reprecipitated to obtain 28.5 g of a silane-modified propylene polymer. The obtained silane-modified polypropylene was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(2) Evaluation of silane-modified polypropylene 5 g of the silane-modified propylene polymer (1) and 20 ml of toluene were placed in a 100 ml flask and dissolved at room temperature. After dissolution, 0.5 ml of water and 0.3 ml of dibutyltin octate were added dropwise and stirred in a 50 ° C. hot water bath for 3 hours. After completion of the reaction, the reaction product was dried under reduced pressure to obtain 4.8 g of a crosslinked silane-modified propylene polymer.
The intrinsic viscosity [η] of the obtained silane-modified propylene polymer crosslinked product increased to 0.54 deciliter / g, indicating that the crosslinking reaction was in progress. The evaluation results are shown in Table 1.

Comparative Example 2
A reactive polyolefin was produced and evaluated in the same manner as in Example 2 except that methacryloxypropyltrimethoxysilane was used instead of trimethoxyvinylsilane. The results are shown in Table 1.

Comparative Example 3
A silane-modified polyolefin commercial product A (Best Plast V206, manufactured by Evonik Degussa) was evaluated in the same manner as in Example 1. The results are shown in Table 1.
In addition to the above, the primary structure of the commercial product A was measured by ¹³ C-NMR, microscopic FTIR (infrared spectroscopy), and GPC. As a result, the monomer composition of the olefinic sites derived from propylene sites 64.8 wt%, ethylene site 9.3 wt%, a butene site 25.9 wt%, the Si-O bond to 1130～1054Cm ^-1 in microscopic FTIR Based on the observed absorption, it was clear that the product was a modified product of a silane compound. The molecular weight distribution determined from GPC was 4.2.

  In the above Examples and Comparative Examples, trimethoxyvinylsilane (TMVS), 2-ethylhexyl acrylate (EHA), polypropylene wax (PPW), methacryloxypropyltrimethoxysilane (100 wt%) in reactive polyolefin (100% by weight) MPTMS) content was measured by infrared absorption spectroscopy. The results are also shown in Table 1.

  In Table 1, in Comparative Examples 1 (1) and 2, the test piece was peeled off immediately, and the adhesive strength could not be evaluated.

[Manufacture of adhesive composition]
Example 9
Reactive polyolefin 20g of Example 1, Imabe P-100 (manufactured by Idemitsu Petrochemical Co., Ltd.) (hydrogenated product of C5 / aromatic copolymer petroleum resin) (thermoplastic resin) 10g, phenolic as tackifying resin Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant is blended in an amount of 0.3 g, placed in a 0.1 liter sample tube, heated to 180 ° C. in an oil bath, and stirred and mixed in a molten state. A resin composition for hot melt adhesive was prepared.

  35 g of the obtained resin composition for adhesive was heated and melted at 180 ° C., 0.07 g of dibutyltin (IV) dilaurate was added as a curing catalyst, and the mixture was sufficiently stirred. 0.5 g of this molten resin is uniformly applied with a stainless steel spatula to 80 mm from the end of a cotton canvas (JIS No. 10) having a width of 25 mm and a length of 200 mm, and a polypropylene having a width of 25 mm, a length of 100 mm, and a thickness of 2 mm. Overlaid on the board. Next, a 2 kg weight was placed on the bonded portion and heat-sealed in an oven at 120 ° C. for 10 minutes, taken out as it was, and cooled to room temperature. The bonded test pieces were cured for 7 days in an atmosphere of 23 ° C. and 50% RH and moisture-cured.

[Production of reactive polyolefin]
Example 10
After a glass cylinder with a 2 liter screw cap was dried and purged with nitrogen, 900 g (100 parts by weight) of low crystalline polyolefin pellets of Production Example 1 were added. Trimethoxyvinylsilane 6 parts by weight, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane as an organic peroxide (trade name Perhexa 25B manufactured by NOF Corporation) 0.20 parts by weight The homogeneous solution consisting of was put in, sealed, and rotated on a roller and mixed.

