JP2006342290A - Modified low molecular weight ethylenic polymer and application of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a modified low molecular weight ethylenic polymer excellent in adhesiveness, printability, compatibility in polymer blends, mold releasability at high temperatures, fixability at low temperatures, dispersibility of pigments, initial lubricity, burnishing properties and the like, and application of the same. <P>SOLUTION: The modified low molecular weight ethylenic polymer (B) having a hetero atom-containing group is prepared by treating a low molecular weight ethylenic polymer (A) defined by the following (i)-(vi). The low molecular weight ethylenic polymer (A) defined by the above (i)-(vi) is (i) a copolymer prepared by copolymerizing ethylene with at least one or more dienes or a copolymer prepared by copolymerizing ethylene with at least one or more olefins selected from 3-12C α-olefins and has (ii) 0.5-4.0 content of unsaturated group per one molecule, (iii) 870-980kg/m<SP>3</SP>density, (iv) 70-130°C melting point, (v) 400-5,000 number average molecular weight and (vi) ≥4.0 Mw(weight average molecular weight)/Mn (number average molecular weight). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a modified low molecular weight ethylene polymer obtained by treating an unsaturated group of a polymer having an olefinically unsaturated bond in a polymer chain with a specific modifier. The present invention relates to a modified low molecular weight ethylene polymer having excellent properties, printability, compatibility with a polymer blend, and the like.

In addition, the present invention is a paint modifier, a polishing agent, a mold release agent for resin molding, a rubber processing aid, a paper quality improver, an ink wear resistance improver, a fiber processing aid, The present invention relates to a melt additive, an electrical insulating agent, a natural wax compounding agent, a polyolefin film antifogging agent, a toner release agent, a pigment dispersant, and a vinyl chloride resin lubricant.

  Ethylene polymers or α-olefin polymers are excellent in cost and mechanical properties, and are most widely used as raw materials for various resin products. However, it has non-polar molecular structure and poor affinity with other substances, giving it high functionality such as printability, paintability, heat resistance, impact resistance, and compatibility with other polar polymers. The high chemical stability is hindered from the viewpoint of In order to improve such drawbacks, attempts have been made to introduce various functional groups into the ethylene polymer or α-olefin polymer.

  As a method for imparting functionality to an ethylene polymer or α-olefin polymer, for example, a method of copolymerizing an olefin and a polar monomer such as vinyl acetate or methacrylate by a radical polymerization method, or in the presence of a peroxide. A method of grafting a polar monomer such as maleic anhydride to a polyolefin is known. However, these methods are difficult to precisely control the structure of the polyolefin moiety in the obtained polymer, and are insufficient to maintain the excellent physical properties of the polyolefin.

  A polyolefin macromonomer having a polymerizable vinyl bond at the end is used as one means for producing a polymer having a polyolefin part having a precisely controlled structure and a function that cannot be expressed only by polyolefin. A graft polymer having a polyolefin side chain can be considered by homopolymerizing or copolymerizing with a variety of vinyl monomers having a functional group. As a method for producing a polyolefin macromonomer for synthesizing such a graft polymer, for example, in JP-A-6-329720, a polymerizable acryloyl group or a terminal of polyethylene synthesized by using a living polymerization method is disclosed. A method for introducing a methacryloyl group is described. JP-A-8-176354 and JP-A-8-176415 disclose a method for introducing a polymerizable styryl group into the terminal of a polypropylene polymer synthesized using a living polymerization method. . However, the method using living polymerization has poor productivity and is not practical.

JP-A-2003-73412 discloses that (1) the structural unit derived from ethylene is in the range of 81 to 100 mol%, the structural unit derived from α-olefin is in the range of 0 to 19 mol%, and (2) GPC (3) The molecular weight distribution (Mw / Mn) is 1.1 ≦ Mw / Mn ≦ 2.5, and (4) a vinyl or vinylidene group is a polymer. Proposals have been made for modified products of various modifiers of low molecular weight ethylene polymers, characterized in that the content of these groups at the end of the main chain, as measured by ¹ H-NMR, is 90% or more of all the ends of one piece. Has been made. In this method, the functional group is only present at the end of the main chain of the polymer, and the number of unsaturated groups into which the functional group can be introduced per molecule of the polymer chain does not exceed 1 at most. There are still problems when designing.

JP-A-6-329720 JP-A-8-176354 JP-A-8-176415 Japanese Patent Laid-Open No. 2003-73412

An object of the present invention is to provide a modified low molecular weight ethylene polymer having a precisely controlled structure, good productivity, and capable of imparting high functions such as adhesion, printability, and compatibility with polymer blends, and the like To provide a use.

That is, the present invention
Modified low molecular weight ethylene polymer having a hetero atom-containing group obtained by treating an unsaturated group of the low molecular weight ethylene polymer (A) defined by (i) to (vi) below with a modifier. (B),
(I) a copolymer obtained by copolymerizing ethylene and at least one diene, or at least one olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene Is a copolymer obtained by copolymerizing
(Ii) 0.1 to 4.0 unsaturated group content per molecule (iii) density of 870 to 980 kg / m ³
(Iv) Melting point is 70-130 ° C
(V) A number average molecular weight of 400 to 5,000
(Vi) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less, and uses thereof.

  Since the low molecular weight ethylene polymer (A) of the present invention has a reactive unsaturated bond in the polymer chain, any functional group can be imparted by various modification techniques. Such a modified low molecular weight ethylene polymer (B) can provide a toner release agent having excellent high-temperature release properties and excellent low-temperature fixability. In addition, the modified low molecular weight ethylene polymer (B) can provide a pigment dispersant excellent in pigment dispersibility and a lubricant for polyvinyl chloride resin excellent in initial lubricity. Furthermore, many useful uses such as paint modifiers and polishes can be provided.

