JPH0415243B2 - - Google Patents

Description

[Detailed description of the invention] The present invention relates to a dispersant for pigments or fillers.

When blending additives (hereinafter sometimes collectively referred to as pigments) that can be dispersed without being substantially dissolved in the polymeric material, such as pigments, fillers, or similar substances, the pigments are added to the polymeric material. Dispersants are often used for the purpose of uniformly blending materials into materials. For example, when coloring synthetic resins with pigments, it is necessary to uniformly disperse the pigments in the synthetic resins so as not to cause undesirable uneven coloring. For this purpose, for example, a method is known in which a master batch of a pigment and a dispersant is prepared in advance and the master batch is blended into synthetic resins.

Various waxes are commercially available as dispersants used in such cases. Synthetic products are also known as such commercially available waxes, such as waxes obtained by thermal decomposition of high-pressure polyethylene, high-pressure polymerized polyethylene waxes obtained by radical polymerization of ethylene at high pressures, and furthermore, waxes made from ethylene or ethylene. Ethylene-based waxes, such as waxes obtained by low-pressure polymerization of olefins and α-olefins such as propylene and 1-butene using a Ziegler type catalyst, are often used.

Conventionally, the above-mentioned pyrolytic polyethylene wax and Ziegler type polymerized polyethylene wax are
It is assumed that this is due to differences in molecular structure and other factors, but there are differences in pigment dispersion ability depending on the type of polymer compound to be colored, and the fields of suitability of each are slightly different. Among conventional waxes, pyrolyzed polyethylene waxes and high-pressure polymerized polyethylene waxes have the drawbacks of poor thermal stability and discoloration, so they are not necessarily good pigment dispersants. However, it was hoped that other substitutes would emerge. On the other hand, Ziegler type polymerized polyethylene wax has the advantage of excellent thermal stability and low tendency to discolor, but as mentioned above, conventional products of this type lack pyrolytic polyethylene wax in terms of pigment dispersibility, etc. For example, pyrolytic polyethylene wax is used as a pigment dispersant for high-pressure polyethylene due to its dispersion performance. Conventional Ziegler type polymerized polyethylene wax could not be used as a substitute.

The present inventors did not lose the advantages of Ziegler-type polymerized polyethylene wax, which has good thermal stability and little tendency to discolor, but rather promoted it, and further improved the performance by making pigment dispersibility comparable to that of pyrolyzed polyethylene wax. We have conducted research to provide a new type of ethylene copolymer wax that has excellent pigment dispersibility in high-pressure polyethylene, such as waxes having the following properties.

As a result, it was discovered that a partial oxide of an ethylene copolymer having the above-mentioned improved performance is excellent as a wax.

The wax has: (A) an intrinsic viscosity of 0.06 measured in decalin at 135°C;
~0.6 dl/g, (B) Density 0.87 to 0.94 g/cm ³ , (C) 120°C or less of the endothermic spectrum with respect to the total area σ ₀ surrounded by the endothermic spectrum line and its baseline by differential scanning calorimeter The area σ surrounded by the endothermic spectrum line and its baseline
(≦120℃) Ratio σ (≦120℃) / σ ₀ is 0.82 or more, (D) Ethylene content 88 to 98 mol%, (E) Methylene chain in which the number of methylene chains in the polymer chain is 7 or more An ethylene copolymer of ethylene and a C ₄ to _{C 10} α-olefin having the following properties: the average number of methylene chains is 60 or less, and (F) the number of double bonds per 1000 carbon atoms is 0.7 or less. It is a wax consisting of oxides (acid value 0.1 to 20).

Therefore, the object of the present invention is to produce an oxide of an ethylene copolymer (acid value 0.1) that also has the above properties (A) to (F).
An object of the present invention is to provide a dispersant for pigments or fillers containing a wax consisting of (20) to (20) as an active ingredient.

The above ethylene copolymer has (A) an intrinsic viscosity of
0.06 to 0.6 dl/g, preferably about 0.1 to about 0.4 dl/g
It is. If the intrinsic viscosity is too small or too large outside the above range, the pigment dispersibility of the resulting wax will deteriorate.

Note that the above-mentioned intrinsic viscosity is a value determined by measurement in decalin at 135°C.

