JP3039792B2 - Hot melt adhesive - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a hot melt adhesive comprising a random copolymer of an α-olefin and an aromatic vinyl monomer. More specifically, it excels in adhesiveness, processability, and environmental aging resistance such as heat aging resistance, and is used for packaging, bookbinding,
The present invention relates to a hot melt adhesive comprising a copolymer of an α-olefin and an aromatic vinyl monomer, which can be used in various fields such as bag making, woodworking, can making, construction, and sanitary.

Technical Background of the Invention In recent years, hot-melt adhesives are superior to conventional solvent-based adhesives in terms of high-speed coating properties, safety, working environment, and energy saving properties, and have rapidly expanded their application fields.

On the other hand, the conventional hot melt adhesive is a compound mainly composed of a base polymer such as natural rubber and a tackifier such as petroleum resin. However, hot-melt adhesives conventionally used are composed of a base polymer such as natural rubber and a tackifier such as petroleum resin, and have a large amount of double bonds, so that the heat stability is poor and the coating is difficult. There is a problem that not only oxidation, decomposition, coloring and the like sometimes occur, but also that the bonding performance changes with time after bonding.
For this reason, for the purpose of simplifying the process and preventing variations in products at the time of compounding, an adhesive resin having a single component and both the performance of a base polymer and a tackifier is desired.

The present inventors have conducted intensive studies to obtain an adhesive resin having excellent environmental aging resistance such as adhesives, processability, and heat aging resistance, and found that a specific α-olefin and an aromatic vinyl monomer were used. This random copolymer was found to be excellent in the above properties, and the present invention was completed.

Objects of the Invention The present invention is intended to solve the problems associated with the prior art as described above, and has excellent adhesiveness, workability, and resistance to environmental aging such as heat aging. It is an object of the present invention to provide a hot-melt adhesive comprising an aromatic vinyl random copolymer.

SUMMARY OF THE INVENTION The hot melt adhesive according to the present invention comprises (a) butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1 and dodecene-. A structural unit derived from one or more α-olefins selected from the group consisting of 50
Α-olefin and aromatic vinyl monomer having a melt viscosity at 200 ° C. in the range of 1,000 to 100,000 centipoise, and a softening point of 40 to 150 ° C. Characterized by containing a random copolymer of the above as a base polymer.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the hot melt adhesive according to the present invention will be specifically described.

The hot melt adhesive according to the present invention comprises butene-1, pentene-1, hexene-1, heptene-1, octene-
Α-olefin / aromatic vinyl, which is a copolymer of one or more α-olefins selected from the group consisting of 1, nonene-1, decene-1, undecene-1 and dodecene-1 with an aromatic vinyl monomer It is composed of a random copolymer.

Butene-1 and pentene-1 are particularly preferably used as the α-olefin. These α-olefins may be used alone or in a combination of two or more.

As the aromatic vinyl monomer constituting the α-olefin / aromatic vinyl random copolymer, specifically, styrene, o-methylstyrene, m-methylstyrene, p-
Alkyl-substituted styrenes such as methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, propylenestyrene and butylstyrene; halogen-substituted styrenes such as chlorostyrene and bromostyrene;
Examples thereof include vinyl naphthalene such as bityl naphthalene, 2-vinyl naphthalene, and 1-vinyl-4-methyl naphthalene.

The aromatic vinyl monomers constituting the α-olefin / aromatic vinyl random copolymer may be used alone or in a combination of two or more.

Further, in addition to the above monomers, other copolymerizable monomers such as ethylene and propylene may be used in the α-olefin / aromatic vinyl random copolymer in a range that does not impair the object of the present invention. Can also be copolymerized.

In the α-olefin / aromatic vinyl random copolymer, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1,
The structural unit derived from one or more α-olefins selected from the group consisting of undecene-1 and dodecene-1 is
In the range of 50-98 mol%, preferably 60-96 mol%,
The constitutional unit derived from the aromatic vinyl monomer is in the range of 2 to 50 mol%, preferably 4 to 40 mol%.

20 of α-olefin / aromatic vinyl random copolymer
Melt viscosity at 0 ° C is 1000 to 100,000 centipoise,
Preferably it is in the range of 2000 to 80,000 centipoise. This characteristic value is a value that is a measure of coatability when the hot melt adhesive of the present invention is used.

