JP5563205B2 - Reactive hot melt adhesive composition - Google Patents

Description

  The present invention contains a specific propylene-based polymer, polyol and polyisocyanate compound, has sufficient strength for practical use in both initial adhesive strength and adhesive strength after curing reaction, and is inexpensive. It relates to a reactive hot melt adhesive composition.

  Reactive hot melt adhesives have the properties of both reactive adhesives and hot melt adhesives. Normally, non-adhesive reactive hot melt adhesives are applied to adherends at room temperature. After the application, a heat press is performed to perform adhesion. As a reactive hot melt adhesive, for example, a urethane prepolymer having an isocyanate group at a molecular terminal as a main component and known to be cured by moisture is known. The initial adhesive strength, the adhesive strength after curing, the heat resistance and the like are relatively good, and are widely used for bonding plastic corrugated cardboard, film laminate sheets, plywood, building members, automobile interior and exterior members, and the like.

  As for reactive hot melt adhesives, various technical developments have been made so far for the purpose of improving various performances, particularly strength. For example, Patent Document 1 discloses a hot-melt adhesive made of an unsaturated alkoxysilane compound graft modified product such as ethylene-vinyl acetate-glycidyl (meth) acrylate terpolymer. Patent Document 2 discloses a hot melt adhesive using a graft modified product obtained by reacting a specific amorphous poly-α-olefin polymer with an alkoxysilane compound. Patent Document 3 discloses a reactive hot melt adhesive composed of a urethane prepolymer and a metallocene polyolefin. Patent Document 4 discloses a reactive hot melt adhesive composed of a urethane prepolymer, an olefin resin, and the like. Patent Document 5 discloses a reactive hot melt adhesive containing a urethane prepolymer obtained by reacting a specific polyolefin resin with a polyisocyanate. Patent Document 6 discloses a reactive hot melt adhesive composed of a polyisocyanate, a urethane prepolymer, and an olefin resin.

  However, there remains room for improvement in these reactive hot melt adhesives. For example, the techniques described in Patent Documents 1 and 2 have problems that it is difficult to control the reaction and that expensive raw materials are required. Regarding the techniques described in Patent Documents 3 and 4, there is a problem that the mixing property between the polyolefin and the polar polymer is poor and the adhesive strength is not sufficient. Regarding the techniques described in Patent Documents 5 and 6, unreacted maleic anhydride needs to be removed, and the process is complicated and has a problem in cost.

Japanese Patent Publication No. 2-50147 JP 2004-176028 A JP 2004-10809 A Japanese Patent Laid-Open No. 11-323301 JP 2006-183000 A JP 2006-169504 A

  The present invention has been made in view of the above circumstances, and provides a reactive hot melt adhesive composition that has sufficient strength for practical use and is inexpensive in both initial adhesive strength and adhesive strength after curing reaction. It is intended to do.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a composition comprising a specific propylene polymer, a polyol and a polyisocyanate compound. The present invention has been completed based on such findings.
That is, the present invention
1. A reactive hot melt adhesive composition comprising a propylene polymer, a polyol and a polyisocyanate compound satisfying the following (a) to (c):
(A) [mmmm] = 20-80 mol%
(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
(C) Acetone-soluble part is 0.5% by mass or less. The reactive hot melt adhesive composition according to the above 1, comprising a catalyst component for producing polyurethane,
3. The content of the propylene polymer is 1 to 99 parts by mass, the content of the polyol is 1 to 99 parts by mass, the content of the polyisocyanate compound is 1 to 99 parts by mass, and the catalyst component for producing the polyurethane is contained. The reactive hot melt adhesive composition according to 1 or 2 above, wherein the amount is 1 part by mass or less,
4). The reactive hot melt adhesive composition according to the above 1, comprising a tackifying resin,
5. The content of the propylene polymer is 1 to 99 parts by mass, the content of the polyol is 1 to 99 parts by mass, the content of the polyisocyanate compound is 1 to 99 parts by mass, and the content of the tackifier resin The reactive hot melt adhesive composition according to 1 or 4 above, wherein is 30 parts by mass or less,
6). The reactive hot melt adhesive composition according to any one of 1 to 5, wherein the propylene polymer is an oxidation-modified propylene polymer and is a propylene polymer satisfying the following (d):
(D) Acid value = 0.1-50 mgKOH / g
Is to provide.

  According to the present invention, when wood, resin, and metal are used as adherends, both initial adhesive strength and adhesive strength after curing reaction have practically sufficient strength and are inexpensive. A hot melt adhesive composition is obtained.

[Propylene polymer]
The propylene polymer used in the present invention is a propylene homopolymer, or a propylene copolymer containing a propylene unit and an ethylene unit and / or 1-butene unit, and has stereoregularity, molecular weight distribution, and acetone. Has specific properties with respect to solubility. That is, in the present invention,
(A) [mmmm] = 20-80 mol%
(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
(C) A propylene polymer satisfying 0.5% by mass or less of the acetone soluble part is used. Each property will be described below.

(A) [mmmm] = 20-80 mol%
The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic meso fraction [rmrm] described later are proposed in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. The meso fraction, the racemic fraction, and the racemic meso-racemic meso fraction in the pentad unit in the polypropylene molecular chain are measured by the methyl group signal of the ¹³ C-NMR spectrum in accordance with the prepared method. As the mesopentad fraction [mmmm] increases, the stereoregularity increases. Further, the mesotriad fraction [mm], the racemic triad fraction [rr] and the mesoracemi fraction [mr] described later were also calculated by the above method.
When the mesopentad fraction [mmmm] of the propylene-based polymer of the present invention is less than 20 mol%, the adhesive strength may be lowered, and when it exceeds 80 mol%, the fluidity at normal temperature is lowered and workability is deteriorated. To do. This mesopentad fraction [mmmm] is preferably 30 to 60 mol%, more preferably 40 to 60 mol%.
The measurement of the ¹³ C-NMR spectrum can be carried out with the following apparatus and conditions in accordance with the attribution of the peak proposed in “Macromolecules, 8, 687 (1975)” by A. Zambelli et al. 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

<Calculation formula>
M = (m / S) × 100
R = (γ / 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
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7-22.5 ppm

(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
In the propylene-based polymer of the present invention, when the molecular weight distribution (Mw / Mn) exceeds 4.0, the sticky component may increase and the adhesion performance may deteriorate. This molecular weight distribution (Mw / Mn) is preferably 3.0 or less, more preferably 2.5 or less.
This molecular weight distribution (Mw / Mn) can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC) method under the following apparatus and conditions. .