  The present invention is described in detail below.

(Low molecular weight ethylene polymer (A))
Examples of the olefin used for the production of the low molecular weight ethylene polymer (A) include at least one olefin selected from ethylene and / or an α-olefin having 3 to 12 carbon atoms. Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene. 1-octene, 1-decene, 1-dodecene and the like are mentioned, preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, particularly preferably. Is propylene, 1-butene, 1-hexene, 4-methyl-1-pentene.

  Dienes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1, 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 2-methyl-1,4-hexadiene, 2- Examples thereof include methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene and the like.

  Of these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, butadiene, isoprene, 2-methyl-1,4-hexadiene or 2-methyl-1,6-octadiene are preferable.

  Non-conjugated dienes include ethylidene norbornene, tetrahydroindene, vinyl norbornene, 5-methylene-2-norbornene, dicyclopentadiene, tetrahydroindene, methyltetrahydroindene, bicyclo- (2,2,1) -hepta-2. 5-Diene, 5-propenyl-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene, 5-cyclohexylidene-2-norbornene and the like can be mentioned.

  The low molecular weight ethylene polymer (A) is obtained by copolymerizing the olefin and the diene as described above. The low molecular weight ethylene polymer (A) is a copolymer of ethylene and diene or ethylene. And a copolymer of at least one α-olefin selected from an α-olefin having 3 to 12 carbon atoms and a diene.

  The low molecular weight ethylene polymer (A) according to the present invention is preferably obtained by copolymerizing an olefin and a diene using a metallocene catalyst as described later.

  In the low molecular weight ethylene polymer (A), a structural unit derived from a diene is usually 0.01 to 5.0 mol%, preferably 0.01 to 4.0 mol%, more preferably 0.1 to 3. mol%. It is desirable to contain in the ratio of 0 mol%.

  When the low molecular weight ethylene polymer (A) is an ethylene copolymer, the structural unit derived from ethylene is usually 80 to 99 mol%, preferably 86 to 99 mol%, more preferably 90 to 99 mol. It is desirable to contain in the range of%. When the low molecular weight ethylene polymer (A) is an ethylene copolymer and the constitutional unit derived from ethylene is within the above range, a modified low molecular weight ethylene polymer having good releasability as a toner release agent. A coalescence (C) can be obtained.

  The low molecular weight ethylene polymer (A) generally has an unsaturated group content of 0.1 to 4.0 / molecule on average, preferably 0.1 to 3.0, more preferably 0.5 to The number is 3.0, most preferably 1.0 to 2.0 / molecule.

  When the unsaturated group content in the low molecular weight ethylene polymer (A) is within the above range, the low molecular weight ethylene polymer (A) can contain a large number of epoxy groups. The effect can be obtained with the system polymer (A). In particular, if the unsaturated group content in the low molecular weight ethylene polymer (A) is 1.0 / molecule or more on average, almost all ethylene polymer (A) can contain an epoxy group. Therefore, a large effect can be obtained with a small amount of low molecular weight ethylene polymer (A).

  In addition, unsaturated group content in a low molecular weight ethylene polymer (A) is measured as follows.

^{By 13} C-NMR, it is obtained by comparing the peak area of the carbon of the unsaturated portion with the peak area of the total carbon. Thereby, the number M of unsaturated groups per 1,000 carbons can be obtained. The unsaturated group content per molecule can be obtained by number average molecular weight (Mn) × M / 14,000. The number M of unsaturated groups per 1,000 carbons is usually 1.4 to 140, preferably 2.8 to 35, and more preferably 4 to 30.

The low molecular weight ethylene polymer (A) has a density measured by a density gradient tube method of 870 to 980 kg / m ³ , preferably 870 to 950 kg / m ³ , more preferably 870 to 920 kg / m ³ , and even more preferably. It is in the range of 880 to 920 kg / cm ³ .

Low molecular weight ethylene polymer (A) has an intrinsic viscosity measured at 135 ° C. in decalin [eta] is usually 0.04~0.47dl · g ^-1, preferably 0.05~0.47dl · g ^-1 More preferably 0.07 to 0.20 dl · g ⁻¹ , still more preferably 0.10 to 0.18 dl · g ⁻¹ .

  A modified low molecular weight ethylene polymer having good releasability as a release agent for toner when the intrinsic viscosity [η] measured in 135 ° C. decalin of the low molecular weight ethylene polymer (A) is within the above range. (C) can be obtained.

  The low molecular weight ethylene polymer (A) has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 4,500, preferably 800 to 4,500, more preferably 1,000 to 1,000. 3000, even more preferably in the range of 1,500 to 2,500.

  The low molecular weight ethylene polymer (A) has a molecular weight distribution (Mw / Mn) measured by GPC of usually 4.5 or less, preferably Mw / Mn of 4.0 or less, more preferably 3.5 or less. The lower limit of the molecular weight distribution is 1.0.

  In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the values of polystyrene conversion by gel permeation chromatography (GPC), and the measurement by GPC is the conditions of temperature: 140 ° C., solvent: orthodichlorobenzene. Done under.

  The low molecular weight ethylene polymer (A) usually has a penetration of 15 dmm or less, preferably 10 dmm or less, more preferably 3 dmm or less, and even more preferably 1 dmm or less. The penetration can be measured according to JIS K2207.

  The low molecular weight ethylene polymer (A) as described above includes, for example, the following metallocene comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table, an organoaluminum oxy compound and / or an ionized ionic compound. It can manufacture using a system catalyst.

(Metallocene compound)
The metallocene compound that forms the metallocene catalyst is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specific examples include compounds represented by the following general formula (1).