The softening point (ring and ball method) of the α-olefin / aromatic vinyl random copolymer is in the range of 50 to 150 ° C, preferably 70 to 130 ° C. This characteristic value is a value that serves as a measure of the upper limit temperature when using the hot melt adhesive of the present invention.

α-olefin / aromatic vinyl random copolymer,
It can be obtained by copolymerizing an α-olefin and an aromatic vinyl monomer in the presence of an olefin polymerization catalyst.

The olefin polymerization catalyst preferably used in the copolymerization is formed from a solid titanium catalyst component (a), an organoaluminum compound catalyst component (b), and, if necessary, an electron donor component (c). .

The solid titanium catalyst component (a) is magnesium,
It contains titanium, halogen and an electron donor as essential components, and magnesium / titanium (atomic ratio) is larger than 1, preferably 3 to 50, particularly preferably 6 to 30, and halogen / titanium (atomic ratio) Is greater than 1, preferably 4 to 100, particularly preferably 6 to 40, and the electron donor / titanium (molar ratio) is preferably 0.1 to 10, particularly preferably 0.2 to 6. Its specific surface area is preferably 3m ² / g or more, more preferably from about 40~1000m ² / g, more preferably about 100~800m ² / g. Normally, the titanium compound is not desorbed by simple means such as hexane washing at room temperature. And the X-ray spectrum shows whether the magnesium compound is microcrystallized regardless of the raw material magnesium compound used for catalyst preparation,
Or, it is desirably in a very finely crystallized state as compared with a crystallized state of an ordinary commercial product of magnesium dihalide. And it may contain other elements, metals, functional groups, etc. other than the above essential components. Further, it may be diluted with an organic or inorganic diluent.

The solid titanium catalyst component (a) uses a magnesium compound, a titanium compound, and, if necessary, an electron donor,
It is prepared by catalyzing these compounds. In the case of preparing the solid titanium catalyst component (a), other reaction reagents, for example, compounds such as silicon, phosphorus and aluminum can be used depending on the case.

As a method for preparing such a solid titanium catalyst component (a), for example, JP-A-50-108385 and JP-A-50-1265
No. 90, No. 51-20297, No. 51-28189,
Nos. 51-64586, 51-92885, 51-136625, 52-87489, 52-100596, and 52
No. 147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 55-13
No. 5102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-11908, No. 56-1860
No. 6, JP-A-58-83006, JP-A-58-138705,
JP-A-58-138706, JP-A-58-138707, JP-A-58-138708
JP-A-58-138709, JP-A-58-138710,
No. 58-138715, No. 60-23404, No. 61-21109, No. 61-37802, and can be produced according to the methods disclosed in the respective patents such as No. 61-37803. .
The method for producing the solid titanium catalyst component (a) will be briefly described below.

For the preparation of the solid titanium catalyst component (a), a magnesium compound can be used. Examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Here, as the magnesium compound having a reducing ability, for example, a compound represented by the formula X _n MgR _2-n (where n is 0 ≦ n <2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or A cycloalkyl group, and when n is 0, two Rs may be the same or different, and X is a halogen).

Specific examples of the organomagnesium compound having such a reducing ability include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamil magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, Examples thereof include butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyloximers such as phenoxymagnesium and dimethylphenoxymagnesium Neshiumu; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having a reducing ability, for example, a magnesium compound having a reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compound is a magnesium compound having a reducing ability and a magnesium compound having no reducing ability as well as a complex compound, a complex compound of the above magnesium compound and another metal, or a mixture of another metal compound. You may. Further, a mixture of two or more of the above compounds may be used, and the compounds may be used in a liquid state or a solid state. When the compound is a solid, it can be liquefied using alcohols, carboxylic acids, aldehydes, amines, metal acid esters and the like.