<GPC measurement device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)

(C) Acetone soluble part 0.5 mass% or less An acetone soluble part is calculated | required with the following method. That is, 0.5 g of a sample is dissolved in 10 ml of toluene and then reprecipitated in 50 ml of acetone. After the precipitate is filtered off, the filtrate is dried at 25 ° C. under reduced pressure, and the amount of residue is measured. Let the ratio of the amount of the residue with respect to a sample be an acetone soluble part. The acetone soluble part of the propylene polymer used in the present invention is preferably 0.1% by mass or less, more preferably 0.05% by mass or less. If the acetone-soluble part exceeds 0.5% by mass, the adhesion performance may deteriorate.

  The propylene polymer used in the present invention preferably satisfies the following properties in addition to the above (a) to (c).

[Rrrr] / (1- [mmmm]) ≦ 0.1
The value of [rrrr] / (1- [mmmm]) is obtained from the above pentad unit fraction and is an index representing the uniformity of the regular distribution of the propylene polymer. As this value increases, the distribution of regularity spreads, resulting in a mixture of highly ordered polypropylene and atactic polypropylene, like conventional polypropylene produced using existing catalyst systems, resulting in increased stickiness and reduced transparency.

[Mm] × [rr] / [mr] ² ≦ 2.2
When the value of [mm] × [rr] / [mr] ^{2 in} the propylene-based polymer is 2.2 or less, a decrease in transparency is suppressed, and the balance between flexibility and elastic recovery rate is improved. [Mm] × [rr] / [mr] ² is preferably in the range of 0.5 to 2.2, more preferably 1.0 to 2.2.

Weight average molecular weight (Mw) = 10,000-200,000
When the weight average molecular weight of the propylene polymer is 10,000 or more, the occurrence of stickiness is suppressed. Moreover, since the viscosity at the time of a fusion | melting will fall that a weight average molecular weight is 200,000 or less, workability | operativity at the time of applying to various uses becomes favorable.

  [Rmrm] of the propylene-based polymer is preferably 1.0 mol% or more. When [rmrm] is 1.0 mol% or more, the randomness of stereoregularity increases, and the balance between low-temperature workability and adhesion is improved. [Rmrm] is preferably 2.5 mol% or less. When [rmrm] is 2.5 mol% or less, the spread of the regular distribution can be suppressed, and the sticky component can be reduced.

  The propylene polymer used in the present invention was obtained by using a differential scanning calorimeter (DSC), holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C./min. A crystalline resin having a melting point (Tm-D) defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve is preferably 60 to 120 ° C. The melting endotherm (ΔH) obtained by calculation from the area of the melting peak obtained in the measurement of the melting point (Tm) is preferably 5 to 80 J / g, more preferably 10 to 60 J / g. is there. When the melting endotherm (ΔH) is 5 J / g or more, the adhesive performance of the adhesive composition is improved, and when it is 80 J / g or less, workability is improved.

In addition, when a propylene-type polymer is a copolymer, it is preferable to satisfy | fill the following prescription | regulations.
Stereoregularity index ([mm]) = 50 to 90 mol%
Stereoregularity index ([mm]) is used the JEOL Ltd. JNM-EX400 type device, the ¹³ C-NMR spectra were measured in the same manner as the above conditions, the propylene chain meso triad ([mm ]) The value obtained by measuring the fraction.
The larger the value of the stereoregularity index ([mm]), the higher the stereoregularity.
In the copolymer, the stereoregularity index ([mm]) is preferably 50 to 80 mol%. When the stereoregularity index ([mm]) is 50 mol% or more, the occurrence of stickiness is suppressed, and when it is 90 mol% or less, the secondary workability is improved.

As the propylene polymer used in the present invention, an oxidation-modified propylene polymer may be used. In this case, it is preferable to satisfy the following (d).
(D) Acid value = 0.1-50 mgKOH / g
When the acid value is 0.1 mgKOH / g or more, the propylene polymer has sufficient adhesion, and when it is 50 mgKOH / g or less, the flexibility of the propylene polymer is sufficient. . The acid value is preferably 0.5 to 35 mgKOH / g, more preferably 1.0 to 25 mgKOH / g. The acid value is measured according to the total acid value measuring method described in JIS K 2501-1980.

When an oxidation-modified propylene polymer is used in the present invention, the propylene polymer used for the production is 4.6 to 5 with respect to the integral value of the peak of 0.75 to 2.00 ppm in the ¹ H-NMR spectrum. The ratio of the integrated value of 3 ppm (vinyl value) is preferably 0.02 to 1.00%, more preferably 0.03 to 0.90. Here, the peak at 0.75 to 2.00 ppm is derived from an alkyl group such as a methyl group on the side chain, a methylene group or methine group on the main chain, and the peak at 4.6 to 5.3 ppm is at the end of the polymer. This is derived from the unsaturated bond. Therefore, the vinyl value is a value related to the amount of unsaturated bonds, and when the vinyl value is 0.02% or more, an oxidation-modified propylene polymer can be easily produced. When it is at most 00%, crosslinking during the oxidation reaction is suppressed.