The above ethylene copolymer has (B) a density of 0.87 to
0.94 g/cm ³ , preferably about 0.89 to about 0.93 g/cm ³ . If the density is too high, exceeding the above-mentioned upper limit, the resulting wax will have poor pigment dispersibility, and if the density is too low, exceeding the above-mentioned lower limit, the resulting wax will have blocking defects and poor workability, making it unsuitable.

The above density was measured by the density gradient tube method in accordance with ASTM D-1505.

The above ethylene copolymer has (C) the endothermic spectrum for the total area σ ₀ surrounded by the endothermic spectrum line and its baseline measured by differential scanning calorimeter.
The ratio σ (≦120°C)/σ ₀ of the area σ (≦120°C) surrounded by the endothermic spectrum line of 120°C or less and its baseline is 0.82 to 1.0, preferably about 0.85 to 1.0.

If the above ratio is less than 0.82, the pigment dispersibility is poor and it is inappropriate.

The measurement and determination of the above σ (≦120°C)/σ ₀ is as follows.

The measurement is performed using a differential scanning calorimeter (DSC) [Model 990 manufactured by DuPont]. Place approximately 4 mg of the sample into the sample case for measurement, weigh it, and attach it to the measuring device. Next, once it was left at 200°C for 5 minutes, it was cooled down to 0°C at a rate of 10°C/min and left for 2 minutes. Using this sample, raise the temperature at a rate of 10°C/min to obtain its endothermic spectrum chart. The total area σ ₀ surrounded by the endothermic spectrum line of the obtained chart and its baseline, and the area σ (≦120°C) surrounded by the endothermic spectrum line below 120°C of the endothermic spectrum and its baseline. , the chart is measured, and the value of the formula σ (≦120°C)/σ ₀ is calculated and determined.

An example of the above-mentioned endothermic spectrum chart is shown in FIG. 1 of the accompanying drawings. An example of the measurement determination method described above will be explained in more detail using this figure.

Since the portion A in FIG. 1 where no endotherm is observed on the high temperature side is almost a straight line, this is extended to the point where it intersects with the endothermic spectrum on the low temperature side. The area surrounded by the straight line AB and the endothermic spectrum is σ ₀ , and the area surrounded by the straight line AB, the endothermic spectrum, and 120℃
The area of the low temperature side part surrounded by the line C drawn above is σ
(≦120℃).

When the above-mentioned ethylene-based copolymer is produced according to the production method described in detail later, a plurality of peaks are often observed in the DSC endothermic spectrum of the obtained copolymer. Even if one of the peaks is at 120° C. or higher, as in the example shown in FIG. 1, if the ratio is 0.82 or higher, the pigment dispersibility is good.

The above ethylene copolymer has (D) an ethylene content of 88 to 98 mol%, preferably about 90 to about 96 mol%
It is. If the ethylene content is too low outside the above range, pigment dispersibility will deteriorate. On the other hand, if the amount is too large, blocking defects occur, resulting in poor workability and unsuitability.

The above ethylene content is determined by quantifying the amount of _C4 to _C10 α-olefin components from an infrared absorption spectrum.

The above ethylene copolymer has an average number of methylene chains of 7 or more in the polymer chain (E) of 60 or less, preferably about 55
It is as follows. For example, it is about 20 to 60. A copolymer with a larger average methylene chain number than the above upper limit means that it has a large number of polyethylene blocks, and the resulting wax has poor pigment dispersibility.

The above average number of methylene chains is calculated by calculating the number of methylene chains having a number of methylene chains of 7 or more from a ¹³ C nuclear magnetic resonance spectrum. That is, in the ethylene copolymer with the following structure, (R is a branch of C ₂ or more) From the signal area Sα of α carbon and the signal area Sδ of δ carbon, the average number of methylene chains of methylene chains with 7 or more methylene chains is calculated by the formula: Sδ/Sα×2+6 It is determined by

The above ethylene copolymer (F) has 0.7 or less double bonds per 1000 carbon atoms, preferably about 0.5
or less, more preferably about 0.3 or less.
For example, the number is about 0.01 to 0.7. If the double bond is too large, exceeding the above upper limit, the resulting wax will have poor heat resistance and is therefore unsuitable.

The number of double bonds per 1000 carbon atoms is determined as follows. Determined from the absorption intensity and film thickness of terminal vinyl (910 cm ^-1 ), trans vinyl (965 cm ^-1 ), and vinylidene (880 cm ^-1 ) from the IR spectrum of a sample film (film thickness 50 to 100 μm) molded using a compression molding machine. The amount of double bonds per 1000 carbon atoms is determined from the absorbance obtained using each calibration curve, and the total amount is determined.