Among these, a magnesium compound having no reducing ability is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

There are various tetravalent titanium compounds used for the preparation of the solid titanium catalyst component (a), and usually Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4). More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl _{3 , Ti (OC 2 H 5)} Br 3, Ti (O-iso-C 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl _{2, Ti (On-C 4} H 9) 2 Cl 2, Ti (OC 2 H 5) 2 Br 2 dihalogenated dialkoxy titanium, such _{as; Ti (OCH 3) 3 Cl} , Ti (OC 2 H 5) 3 Cl _{, Ti (On-C 4 H} 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br; Ti (OCH 3) 4} , Ti (OC 2 H 5) 4, Ti (On Tetraalkoxy titanium such as —C ₄ H ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ can be exemplified. Among them, particularly preferred are titanium tetrahalides and alkoxy titanium trihalides, and particularly preferred is use of alkoxy titanium trihalides. These titanium compounds may be used alone or in combination of two or more. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

When preparing the solid titanium catalyst component (a), an electron donor can be used if necessary. Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, Amine,
Nitrogen-containing electron donors such as nitriles and isocyanates can be used. More specifically, alcohols having 1 to 18 carbon atoms such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol; phenol Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol; acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, cyclohexane C3-15 ketones such as benzoquinone, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, Le aldehydes, aldehydes having 2 to 15 carbon atoms such as naphthoquinone tolualdehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate Propyl acid butyl, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethoxy benzoate Organic acid esters having 2 to 18 carbon atoms such as ethyl acid, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and the like C2 to C15 acid halides; C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acetic acid N, N-dimethylamide, benzoic acid Acid amides such as N, N-diethylamide, toluic acid N, N-dimethylamide; methylamine, ethylamine, diethylamine, trimethylamine, triethylamine, tributylamine,
Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile; P- such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having an OC bond; examples thereof include alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane.

Further, as the organic acid ester, a polycarboxylic acid ester can be mentioned as a particularly preferred example,
As such a polycarboxylic acid ester, the following general formula: (However, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group,
R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of them is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other. Often, when the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a heteroatom such as N, O, S, etc.
O-C, COOR, COOH, OH, SO 3 H, -C-N-C-, NH 2
And a skeleton represented by the following formula:

As such polycarboxylic acid esters, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate , Diethyl butylmalonate, diethylphenylmalonate, diethyldiethylmalonate, diethyldibutylmalonate, monooctylmaleate, dioctylmaleate, dibutylmaleate, dibutylbutylmaleate, diethylbutylbutylmaleate, diisopropylβ-methylglutarate , Diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylic acid esters such as diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Esters, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate,
Ethyl isobutyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, Aromatic polycarboxylic esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and butyl trimellitate, and heterocyclic polycarboxylic esters such as 3,4-furandicarboxylic acid. Preferred examples can be given.

Other examples of the polycarboxylic acid ester include long adipates such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Esters of chain dicarboxylic acids and the like can be mentioned. Among these compounds, it is preferable to use a carboxylic acid ester, particularly a polyvalent carboxylic acid ester,
Particularly, phthalic esters are preferably used.

The electron donor preferably contained in the solid titanium catalyst component (a) is an ester of an organic or inorganic acid, an alkoxysilane compound, an aryloxysilane compound, an ether, a ketone, a tertiary amine, an acid halide, an acid anhydride. Compounds having no active hydrogen, such as organic acid esters, alkoxysilane compounds, and aryloxysilane compounds. Among them, esters of an aromatic monocarboxylic acid and an alcohol having 1 to 8 carbon atoms, malonic acid, Substituted malonic acid, substituted succinic acid, maleic acid, substituted maleic acid, 1,
Esters of dicarboxylic acids such as 2-cyclohexyldicarboxylic acid and phthalic acid with alcohols having 2 or more carbon atoms are particularly preferred.

These electron donors do not necessarily need to be used as starting materials, and can be produced in the process of preparing the solid titanium catalyst component. Further, the solid titanium catalyst component, the magnesium compound, the titanium compound and
If necessary, a carrier compound, a reaction aid, or the like may be used in addition to the electron donor to bring them into contact with each other.

Such carrier compounds include Al ₂ O ₃ , SiO ₂ , B
Resins such as ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, ZnO ₂ , SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Among them, Al ₂ O ₃ , SiO ₂ and styrene
Divinylbenzene copolymer is preferred.

Organic and inorganic compounds containing silicon, phosphorus, aluminum and the like can be used as reaction aids.

The solid titanium catalyst component (a) is prepared by contacting a magnesium compound, a titanium compound, if necessary, an electron donor, and, if necessary, a carrier compound.

The method for preparing such a solid titanium catalyst component (a) is not particularly limited, but the method will be briefly described below with several examples.

