JP3340880B2 - Graft modified polyethylene wax - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a graft-modified polyethylene wax, and more particularly to a graft-modified polyethylene wax having a narrow molecular weight distribution, a low melting point and a low softening point.

[0002]

2. Description of the Related Art Modified polyethylene waxes graft-modified with vinyl monomers, unsaturated carboxylic acids or derivatives thereof are used for various polyolefin modifiers, pigment dispersants, hot melt adhesives, water dispersants and the like. It is used for In any of these applications, good workability is desired, for example, it is required that no white smoke is generated during kneading, that it is not sticky, and that it is easy to flow. Further, for applications such as water dispersants, those having a smaller dispersed particle size are desired. In order to meet these demands, there is a strong demand for a wax having less stickiness and cohesiveness on the surface, that is, a wax having a narrow molecular weight distribution.

Meanwhile, a modified polyethylene wax graft-modified with a vinyl monomer, an unsaturated carboxylic acid or a derivative thereof is produced by graft copolymerizing these monomers with an ethylene polymer wax.

Further, as a method for producing an ethylene polymer wax which is a main component of a modified polyethylene wax, a titanium catalyst comprising a titanium compound and an organic aluminum compound, or a vanadium catalyst comprising a vanadium compound and an organic aluminum compound is used. A method of polymerizing or copolymerizing ethylene in the presence of is conventionally known.

[0005]

However, the ethylene-based polymer wax obtained with the conventional titanium-based catalyst has a wide molecular weight distribution and does not have sufficient performance with respect to surface stickiness and cohesiveness. Similarly, the ethylene-based polymer wax obtained with a vanadium catalyst has a narrower molecular weight distribution than that obtained with a titanium-based catalyst, but is still insufficient for applications in which the performance is strictly required. Yes, for example, in order to obtain an aqueous dispersion having a small particle size, a treatment for separating and removing the low melting point component is still required, and in order to obtain a product having the required performance, the manufacturing process is complicated. There was a problem.

Therefore, a first object of the present invention is to narrow the molecular weight distribution, and in particular, to reduce the number of low molecular weight portions that are trailing.
Therefore, it is an object of the present invention to provide a novel graft-modified ethylene wax having low stickiness and low cohesion.

[0007] A second object of the present invention is to provide,
Graft suitable for applications such as film modifiers, pigment dispersants, hot melt adhesives, and water dispersants with small particle diameters because of its properties of producing no white smoke, non-greasy, easy to flow, etc. An object of the present invention is to provide a modified polyethylene wax.

[0008]

In order to solve the above-mentioned problems, the present invention provides an ethylene-based polymer obtained by polymerizing ethylene alone or ethylene and an α-olefin having 3 to 10 carbon atoms in the presence of a metallocene catalyst. For coalescing wax (a),
An object of the present invention is to provide a graft-modified polyethylene wax obtained by graft copolymerizing at least one compound (b) selected from a styrene monomer, a vinyl alcohol derivative and an unsaturated carboxylic acid monomer.

Hereinafter, the graft-modified polyethylene wax of the present invention (hereinafter referred to as “wax of the present invention”) will be described in detail.

The wax of the present invention is obtained by graft-modifying the ethylene polymer wax (a).

The ethylene polymer wax (a) used as a main component of the wax of the present invention may be ethylene alone or in combination with ethylene having 3 to 3 carbon atoms in the presence of a metallocene catalyst.
It is obtained by polymerizing 10 α-olefins. Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-hexene, and 4-methyl-1-
Penten, 1-octene, 1-decene and the like can be mentioned.
In the present invention, the ethylene-based polymer wax may contain one kind of the α-olefin having 3 to 10 carbon atoms, or may contain two or more kinds thereof.

The metallocene catalyst used in the production of the ethylene polymer wax (a) is not particularly limited.
For example, (A) IVb, Vb, and VIb of the periodic table
Examples of the metallocene catalyst include a combination of at least one transition metal compound selected from the group consisting of a group and (B) a cocatalyst.