M ¹ Lx (1)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, x is a valence of the transition metal M ¹ , and L is a ligand. Examples of the transition metal represented by M ¹ include zirconium, titanium, hafnium and the like. L is a ligand coordinated to the transition metal M ^1, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having this cyclopentadienyl skeleton. The ligand may have a substituent. Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, n-, alkyls such as i-, sec- or t-butylcyclopentadienyl, dimethylcyclopentadienyl, methylpropylcyclopentadienyl, methylbutylcyclopentadienyl, methylbenzylcyclopentadienyl, etc. An alkyl-substituted cyclopentadienyl group; and an indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like. The hydrogen of the ligand having a cyclopentadienyl skeleton may be substituted with a halogen atom or a trialkylsilyl group.

  When the metallocene compound has two or more ligands having a cyclopentadienyl skeleton as the ligand L, the ligands having two cyclopentadienyl skeletons are ethylene, propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

Examples of ligands other than ligands having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfones. Acid-containing group (—SO ₃ R ¹ ), halogen atom or hydrogen atom (where R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an alkyl group) A substituted aryl group).

(Example of metallocene compound-1)
When the metallocene compound represented by the general formula (1) has a transition metal valence of 4, for example, it is more specifically represented by the following general formula (2).
R ² _k R ³ _l R ⁴ _m R ⁵ _n M ¹ (2)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are each independently cyclopentadienyl. A group (ligand) having or not having a skeleton. k is an integer of 1 or more, and k + l + m + n = 4.

Examples of metallocene compounds in which M ¹ is zirconium and contains at least two ligands having a cyclopentadienyl skeleton are given below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride and the like.

  Among the above compounds, a compound in which the 1,3-position substituted cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl group can also be used.

As another example of the metallocene compound, in the general formula (2), at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton ( A bridge type metallocene compound in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. At this time, R ⁴ and R ⁵ are each independently the same as the ligand L other than the ligand having the cyclopentadienyl skeleton described above.

  Examples of such bridge-type metallocene compounds include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methyl Examples include phenylsilylene bis (indenyl) zirconium dichloride.

(Example of metallocene compound-2)
Examples of the metallocene compound include metallocene compounds described in JP-A-4-268307 represented by the following general formula (3).

Here, M ¹ is a Group 4 transition metal of the periodic table, and specifically includes titanium, zirconium, and hafnium.

R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Aryloxy group having 6 to 10 carbon atoms; alkenyl group having 2 to 10 carbon atoms; arylalkyl group having 7 to 40 carbon atoms; alkylaryl group having 7 to 40 carbon atoms; arylalkenyl group having 8 to 40 carbon atoms Or a halogen atom, and R ¹¹ and R ¹² are preferably chlorine atoms.

R ¹³ and R ¹⁴ may be the same or different from each other, and are a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; (R ²⁰ ) ₂ , —SR ²⁰ , —OSi (R ²⁰ ) ₃ , —Si (R ²⁰ ) ₃ or —P (R ²⁰ ) ₂ groups.

R ²⁰ is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. R ¹³ and R ¹⁴ are particularly preferably hydrogen atoms.

R ¹⁵ and R ¹⁶ are the same as R ¹³ and R ¹⁴ except that they do not contain a hydrogen atom, and may be the same or different from each other, preferably the same. R ¹⁵ and R ¹⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. Particularly preferred is methyl.

In the general formula (3), R ¹⁷ is selected from the following group.

^{= BR 21, = AlR 21,} -Ge -, - Sn -, - O -, - S -, = SO, = SO 2, = NR 21, = CO, = PR 21, = P (O) R 21 , etc. . M ² is silicon, germanium or tin, preferably silicon or germanium. Here, R ²¹ , R ²² and R ²³ may be the same or different from each other, and are hydrogen atom; halogen atom; alkyl group having 1 to 10 carbon atoms; fluoroalkyl group having 1 to 10 carbon atoms; carbon atom An aryl group having 6 to 10 carbon atoms; a fluoroaryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms; An arylalkenyl group having 8 to 40 carbon atoms; or an alkylaryl group having 7 to 40 carbon atoms. “R ²¹ and R ²² ” or “R ²¹ and R ²³ ” may form a ring together with the atoms to which they are bonded. R ¹⁷ may be = CR ²¹ R ²² , = SiR ²¹ R ²² , = GeR ²¹ R ²² , -O-, -S-, = SO, = PR ²¹ or = P (O) R ^21. preferable. R ¹⁸ and R ¹⁹ may be the same as or different from each other, and examples thereof include the same as R ²¹ . m and n may be the same or different and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Examples of the metallocene compound represented by the general formula (3) include the following compounds. rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium dichloride, and the like. These metallocene compounds can be produced, for example, by the method described in JP-A-4-268307.

(Example of metallocene compound-3)
Moreover, as a metallocene compound, the metallocene compound represented by following General formula (4) can also be used.

In Formula (4), M ³ represents a transition metal atom of Group 4 of the periodic table, and specifically, titanium, zirconium, hafnium, and the like. R ²⁴ and R ²⁵ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, oxygen A containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; R ²⁴ is preferably a hydrocarbon group, and particularly preferably an alkyl group having 3 to 3 carbon atoms of methyl, ethyl or propyl. R ²⁵ is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Indicates a group. Among these, a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable. At least one of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , and R ²⁸ and R ²⁹ may form a monocyclic aromatic ring together with the carbon atoms to which they are bonded. Good. When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming the aromatic ring, they may be bonded to each other to form a ring. When R ²⁹ is a substituent other than an aromatic group, it is preferably a hydrogen atom. X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen atom-containing group or Y representing a sulfur atom-containing group is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or divalent germanium. containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 30 -, - P (R 30) -, - P (O) ( R ³⁰ ) —, —BR ³⁰ — or —AlR ³⁰ — (wherein R ³⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Indicates.

In the formula (4), at least one pair of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ is bonded to each other, and is coordinated to M ³ Examples of the ligand include those represented by the following formula.