(1) A method in which a magnesium compound, an electron donor, and a titanium compound are contacted and reacted in an arbitrary order. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing ability;
A method of reacting a liquid titanium compound in the presence of an electron donor to precipitate a solid magnesium-titanium composite.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A method in which a solid obtained by pulverizing a magnesium compound, an electron donor, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. In addition, this method may include a step of pulverizing only the magnesium compound, a complex compound composed of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, an organomagnesium compound, and a halogen-containing compound with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(9) A method of reacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium, a titanium compound, an electron donor and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound.

(10) A method in which a magnesium compound in a liquid state having no reducing ability is reacted with an organoaluminum compound to precipitate a solid magnesium-aluminum complex, and then an electron donor and a titanium compound are reacted.

When the solid titanium catalyst component (a) is produced by such a method, the amounts of the magnesium compound, the titanium compound, and the electron donor added as needed are determined by the type, the catalyst conditions, and the catalyst order. The electron donor varies with respect to 1 mol of magnesium,
It is preferably used in an amount of 0.01 mol to 5 mol, particularly preferably 0.1 mol to 1 mol.
It is used in an amount of 1 mol to 1000 mol, particularly preferably 1 mol to 200 mol.

The temperature for contacting these compounds is usually -70 ° C.
To 200 ° C, preferably 10 ° C to 150 ° C.

After completion of the reaction, the solid titanium catalyst component (a) obtained by any of the above methods can be purified by sufficiently washing it with a liquid inert hydrocarbon. Inert hydrocarbons used for this purpose include n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-
Octane, isooctane, n-decane, n-dodecane,
Aliphatic hydrocarbons such as kerosene and liquid paraffin; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and cymene; chlorobenzene; Examples thereof include halogenated hydrocarbons such as dichloroethane and mixtures thereof.

The catalyst for olefin polymerization used in producing the α-olefin / aromatic vinyl random copolymer used in the hot melt adhesive according to the present invention comprises a solid titanium catalyst component (a) as described above, And an aluminum compound catalyst component (b).

As the organoaluminum compound catalyst component (b), for example, (1) the general formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein, R ¹ and R ² are from 1 to 15 carbon atoms, It is preferably a hydrocarbon group containing from 1 to 4, which may be the same or different, and X represents a halogen atom;
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
A number of q <3, moreover organic aluminum compound represented by a is) m + n + p + q = 3; (2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ Are the same as those described above) and a complex alkylated product of a Group I metal and aluminum.

As the organoaluminum compound belonging to the above (1), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.5
≦ m ≦ 3), a general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above; X is a halogen, m is preferably 0 <m <3); and a general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above; m is preferably 2 ≦ m <3); and a general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² is the same as above, X is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

As the aluminum compound belonging to (1), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide, partially alkoxylated alkyl aluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 ; diethyl aluminum chloride, dibutyl Dialkylaluminum halides such as aluminum chloride and diethylaluminum bromide; ethylaluminum sesqui Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Alcohol such as aluminum ethoxy bromide Shi reduction and halogenated alkylaluminum can be exemplified.

Examples of the compound similar to (1) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, Methyl aluminoxane and the like can be mentioned.

Compounds belonging to the above (2) include LiAl (C
_{2 H 5) 4, LiAl (} C 7 H 15) 4 and the like.

Among the above (1) and (2), it is particularly preferable to use a trialkylaluminum or an alkylaluminum to which two or more aluminum compounds described above are bonded.

The olefin polymerization catalyst used in the production process of the α-olefin / aromatic vinyl random copolymer constituting the hot melt adhesive according to the present invention includes the solid titanium catalyst component (a) and the organoaluminum compound catalyst component. (B) and, if necessary, an electron donor (c). Examples of the electron donor (c) include amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, Examples include acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and amides and salts of metals belonging to Groups I to IV of the periodic table. Salts can be formed by the reaction of an organic acid with an organometallic compound.

Specific examples of the electron donor (c) include, for example, the electron donor used in the preparation of the solid titanium catalyst component (a) described above. Good results are obtained when organic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, acid anhydrides, amines and the like are used as the electron donor (c). In particular, when the electron donor in the solid titanium catalyst component (a) is a monocarboxylic acid ester, it is preferable to use an alkyl ester of an aromatic carboxylic acid as the electron donor (c).