After 3 hours, no residual liquid or deposits were observed on the pellets, and impregnated pellets with good fluidity were obtained. The obtained impregnated pellets were melt extruded under the following conditions to obtain reactive polyolefins and evaluated. The results are shown in Table 2.
Extruder: Toyo Seiki Co., Ltd. twin screw lab plast mill 20mmΦ, L / D = 27)
Temperature: Below the hopper Room temperature, barrel temperature controlled from the hopper side to the first barrel (C1) 110 ° C, the second (C2) to 5 (C5) barrel 210 ° C, and the die 210 ° C Screw rotation speed: 100rpm
Discharge rate: 2.45 kg / h

Examples 11-21
A reactive polyolefin was produced and evaluated in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 2. The results are shown in Table 2.

  From Table 2, it was clear that the viscosity could be controlled by the amount of organic peroxide charged and the melt reaction extrusion temperature. Furthermore, it was possible to control the content of trimethoxyvinylsilane in the reactive polyolefin by adjusting the amount of trimethoxyvinylsilane charged.

Examples 22-26
A reactive polyolefin was produced and evaluated in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 3 and the rotational speed was changed to 180 rpm. The results are shown in Table 3.
As is apparent from Table 3, if the organic peroxide decomposes in the temperature range where polyolefin radicals are generated, the viscosity can be controlled by the amount of organic peroxide charged and the temperature.

Comparative Examples 4 and 5
A reactive polyolefin was produced and evaluated in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 4. The results are shown in Table 4. In addition, tr in the table indicates that absorption of a trace level (less than 0.1% by weight) was observed.
Even when radicals were generated, the decomposition reaction of the low-order polyolefin did not proceed at low temperatures, and the addition reaction of vinyl alkoxysilane hardly proceeded.

The one-minute half-life temperatures of azobisisobutyronitrile and diisopropyl peroxide are 120.2 ° C. and 85.1 ° C., respectively.
One minute half-life temperature of azobisisobutyronitrile is the frequency factor and activity shown in J. Am. Chem. Soc., 80, 779 (1958). J. P. Van Hook and A. v. Tobolsky. Using the value of chemical energy, it was calculated by Arrhenius equation.
The one-minute half-life temperature of diisobutyl peroxide is a value described in the trade name Parroyl IB of the organic peroxide published by NOF Corporation.

Examples 27-31
Impregnated pellets were prepared in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 5.
That is, after a glass cylinder with a 2 liter screw cap was dried and purged with nitrogen, 900 g (100 parts by weight) of the low crystalline polyolefin pellets of Production Example 1 and the polyolefin (2) shown in Table 5 were charged. A homogeneous solution consisting of 6 parts by weight of trimethoxyvinylsilane and an organic peroxide (t-butylperoxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation)) in the amount shown in Table 5 was added to this and sealed. Then, it was rotated on a roller and mixed.
The obtained impregnated pellets were melt extruded under the following conditions to obtain reactive polyolefins and evaluated. The results are shown in Table 5.

In Table 5, the ethylene octene copolymer is Affinity 1900 manufactured by Dow, and the ethylene vinyl acetate copolymer is Ultrasen 725 manufactured by Tosoh.
The temperature was: C1 / 160 ° C., C2-C5 and dice / 180 ° C., and the rotation speed was 180 rpm.

In addition, glass transition temperature (Tg), gel, etc. were evaluated as follows.
(1) Glass transition temperature (Tg)
The glass transition temperature (Tg) of the reactive polyolefin was measured using an EXSTAR DMS6100 viscoelastic spectrometer manufactured by SII Nanotechnology. A measurement sample was prepared by preparing a sheet having a thickness of about 1 mm by hot pressing and cutting it into a strip shape having a length of 20 mm and a width of 9 mm. The sample was subjected to dynamic strain at a frequency of 1 Hz, and the storage elastic modulus (E ′) and loss elastic modulus (E ″) were measured at a measurement temperature of −90 ° C. to 200 ° C. and a heating rate of 2 ° C./min. The glass transition temperature (Tg) was obtained from the temperature giving the maximum value of the rate (E ″).