(In the formula, Y is the same as that shown in the previous formula.)

(Example of metallocene compound-4)
As the metallocene compound, a metallocene compound represented by the following general formula (5) can also be used.

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as those in the general formula (4). Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , two groups including R ²⁶ are preferably alkyl groups, and R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are alkyl groups. preferable. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and silicon-containing group include the substituents exemplified for R ²⁴ and R ²⁵ . Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , the group other than the alkyl group is preferably a hydrogen atom. R ²⁶ , R ²⁷ , R ^28, and R ²⁹ may form a monocyclic ring or a polycyclic ring other than an aromatic ring by combining two groups selected from these groups. Examples of the halogen atom are the same as those described above for R ²⁴ and R ²⁵ . Examples of X ¹ , X ² and Y are the same as those described above.

  Specific examples of the metallocene compound represented by the general formula (5) are shown below. rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 , 4,6-Trimethyl-1-indenyl) zirconium dichloride and the like.

  In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used. The transition metal compound is usually used as a racemate, but can also be used in the R-type or S-type.

(Example of metallocene compound-5)
As the metallocene compound, a metallocene compound represented by the following general formula (6) can also be used.

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as those in the general formula (4). R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. R ²⁵ represents an aryl group having 6 to 16 carbon atoms. R ²⁵ is preferably phenyl or naphthyl. The aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  Specific examples of the metallocene compound represented by the general formula (6) are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl) -4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 -Methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride and the like. In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

(Example of metallocene compound-6)
As the metallocene compound, a metallocene compound represented by the following general formula (7) can also be used.
LaM ⁴ X ³ ₂ (7)

Here, M ⁴ is a periodic table group 4 or lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group imparting a constraining geometry to the metal M ⁴ active site. X ³ may be the same or different from each other, and is a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium.

  Among these compounds, a compound represented by the following formula (8) is preferable.

In the formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is the same as that described in the general formula (7). Cp is a substituted cyclopentadienyl group having a π bond to M ⁴ and having a substituent Z. Z is oxygen, sulfur, boron or an element belonging to Group 4 of the periodic table (for example, silicon, germanium or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring. Specific examples of the metallocene compound represented by the formula (8) are shown below. (Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium Dichloride etc. In the metallocene compound, a compound in which titanium is replaced with zirconium or hafnium can be exemplified.

(Example of metallocene compound-7)
Moreover, as a metallocene compound, the metallocene compound represented by following General formula (9) can also be used.

In formula (9), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³¹ may be the same as or different from each other, and at least one of them is an aryl group having 11 to 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms, an arylalkenyl group having 13 to 40 carbon atoms, carbon An alkylaryl group having 12 to 40 atoms or a silicon-containing group, or at least two adjacent groups among the groups represented by R ³¹ , together with the carbon atoms to which they are bonded, one or more aromatic rings Or an aliphatic ring is formed. In this case, the ring formed by R ^31, it is 4 to 20 carbon atoms in all including carbon atoms to which R ³¹ is bonded. Aryl group, arylalkyl group, arylalkenyl group, an alkylaryl group and an aromatic ring, R ³¹ other than R ³¹ that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms Or a silicon-containing group. R ³² may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Further, at least two adjacent groups among the groups represented by R ³² may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R ³² has 4 to 20 carbon atoms in all including carbon atoms to which R ³² is bonded, an aromatic ring, other than R ³² that forms an aliphatic ring R ³² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group. The group in which the two groups represented by R ^{32 form} one or more aromatic rings or aliphatic rings includes an embodiment in which the fluorenyl group has a structure represented by the following formula.

R ³² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. A suitable example of such a fluorenyl group having R ³² as a substituent is a 2,7-dialkyl-fluorenyl group. In this case, the 2,7-dialkyl alkyl group has a carbon number of 1 to 5 alkyl groups. R ³¹ and R ³² may be the same as or different from each other. R ³³ and R ³⁴ may be the same as or different from each other, and are the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups, arylalkyl groups having 7 to 40 carbon atoms, arylalkenyl groups having 8 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, A nitrogen-containing group or a phosphorus-containing group. Of these, at least one of R ³³ and R ³⁴ is preferably an alkyl group having 1 to 3 carbon atoms. X ¹ and X ² may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . As the conjugated diene residue formed from X ¹ and X ² , residues of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene and 1,4-diphenylbutadiene are preferable. These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. X ¹ and X ² are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, —O—, —CO—, —S—, —SO—, —SO ₂ —, —NR ³⁵ —, —P (R ³⁵ ) —, —P (O) (R ³⁵ ) —, — BR ³⁵ - or -AlR ³⁵ - (provided that, R ³⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms) shows a. Among these divalent groups, those in which the shortest connecting portion of -Y- is composed of one or two atoms are preferable. R ³⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, more preferably a divalent silicon-containing group. Particularly preferred is silylene, alkylarylsilylene or arylsilylene.

(Example of metallocene compound-8)
As the metallocene compound, a metallocene compound represented by the following general formula (10) can also be used.

In formula (10), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³⁶ may be the same as or different from each other, and includes a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and silicon-containing Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. The alkyl group and alkenyl group may be substituted with a halogen atom. Of these, R ³⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a hydrocarbon group having 1 to 3 carbon atoms of methyl, ethyl, n-propyl, i-propyl, phenyl, α-naphthyl. An aryl group such as β-naphthyl or a hydrogen atom is preferable. R ³⁷ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a carbon atom. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Note that the alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group, and alkylaryl group may be substituted with halogen. Of these, R ³⁷ is preferably a hydrogen atom or an alkyl group, and particularly a hydrogen atom or a carbon atom having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, or tert-butyl. A hydrogen group is preferred. R ³⁶ and R ³⁷ may be the same as or different from each other. One of R ³⁸ and R ³⁹ is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Among these, it is preferable that any one of R ³⁸ and R ³⁹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, and propyl, and the other is a hydrogen atom. X ¹ and X ² may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . Among these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, —O—, —CO—, —S—, —SO—, —SO ₂ —, —NR ⁴⁰ —, —P (R ⁴⁰ ) —, —P (O) (R ⁴⁰ ) —, — BR ⁴⁰ -or -AlR ^40- (wherein R ⁴⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group, and more preferably a divalent silicon-containing group. An alkylsilylene, an alkylarylsilylene or an arylsilylene is particularly preferable.