(A) IVb, Vb and V in the periodic table
Examples of the at least one transition metal compound selected from the group consisting of Group Ib include a compound represented by the following general formula: ML _X [1]. In equation [1],
M is a group IVb transition metal atom, for example, zirconium, titanium, hafnium and the like. L represents a ligand or a group which coordinates to the transition metal M, and at least 1
L is a ligand having a cyclopentadienyl skeleton such as cyclopentadienyl and indenyl, and the other L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, alkylsilyl group, -SO ₃ R
¹ (where R ¹ is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom, and one kind of group or atom selected from the group consisting of hydrogen. Further, when the transition metal compound represented by the general formula [1] contains two or more ligands having a cyclopentadienyl skeleton, two of the ligands having a cyclopentadienyl skeleton are It may be bonded via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, or a substituted silylene group such as a silylene group or a dimethylsilylene group or a diphenylsilylene group. Further, x is the valence of the transition metal, and indicates the number of L.

Specific examples of the transition metal compound represented by the general formula [1] include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, and bis (ethylcyclopentadienyl). ) Zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propyl) Cyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadiene) Le) zirconium dibromide,
Bis (n-butylcyclopentadienyl) zirconium methoxy chloride, bis (n-butylcyclopentadienyl) zirconium ethoxychloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadiene) Enyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n
-Butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) zirconium phenyl chloride, bis (n-
(Butylcyclopentadienyl) zirconium hydride chloride, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) ethyl Zirconium monochloride, ethylene bis (indenyl)
Methyl zirconium monobromide, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis ｛1-
(4,5,6,7-tetrahydroindenyl)｝ dimethylzirconium, ethylenebis ｛1- (4,5,6,7
-Tetrahydroindenyl)｝ methylzirconium monochloride, ethylenebis ｛1- (4,5,6,7-tetrahydroindenyl)｝ zirconium dichloride, ethylenebis ｛1- (4,5,6,7-tetrahydroindenyl) )｝ Zirconium dibromide, ethylenebis ｛1-
(4-methylindenyl) zirconium dichloride,
Ethylene bis {1- (5-methylindenyl)} zirconium dichloride, ethylene bis {1- (6-methylindenyl)} zirconium dichloride, ethylene bis {1- (7-methylindenyl)} zirconium dichloride, ethylene bis {1- (5-methoxyindenyl)} zirconium dichloride, ethylenebis {1-
(2,3-dimethylindenyl) {zirconium dichloride, ethylene bis} 1- (4,7-dimethylindenyl)} zirconium dichloride, ethylene bis {1-
(4,7-dimethoxyindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-2,7-di-t-butylfluorenyl) zirconium dichloride, Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadiene) Enyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconi Zirconium compounds such as mudichloride and diphenylsilylenebis (indenyl) zirconium dichloride (in the above-mentioned compounds, the disubstituted cyclopentadienyl ring may be a 1,2-substituted or a 1,3-substituted And the trisubstituted form includes both 1,2,3-substituted form and 1,2,4-substituted form), or zirconium in the above exemplified compound is replaced with titanium or hafnium. And the like.

The cocatalyst (B) is not particularly limited, and a conventionally known cocatalyst can be used. For example, aluminoxane (B-1), a compound (B-) which reacts with the transition metal compound (A) to form an ionic complex
2) and the like.

As the aluminoxane (B-1), for example, the following general formula [2] or [3]:

[0017]

Embedded image

Compounds represented by the following formulas can be exemplified. R ² in the formulas [2] and [3] represents a hydrocarbon group, for example, methyl group, ethyl group, propyl group, n
-Butyl group, iso-butyl group, phenyl group, phenylmethyl group and the like, and preferably a methyl group, an ethyl group or an iso-butyl group. M represents an integer of 2 or more, preferably an integer of 3 to 50, and particularly preferably an integer of 3 to 40.