Further, the electron donor in the solid titanium catalyst component (a) is
In the case of an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms exemplified as preferred above, it is preferable to use an electron donor (c) an organosilicon compound represented by the following general formula.

R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxysilane. , T-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o
-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltriethyl Methoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethoxysilane Ethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-
Norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,
Trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane; cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3- Dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tri Cyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxy Sisilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxy Silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used. That. These organosilicon compounds can be used as a mixture of two or more kinds. Examples of the olefin polymerization catalyst used in the copolymerization include a catalyst formed from a metallocene component (d) and an aluminoxane component (e).

The metallocene component (d) has a general formula: (In the formula, M is zirconium, titanium or hafnium, L is a ligand having a cycloalkadienyl skeleton, and two Ls are linked via an alkylene group, a substituted alkylene group, or a silylene group. And X and Y are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen).

As the ligand having a cycloalkadienyl skeleton,
For example, an alkyl-substituted cyclopentadienyl group such as a cyclopentadienyl group, a methylcyclopentadienyl group, and a pentamethylcyclopentadienyl group, an indenyl group, and a fluorenyl group can be exemplified.

Examples of the alkylene group include a methylene group, an ethylene group, and a propylene group. Examples of the substituted alkylene group include an isopropylidene group. Examples of the substituted silylene group include a dimethylsilylene group and a diphenylsilylene group.

X and Y are a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group,
Aryloxy group, halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group.Examples of the aralkyl group include a benzyl group, A neofil group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Hereinafter, specific examples of the selected metal compound containing a ligand having a cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (methylcyclopenta Dienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (silolpentadienyl) zirconium ethoxycyclolide, ethylenebis (indenyl) Dimethyl zirconium, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride , Dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (indenyl) zirconium dichloride, dimethylsilylene bis (methylcyclopentadienyl) zirconium dichloride.

Further, in the zirconium compound as described above, a compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

The aluminoxane component (e) can be produced, for example, by the following method.

(1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate,
In a suspension of a hydrocarbon medium such as ceric chloride hydrate,
A method in which an organoaluminum compound such as trialkylaluminum is added and reacted to recover a hydrocarbon solution.

(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover a hydrocarbon solution.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

Examples of the organoaluminum compound used for producing the solution of aluminoxane include the compounds exemplified as the organoaluminum compound catalyst component (b) described above.

Of these, trialkyl aluminum is particularly preferably used.

The above-mentioned organoaluminum compounds are used alone or in combination.

Examples of the catalyst used in the solution of aluminoxane include:
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, etc. Petroleum fractions such as alicyclic hydrocarbons, gasoline, kerosene and light oil, or hydrocarbon solvents such as the above aromatic hydrocarbons, aliphatic hydrocarbons and halides of alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. No. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

As the inert hydrocarbon medium used when copolymerizing the α-olefin and the aromatic vinyl monomer, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene Aliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; Mixtures and the like can be mentioned. At the polymerization reaction temperature described below, the liquid α-
Olefin or aromatic vinyl monomers can also be used.

The amount of each catalyst component used in the polymerization system is 1 reaction volume.
Per unit, the component (a) is converted to titanium atom to about 0.0001
The component (b) is used in an amount of about 1 to about 1.0 mmol.
Component (c) is used in an amount of 0.001 to about 10 moles, preferably about 0.01 to about 2 moles, and particularly preferably about 0.05 to about 1 mole, per mole of metal atom in component (b). It is preferable that

The polymerization temperature can be appropriately selected, preferably from about 20 to about 200.
° C., more preferably from about 50 to about 180 ° C. approximately, the pressure can also be suitably selected, preferably carried out under increased pressure conditions of atmospheric pressure to about 50 kg / cm ^2. The polymerization can be performed by any of a batch system, a semi-continuous system, and a continuous system.

The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the proportion of the catalyst component used. However, it is most effective to add hydrogen to the polymerization system.

Various additives can be added to the adhesive according to the present invention as needed. Examples thereof include softeners such as dioctyl phthalate and dibutyl phthalate, waxes such as petroleum paraffin wax, polyolefin wax, and micro wax, phenol-based or bisphenol-based organic compounds, and antioxidants such as metal soap.

In the present invention, in addition to the α-olefin / aromatic vinyl random copolymer, other base polymers and tackifiers can be used in combination within a range that does not substantially impair the effects of the present invention.