The propylene polymer of the present invention can be produced by homopolymerizing propylene using a metallocene catalyst or by copolymerizing propylene with ethylene and / or 1-butene.
In the present invention, among the metallocene catalysts, those using a transition metal compound in which a ligand forms a crosslinked structure via a crosslinking group are preferred, and among these, crosslinking via two crosslinking groups is preferred. A method in which propylene is homopolymerized or copolymerized using a metallocene catalyst obtained by combining a transition metal compound forming a structure and a cocatalyst is more preferable. Specifically, (A) the following general formula (I)

And (B) (B-1) a compound capable of reacting with the transition metal compound of component (A) or a derivative thereof to form an ionic complex, and (B-2) an aluminoxane. And a method of homopolymerizing or copolymerizing propylene in the presence of a polymerization catalyst containing a component selected from:
In the above general formula (I), M represents a metal element belonging to Groups 3 to 10 of the periodic table. Specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. A 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), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same or different from each other. As E ¹ and E ² , a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group are preferable.
X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y. Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, and carbon. Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group; a vinyl group, a propenyl group, and a cyclohexenyl group. An arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group Group, anthracenyl group, aryl group such as phenanthonyl group, and the like. Of these, alkyl groups such as methyl group, ethyl group, and propyl group, and aryl groups such as phenyl group are preferable.

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

  Examples of the phosphide group having 1 to 20 carbon atoms include dialkyl phosphide groups, diethyl phosphide groups, dipropyl phosphide groups, dibutyl phosphide groups, dihexyl phosphide groups, dicyclohexyl phosphide groups, and dioctyl phosphide groups. A diaryl phosphide group such as a dibenzyl phosphide group, a diphenyl phosphide group, and a dinaphthyl phosphide group.

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

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

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

  Examples of phosphines include phosphines having 1 to 20 carbon atoms. Specifically, monohydrocarbon substituted phosphines such as methylphosphine, ethylphosphine, propylphosphine, butylphosphine, hexylphosphine, cyclohexylphosphine, octylphosphine; dimethylphosphine, diethylphosphine, dipropylphosphine, dibutylphosphine, dihexylphosphine, dicyclohexyl Dihydrocarbon-substituted phosphines such as phosphine and dioctylphosphine; alkylphosphines such as trihydrocarbon-substituted phosphines such as trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trihexylphosphine, tricyclohexylphosphine, and trioctylphosphine Such as phosphine, propenyl phosphine, cyclohexenyl phosphine, etc. Dialkenyl phosphine in which two alkenyls are substituted with alkenyl phosphine or phosphine hydrogen atom; Trialkenyl phosphine in which alkenyl is substituted with three alkenyl hydrogen atoms; Aryl alkyl phosphine such as benzyl phosphine, phenylethyl phosphine, phenylpropyl phosphine; Diarylalkylphosphine or aryldialkylphosphine having three hydrogen atoms substituted with aryl or alkenyl; phenylphosphine, tolylphosphine, dimethylphenylphosphine, trimethylphenylphosphine, ethylphenylphosphine, propylphenylphosphine, biphenylphosphine, naphthylphosphine, methylnaphthyl Phosphine, Anthracenylphosphine, Phenanthonylphosphine; And an aryl phosphines such as tri (alkylaryl) phosphines a hydrogen atom alkylaryl has three substituents phosphine; a hydrogen atom fin alkylaryl two substituted di (alkylaryl) phosphines. Examples of the thioethers include the aforementioned sulfides.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among such crosslinking groups, at least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms. Examples of such a bridging group include a general formula

(D is carbon, silicon, germanium or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisylylene group, and a diphenyldisilylene group. Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable from the viewpoint of higher polymerization activity. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the above general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I). X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I). Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged ligand.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) ( 2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) ( 2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, ( 1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bi (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) zirconium Dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene)- Bis (indenyl) zirconium dichloride,

(1,2′-methylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2 1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4- Isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ) Bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2 ' -Dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methyl Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis ( Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1 2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (indenyl) zirconium dichloride , (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis ( 3-isopropylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride,

(1,2′-Diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis ( 3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2 , 1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadiene) ) Zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) ) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3 -Methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'- Methylcyclopentadienyl) zirconium dichloride,

(1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ( 2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-eth ) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,

(1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′- Isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2 , 1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2, 1'-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) di Conium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopenta) Dienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadi) Enyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3 '-Methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3'- Methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′- Methyl-5′-n-butylcyclopentadienyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2 '-Dimethylsilylene) (2,1'-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butyl Clopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopenta Dienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) Zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride ,

(1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1, 2′-methylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride and the like and these compounds The thing which substituted zirconium with titanium or hafnium can be mentioned. Of course, it is not limited to these. Further, it may be an analogous compound of another group or a lanthanoid series metal element.
Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). Although it can be used, those represented by the following general formula (III) or (IV) can be preferably used.

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

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine; thioethers such as tetrahydrothiophene, benzoic acid Examples include esters such as ethyl acid; nitriles such as acetonitrile and benzonitrile.
Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl. Group, ethylcyclopentadienyl group, pentamethylcyclopentadienyl group and the like.
Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphine, phthalocyanine, allyl, and methallyl. .
Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, I ^{3 and the} like. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn. Etc.

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

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

  Specific examples of the ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the compound of the component (B-1) include triethylammonium tetraphenylborate, tetraphenyl Tri-n-butylammonium borate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyl tetraphenylborate Diphenylammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl ruborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) ) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (penta Fluorophenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate Tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) borate trimethyl anilinium,

Methyl pyridinium tetrakis (pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), Methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, Silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluoropheny ) Ferrocenium borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, silver tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Trityl borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) tetraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, Examples thereof include silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate. This compound of the component (B-1) may be used singly or in combination of two or more.
On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

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

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method. For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) a metal There are methods such as crystal water contained in salt, water adsorbed on inorganic and organic substances and reaction with organoaluminum compound, (4) method of reacting tetraalkyldialuminoxane with trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in hydrocarbon solvents such as toluene. These aluminoxanes may be used alone or in combination of two or more.

The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit weight polymer becomes high, which is not practical.
When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical. As the catalyst component (B), (B-1) and (B-2) may be used alone or in combination of two or more.