  The metallocene compounds described above are used alone or in combination of two or more. The metallocene compound may be diluted with a hydrocarbon or a halogenated hydrocarbon.

(Organic aluminum oxy compound)
The organoaluminum oxy compound may be a known aluminoxane or a benzene-insoluble organoaluminum oxy compound. Such a known aluminoxane is specifically represented by the following formula.

  Here, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably 5 to 40. Is an integer.

  The aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ′)) and an alkyloxyaluminum unit represented by the formula (OAl (R ″)) (where R ′ and R ″ are R And R ′ and R ″ represent different groups.) And may be formed from mixed alkyloxyaluminum units. The organoaluminum oxy compound may contain a small amount of a metal organic compound component other than aluminum.

(Ionized ionic compounds)
Examples of ionized ionic compounds (sometimes referred to as ionic ionized compounds and ionic compounds) include Lewis acids, ionic compounds, borane compounds, and carborane compounds. As the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group or fluorine) can be used. Specific examples of the Lewis acid include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris ( Pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Examples of the trialkyl-substituted ammonium salt as the ionic compound include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n-butyl) ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt as the ionic compound include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like. .

  Examples of the borane compound include decaborane (9); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydridododeca Examples thereof include salts of metal borane anions such as borate) nickelate (III).

  Examples of the carborane compounds include 4-carbanonaborane (9), 1,3-dicarbanonaborane (8), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelic acid. And salts of metal carborane anions such as salt (IV).

  Such ionized ionic compounds may be used alone or in combination of two or more.

  In forming the metallocene catalyst, the following organoaluminum compounds may be used together with the organoaluminum oxy compound and / or the ionized ionic compound.

(Organic aluminum compound)
As the organoaluminum compound used as necessary, a compound having at least one Al-carbon bond in the molecule can be used. As such a compound, for example, an organoaluminum represented by the following general formula (11) Compound,
_{^{(R 6) m Al (OR}} 7) n H p X 4 q ... (11)
(In the formula, R ⁶ and R ⁷ may be the same or different from each other, and are a hydrocarbon group usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X ⁴ is a halogen atom. Is a number satisfying 0 ≦ m <3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3) and the following general formula ( And a complex alkylated product of Group 1 metal and aluminum represented by 12).

(M ⁵ ) Al (R ⁶ ) (12)
(In the formula, M ⁵ is Li, Na or K, and R ⁶ is the same as R ^{6 in the} general formula (11).)

(polymerization)
In the low molecular weight ethylene polymer (A) used in the present invention, ethylene and diene are usually copolymerized in the liquid phase in the presence of the metallocene catalyst, or ethylene, diene and α-olefin are copolymerized. Can be obtained. In this case, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. The monomers used here are as described above.

  The polymerization method includes suspension polymerization in which the low molecular weight ethylene polymer (A) is present as particles in a solvent such as hexane, gas phase polymerization without using a solvent, and a polymerization temperature of 140 ° C. or higher. Thus, it is possible to perform solution polymerization in which the low molecular weight ethylene polymer (A) coexists with a solvent or is melted alone, and among them, solution polymerization is preferable in terms of both economy and quality.

  The polymerization reaction may be performed by either a batch method or a continuous method. When the polymerization is carried out by a batch method, the above catalyst components are used in the concentrations described below.

  The concentration of the metallocene compound in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter.

  The organoaluminum oxy compound is supplied in an amount of 1 to 10,000, preferably 10 to 5,000, in a molar ratio of aluminum atom to transition metal (Al / transition metal) in the metallocene compound in the polymerization system.

  The ionized ionic compound is represented by the molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound), and is supplied in an amount of 0.5 to 20, preferably 1 to 10. .

  When an organoaluminum compound is used, it is generally used in an amount of about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.

The polymerization reaction is usually performed at a temperature of −20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and a pressure exceeding 0 to 7.8 MPa (80 kgf / cm ² , gauge pressure), preferably Is performed under the condition of more than 0 and 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

  In the polymerization, ethylene and the α-olefin used as necessary are supplied to the polymerization system in such a proportion that the low molecular weight ethylene polymer (A) having the specific composition described above can be obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.

  When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, and thus a low molecular weight ethylene polymer (A) can be obtained by treatment by a conventional method.

  In the polymerization reaction, it is particularly preferable to use a catalyst containing a metallocene compound shown in (Example 6 of metallocene compound).

(Modified low molecular weight ethylene polymer (B))
The low molecular weight ethylene polymer according to the present invention converts an unsaturated group contained in the polymer into a modifier, that is, an oxidizing agent, a sulfonating agent, maleic anhydride and derivatives thereof, a hydroborating agent, and an organoaluminum. A heteroatom-containing group, that is, an oxygen-containing group, sulfur-containing group, metal-containing group (silicon-containing group, boron-containing group), halogen-containing group It is possible to denature. Examples of the epoxidizing agent used as a modifier in the present invention include formic acid-hydrogen peroxide (H ₂ O ₂ ) and m-chloroperbenzoic acid. A sulfonating agent is sulfuric acid-acetic anhydride. Examples of hydroborating agents include diborane, trimethylborane, 9-boranebicyclo [3.3.1] nonane. Examples of the organic aluminum hydride include diisobutylaluminum hydride. Examples of the silylating agent include triethoxysilyl hydride / H ₂ PtCl ₂ and trimethoxysilyl hydride / H ₂ PtCl ₂ . Examples of the halogenating agent include hydrogen bromide, hydrogen chloride, hydrogen iodide and the like.