The aluminoxane (B-1) is prepared by, for example, (1) using a compound containing adsorbed water or a salt containing water of crystallization, such as hydrated magnesium chloride or copper sulfate, in a hydrocarbon medium. A method in which an organoaluminum compound is added to a suspended suspension and reacted with water to recover a hydrocarbon solution. (2) A method in which water, ice, steam, or the like is allowed to directly react with an organoaluminum compound in a medium such as benzene or toluene to cause a reaction, and the compound is recovered as a hydrocarbon solution. And the like.

Examples of the organoaluminum compound used for producing the aluminoxane (B-1) include, for example, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum,
Tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-t
Trialkyl aluminums such as ert-butyl aluminum and tripentyl aluminum are exemplified.

The compound (B-2) which forms an ionic complex by reacting with the transition metal compound (A) is, for example, a compound comprising a cation and an anion having a plurality of groups bonded to an element. And particularly a coordination complex compound.

Specific examples of this compound (B-2) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, dimethylanilinium tetra (pentafluorophenyl) borate, (Pentafluorophenyl) triethylammonium borate,
Tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, ferrocenium tetraphenylborate, trityl tetraphenylborate, ferrocenium tetra (pentafluorophenyl) borate, methylferrotetra (pentafluorophenyl) borate Cenium, decamethylferrocenium tetra (pentafluorophenyl) borate, silver tetra (pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate , Silver perchlorate, silver hexafluoroantimonate, silver trifluoroacetate, silver trifluoromethanesulfonate, tetra (pentafluorophenyl) borate (N-benzyl-
2-cyanopyridinium), tetra (pentafluorophenyl) borate (N-benzyl-3-cyanopyridinium), tetra (pentafluorophenyl) borate (N-benzyl-4-cyanopyridinium), tetra (pentafluorophenyl) borate ( N-methyl-2-cyanopyridinium), tetra (pentafluorophenyl) borate (N
-Methyl-3-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methyl-4-cyanopyridinium), trimethylanilinium tetra (pentafluorophenyl) borate, trimethyltetra (pentafluorophenyl) borate (m-tri Fluoromethylphenyl) ammonium, tetra (pentafluorophenyl)
Benzylpyridinium borate and the like.

Further, together with the cocatalyst (B), an organoaluminum compound (C) may be used, if necessary. Examples of the organoaluminum compound (C) include compounds represented by the following general formula [4]. R ³ _n AlX _3-n ... [4]

In the above formula [4], R ³ has 1 to 1 carbon atoms.
X is a halogen atom or a hydrogen atom, and n is an integer of 1 to 3. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, and an aryl group, and specifically, a methyl group,
Examples include ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specific examples of the organoaluminum compound (C) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri2aluminum.
Trialkylaluminums such as ethylhexylaluminum; alkenylaluminums such as triisoprenylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum Sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride. .

In the present invention, the metallocene-based catalyst used in the production of the ethylene-based polymer wax (a) comprises (A) the transition metal compound, (B) a co-catalyst, and, if necessary, What consists of a combination with the organoaluminum compound (C) represented by the formula [4] is used. The metallocene-based catalyst comprises one or more (A)
It may be composed of a combination of a transition metal compound and one or more (B) aluminoxane.

In the present invention, the production of the ethylene polymer wax (a) is carried out by subjecting ethylene alone or ethylene and an α-olefin having 3 to 10 carbon atoms to a polymerization reaction in a hydrocarbon medium in the presence of a metallocene catalyst. This can be done by causing

As specific examples of the hydrocarbon medium used,
Butane, isobutane, pentane, hexane, octane,
Aliphatic hydrocarbons such as decane, dodecane, hexadecane and octadecane; cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; gasoline; Examples include petroleum fractions such as kerosene and light oil. Ethylene used as a raw material and α-olefin having 3 to 10 carbon atoms can also be used as a hydrocarbon medium. Among these hydrocarbon media, aromatic hydrocarbons are preferred.