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

In the production of the propylene-based polymer used in the present invention, preliminary contact may be performed using the above-described component (A), component (B) and component (C). The preliminary contact can be performed by, for example, bringing the component (A) into contact with the component (B), but the method is not particularly limited, and a known method can be used. This preliminary contact is effective in reducing the catalyst cost, such as improving the catalytic activity and reducing the proportion of the (B) component used as the promoter. Moreover, the molecular weight improvement effect is seen with the said effect by making (A) component and (B-2) component contact.
The preliminary contact temperature is usually about -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C. In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.
The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, the organoaluminum compound is wasted and a large amount may remain in the polymer.
In the preliminary contact, an olefinic compound may coexist. Examples of the olefin compound to be coexisted include ethylene or an α-olefin compound having 3 to 20 carbon atoms. Specific examples include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. The amount of the olefinic compound added is about 0.5 to 20% by mass, preferably 1 to 15% by mass of the solvent used in the preliminary contact.

In the present invention, at least one of the catalyst components can be supported on a suitable carrier and used. The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, glass fiber and the like. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable. The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, examples of the carrier other than the above include a magnesium compound represented by the general formula MgR ¹⁷ _x X ¹ _y represented by magnesium compounds such as MgCl ₂ and Mg (OC ₂ H ₅ ) ₂ , and complex salts thereof. it can. Here, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, X ¹ represents a halogen atom or an alkyl group having 1 to 20 carbon atoms, x is 0 to 2, y is 0 to 2, and x + y = 2. Each R ¹⁷ and each X ¹ may be the same or different.
Examples of the organic carrier include polymers such as polystyrene, styrene-divinylbenzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, starch, and carbon.

As the carrier used in the present invention, MgCl ₂ , MgCl (OC ₂ H ₅ ), Mg (OC ₂ H ₅ ) _{2 and the} like are preferable. Moreover, although the shape of a support | carrier changes with the kind and manufacturing method, an average particle diameter is 1-300 micrometers normally, Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers. If the particle size is small, fine powder in the polymer increases, and if the particle size is large, coarse particles in the polymer increase, which causes a decrease in bulk density and clogging of the hopper.
The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 500 m ² / g, and the pore volume is usually 0.1 to ⁵ cm ³ / g, preferably 0.3 to ³ cm ³ / g. is there. When either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease.
The specific surface area and pore volume of the support can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method (Journal of the American Chemical Society, Vol. 60, p. 309 (1983). )reference).
Further, when the carrier is an inorganic oxide carrier, it is usually desirable to use it after baking at 150 to 1000 ° C, preferably 200 to 800 ° C.
When at least one kind of catalyst component is supported on the carrier, it is desirable to support at least one of (A) catalyst component and (B) catalyst component, preferably both (A) catalyst component and (B) catalyst component. .

  The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, (1) At least one of the component (A) and the component (B) is mixed with the carrier. (2) A method in which the support is treated with an organoaluminum compound or a halogen-containing silicon compound and then mixed with at least one of the component (A) and the component (B) in an inert solvent, (3) the support and (A (4) Method of reacting component and / or component (B) with an organoaluminum compound or halogen-containing silicon compound, (4) (B) component or (B) A) a method of mixing with the component, (5) a method of mixing the contact reaction product of the component (A) with the component (B) with the carrier, (6) in the contact reaction of the component (A) with the component (B) A method of allowing a carrier to coexist can be used. In the above reactions (4), (5) and (6), an organoaluminum compound (C) can also be added.

In the present invention, when contacting the above (A), (B), and (C), a catalyst may be prepared by irradiating elastic waves. Examples of the elastic wave include a normal sound wave, particularly preferably an ultrasonic wave. Specifically, an ultrasonic wave having a frequency of 1 to 1000 kHz, preferably an ultrasonic wave having a frequency of 10 to 500 kHz can be mentioned.
The catalyst thus obtained may be used for polymerization after once removing the solvent and taken out as a solid, or may be used for polymerization as it is. Moreover, in this invention, a catalyst can be produced | generated by performing the carrying | support operation to the support | carrier of at least one of (A) component and (B) component within a polymerization system.
For example, at least one of the component (A) and the component (B), a support, and, if necessary, the organoaluminum compound of the component (C) are added, and an olefin such as ethylene is added at normal pressure to 2 MPa, and the temperature is -20 to 200 ° C. A method of preliminarily polymerizing for about 1 minute to 2 hours to produce catalyst particles can be used.

In the present invention, the use ratio of the component (B-1) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500 in terms of mass ratio. -2) The use ratio of the component and the carrier is preferably 1: 0.5 to 1: 1000, more preferably 1: 1 to 1:50 in terms of mass ratio. When using 2 or more types as a component (B), it is desirable that the use ratio of each component (B) and the carrier is within the above range in terms of mass ratio.
In addition, the ratio of the component (A) to the carrier used is, by mass ratio, preferably 1: 5 to 1: 10000, more preferably 1:10 to 1: 500. If the ratio of component (B) [component (B-1) or component (B-2)] and the carrier, or component (A) and carrier is outside the above range, the activity may decrease. is there.
The average particle diameter of the polymerization catalyst thus prepared is usually 2 to 200 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50-500 m ² / g. When the average particle size is 2 μm or more, increase of fine powder in the polymer is suppressed, and when it is 200 μm or more, increase of coarse particles in the polymer is suppressed. Moreover, the fall of activity is suppressed as a specific surface area is 20 m < ² > / g or less, and the fall of the bulk density of a polymer is suppressed as it is 1000 m < ² > / g or less.
In the catalyst used in the present invention, the amount of transition metal in 100 g of the support is preferably 0.05 to 10 g, particularly preferably 0.1 to 2 g. When the amount of transition metal is within the above range, a decrease in activity is suppressed.
In this way, a polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting it on a carrier.