As a method of preparing the hot melt adhesive according to the present invention, if necessary, a mixture comprising the various additives described above is stirred under heating and melted to prepare a uniform melt, and according to the intended use. It is formed under cooling into granules, flakes, pellets, rods, etc. This hot melt adhesive is melted again and used for bonding. For example, in the corner bonding of a molded product, a rod-shaped adhesive is used to fill a welding gun.

Effects of the Invention The hot melt adhesive of the present invention has excellent adhesiveness, workability, and excellent environmental aging resistance such as heat aging resistance, and is used for packaging, bookbinding, woodworking, canning, construction, sanitary, and the like. It can be used in various fields such as applications.

EXAMPLES Hereinafter, the present invention will be described with reference to examples.
It is not limited to these examples.

Example 1 As an α-olefin random copolymer, butene
1) Content of 90.2 mol%, viscosity (η _B ) measured with a Brookfield viscometer at 200 ° C. is 7100 centipoise, and softening point (R & B softening point) measured by ring and ball method.
Was melt-coated uniformly on a polyethylene terephthalate surface and allowed to cool naturally. The coating thickness was 56 μm. Overlay a biaxially stretched polypropylene film on top of it,
Heat sealing was performed under the conditions of kg / cm ² and 10 seconds to obtain a sample for evaluating adhesive strength. The evaluation of the adhesive strength of the sample was performed by the following method.

[T-type peeling test] Peeling speed: 30 cm / min [Shear Adhesive Failure Temperature (SAFT) measurement] Heating rate: 25 ° C / hour Load: 500 g The test results are shown in Table 1.

In Table 1, η _B is calculated using a Brookfield viscometer.
R denotes the viscosity measured at 200 ° C., and η _E denotes the viscosity measured at 200 ° C. using an Emmirror viscometer.
& B softening point indicates the softening point measured by the ring and ball method. Also
PET indicates polyethylene terephthalate, and OPP indicates a biaxially stretched film of polypropylene.

Examples 2 and 3 The same operation as in Example 1 was performed, except that the α-olefin / aromatic vinyl random copolymer or the adhesive base material was changed as shown in Table 1. Table 1 shows the results.

Comparative Example 1 The same operation as in Example 1 was performed, except that polybutene-1 was used instead of the α-olefin / aromatic vinyl random copolymer. Table 1 shows the results.

Comparative Example 2 In Example 1, butene-1 was used as the α-olefin.
Instead, the same operation as in Example 1 was performed except that propylene was used. Table 1 shows the results.

Continuing from the front page (72) Inventor Junichi Yoshitake No. 580 No. 32, Nagaura Taku, Sodegaura-cho, Kimitsu-gun, Chiba Prefecture (56) References JP-A-48-54147 (JP, A) JP-A-48-47931 (JP, A) JP-A-60-104144 (JP, A) JP-A-49-128945 (JP, A) JP-A-51-133390 (JP, A) JP-A-3-188184 (JP) JP-A-1-98646 (JP, A) JP-A-51-109038 (JP, A) JP-A-2-298570 (JP, A) JP-A-52-150494 (JP, A) 3-20381 (JP, A) JP-A-2-196878 (JP, A) JP-A-51-89591 (JP, A) JP-A-56-76416 (JP, A) JP-A-59-25856 (JP, A) A) JP-A-59-15467 (JP, A) Japanese Patent No. 2894452 (JP, B2) Patent 2854945 (JP, B2) Patent 2854088 (JP, B2) Japanese Patent No. 2894452 (JP, B2) B2) Tokiko 7-23413 (JP, B2) Tokiko JP 2-2425 (JP, B2) JP 51-5587 (JP, B1) JP 6-502447 (JP, A) JP 54-500078 (JP, A) JP 54-500034 (JP) , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 1/00-201/10 CA (STN) WPI / L (QUESTEL)

Claims (1)

(57) [Claims] (A) one selected from the group consisting of butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1 and dodecene-1; The structural unit derived from the above α-olefin is in the range of 50 to 98 mol%, (b) the melt viscosity at 200 ° C is in the range of 1,000 to 100,000 centipoise, and (c) the softening point is 40 to 150 ° C. A hot-melt adhesive comprising, as a base polymer, a random copolymer of an α-olefin and an aromatic vinyl monomer.