As mentioned above, the above ethylene and C ₄ ~
The ethylene copolymer with _C10 α-olefin has properties (A) to (F), but in a particularly preferred embodiment, (G) the average number of methylene chains of (E) and the The difference between the number of methylene chains of the ethylene copolymer and a completely random copolymer having the same monomer composition is 30 or less, more preferably about 25 or less. For example, it is about 10 to 30.

This characteristic (G) is one of the measures expressing the randomness of the above copolymer, and the difference between the value for a completely random copolymer (calculated and determined by the content of ethylene and α-olefin) is The smaller the value, the better the randomness.

Preferably, the ethylene-based copolymer of ethylene and C ₄ to C ₁₀ α-olefin has a maximum melting point measured by (H) differential scanning calorimetry (DSC).
The temperature is 105°C or higher, more preferably about 110°C or higher.

For example, it exhibits a maximum melting point (the highest temperature in the peak of the DSC spectrum) in a range such as 105 to 120°C. Further, in many cases, the above-mentioned preferred ethylene copolymers have a melting point (the point at which the maximum amount of heat absorption occurs in the DSC spectrum) is about 80° C. or higher.

In the above ethylene copolymer, examples of C ₄ to _{C 10} α-olefins copolymerized with ethylene include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Nonen,
Examples include 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and 6-methyl-1-heptene. In particular, α- having 5 to 10 carbon atoms
Olefins, especially branched α-olefins, are preferred.

The above ethylene copolymer consists of (A) a highly active titanium catalyst component activated with a magnesium compound, (B)
an organoaluminum compound having a halogen/Al (atomic ratio) of 1 to 2, preferably 1.05 to 1.4; and
(C) It can be obtained by copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms at a temperature of 100° C. or higher in the presence of hydrogen in the presence of a catalyst formed from ether.

The highly active titanium catalyst component (A) is a titanium catalyst component that has been highly activated by using a magnesium compound, and the magnesium compound and titanium compound may be allowed to interact with each other before use, or the magnesium compound may be added in a polymerization system. High activation can be achieved by bringing the titanium compound into contact with the titanium compound.

The catalyst component (A) may be a titanium catalyst component supported on a magnesium compound, or the magnesium compound and the titanium compound may be dissolved in a hydrocarbon or the like by using a solubilizing agent such as an alcohol. It can be something. Titanium in the catalyst component (A) is usually tetravalent and/or trivalent. The solid catalyst component (A) usually preferably has a titanium content of about 0.2 to about 18% by weight, more preferably about
0.3 to about 15% by weight, and the halogen/titanium (molar ratio) is preferably about 4 to about 300,
More preferably from about 5 to about 200. Furthermore,
The specific surface area is preferably about 10 m ² /g or more, more preferably about 20 to about 1000 m ² /g, even more preferably about 40 to about 900 m ² /g.

Such a solid highly active titanium catalyst component (A) is widely known, and basically, a reactant with a large specific surface area is obtained by reacting a magnesium compound and a titanium compound, or a reactant with a large specific surface area is obtained. A method of reacting a titanium compound with a magnesium compound is often used. For example, co-pulverization of a magnesium compound and a titanium compound, thermal reaction of a magnesium compound with a sufficiently large specific surface area and a titanium compound, thermal reaction of an oxygen-containing magnesium compound and a titanium compound, and a method of co-pulverizing a magnesium compound treated with an electron donor. Typical examples include a method in which the material is treated in advance with an organic aluminum compound or a halogen-containing silicon compound, or is reacted with a titanium compound without treatment.

There are various magnesium compounds used for producing the solid highly active titanium catalyst component (A). For example, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, magnesium hydroxide, magnesium oxide, magnesium hydroxyhalide, alkoxymagnesium, alkoxymagnesium halide, allyloxymagnesium, allyloxymagnesium halide, alkylmagnesium halide, or these. Examples include mixtures. These may be made by any manufacturing method. The magnesium compound may also contain other metals, electron donors, and the like.