When this polymerization reaction is carried out by a liquid phase polymerization method, the amount of the transition metal compound (A) used is usually from 10 ^-8 to 10 ^-2 as the concentration of the transition metal atom in the polymerization reaction system.
Gram atoms / l, preferably 10 ^-7 to 10 ^-3 gram atoms / l. The amount of the co-catalyst (B) used is usually 10 ^-4 to 10 ^-1 gram atom / l, preferably 10 ^-3 , as the concentration of aluminum atoms in the polymerization reaction system.
~ 5 × 10 ^-2 gram atoms / l, and
The ratio of aluminum atom to transition metal atom in the polymerization reaction system is usually 4 to 10 ⁷ , preferably 10 to 10 ⁷ .
10 ⁶ is in the range of.

In this polymerization reaction, the molecular weight of the resulting ethylene polymer wax (a) can be adjusted by adjusting the amount of hydrogen and / or the polymerization temperature in the polymerization reaction system. The polymerization temperature is usually 20 ° C. or higher, preferably 40 ° C. or higher, particularly preferably 50 to 23.
It is in the range of 0 ° C. Further, the amount of hydrogen supplied into the polymerization reaction system is usually a molar ratio of hydrogen to ethylene,
It is in the range of 0.01 to 4, preferably 0.05 to 2.

In the present invention, the ethylene polymer wax (a) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of preferably 0.6 dl / g or less, particularly preferably 0.005 to 0. .40 dl / g.

The ethylene polymer wax (a) has an ethylene content of 80 mol% or more, preferably 85 mol% or more.

Further, this ethylene polymer wax (a) has a molecular weight distribution (Mw / Mn) by GPC,
Usually, it is 2.5 or less, preferably 1.1 to 2.0. In the present invention, the molecular weight distribution (Mw / Mn) of the ethylene-based polymer wax (a) was determined by using GPC-150C manufactured by Waters, and using GMH-HT (60 cm) and GMH-HTL (60c) manufactured by Tosoh Corporation as columns.
m), the temperature was 140 ° C., the solvent was o-dichlorobenzene, and the measured flow rate was 1.0 ml / m.
in, concentration: 0.1% by weight, determined by the viscosity equation of polyethylene.

In the present invention, the ethylene polymer wax (a) obtained in the presence of a metallocene catalyst can obtain a polymer having a narrower molecular weight distribution than that obtained using a conventional catalyst. Therefore, even when it is necessary to further narrow the molecular weight distribution by the method described later, this can be efficiently performed. Further, in the present invention, the ethylene homopolymer or ethylene polymer obtained by the above method, a method of degassing under vacuum at a temperature equal to or higher than the melting point, hexane, dissolved in a solvent such as acetone and low molecular weight part By removing the high molecular weight part according to the method of removing the whole amount or dissolving the whole amount in a solvent and then precipitating at a specific temperature, the ethylene polymer (a) having a narrower molecular weight distribution can be converted into a sticky one. It is easy to flow and is advantageous in improving workability, and is effective in that an emulsion having a small particle size can be obtained.

The wax of the present invention is obtained by adding at least one compound (b) selected from a styrene monomer, a vinyl alcohol derivative and an unsaturated carboxylic acid monomer to the ethylene polymer wax (a). It is obtained by graft copolymerization.

Examples of the styrene monomer used for the graft copolymerization include styrene, α-methylstyrene,
2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 2,4,6-trimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4- Butylstyrene, 4-sec-butylstyrene, 4-tert-butylstyrene, 4-hexylstyrene, 4-nonylstyrene, 4-octylstyrene, 4-phenylstyrene,
-Decylstyrene, 4-dodecylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene,
2,4-dichlorostyrene, 3,4-dichlorostyrene, 2-methoxystyrene, 4-methoxystyrene,
-Ethoxystyrene and the like.

Examples of the vinyl alcohol derivatives include vinyl acetate, isopropenyl acetate, vinyl propionate, and isopropenyl propionate.