The propylene-based polymer used in the present invention is produced by homopolymerizing or copolymerizing propylene using the above-described polymerization catalyst. In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legal is particularly preferred.
About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC. The ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , preferably from raw material monomer / component (A) (molar ratio). Furthermore, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is preferably from normal pressure to 20 MPa (G), particularly preferably from normal pressure to 10 MPa (G).
Examples of the method for adjusting the molecular weight of the polymer include selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen. When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Moreover, you may use monomers, such as an alpha olefin, as a solvent. In addition, depending on the polymerization method, the reaction can be performed without a solvent.

  In the case of using an oxidation-modified propylene polymer in the present invention, as a method of oxidizing and modifying the propylene polymer, there is a method of oxidizing the propylene polymer in the presence of molecular oxygen and / or ozone-containing gas. Can be mentioned.

  At the time of the oxidation reaction with a gas containing molecular oxygen or ozone, a radical initiator may coexist as necessary. The radical initiator is not particularly limited, and is appropriately selected from conventionally known radical initiators such as various organic peroxides and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Of these, organic peroxides are preferred.

  Examples of the organic peroxide include dibenzoyl peroxide, di-8,5,5-trimethylhexanoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, and di (2,4-dichlorobenzoyl) peroxide. Diacyl peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, hydroperoxides such as 2,5-dimethylhexane-2,5-dihydroperoxide, di-t- Butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 , Α, α′bis (t-butylperoxy) diisopropylbenzene Peroxides, peroxyketals such as 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis (t-butylperoxy) butane, t-butylperoxyoct , Alkyl peresters such as t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di Examples thereof include peroxycarbonates such as -sec-butyl peroxydicarbonate and t-butylperoxyisopropyl carbonate. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The radical initiator may be diluted with water, an inert solvent, or an emulsion solution of an inert inorganic compound. Specific examples of the inert solvent include octane, decane, xylene, and silicone oil. Examples of the inert inorganic compound include silica gel, alumina, calcium carbonate, and aluminum hydroxide. By performing this dilution, the risk of the radical initiator can be reduced. Moreover, since the solid radical initiator has a specific gravity different from that of the base polymer, classification is likely to occur at the time of feeding, but there is also an effect of suppressing this.
There is no restriction | limiting in particular as the usage-amount of the said radical initiator, According to the desired physical property of the target oxidation modification propylene polymer, it selects suitably. The usage-amount of a radical initiator is about 0.01-10 mass parts normally with respect to 100 mass parts of propylene-type polymers, Preferably it is the range of 0.01-5 mass parts.

In the present invention, for example, a propylene-based polymer is used in a molecular form at a temperature of 100 to 300 ° C., preferably 120 to 200 ° C., for about 0.01 to 10 hours, using a roll mill, a Banbury mixer, an extruder or the like. The propylene-based polymer can be oxidized by a method in which a gas containing oxygen and / or ozone is reacted by melting and kneading in the presence of a gas containing molecular oxygen and / or ozone.
When an oxidation-modified propylene-based polymer is used in the present invention, it has high adhesion to polyolefin and the like, and can impart high strength, softness and the like to the adherend.

[Polyol]
In the reactive hot melt adhesive composition of the present invention, a polyol is used. Examples of the polyol include polyester polyol, polyether polyol, polyacryl polyol, polyolefin polyol, polybutadiene polyol, polyisoprene polyol, rosin-modified polyol, polyethylene butylene polyol, polycarbonate polyol, and polycaprolactone polyol. Specifically, polypropylene glycol, polytetramethylene glycol, polycaprolactone polyol, polycarbonate diol, polytetrahydrofuran, 1,4-butanediol, 1,5-pentadiol, 1,6-hexanediol, polybutadiene polyol, trimethylolpropane , Neopentyl glycol, and methylpentadiol. Among these, polyether polyol, polybutadiene polyol, polyisoprene polyol, polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, and polybutadiene polyol are preferable.

[Polyisocyanate compound]
In the reactive hot melt adhesive composition of the present invention, a polyisocyanate compound is used. The polyisocyanate compound used in the present invention is an organic compound having two or more isocyanate groups in one molecule, and has an isocyanate group reactive to a hydroxyl group such as a polyol. is there. Examples of the polyisocyanate compound include aromatic, aliphatic or alicyclic polyisocyanates.

  Specific examples of the aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, and a mixture of 4,4′- and 2,2′-diphenylmethane diisocyanate. , Tolylene diisocyanate (TDI), carbodiimide-modified diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, naphthalene-1,5-diisocyanate, o-toluidine diisocyanate, triphenylmethane triisocyanate Examples thereof include narate, tris (isocyanatophenyl) thiophosphate, isopropylbenzene-2,4-diisocyanate, and the like.

  Further, aliphatic-aromatic polyisocyanates such as xylylene diisocyanate (XDI) and tetramethylxylylene diisocyanate (TMXDI) (referred to polyisocyanates having no isocyanate group directly bonded to an aromatic ring). ) Can also be mentioned as specific examples of polyisocyanate compounds.

  Specific examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, dodecane diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate. Examples thereof include nate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, and the like.

  Specific examples of alicyclic polyisocyanates include transcyclohexane-1,4-diisocyanate, bicycloheptane triisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated Examples include tolylene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.

  Other specific examples of the polyisocyanate include a cyclized trimer (isocyanurate modified product) of the polyisocyanate compound, a burette modified product, an addition reaction product of a polyol compound and the polyisocyanate compound, and the like. Used. As the polyol compound, ethylene glycol, 1,4-butanediol, propylene glycol, dipropylene glycol, trimethylolpropane, polyether polyol, polymer polyol, polytetramethylene ether glycol, polyester polyol, acrylic polyol, hydrogenated Dimer acid diisocyanate, polyalkadiene polyol, hydride of polyalkadiene polyol, partially saponified ethylene-vinyl acetate copolymer, castor oil-based polyol, and the like.

  In the present invention, the isocyanate group of the polyisocyanate compound is phenols, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α-pyrrolidone, diethyl malonate, sodium bisulfite, boric acid. A so-called blocked isocyanate compound blocked with a blocking agent such as the above can also be used.