Ti(OR) ₄ −mXm(R
is a hydrocarbon group, such as a _C2 - _C6 alkyl group,
C ₆ - C ₁₂ aryl group, X is halogen, 0≦m≦
The tetravalent titanium compound shown in 4) can be exemplified. Examples of such titanium compounds are
_TiCl4 , _TiBr4 , Ti( _OC2H5 ) _{Cl3 ,} Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₆ H ₅ ) ₃ Cl, Ti(OC ₂ H ₅ ) ₄ ,
Examples include Ti( _{OC4H9 )4 .} Furthermore,
Titanium tetrahalide, aluminum, titanium,
Examples include various titanium trihalides obtained by reduction with a reducing agent such as hydrogen or an organic aluminum compound, such as titanium trichloride. These titanium compounds can be used in combination of two or more types.

Typical methods for obtaining such a solid highly active titanium catalyst component (A) include, for example, Japanese Patent Publication No. 46-34092, Japanese Patent Publication No. 46-34094, Japanese Patent Publication No. 46-34098, Japanese Patent Publication No. 47-1986.
41676, Japanese Patent Publication No. 47-46269, Japanese Patent Publication No. 50-32270, Japanese Patent Publication No. 53-1796, etc., and can be used in the present invention.

An example of a soluble highly active titanium catalyst component is
It is shown in Special Publication No. 53-151998.

The organoaluminum compound used together with the titanium catalyst component (A) has a halogen/Al (atomic ratio) in the range of 1 to 2, preferably 1.05 to 1.4;
A mixture of two or more types may be used, or trialkylaluminum, trihalogenated aluminum, etc. may be used as one component when used in combination. Such organoaluminum compounds include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, propylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride, octylaluminum sesquichloride, etc. Typical examples include alkylaluminum sesquichlorides such as chloride, alkyl aluminum dichlorides such as ethyl aluminum dichloride, and butyl aluminum dichloride, or mixtures thereof, or mixtures thereof with trialkylaluminum and/or trihalogenated aluminum. I can give it to you. Even if a trialkylaluminium or the like is used in place of such an organoaluminum compound, the wax of the present invention cannot be obtained.

As the ether (C), diethyl ether, diisopropyl ether, di-n-propyl ether,
Di-n-butyl ether, ethyl n-butyl ether, diisobutyl ether, diisoamyl ether, dihexyl ether, dioctyl ether,
Ethers having 2 to 20 carbon atoms such as ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran and anisole are preferably used. The amount of ether used is
Preferably, the ether/halogen-containing organoaluminium compound (molar ratio) ranges from about 0.05 to about 1, especially from about 0.1 to about 0.8.

The ethylene-based copolymers described above can also be formed in other manners. For example, the highly active titanium catalyst component (A) can be obtained by reacting a complex of magnesium halide and alcohol directly with a titanium compound, or by reacting the complex with an organoaluminum compound and then reacting with a titanium compound. When the organoaluminum compound (B) has a halogen/Al (atomic ratio) between 1 and 1.5, preferably between 1.05 and 1.4, the above ether (C) can be used in combination. It can be manufactured without

The copolymerization reaction is carried out in the presence of hydrogen at a temperature of 100° C. or higher, preferably about 120 to about 230° C., under conditions such that the copolymer produced dissolves in the reaction medium. The copolymerization is preferably carried out under conditions that provide a homogeneous phase. Hydrocarbons are preferably used as reaction medium, for example hexane, heptane, octane, decane, kerosene, cyclohexane, benzene,
Toluene, xylene, etc. can be used. It can be changed as appropriate depending on the ethylene content, intrinsic viscosity or polymerization temperature, amount of catalyst supplied, etc. of the target ethylene copolymer, but the number of carbon atoms relative to ethylene is 4.
-10 α-olefin supply ratio (mole ratio)
is preferably about 0.02 to about 0.30, and the hydrogen/ethylene (mole ratio) in the gas phase in the polymerization vessel is preferably about 0.1 to about 10. Advantageously, the copolymerization reaction is carried out in continuous mode. The catalyst in the obtained copolymer can be removed by known means such as filtration and washing.

In the present invention, the ethylene copolymer having the properties (A) to (F) as described above is preferably oxidized to an acid value of 0.1 to 20, particularly preferably about 0.3 to about 10.

Acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids contained in 1 g of wax. 1 g of the sample was dissolved in 50 ml of toluene, titrated with a 0.1N aqueous potassium hydroxide solution, and the amount of neutralization was calculated.

The means for producing oxidized waxes are known per se; for example, the above-mentioned ethylene copolymers in the molten state or the copolymers dispersed in water are heated at temperatures of about 120 to 200°C, especially about 140 to about 170°C. This can be suitably carried out by contacting with an oxygen-containing gas at .degree.