  For specific modification conditions (temperature, time, catalyst type, catalyst amount, etc.) with these modifiers, conform to the conditions described in Die Makromolecular Chemie Makromolecular Symposia 48/49, 317-332, 1991. Is possible. For example, an oligomer having an oxygen-containing group in which an unsaturated group is modified with maleic anhydride, an oligomer containing an amide group and an amine group, and the like are suitable for paint additives and pigment dispersants for imparting thixotropy. In addition, oligomers having silicon-containing groups and tin-containing groups are suitable for use as polyvinyl chloride lubricants, lubricants such as engineering plastics, and paper treatment agents.

  The paint modifier according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This paint modifier has an excellent matting effect and improves the abrasion resistance of the coating film. Specifically, it imparts a high-class feeling to the woodwork paint and improves the durability.

  The polishing agent according to the present invention contains a low molecular weight ethylene polymer that may have a terminal modified as described above. This polish is excellent in gloss and improves the physical properties of the coating film. Specifically, the performance of car wax and floor polish is improved.

  The mold release agent for resin molding according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This release agent imparts release properties to thermoplastic resins and thermosetting resins. For this reason, it is possible to improve the molding cycle of the resin.

  The rubber processing aid according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This auxiliary agent is excellent in releasability and fluidity, and improves the dispersibility of the filler and the pigment. Specifically, the molding cycle and extrusion characteristics are improved.

  The paper quality improver according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This paper quality improver improves moisture resistance, gloss, surface hardness, blocking resistance, and abrasion resistance. Specifically, it gives a high-class feeling and improves durability.

  The antiwear improver for ink according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This abrasion resistance improver imparts abrasion resistance and heat resistance to the ink surface. Specifically, the freshness of the ink is improved.

  The fiber processing aid according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This auxiliary agent imparts flexibility and lubricity during resin processing of fibers. Specifically, high-speed sewing properties and tear strength are improved.

  The hot melt additive according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This additive imparts heat resistance and fluidity to the hot melt adhesive. Specifically, improve the quality in heat-resistant fields (automobiles, building materials).

  The electrical insulating agent according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This electrical insulating agent has excellent electrical properties and improves the softening point. Specifically, the electrical insulation characteristics of the film capacitor are improved.

  The natural wax compounding agent according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This compounding agent improves surface hardness and softening point. Specifically, it improves the performance of crayons and candles.

  As described above, the antifogging agent for polyolefin film according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B). This antifogging agent is excellent in compatibility with the resin and suppresses bleed-out to the resin surface. Specifically, the durability of the film is improved.

  The toner release agent according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This toner release agent imparts offset resistance to the fixing roll. Specifically, the image clarity is improved.

  The pigment dispersant according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This pigment dispersant is excellent in wetting with various pigments and improves sustainability. Specifically, a high concentration master batch is made possible. The lubricant for a vinyl chloride resin according to the present invention contains the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as described above. This lubricant has an excellent balance of lubricant and is durable. Specifically, productivity is improved and power consumption is reduced.

  Furthermore, the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) synthesized in this way is polymerized alone as a macromonomer, or ethylene and an α-olefin having 3 to 10 carbon atoms. It is possible to copolymerize with at least one olefin selected from the above, and it can also be used in a coupling reaction. Examples of the α-olefin having 3 to 10 carbon atoms used at this time include α-olefins used in the production of the low molecular weight ethylene polymer (A). The polymer obtained by using the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) as a macromonomer is a novel polymer having a new skeleton, and itself or a resin containing the polymer It is used for various uses as a composition. For example, by copolymerizing with ethylene, a long-chain branched polyethylene in which the number of branched chains and the molecular weight of the branched portion are freely controlled can be produced. Furthermore, when an amorphous polymer is produced in the copolymerization of ethylene / α-olefin, it is possible to coexist amorphous and crystalline parts in the polymer molecule by copolymerizing polyethylene macromonomer. Thus, a high-performance copolymer can be produced. Moreover, this copolymer can also be used as a modifier for polypropylene resins, and can be blended in a proportion of, for example, 1 to 30 parts by weight with respect to the polypropylene resin.

  The toner release agent of the present invention is used as a component of a toner for developing an electrostatic image together with a binder resin, a colorant, and, if necessary, a charge control agent. The number average molecular weight of the release agent is in the range of 300 to 2000, preferably in the range of 400 to 1000.

  The binder resin is not particularly limited as long as it is made of a thermoplastic resin generally blended in a developer for developing an electrostatic charge image. For example, styrene resin, styrene-acrylic ester acid copolymer, acrylic resin, styrene-butadiene resin, ketone resin, maleic acid resin, polyester resin, polyvinyl acetate resin, coumarone resin, phenol resin, silicone resin, polyurethane, epoxy resin Terpene resin, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, ethylene-vinyl acetate copolymer, rosin resin, and the like. Among these, styrene-acrylic acid ester copolymers, polyester aromatic resins, and epoxy resins are particularly preferable because of their suitable softening point (90 ° C. to 120 ° C.) and good fixability.

  The colorant is not particularly limited as long as it is generally blended with an electrostatic charge image developer. For example, pigments or dyes such as carbon black, phthalocyanine blue, aniline blue, arco oil blue, chrome yellow, ultramarine blue, quinoline yellow, lamp black, rose bengal, diazo yellow, rhodamine B lake, carmine 6B, quinacridone derivatives, etc. These may be used alone or in combination of two or more.