Further, examples of the unsaturated carboxylic acid monomer include methyl acrylate, ethyl acrylate, butyl acrylate, sec-butyl acrylate, isobutyl acrylate, propyl acrylate, isopropyl acrylate, acrylic 2-octyl acid, dodecyl acrylate, stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate, 2-chlorophenyl acrylate, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxy acrylate Rate, acrylic acid-2,
Acrylic esters such as 2,2-trifluoroethyl; methyl methacrylate, ethyl methacrylate, butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, isopropyl methacrylate, methacrylic acid-2 -Octyl, dodecyl methacrylate, stearyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, 2-chlorohexyl methacrylate, diethylaminoethyl methacrylate, 2-hexylethyl methacrylate, methacrylic acid −2,
Methacrylic esters such as 2,2-trifluoroethyl: maleic esters such as ethyl maleate, propyl maleate, butyl maleate, diethyl maleate, dipropyl maleate and dibutyl maleate: ethyl fumarate, fumaric acid Fumaric acid esters such as butyl and dibutyl fumarate; dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, crotonic acid, nadic acid and methylhexahydrophthalic acid; maleic anhydride, itaconic anhydride, citraconic anhydride, anhydride Examples thereof include anhydrides such as allyl succinic acid, glutaconic anhydride, and nadic acid anhydride.

The production of the wax of the present invention is not particularly limited, and can be carried out according to various conventionally known methods. For example, there is a method in which the ethylene-based polymer wax (a) and the compound (b) are heated and melted and mixed in the presence of a radical polymerization initiator to cause a reaction. In this reaction, the reaction temperature is preferably about 125 to 325 ° C., and the radical initiator used is a peroxide such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, or azobisisobutyric acid. An azo compound such as lonitrile is exemplified.

In the wax of the present invention, the content ratio of the compound (b) to the modified ethylene polymer wax, that is, the modification ratio, has good and good affinity with a polar polymer such as polystyrene / ethylene-vinyl acetate or water. In order to obtain a graft-modified polyethylene wax having excellent workability, the modified ethylene-based polymer wax is
When it is 0 parts by weight, it is preferably 2 to 60 parts by weight, more preferably 5 to 30 parts by weight.

Various additives can be added to the wax of the present invention, if necessary, as long as the object of the present invention is not impaired. For example, a softener, a stabilizer, a filler, an antioxidant, and the like can be added. In particular, when the wax of the present invention is used for an aqueous dispersion, it is useful to add a thickener such as polyacrylate or silica gel as a stabilizer.

[0042]

EXAMPLES Hereinafter, Examples and Comparative Examples of the present invention will be described.
The present invention will be described more specifically.

(Preparation Example 1) Preparation of methylaluminoxane In a 400 ml glass flask whose inside was sufficiently replaced with argon, 13.9 g of magnesium chloride hexahydrate and 125 ml of toluene were charged, and the temperature was lowered to 0 ° C. After cooling, 250 mmol of triethylaluminum diluted with 125 ml of toluene was added dropwise. After completion of the dropwise addition, the temperature was raised to 70 ° C., and the reaction was carried out for 96 hours while maintaining the temperature. After completion of the reaction, the reaction mixture was subjected to solid-liquid separation by filtration, and toluene was removed from the obtained separation liquid under reduced pressure to obtain 7.3 g of methylaluminoxane as a white solid. The molecular weight of the methylaluminoxane determined by freezing point depression in benzene was 1910. This aluminoxane had m in the above formula [2] or [3] of 31.

Polymerization In a continuous polymerization reactor, purified hexane was charged at 200 l / h.
r, dissolving the aluminoxane obtained above in toluene, converting the solution to 0.2 mol / hr of aluminum atom of methylaluminoxane, 0.1 mol / hr of trimethylaluminum, and bis (n-butyl (Cyclopentadienyl) zirconium dichloride was continuously supplied at a rate of 1 mmol / hr in terms of zirconium atoms.
At this time, in the gas phase in the polymerization reactor, the molar ratio of hydrogen to ethylene (H ₂ / C ₂ ) is 0.18, the molar ratio of propylene to ethylene (C ₃ / C ₂ ) is 0.08, and the total pressure is Is 3
Ethylene, propylene and hydrogen were continuously supplied so as to be 0 kg / cm ² G, and polymerization was carried out under the conditions of a polymerization temperature of 140 ° C., a residence time of 0.5 hour, and a solid concentration of 58 g / l, A polymer wax was obtained.
The resulting ethylene polymer wax has an intrinsic viscosity [η]
Is 0.13 dl / g and the molecular weight distribution (Mw / Mn) is 2.
One.