The wax (oxide wax) made of an oxide of an ethylene copolymer of the present invention exhibits excellent performance as a pigment dispersant. When used as a dispersant, for example, a pigment or the like is mixed in a proportion of about 20 to about 140 parts by weight to 100 parts by weight of the ethylene copolymer oxide wax of the present invention. A color base can be prepared by kneading at high temperature, cooling and solidifying, and then pulverizing to a suitable particle size, for example, about 20 to about 200 meshes. Next, the material may be melted and diluted in advance with the polymer compound to be colored, or may be directly added to the polymer compound in an amount that will give the required degree of coloring, and then molded. The pigments used may be organic or inorganic, and a representative example is the Latest Pigment Handbook (Seibundo Shinkosha, January 10, 1970).
(Published in Japan) on pages 216-221. As well as pigments, the oxide waxes of the invention can also be used for dispersing other additives such as fillers to be dispersed in polymeric compounds. Examples of these pigments or fillers include titanium oxide, iron oxide, magnesium hydroxide, calcium carbide, talc, carbon black, silica, magnesium carbonate, aluminum hydroxide, kaolin, asbestos, glass fiber, hydrotalcite, and zinc oxide. Examples include inorganic materials such as azo-based, isoindolinone-based, anthrone-based, phthalocyanine-based, dioxazine-based, perylene-based, perinone-based, and quinophthalone-based organic pigments. Various polymer compounds can be selected as the polymer compound to be colored, but polyolefin resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, etc.
Preference is given to application to base density polyethylene.

The ethylene copolymer oxide wax of the present invention can be used as a lubricant, hot melt resin, ink, etc. by itself or after reacting with maleic anhydride.
It can also be used for applications such as paint.

Next, an example will be explained.

The viscosity average molecular weight Mv in the examples was calculated from the limiting viscosity [η] using the following formula.

Mv=2.51× ¹⁰⁴ ×[η] ^{1. 235Example} 1 10 kg of dehydrated hexane and 10 kg of anhydrous magnesium chloride (average particle size 150μ) were charged into a 50 glass-lined reactor equipped with a stirrer under a nitrogen blanket, and the mixture was stirred at room temperature. The dropwise addition of 5 kg of ethanol was completed in 1 hour, and stirring was continued for 3 hours. Next, stop stirring and let stand, remove the supernatant hexane layer, charge 20 kg of titanium tetrachloride to make a slurry, react at 110℃ for 2 hours with stirring, let stand, and remove the supernatant. After removal, it was rinsed once with cold titanium tetrachloride, and titanium tetrachloride was replaced with hexane. The solid catalyst thus obtained contained 42 mg of titanium per gram.

Dehydrated hexane 100/hr, the above solid catalyst 2.8 mM/hr, ethyl aluminum sesquichloride 30 mM/hr, and diisoamyl ether 10 mM/hr were continuously fed to a pressurized continuous device equipped with a stirrer. In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the total pressure was 32 at a polymerization temperature of 140°C.
Continuous polymerization was carried out at a rate of Kg/cm ² and an average residence time of 1 hour in hexane, and the mixture was discharged from the reactor. The molecular weight of the wax obtained by continuously flashing hexane from the polymer solution is adjusted by the hydrogen/ethylene molar ratio in the reactor, and the density is adjusted by the 4-methyl-1-pentene/ethylene supply ratio. average molecular weight
5500 (intrinsic viscosity 0.29 dl/g), density 0.906, ethylene content 93.8 mol% ethylene-4-methyl-1
-Pentene copolymer was obtained at a rate of 14 Kg/hr. σ (≦120
°C)/σ ₀ = 0.98, DSC main peak 112 °C, ¹³ C
The average methylene chain length determined from NMR was 42. The number of double bonds determined by infrared absorption spectrum was 0.1 per 1000 carbon atoms.

Next, the above copolymer was stirred vigorously at 160°C in the absence of a catalyst and air was sucked in to obtain an acid value.
An oxide wax of 2.2 was obtained. The molecular weight of this oxide wax is 4800 (intrinsic viscosity 0.26 dl/g) and the density is
0.907, σ(≦120℃)/σ ₀ from the DSC curve
= 1.0, the DSC main peak was at 107°C.