  The mixing ratio of the release agent for toner of the present invention is usually such that the ratio of binder resin / colorant / charge control agent / release agent of the present invention is 100/1 to 10/0 to 5/0 by weight. It is about 5-40, Preferably it is 100 / 1-6 / 0.5-2 / 10-20.

  The pigment dispersant of the present invention is mixed with a pigment and then mixed with a resin to be colored, and then kneaded and granulated with an extruder, and used as a dry color, a color compound or a master batch. The blending ratio of the pigment dispersant is usually 25 to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the pigment. The number average molecular weight is in the range of 1000 to 5000, preferably in the range of 1500 to 3000. Examples of the resin to be colored include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polyolefin resins such as ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polystyrene, ABS, and the like. Heat of styrene resin, polycarbonate resin obtained from bisphenol-A and phosgene, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, thermoplastic resin such as polyamide resin, polyphenylene oxide resin and polyvinyl chloride, and phenol resin and epoxy resin A curable resin can be mentioned.

In particular, the pigment dispersant of the present invention can be suitably used for thermoplastic resins. The pigments that can be used can be used for all pigments conventionally known for coloring synthetic resins. Specific examples of pigments include metals such as aluminum, silver and gold; carbonates such as calcium carbonate and barium carbonate; oxides such as ZnO and TiO ₂ ; Al ₂ O ₃ · nH ₂ O and Fe ₂ O ₃ · Hydroxides such as nH ₂ O; sulfates such as CaSO ₄ and BaSO ₄ ; nitrates such as Bi (OH) ₂ NO ₃ ; chlorides such as PbCl ₂ ; chromates such as CaCrO ₄ and BaCrO ₄ ; CoCrO ₄ Chromite, manganate and permanganate; Cu (BO) ₂ and other borates; Na ₂ U ₂ O ₇ · 6H ₂ O and other uranates; K ₃ Co (NO ₂ ) ₆・ Nitrites such as 3H ₂ O; Silicates such as SiO ₂ ; Arsenates and arsenites such as CuAsO ₃ and Cu (OH) ₂ ; Cu (C ₂ H ₃ O ₂ ) ₂ and Cu (OH) acetates such as _2; phosphates such as _{(NH 4) 2 MnO 2 (} P 2 O 7) 2; aluminum salt, molybdate, zincate, antimonate, tungstate selenides, titanates , Inorganic such as iron cyanide, phthalate, CaS, ZnS, CdS Pigments, natural organic pigments such as cochineal lake, mudder lake, nitroso pigments such as naphthol green Y and naphthol green B; nitro pigments such as naphthol yellow S, pigment chlorin 2G; permanent red 4R;・ Azo pigments such as Carmine 68 and Scarlet 2R; basic dye lakes such as Maracaine Green and Rhodamine B; acidic dye lakes such as Acid, Green Lake and Eosin Lake; mordant dyes such as Alizarin Lake and Purpurin Lake Examples thereof include organic pigments such as vat dyes such as lake, thio, indigo, red B, and intrene / orange, and phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.

  The pigment dispersant of the present invention can be used for coloring by any one of coloring by a dry color method, coloring by a color compound method, or coloring by a masterbatch method. it can. The lubricant for polyvinyl chloride resin according to the present invention comprises the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) of the present invention. In the polyvinyl chloride composition using the lubricant of the present invention, the blending ratio of the lubricant is in the range of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of polyvinyl chloride. Parts by weight. The polymer used as the lubricant has a number average molecular weight in the range of 400 to 4000 parts by weight, preferably in the range of 500 to 1000 parts by weight, and the acid value in the range of 2 to 70, preferably The acid value ranges from 10 to 50. When the acid value of the modified low molecular weight ethylene polymer (B) is 70 or more, the initial lubricity of the lubricant is lowered, and when it is 10 or less, the tackiness preventing effect is lowered. Further, when the number average molecular weight of the lubricant is 400 or less, the effect of preventing adhesion to metal is inferior, and when it is 4000 or more, the slipperiness decreases in the initial and late stages. In addition, if the amount of the lubricant is 0.05 parts by weight or less, the lubricity effect is insufficient, and if it is 5 parts by weight or more, the slipperiness becomes excessive, making it difficult to plasticize the composition.

  In order to use the above-mentioned modified low molecular weight ethylene polymer (B) as a lubricant, as a monomer for modifying the polymer chain unsaturated group-containing oligomer of the low molecular weight ethylene polymer (A) according to the present invention, unsaturated Examples thereof include carboxylic acid or anhydride thereof, and specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, itaconic acid, itaconic anhydride, 3-cyclohexene carboxylic acid 4-cyclohexene carvone, 5-norbornene-2.3-dicarboxylic acid and the like.

  The polyvinyl chloride resin containing the polyvinyl chloride resin additive of the present invention includes polyvinyl chloride, or polyvinyl chloride, polyethylene, polypropylene, ABS resin, MBS resin, ethylene-vinyl acetate copolymer, polymethyl methacrylate, etc. Even if it is mixed, it cannot be used. Moreover, you may mix | blend a heat-resistant stabilizer with these compositions.

  Any heat stabilizer may be used as long as it exhibits a stabilizing effect on the polyvinyl chloride resin. For example, lead compound, cadmium compound, barium compound, calcium compound, zinc compound, organotin compound, epoxy compound , Chelators and the like and mixtures thereof. The polyvinyl chloride composition containing the lubricant according to the present invention may further contain other lubricants, fillers, pigments, dyes, plasticizers, antistatic agents, and weathering stabilizers.

  Since the composition containing the lubricant according to the present invention has excellent initial lubricity, the adhesiveness to metal is reduced, the composition can be stably molded, and continuous operation can be performed for a long time. The low molecular weight ethylene polymer according to the present invention can be widely used in applications where known low molecular weight polyethylene such as wax is used. In this case, various additives can be added and used as necessary.