(Production Example 2) In the polymerization reaction of Production Example 1, the feed gas was hydrogen and ethylene, and the molar ratio (H ₂ / C ₂ ) of hydrogen and ethylene in the gas phase in the polymerization reactor was adjusted to 0.25. A polymerization reaction was carried out in the same manner as in Production Example 1 except for changing, to obtain an ethylene-based polymer wax. The obtained ethylene polymer wax has an intrinsic viscosity [η] of 0.10.
dl / g and Mw / Mn were 1.8.

Example 1 (Production of Modified Resin) 600 g of the ethylene polymer wax obtained in Production Example 1 was charged into a 300 cc glass reactor equipped with a stirring blade, and heated and melted at 160 ° C. Was.
Then, while maintaining the temperature, 19 g of maleic anhydride in a molten state and 4 g of di-tert-butyl peroxide were added in 3 g.
It was dropped over time. After the completion of the dropping, the reaction was further performed for 1 hour. Next, the reaction mixture was kept in a molten state in a vacuum (10
mmHg) for 1 hour to remove volatile components by degassing, followed by cooling to obtain a maleic anhydride-grafted polyethylene wax. The obtained maleic anhydride graft-modified polyethylene wax has an intrinsic viscosity [η] of 0.15 dl / g and a graft ratio of maleic anhydride of 2.
It was 9% by weight.

(Production of Aqueous Dispersion) The limiting viscosity is 0.12.
dl / g, density 0.89 g / cm ³ , melting point 144 ° C., 60 g of polypropylene wax, and 140 g of the maleic anhydride graft-modified polyethylene prepared in Example 1.
Was charged into a 1-liter autoclave equipped with stirring blades and melt-mixed at 150 ° C.

Next, 1500 ml of water and 8.4 g of potassium hydroxide were put into a pressure-resistant homomixer having an internal volume of 4 liters, and the above-mentioned molten mixture was stirred at 5,000 rpm with a gear pump while heating at 140 ° C. and stirred at 5,000 rpm. Supplied over time. Thereafter, the mixture was further stirred for 15 minutes and cooled to room temperature to obtain an aqueous dispersion. When the average particle size of the obtained aqueous dispersion was measured, it was 0.8 μm. This aqueous dispersion did not separate even after standing for one week.

(Comparative Example 1) (Production of Modified Product) In Example 1, an intrinsic viscosity [η] of 0.14 dl /
g, Mw / Mn 2.7, and the density was 0.92 g / cm ³ , except that the polyethylene was changed to the same as in Example 1.
A modified polyethylene having an intrinsic viscosity [η] of 0.16 dl / g and a graft ratio of maleic anhydride of 2.9% by weight was obtained.

(Production of Aqueous Dispersion) An aqueous dispersion was produced in the same manner as in Example 1 except that the modified polyethylene was changed to the above-mentioned modified polyethylene. Although the obtained aqueous dispersion did not separate even after one week, the average particle size was 1.6 μm, and did not fall below 1 μm, which is usually required for an aqueous dispersion.

Example 2 (Production of Modified Product) 600 g of the ethylene-based polymer wax obtained in Production Example 2 was mixed with an inner volume of 300 cc equipped with a stirring blade.
And heated to 160 ° C. to be melted. Next, while maintaining the temperature, 35 g of dibutyl fumarate, 35 g of styrene, and di-te
6 g of rt-butyl peroxide was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was further reacted for 1 hour, and then deaerated in a vacuum (10 mmHg) for 1 hour in a molten state to remove volatile components. Thereafter, the mixture was cooled to obtain a graft-modified polyethylene wax. The intrinsic viscosity of the obtained graft-modified polyethylene wax is 0.09 dl /
g, and the total amount of graft modification of dibutyl fumarate / styrene was 9% by weight.