The above wax (particle size: about 60 mesh) and pigment (phthalocyanine blue) were mixed in a 1:1 ratio and kneaded at 120°C using a triple roll. After kneading 1 g of this material and 38 g of high-pressure polyethylene using a Brabender Plastograph, it was made into a 100μ thick 24mm x 34mm.
Create a press sheet with a size of
Judgments were made in four stages: 2, 3, and 4 (5 or less items of 10μ or more). A pigment dispersion rating of 2 or less is poor and causes many practical problems, and the higher the number, the better the degree of dispersion. The degree of dispersion of this wax was 4. A press sheet of this material with a thickness of 2 mm was made and a bending test was conducted at room temperature with a span of 32 mm, and the maximum bending deflection was 6.2 mm, indicating excellent flexibility.

Reference example 1 Dehydrated hexane 50/hr, solid catalyst of Example 1 3mM/hr, ethylaluminum sesquichloride 43.5mM/hr in a pressurized continuous device equipped with a 200° stirrer.
hr, triethyl aluminum 6.5mM/hr (halogen/Al ratio 1.31), diisoamyl ether 10mM/hr
hr was continuously supplied. Furthermore, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and 170
Continuous polymerization was carried out at a polymerization temperature of ℃ at a total pressure of 38 Kg/cm ² and an average residence time of 2.4 hours in hexane, and then extracted from the reactor.
Treated in the same manner as in Example 1, the viscosity average molecular weight was 4500.
(intrinsic viscosity 0.25 dl/g), density 0.897 g/cm ³ , ethylene content 91.6 mol% ethylene-4-methyl-
A 1-pentene copolymer was obtained at a rate of 18 kg/hr.
σ (≦120
°C)/σ ₀ = 0.88, DSC main peak 120 °C, ¹³ C
The average methylene chain length determined from NMR was 31. The number of double bonds determined by infrared absorption spectrum was 0.03 per 1000 carbon atoms.
The pigment dispersion performance of this product was 3 to 4.

Reference Example 2 Dehydrated hexane 50/hr, solid catalyst of Example 1 0.7mM/hr,
Diethylaluminum chloride 45mM/hr, ethylaluminum sesquichloride 5mM/hr, and diisoamyl ether 10mM/hr were continuously supplied.
In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the total pressure was increased at a polymerization temperature of 170°C.
Continuous polymerization was carried out at 37 Kg/cm ² and an average residence time of 2.4 hours in hexane, and the mixture was extracted from the reactor and treated in the same manner as in Example 1, resulting in a viscosity average molecular weight of 4300 (intrinsic viscosity 0.24 dl/
g), an ethylene-4-methyl-1-pentene copolymer having a density of 0.897 g/cm ³ and an ethylene content of 92.9 mol% was obtained at a rate of 15.3 Kg/hr. σ (≦120℃) / σ ₀ = 0.82, DSC analyzed from the DSC curve of this product
The main peak was 115°C, and the average methylene chain length determined from ^13C NMR was 36. The number of double bonds determined by infrared absorption spectrum was 0.08 per 1000 carbon atoms. Pigment dispersibility was 3.

Reference Example 3 1 kg of anhydrous magnesium chloride (100 mesh passes, specific surface area 4 m ² /g) and 100 g of titanium tetrachloride were co-milled in a vibrating ball mill at room temperature for 6 hours. 24 mg of Ti was fixed on this co-pulverized solid catalyst.

100/hr of dehydrated hexane, 3.6 mM/hr of the above solid catalyst, 90 mM/hr of ethylaluminum sesquichloride, and 30 mM/hr of diisoamyl ether were continuously fed to a pressurized continuous device equipped with a stirrer. In addition, ethylene, 1-butene and hydrogen were continuously supplied, and the polymerization was carried out continuously at a polymerization temperature of 150° C. under a total pressure of 31 Kg/cm ² and an average residence time of hexane of 1 hour. Viscosity average molecular weight 4600 (intrinsic viscosity 0.25 dl/g), density 0.910 g/g
cm ³ , ethylene-1- with ethylene content of 93.5 mol%
Butene copolymer was obtained at a rate of 14 Kg/hr. σ (≦120℃) / σ ₀ = analyzed from the DSC curve of this product
0.97, DSC main peak 97℃, maximum melting point 112℃, ^13C
The average methylene chain length determined from NMR was 40. The number of double bonds determined by infrared absorption spectrum was 0.05 per 1000 carbon atoms, and the pigment dispersion rating was 3 to 4.