(2) Gel 10 g of reactive polyolefin was melted by heating at 180 ° C., and 0.03 g of dibutyltin dilaurate was added thereto as a curing catalyst and sufficiently stirred. The resin composition was held in a molten state at 180 ° C. for 10 minutes, and then molded into a sheet having a thickness of about 1 mm by hot pressing. The obtained sheet was moisture-cured in an environment having a temperature of 23 ° C. and a relative humidity of 40% (absolute humidity of about 8 g / m 3).

About 100 g of the reactive polyolefin composition sheet that had been moisture-cured for a predetermined time was placed in 100 ml of toluene, heated to 100 ° C. with a block heater, and stirred for 1 hour. This hot toluene solution was quickly filtered with a laboratory tissue (Nippon Paper Crecia Co., Ltd. JK Wiper), and the swollen gel remaining on the wiper was vacuum-dried at 80 ° C. for 2 hours to completely remove toluene. The amount of gel was calculated from the fraction of the weight of the hot toluene insoluble gel relative to the weight of the original composition sheet.
The amount of gel at the time when 24 hours have passed after the addition of the curing catalyst is shown in Table 5 as the gel fraction for 24 hours.
Further, the amount of gel was measured over time, and the final reached gel fraction was listed in Table 5 as a value at which the amount of gel did not change with time.

(3) Calculated creep value The most preferable range was obtained from the following formula.
18.2 log [B] +2

(4) Acetone soluble part (actual measured value and calculated value)
The calculated value was obtained from the following formula.
0.95 × TMVS content The measured value was measured by the method described in the above embodiment.

[Production of Reactive Polyolefin Composition]
Examples 32-38
After a glass cylinder with a 2 liter screw cap was dried and purged with nitrogen, 900 g (100 parts by weight) of pellets of the low crystalline polyolefin (polyolefin (1)) of Production Example 1 were charged. From this, from 6 parts by weight of trimethoxyvinylsilane, 0.20 part by weight of t-butyl peroxyisopropyl monocarbonate (trade name Perbutyl I, manufactured by NOF Corporation) as an organic peroxide, a curing accelerator or a curing agent shown in Table 5 The homogeneous solution was charged and sealed, and then rotated and mixed on a roller to obtain impregnated pellets.
The obtained impregnated pellets were melt-extruded under the same conditions as in Example 10 to obtain a reactive polyolefin composition and evaluated. The results are shown in Table 5.

Example 39
A reactive polyolefin composition was obtained and evaluated in the same manner as in Example 32 except that the polyolefin (2) shown in Table 5 was added. The results are shown in Table 5.

Example 40
100 parts by weight of the reactive olefin of Example 24 and 20 parts by weight of an ethylene octene copolymer (manufactured by Dow Co., Ltd., Affinity 1900) were melt-kneaded at 160 ° C. and 100 rpm for 10 minutes using a Toyo Seiki lab plast mill to obtain a composition. . The results are shown in Table 5.
The reactive olefin of Example 24 was similarly evaluated and the results are shown in Table 5.

From Table 5, when manufactured in the state where polyolefin (2) and polyolefin (1) coexisted (Examples 27 to 31), the glass transition temperature (Tg) is lowered and the low temperature characteristics are excellent and the curing rate is increased. Was shown to do.
It was also shown that the curing rate was increased by the presence of the curing accelerator. Furthermore, it was shown that the presence of a curing agent improves the curing rate and heat resistance.