  Among these, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate (TDI), phenylene diisocyanate, xylylene diisocyanate (XDI), and cyclized trimer of the polyisocyanate compound (isocyanurate modified) Body) is preferred.

  In this invention, a polyisocyanate compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. Since preferable properties are obtained as an adhesive, the polyol and the polyisocyanate compound are usually used in a range of -NCO / -OH ratio of 0.9 to 1.1, preferably 0.95 to 1. Used in the range of 05.

The reactive hot melt adhesive composition of the present invention may contain a catalyst for polyurethane production. Examples of the catalyst for polyurethane production include dibutyltin dilaurate, dibutyltin octate, dimethylcyclohexylamine, dimethylbenzylamine, and trioctyl. An amine etc. are mentioned. Of these, dibutyltin dilaurate and dimethylcyclohexylamine are preferred.
In the reactive hot melt adhesive composition, the content of the propylene polymer is 1 to 99 parts by mass, the content of the polyol is 1 to 99 parts by mass, and the content of the polyisocyanate compound is 1 to 99 parts by mass. The content of the catalyst for producing polyurethane is preferably 1 part by mass or less, more preferably 1 to 50 parts by mass of the propylene polymer, 30 to 99 parts by mass of the polyol, and the polyisocyanate compound. The content is 1 to 50 parts by mass, the content of the catalyst for polyurethane production is 0.1 to 1 part by mass, more preferably 1 to 40 parts by mass of the propylene polymer, and the content of polyol is 40. -90 mass parts, content of a polyisocyanate compound is 1-30 mass parts, and content of the catalyst for polyurethane manufacture is 0.1-1 mass part.

The reactive hot-melt adhesive composition of the present invention may contain a tackifying resin, and as the tackifying resin, rosin resin made from raw pine ani, α-pinene obtained from pine essential oil , Terpene resins made from β-pinene, petroleum resins obtained by polymerizing fractions containing unsaturated hydrocarbons produced as by-products by thermal decomposition of petroleum naphtha, etc., and hydrogenated products thereof Is mentioned. Specifically, Idemitsu Petrochemical's Imabu P-125, Imabu P-100, Imabu P-90, Sanyo Chemical Industries Umex 1001, Mitsui Chemicals Highlets T1115, Yashara Chemicals Clearon K100, Tonex ECR227, 2101, Alcon P100 manufactured by Arakawa Chemical, Regalrez 1078 manufactured by Hercules.
In the reactive hot melt adhesive composition, the content of the propylene polymer is 1 to 99 parts by mass, the content of the polyol is 1 to 99 parts by mass, and the content of the polyisocyanate compound is 1 to 99 parts by mass. The content of the tackifying resin is preferably 30 parts by mass or less, more preferably 1 to 50 parts by mass of the propylene polymer, 30 to 99 parts by mass of the polyol, and the content of the polyisocyanate compound. The amount is 1 to 50 parts by mass, the content of the tackifying resin is 1 to 20 parts by mass, and more preferably the propylene polymer content is 1 to 40 parts by mass, and the polyol content is 40 to 90 parts by mass. Part, the content of the polyisocyanate compound is 1 to 30 parts by mass, and the content of the tackifying resin is 1 to 15 parts by mass.

  The reactive hot melt adhesive composition of the present invention may contain other components as necessary. Examples of other components include thermoplastic polymers, fillers, pigments, antioxidants, ultraviolet absorbers, surfactants and flame retardants.

  Examples of the thermoplastic polymer include polyurethane, an ethylene copolymer, a propylene copolymer, a vinyl chloride copolymer, an acrylic copolymer, and a styrene-conjugated diene block copolymer.

  Examples of the filler include inorganic fillers and organic fillers. Inorganic fillers include zinc, aluminum, copper, nickel, glass sphere, glass flake, glass fiber, carbon black (channel black, furnace black, acetylene black, thermal black), carbon fiber, graphite, asbestos, kaolin clay, wax Stone clay, talc, gypsum, cryolite, wollastonite, diatomaceous earth, slate powder, whiting, feldspar powder, mica, gypsum, quartz powder, fine silica, attapulgite, sericite, volcanic ash, meteorite, silica, alumina , Zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, molybdenum dioxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zeolite, potassium titanate, nitriding C arsenide, boron nitrite, mention may be made of molybdenum disulfide.

Organic fillers include rubber powder, cellulose, lignin, chitin, leather powder, coconut shell, wood powder, cotton, hemp, wool, silk and other natural fibers, nylon, polyester, vinylon, acetate, acrylic, etc. Examples thereof include synthetic resin powder or granules such as fiber, PE, PP, PS, ABS, PC, PET, PBT, PMMA, PVC, epoxy, and phenol.
Although there is no restriction | limiting in particular about the compounding quantity of these inorganic fillers and organic fillers, Usually, it is 500 mass parts or less with respect to 100 mass parts of polyol compounds, Preferably it is 200 masses or less.

  The reactive hot melt adhesive composition of the present invention is prepared by blending the above components in the above proportions. In preparing the composition, using a mixing device, a kneading device, etc., stirring and mixing at a temperature of 0 to 120 ° C., preferably 15 to 100 ° C., for 0.5 second to 8 hours, preferably 1 second to 5 hours. To do. Usually, the composition is prepared and cured by a method called a one-shot method or a method called a prepolymer method.

  In the one-shot method, first, at least the components other than the polyisocyanate compound are blended and mixed at the above temperature and time to obtain a mixture. A polyisocyanate compound and additive components not used in the previous mixing are added to this mixture and mixed at the above temperature and time to obtain a liquid polymer composition. The preferable NCO / OH at this time is 0.5 to 2.5.

  In the prepolymer method (1), the hydroxyl group-containing compound and the polyisocyanate compound are reacted with NCO / OH in the range of 1.7 to 25 in the presence or absence of some or all of the other additives. To obtain a prepolymer. The reaction temperature is the same as above, and the time is usually 0.1 to 10 hours, preferably 0.5 to 8 hours. The remaining components are mixed with the prepolymer at the above temperature and time to obtain a liquid polymer composition. The preferable NCO / OH at this time is 0.5 to 2.5.