(Preparation of Hot Melt Adhesive Composition and Performance Evaluation) Ethylene-vinyl acetate copolymer (EVA # 22)
0: 40 g of Mitsui DuPont Polychemical Co., Ltd., 40 g of an aliphatic petroleum resin (Heirez T-500X: manufactured by Mitsui Petrochemical Industries), and 20 g of the graft-modified polyethylene obtained above were melt-mixed at 180 ° C. A hot melt adhesive composition was prepared. The melt viscosity of the obtained hot melt adhesive composition was 4000 cps at 160 ° C., and 1
It was 2550 cps at 80 ° C.

This hot melt adhesive composition was applied to an aluminum foil (thickness: 50 μm) to a thickness of 15 μm, and the coated surfaces were adhered to each other. ° C., the lower bar temperature of 70 ° C., pressure 1 kg / cm ^2, to create a laminated sheet heat sealed under the conditions of the pressing time 2 seconds. This laminated sheet is 25mm
A sample is prepared by cutting into widths, and T is measured at a measurement temperature of 0 to 80 ° C.
A mold peeling test (pulling speed 300 mm / min) was performed to measure the adhesive strength. The results are shown in Tables 1 and 2.

(Comparative Example 2) (Preparation of hot melt adhesive composition and performance evaluation) In the same manner as in Example 2, except that a sasol wax was used in place of the graft-modified polyethylene wax. Then, a hot melt adhesive composition was prepared, and the melt viscosity and the adhesive strength were measured by a T-peel test. The results are shown in Tables 1 and 2.

Comparative Example 3 (Preparation of Hot Melt Adhesive Composition and Performance Evaluation) In Example 2, instead of the graft-modified polyethylene wax, unmodified polyethylene (Mitsui High Wax 220) was used.
P: Except for using intrinsic viscosity of 0.14 dl / g, Mw / Mn 2.7, and density of 0.92 g / cm ³ ), a hot melt adhesive composition was prepared in the same manner as in Example 2, and the melt viscosity, The adhesive strength was measured by a T-type peel test. The results are shown in Tables 1 and 2.

[0056]

[0057]

[0058]

The graft-modified polyethylene wax of the present invention has a narrow molecular weight distribution, and in particular, a low-molecular-weight portion with a low tail, and therefore has low stickiness and low cohesiveness. Therefore, the graft-modified polyethylene wax of the present invention has properties such as not generating white smoke, non-greasy, and easy to flow when used, so that it is excellent in workability, a film modifier, a pigment dispersant, and a hot melt adhesive. It is suitable for use as an agent and a water dispersant having a small particle size.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-6-206947 (JP, A) JP-A-5-271357 (JP, A) JP-A-58-65713 (JP, A) JP-A-5-65713 202148 (JP, A) JP-A-62-272709 (JP, A) JP-A-7-292042 (JP, A) JP-A-8-41137 (JP, A) JP-A-7-267694 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 255/00-255/10

Claims (2)

(57) [Claims] An ethylene polymer wax (a) obtained by polymerizing ethylene alone or ethylene and an α-olefin having 3 to 10 carbon atoms in the presence of a metallocene catalyst, a styrene monomer and vinyl alcohol. A graft-modified polyethylene wax obtained by graft-copolymerizing at least one compound (b) selected from a derivative and an unsaturated carboxylic acid monomer. 2. The ethylene-based polymer wax (a) comprises:
When the intrinsic viscosity [η] is 0.6 dl / g or less, the molecular weight distribution (M
2. The graft-modified polyethylene wax according to claim 1, wherein (w / Mn) is 2.5 or less and the ethylene content is 80 mol% or more.