[Production of reactive polyolefin]
Example 41
700 g (100 parts by weight) of the low crystalline polypropylene of Production Example 1 was put into a 2-liter glass cylindrical container with a screw cap and purged with nitrogen, and then 6 parts by weight of trimethoxyvinylsilane and 2,5 as an organic peroxide. -Dimethyl-2,5-di (t-butylperoxy) hexane (Nippon Yushi Co., Ltd., trade name Perhexa 25B) A homogeneous solution consisting of 0.81 part by weight was charged, sealed, and rotated on a roller. Mixed. After 3 hours, no residual liquid or deposits were observed on the pellets, and impregnated pellets with good fluidity were obtained.

The resulting impregnated pellets were melt extruded under the following conditions to obtain and evaluate reactive polyolefins. The results are shown in Table 6.
Extruder: Toyo Seiki Co., Ltd. twin screw lab plast mill 20mmΦ, L / D = 27)
Temperature: room temperature under the hopper, barrel temperature from the hopper side to the first barrel (C1) 140 ° C,
2nd (C2) to 5 (C5) barrel 200 ° C. and die 200 ° C. Screw rotation speed: 180 rpm
Discharge rate: 4.9 kg / h, residence time: 93 seconds

Example 42
A reactive polyolefin was produced and evaluated in the same manner as in Example 41 except that the low crystalline polypropylene of Production Example 1 was changed to the low crystalline polypropylene of Production Example 3. The results are shown in Table 6.
Comparison with Examples 41 and 42 showed that the amount of gel required for improving heat resistance was high when low crystalline polypropylene having a terminal vinylidene group was used.

Comparative Example 6
30 g of the propylene polymer produced in Comparative Example 1 (1) and 250 ml of toluene were placed in a 1000 ml separable three-necked flask equipped with a stirring blade, heated to 110 ° C., and then 0.2 g of di-t-butyl peroxide. 5 g of methacryloxypropyltrimethoxysilane was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solvent toluene was almost distilled off by distillation under reduced pressure after stirring at 110 ° C. for about 240 minutes. Further, it was heated to 140 ° C. to remove unreacted methacryloxypropyltrimethoxysilane in a high vacuum state. The yield of the obtained silane-modified polypropylene was 31.4 g, and the methacryloxypropyltrimethoxysilane content calculated from the weight increase was 4.5% by weight.
The silane-modified polypropylene was subjected to an acetone extraction operation according to the method described in the above embodiment. The content of methacryloxypropyltrimethoxysilane in the acetone-insoluble part was 0.05% by weight.
All the above operations were performed using a dehydrating reagent in a nitrogen atmosphere.

Evaluation Example 1
With respect to the uniformity of the reactive polyolefin of Example 24 and the silane-modified polypropylene before extraction of acetone of Comparative Example 6, electron microscope observation and elemental analysis were performed by the method described in the above embodiment.

  In the reactive polyolefin of Example 24, “islands” did not exist, and 2.9% by weight of vinylalkoxysilane was detected by infrared spectrum evaluation. Further, in the elemental analysis of the “sea” under an electron microscope. Silicon atoms were present.

  In the polymer of Comparative Example 6, an “island” structure was observed, and silicon atoms were present at a high concentration in the “island” portion by elemental analysis. Further, silicon atoms could not be detected in the “sea” portion by elemental analysis.

Examples 43 and 44
Using a kneading extruder Labotex (TEX-44 L / D = 52, manufactured by Nippon Steel), 100 parts by weight of the low stereoregular polyolefin of Production Example 1 was top-feeded from the most upstream, and the amount of tri-layer shown in Table 7 was obtained. A homogeneous solution consisting of methoxyvinylsilane and organic peroxide was directly charged into the downstream barrel at a constant flow rate using a metering pump. Unreacted substances were removed by a vacuum vent installed in the reaction end zone, and the reactive polyolefin was recovered through a die. The screw rotation speed was 400 rpm, and the residence time of reactive extrusion was 36 seconds.
The temperature of the low stereoregular polyolefin injection site was controlled at room temperature, the supply site of trimethoxyvinylsilane and organic peroxide was 100 ° C., and the reaction zone was controlled at 190 ° C. The temperature after venting was set to 150 ° C.
Table 7 shows the evaluation results of the reactive polyolefin.