  In the prepolymer method (2), NCO / OH is in the range of 1.7 to 5.0, and all components are blended and reacted to obtain a prepolymer. The reaction temperature is the same as above, and the time is usually 0.1 to 10 hours, preferably 0.5 to 8 hours. This prepolymer is reacted with moisture (water) in the air.

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

Production Example 1 [Synthesis of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride]
In a Schlenk bottle, 3.0 g (6.97 mmol) of a lithium salt of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of tetrahydrofuran (THF) and brought to -78 ° C. Cooled down. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. Obtained (yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. And 50 ml of ether. It cooled at -78 degreeC and the hexane solution (1.54 mol / L, 7.6 ml (11.7 mmol)) of n-butyltylium (n-BuLi) was dripped. After raising to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 ml of hexane to obtain 3.06 g (5.07 mmol) of the lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows.
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2- 7.7 (m, 8H, Ar-H)

Under a nitrogen stream, the lithium salt obtained above was dissolved in 50 ml of toluene. The mixture was cooled to -78 ° C, and a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 ml) was added dropwise thereto. After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off. The obtained residue was recrystallized from dichloromethane to obtain 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)

Production Example 2 [Production of Propylene Polymer I]
In a heat-dried stainless steel autoclave with an internal volume of 1 L, heptane 400 ml, triisobutylaluminum 1.0 mmol, methylanilinium tetrakis (perfluorophenyl) borate 1.5 μmol, and produced in Production Example 1 (1,2′- Dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylindenyl) zirconium dichloride 0.5 μmol was added.
While stirring, the temperature was raised to 70 ° C., and propylene gas was introduced up to 0.8 MPa in total pressure. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 60 minutes. After completion of the polymerization reaction, 5 ml of methanol was added, and after depressurization, the solution was taken out and dried under reduced pressure to obtain 40 g of a propylene homopolymer.
About the obtained propylene homopolymer, the physical property was measured by the method mentioned above. The results are shown in Table 1.

Production Example 3 [Production of Propylene Polymer II]
In a heat-dried stainless steel autoclave with an internal volume of 1 L, heptane 400 ml, triisobutylaluminum 0.4 mmol, methylanilinium tetrakis (perfluorophenyl) borate 0.8 μmol, and produced in Production Example 1 (1,2′- Dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylindenyl) zirconium dichloride 0.2 μmol was added.
While stirring, the temperature was raised to 80 ° C., and propylene gas was introduced up to a hydrogen pressure of 0.04 MPa and a total pressure of 0.89 MPa. During the polymerization reaction, propylene gas was supplied by a pressure regulator so that the pressure was constant, and polymerization was performed for 15 minutes. After completion of the polymerization reaction, 5 ml of methanol was added, and after depressurization, the solution was taken out and dried under reduced pressure to obtain 75 g of a propylene homopolymer.
About the obtained propylene homopolymer, the physical property was measured by the method mentioned above. The results are shown in Table 1.

Production Example 4 [Production of Propylene Polymer Ia]
30 g of the propylene-based polymer I obtained in Production Example 2 was charged into a Sepa glass reactor (internal volume 500 ml) equipped with an air blowing tube, an exhaust port and a stirring blade while stirring at a rotation speed of 50 rpm. The temperature was raised to 180 ° C. Next, dry air was introduced for 5 hours through an air blowing tube. Thereafter, the blowing of air was stopped, purged with nitrogen, and then cooled to room temperature to obtain a light yellow oxidation-modified propylene homopolymer.
The obtained oxidation-modified propylene homopolymer was measured for physical properties by the method described above. The wettability was measured by the following method.

<Wetting tension>
Wet tension was evaluated as a measure of the ability of the plastic film surface to retain ink, coating, or adhesive. It has been empirically known that as the wetting tension on the surface of the plastic film increases, the holding ability of ink, coating, adhesive, etc. is improved.
The evaluation was based on “Plastic-film and sheet-wetting tension test method” defined in JIS K6768. A modified propylene polymer is sandwiched between Teflon (registered trademark) sheets and pressed at 180 ° C. using a 0.3 mm spacer to produce a film for evaluation. This film is placed in a desiccator for 8 hours or more at room temperature. I left it alone.
Wet mixture test solution manufactured by Wako Pure Chemical Industries, Ltd. is used as the test mixture, and the mixture is applied to the film with a cotton swab containing the mixture, and the liquid film does not break after 2 seconds. Thus, when the original state was maintained, it was determined to be “wet”. Tests were sequentially performed from a test liquid mixture having a small surface tension, and the surface tension of the maximum liquid mixture determined to be “wet” was defined as the wetting tension (mN / m) of the film.

Example 1
Oxidized modified propylene polymer Ia obtained in Production Example 4 in a 300 mL polyethylene cup, 10 g, polybutadiene (epol, hydroxyl group content = 0.84 meq / g, number average molecular weight = 2590, viscosity, manufactured by Idemitsu Kosan Co., Ltd. = 5.1 Pa · s / 30 ° C.) was mixed at 90 ° C. with stirring. Thereafter, the mixture was cooled to about 20 ° C., 8.8 g of isophorodiisocyanate and 0.05 g of dibutyltin dilaurate were added, and mixed well to obtain an adhesive composition (isocyanate / hydroxyl group = about 1).

Examples 2 and 3
An adhesive composition was obtained in the same manner as in Example 1 except that the blending amounts shown in Table 2 were changed.

Example 4
Propylene polymer II obtained in Production Example 3 in a 300 mL polyethylene cup, 10 g, polybutadiene (epol, hydroxyl group content = 0.84 meq / g, number average molecular weight = 2590, viscosity = 5.1 Pa, manufactured by Idemitsu Kosan Co., Ltd. * S / 30 degreeC) 90g was mixed at 90 degreeC, stirring. Thereafter, the mixture was cooled to about 20 ° C., 8.8 g of isophorodiisocyanate and 0.05 g of dibutyltin dilaurate were added, and mixed well to obtain an adhesive composition (isocyanate / hydroxyl group = about 1).