Comparative Reference Example 1 Dehydrated hexane 50/hr, solid catalyst of Example 1 2.5mM/hr,
Triethylaluminum was continuously supplied at 50mM/hr. In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the polymerization temperature was 180°C.
Continuous polymerization was carried out in hexane with an average residence time of 2.4 hours, and the mixture was extracted from the reactor and treated in the same manner as in Example 1.
17.5 g/cm ³ of ethylene-4-methyl-1-pentene copolymer with an ethylene content of 92.0 mol%
Obtained at the rate of Kg/hr. σ (≦120°C)/σ ₀ =0.78, which was analyzed from the DSC curve of this product. The pigment dispersion rating for this product was 2.

Comparative Reference Example 2 Dehydrated hexane 50/hr, solid catalyst of Example 1 2.2mM/hr,
Triethylaluminum was continuously supplied at 50mM/hr. In addition, ethylene, propylene and hydrogen were continuously supplied, and the polymerization temperature was 180°C, with a total pressure of 38Kg/cm ² ,
Continuous polymerization was carried out in hexane with an average residence time of 2.4 hours, and the polymer was extracted from the reactor and treated in the same manner as in Example 1.
An ethylene-propylene copolymer having a weight of 0.916 g/cm ³ and an ethylene content of 95.8 mol% was obtained at a rate of 15.2 Kg/hr. σ(≦
120°C)/σ ₀ =1.0, and the average methylene chain length determined from ¹³ C NMR was 32, but the pigment dispersion score was 1 to 2.

Comparative Reference Example 3 Dehydrated hexane 100/hr, solid catalyst of Example 1 4.4mM/hr,
Ethylaluminum sesquichloride 60mM/
hr, diisoaluminum ether 15mM/hr was continuously supplied. In addition, ethylene, propylene and hydrogen are continuously supplied, and the total pressure is increased at a polymerization temperature of 140℃.
27.5Kg/cm ² and continuous polymerization in hexane average residence time of 1 hour, extracted from the reactor and treated in the same manner as in Example 1 to obtain a viscosity average molecular weight of 4000 (intrinsic viscosity 0.23dl/
g), 7.5Kg/hr of ethylene-propylene copolymer with density 0.920g/cm ³ and ethylene content 96.0mol%
obtained at a rate of Although σ (≦120°C)/σ ₀ =1.0, which was analyzed from the DSC curve of this product, the pigment dispersion score was 2.

Comparative Reference Example 4 Dehydrated hexane 50/hr, solid catalyst of Example 1 2.5mM/hr,
Triethylaluminum was continuously supplied at 50mM/hr. In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the mixture was continuously polymerized at a polymerization temperature of 180°C with an average residence time of 2.4 hours in hexane, and then extracted from the reactor and treated in the same manner as in Example 1. , viscosity average molecular weight 6000 (intrinsic viscosity 0.31 dl/g), density
19.0 g/cm ³ of ethylene-4-methyl-1-pentene copolymer with an ethylene content of 93.0 mol%
Obtained at the rate of Kg/hr. σ (≦120℃) / σ ₀ = 0.82 analyzed from the DSC curve of this product, the main peak of DSC is 120℃, the average methylene chain length determined from ¹³ C NMR is 72, and the pigment dispersion score is 2 to 3. Ta.

[Brief explanation of drawings]

FIG. 1 is a drawing showing an example of an endothermic spectrum in a wax differential scanning calorimeter according to the present invention.

Claims (1)

[Claims] 1 The following (A) to (F) (A) Intrinsic viscosity measured in decalin at 135°C: 0.06
~0.6 dl/g, (B) Density 0.87 to 0.94 g/cm ³ , (C) 120°C or less of the endothermic spectrum with respect to the total area σ ₀ surrounded by the endothermic spectrum line and its baseline by differential scanning calorimeter The area σ surrounded by the endothermic spectrum line and its baseline
(≦120℃) Ratio σ (≦120℃) / σ ₀ is 0.82 or more, (D) Ethylene content 88 to 98 mol%, (E) Methylene chain in which the number of methylene chains in the polymer chain is 7 or more Oxidation of an ethylene-based copolymer of ethylene and a C ₄ to _{C 10} α-olefin having the following properties: the average number of methylene chains is 60 or less, and (F) the number of double bonds per 1000 carbon atoms is 0.7 or less. A dispersant for pigments or fillers, characterized by containing monowax (acid value 0.1 to 20) as an active ingredient.