Example 45
(1) Production of polyolefin (1) In a heat-dried stainless steel autoclave with an internal volume of 5 L, dried heptane 2.5 L, triisobutylaluminum 1.4 mmol heptane solution 1.4 ml, dimethylanilinium tetrakis (pentafluorophenyl) 2 ml of 15.4 μmol of heptane slurry of borate was added and stirred for 10 minutes while controlling at 50 ° C.
Furthermore, 6 ml of a 3.8 μmol heptane slurry of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene)-(indenyl) (3-trimethylsilylmethylindenyl) zirconium dichloride of the transition metal compound complex was added. .
Further, after adding 50 ml of hydrogen, the temperature was raised to 50 ° C. while stirring, and propylene gas was introduced to a partial pressure of 0.9 MPa.
During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure became constant, and polymerization was performed for 100 minutes, followed by cooling.
The contents were air-dried and further dried at 80 ° C. under reduced pressure for 8 hours to obtain 790 g of polypropylene.

  The weight average molecular weight (Mw) of polypropylene is 109000, the molecular weight distribution (Mw / Mn) is 1.84, the stereoregularity [mmmm] is 58.2 mol%, the number of terminal unsaturated groups is 0.95 vinylidene group / molecule. Met.

(2) Reaction with trimethoxyvinylsilane A reactive polyolefin was produced in the same manner as in Example 24 except that 700 g (100 parts by weight) of the above polypropylene pellets were used. As a result, the B viscosity was 29000 mPas, the molecular weight distribution was 1.91, the stereoregularity [mmmm] was 58 mol%, and the trimethoxyvinylsilane content was 2.8 wt%. The heat resistant creep temperature was 96 ° C.

  The reactive polyolefin of the present invention comprises a reactive hot melt adhesive, a sealing agent, a resin / elastomer modifier, a wax blend agent, a filler blend agent, a resin modifier, a paint component, an ink component, an adhesive component, and a primer component. It can be suitably used for high-performance wax and the like.

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The entire contents of the documents described in this specification are incorporated herein by reference.

Claims (17)