Examples 5 and 6
An adhesive composition was obtained in the same manner as in Example 4 except that the blending amounts shown in Table 2 were changed.

Comparative Example 1
In a 300 mL polyethylene cup, 100 g of polybutadiene (Epol, hydroxyl group content = 0.84 meq / g, number average molecular weight = 2590, viscosity = 5.1 Pa · s / 30 ° C.) manufactured by Idemitsu Kosan Co., Ltd. Then, 9.8 g of isophorodiisocyanate and 0.05 g of dibutyltin dilaurate were added and mixed well to obtain an adhesive composition (isocyanate / hydroxyl group = about 1).

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

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

(Measurement condition)
Test speed: 50 mm / min
Testing machine: Tensile testing machine AUTOGRAPH AG-X manufactured by Shimadzu Corporation

[Measurement of 180 ° peeling strength]
In accordance with JIS-K6854-2, polycarbonate or polypropylene was used as the rigid adherend, and 180 ° peel strength was measured. The test piece manufacturing method and measurement conditions are shown below, and the maximum stress (average value of five test pieces) obtained by the measurement is shown in Table 3.

(Test piece manufacturing method)
Adhesive composition obtained in Examples or Comparative Examples with a thickness of 1 to 2 mm over the entire surface of a rigid adherend made of polypropylene or polycarbonate having a width of 25.0 mm, a length of 100 mm, and a thickness of 1.5 mm. The material was applied, and immediately after a cotton canvas having a width of 25 mm and a length of 200 mm was overlaid, it was pressure-bonded using a rubber roller and left at room temperature for 3 days. Furthermore, after being left at 70 ° C. for 1 hour, it was left at room temperature for 4 days. Before the measurement, a cotton canvas and a cured adhesive composition part having a width of 25 mm were cut with a cutter knife in the length direction.

(Measurement condition)
Test speed: 200 mm / min Test machine: Tensile tester AUTOGRAPH AG-X manufactured by Shimadzu Corporation

Example 7
To a separable flask equipped with a thermometer, a stirrer, a condenser and a nitrogen gas introduction tube, polybutadiene (epol, hydroxyl group content = 0.84 meq / g, number average molecular weight = 2590, viscosity = 5.1 Pa · s, manufactured by Idemitsu Kosan Co., Ltd.) / 30 ° C.) 80 g, and oxidation-modified polypropylene homopolymer Ia, 30 g, were charged and heated with stirring. After removing water under reduced pressure at 90 ° C., 20 g of diphenylmethane diisocyanate was added and the temperature was raised. After reacting at a temperature of 120 ° C. for 1 hour in a nitrogen atmosphere, the reaction was continued for 1 hour while degassing under reduced pressure. Hot melt adhesive was obtained (isocyanate / hydroxyl group = about 2.4). This reactive hot melt adhesive was applied to a canvas at a coating temperature of 120 ° C. at a rate of 100 g / day, and immediately laminated with a polypropylene plate and pressure-bonded for 10 seconds at a pressure of 0.049 MPa. The initial peel adhesive strength after 5 minutes of adhesion was measured at 20 ° C., and the peel adhesive strength after curing for 48 hours at 20 ° C. and 65% RH was measured at 20 ° C. and 80 ° C. The measurement results are shown in Table 5.

Examples 8 and 9, Comparative Example 2
An adhesive composition was produced in the same manner as in Example 7 except that the blending amounts shown in Table 4 were changed, and the adhesive strength was measured. The measurement results are shown in Table 5.
In addition, petroleum resin (Imabe, P-90, Idemitsu Kosan Co., Ltd.) was used as a tackifier, and polypropylene glycol (diol type, average molecular weight 2000) manufactured by Wako Pure Chemical Industries, Ltd. was used as polypropylene glycol.

  According to the present invention, when wood, resin, and metal are used as adherends, both initial adhesive strength and adhesive strength after curing reaction have practically sufficient strength and are inexpensive. A hot melt adhesive composition is obtained.

Claims (8)

A reactive hot melt adhesive composition comprising an oxidation-modified propylene polymer, a polyol and a polyisocyanate compound satisfying the following (a) to (d).
(A) [mmmm] = 20-80 mol%
(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
(C) Acetone soluble part is 0.5 mass% or less (d) Acid value = 0.1-50 mgKOH / g Reactive hot melt adhesive comprising 1 to 40 parts by mass of a propylene polymer satisfying the following (a) to (c), 40 to 90 parts by mass of a polyol and 1 to 30 parts by mass of a polyisocyanate compound. Composition.
(A) [mmmm] = 20-80 mol%
(B) Molecular weight distribution (Mw / Mn) ≦ 4.0
(C) Acetone soluble part is 0.5 mass% or less Containing polyurethane producing catalyst component, the reactive hot melt adhesive composition of claim 1. The reactive hot-melt-adhesive composition of Claim 2 containing the catalyst component for polyurethane manufacture. The content of the oxidation-modified propylene polymer is 1 to 99 parts by mass, the content of the polyol is 1 to 99 parts by mass, the content of the polyisocyanate compound is 1 to 99 parts by mass, and the catalyst component for polyurethane production The reactive hot-melt-adhesive composition of Claim 3 whose content of is 1 mass part or less.   The reactive hot-melt-adhesive composition of Claim 1 containing tackifying resin. The content of the oxidation-modified propylene polymer is 1 to 99 parts by mass, the content of the polyol is 1 to 99 parts by mass, the content of the polyisocyanate compound is 1 to 99 parts by mass, The reactive hot-melt-adhesive composition of Claim 6 whose content is 30 mass parts or less.   The reactive hot-melt-adhesive composition of Claim 2 containing tackifying resin.