A structure (A) derived from a vinylalkoxysilane represented by the following formula (I), and a chain obtained by polymerizing at least one selected from ethylene and an α-olefin having 3 to 20 carbon atoms, It has a structure (B) except in some cases,
Reactive polyolefin satisfying the following (1) to (4).
[Vinylalkoxysilane]
^{_{CH 2 = CR 1 -Si (OR}} 2) 3-n R 3 n (I)
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms.
n is an integer of 0, 1 or 2. )
[Physical properties of reactive polyolefin]
(1) Mesopentad fraction [mmmm] representing average stereoregularity is 25 to 85 mol%
(2) Content of structure (A) is 0.1 to 20% by weight
(3) Molecular weight distribution (Mw / Mn) = 1.5-10
(4) Melt viscosity measured at 190 ° C. is 2000 to 80000 mPas The reactive polyolefin of Claim 1 which has 1-35 weight% of structures (C) induced | guided | derived from the vinyl monomer represented by following formula (II).
X ¹ -CR ³ = CR ⁴ -X ² formula (II)
(Wherein X ¹ and X ² are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X ¹ and X ² are bonded to each other to form a ring. Provided that when ^one of X ¹ and X ² is a hydrogen atom, the other is a functional group containing an oxygen, nitrogen, or sulfur atom.
R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )   The structure (B) is any one of a homopolypropylene chain, a chain composed of a copolymer of propylene and ethylene, and a chain composed of a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms. Reactive polyolefin as described in 1.   The reactive polyolefin according to any one of claims 1 to 3, wherein the structure (B) is a polyolefin chain having 0.5 to 1.0 terminal unsaturated groups per molecule. The reactive polyolefin in any one of Claims 1-4 which satisfy | fills one or more of following (5)-(7).
(5) Heat-resistant creep temperature after moisture curing is 65 to 130 ° C
(6) Open time is 15 seconds to 5 minutes (7) Acetone dissolution amount at 25 ° C. is the following formulas (7-1) and (7-2), or the following formulas (7-3) and (7-4) Meet.
[When the reactive polyolefin has the structure (A) and the structure (B) and does not have the structure (C)]
(7-1) Acetone-soluble amount (% by weight) ≦ 1.1 × [structure (A) content (% by weight)]
(7-2) Acetone soluble amount (% by weight) ≦ 5% by weight
[When the reactive polyolefin has the structure (A), the structure (B), and the structure (C)]
(7-3) Acetone-soluble amount (% by weight) ≦ 0.88 × [structure (A) and (B) content (% by weight)]
(7-4) Acetone soluble amount (% by weight) ≦ 20% by weight   The reactive polyolefin according to any one of claims 1 to 5, wherein a vinylalkoxysilane residue is present in the "sea" component observed based on morphological observation with an electron microscope. Mesopentad fraction [mmmm] is in the range of 20 to 80 mol%, weight average molecular weight (Mw) is in the range of 10,000 to 500,000, and molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4.0. A polyolefin obtained by polymerizing one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms, excluding the case where it is a homopolyethylene (1) 100 parts by weight,
A vinyl alkoxysilane represented by the following formula (I) 0.5 to 25 parts by weight and an organic peroxide 0.01 to 5 parts by weight in a molten state of the polyolefin (1) at a temperature range of 120 to 260 ° C. A process for producing a reactive polyolefin.
^{_{CH 2 = CR 1 -Si (OR}} 2) 3-n R 3 n (I)
(In the formula, ^{R 1} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
R ² and R ³ are each an alkyl group having 1 to 10 carbon atoms.
n is an integer of 0, 1 or 2. )   The method for producing a reactive polyolefin according to claim 7, wherein the polyolefin (1) is a polyolefin having 0.5 to 1.0 terminal unsaturated groups per molecule. The method for producing a reactive polyolefin according to claim 7 or 8, wherein 1 to 40 parts by weight of a vinyl monomer represented by the following formula (II) is further used.
X ¹ -CR ³ = CR ⁴ -X ² formula (II)
(Wherein X ¹ and X ² are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X ¹ and X ² are bonded to each other to form a ring. Provided that when ^one of X ¹ and X ² is a hydrogen atom, the other is a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom.
R ³ and R ⁴ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )   The method for producing a reactive polyolefin according to any one of claims 7 to 9, wherein 0.2 to 30 parts by weight of the crystalline polyolefin (2) is further used.   The method for producing a reactive polyolefin according to claim 10, wherein the crystalline polyolefin (2) is an ethylene polymer or a crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80%.   The crystalline polyolefin (2) is homopolyethylene, an ethylene / α-olefin copolymer, an olefin copolymer containing a polar group, or a polypropylene having a mesopentad fraction [mmmm] of more than 80%. A process for producing a reactive polyolefin.   A composition comprising the reactive polyolefin according to claim 1 and at least one of a curing agent and a curing accelerator.   An adhesive composition comprising 100 parts by weight of the reactive polyolefin according to any one of claims 1 to 6, 0 to 200 parts by weight of a thermoplastic resin, and 0 to 100 parts by weight of an oil. Furthermore, it contains 1 × 10 ^{−6 to} 0.5 part by weight of a curing catalyst,
The adhesive composition according to claim 14, which is moisture curable under an atmosphere substantially containing water.   The adhesive composition according to claim 14 or 15, which is a reactive hot melt agent.   An adhesive, a coating agent, a filler treatment agent, a paint, a dispersion, an ink, or a resin modifier containing the reactive polyolefin according to any one of claims 1 to 6 or the composition according to claim 13.