  For example, when the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) according to the present invention is used as a coating modifier, the coating surface can be modified, for example, a matte effect. It is excellent in that it can improve the abrasion resistance of the coating film, can impart a high-class feeling to the woodwork paint, and can improve the durability. In addition, when the low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) according to the present invention is used as a polishing agent for car wax, floor polish, etc., it is excellent in gloss and improves coating film properties. Can be made.

  The low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) according to the present invention is suitable as a mold release agent for resin molding, and has a mold release property for a thermoplastic resin or a thermosetting resin. To improve the molding cycle. The low molecular weight ethylene polymer according to the present invention is excellent in compatibility with rubber, is suitable as a rubber processing aid for imparting releasability to rubber and adjusting viscosity, and used as a rubber processing aid. Sometimes, the dispersibility of the filler and the pigment is improved, and the release property and fluidity are imparted to the rubber, so that the molding cycle and the extrusion characteristics at the time of rubber molding can be improved.

  The low molecular weight ethylene polymer (A) or modified low molecular weight ethylene polymer (B) according to the present invention is suitable as a paper quality improver for improving the slipperiness and surface modification of paper, and is used as a paper quality improver. When it is, moisture resistance, gloss, surface hardness, blocking resistance, and abrasion resistance can be improved, and a high-class feeling can be imparted to the paper and durability can be improved. The low molecular weight ethylene polymer according to the present invention is suitable as an abrasion resistance improver for ink, and when used as an abrasion resistance improver, it can improve the abrasion resistance and heat resistance of the ink surface.

  The low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) according to the present invention is suitable as a fiber processing aid, and when used as a fiber processing aid when a fiber is resin-processed. The fiber can be given flexibility and lubricity. The low molecular weight ethylene polymer according to the present invention is suitable as a hot melt additive, and can impart heat resistance and fluidity to the hot melt adhesive. It is possible to improve the quality of hot melt adhesives in fields requiring heat resistance such as automobiles and building materials.

The low molecular weight ethylene polymer (A) or the modified low molecular weight ethylene polymer (B) according to the present invention is suitable as an electrical insulating agent, and can improve, for example, the electrical insulation and heat resistance of a film capacitor. . The low molecular weight ethylene polymer according to the present invention is suitable as a compounding agent for natural waxes such as crayons and candles, and can improve surface hardness and softening point.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Unless otherwise specified, “%” described below means “mass%”.

[Synthesis Example 1]
(Synthesis of low molecular weight ethylene polymer)
A stainless steel autoclave with an internal volume of 2 liters, which was sufficiently purged with nitrogen, was charged with 1000 ml of hexane and 50 ml of vinylnorbornene (2,2,1] hept-2-ene), and hydrogen was supplied at 0.3 MPa (gauge pressure). ) Was introduced until. Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and vinyl norbornene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure.

As described above, the unsaturated group content per 1,000 carbons is 11.8, and the vinyl norbornene content is 10.3% by weight (unsaturated group content (average) = 1.1 / molecule). The density is 956 kg / m ³ , the melting point is 117 ° C., the penetration is 1 or less, the Mn is 1,300, the Mw is 3,700, and the Mw / Mn is 2.8. A low molecular weight ethylene polymer (A-1) was obtained.

[Synthesis Example 2]
(Synthesis of low molecular weight ethylene polymer)
950 ml of hexane, 50 ml of propylene, and 70 ml of isoprene were charged into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and hydrogen was introduced to 0.2 MPa (gauge pressure). Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and propylene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure.

As described above, the unsaturated group content per 1,000 carbons is 6.0, the isoprene content is 2.4% by weight (unsaturated group content (average) = 1.5 / molecule), and the density Is 915 kg / m ³ , melting point is 104 ° C., penetration is 4, Mn is 3,500, Mw is 5,600, and Mw / Mn is 1.6 Ethylene polymer (A-2) was obtained.

[Synthesis Example 3]
(Synthesis of low molecular weight ethylene polymer)
A stainless steel autoclave with an internal volume of 2 liters that was sufficiently purged with nitrogen was charged with 980 ml of hexane, 20 ml of propylene, and 80 ml of vinylnorbornene (5-vinylcyclo [2,2,1] hept-2-ene), and hydrogen was supplied at 0.3 MPa. It was introduced until (gauge pressure). Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and vinyl norbornene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure.

As described above, the unsaturated group content per 1,000 carbons is 23.0, and the vinyl norbornene content is 20.0% by weight (unsaturated group content (average) = 1.8 / molecule). The density is 943 kg / m ³ , the melting point is 112 ° C., Mn is 1,100, the penetration is 3, Mw is 3,400, and Mw / Mn is 3.1. A molecular weight ethylene polymer (A-3) was obtained.

[Example 1]
In a 200 ml glass flask, 0.5 g of low molecular weight ethylene polymer (A-1), n-decane 90 ml, diisobutylaluminum hydride heptane solution (1.0 mmol / ml) 1.19 ml (1.09 mmol) In addition, the mixture was stirred at 100 ° C. for 7 hours. Subsequently, while maintaining the temperature at 100 ° C., dry air was circulated at 100 L / h for 6 hours. The reaction product was added to a methanol / acetone mixed solution (1.5 L / 1.5 L) containing a small amount of hydrochloric acid to precipitate the product. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. A hydroxylated low molecular weight ethylene polymer (B-1) was obtained.

[Example 2]
5 g of low molecular weight ethylene polymer (A-2) and 100 ml of toluene were added to a 300 ml glass flask, and the temperature was raised to 110 ° C. in a nitrogen atmosphere. Subsequently, 0.34 g of m-chloroperbenzoic acid was added and stirred for 3 hours. After the reaction, the product was added to 800 ml of methanol to precipitate the product. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. A hydroxylated low molecular weight ethylene polymer (B-2) was obtained.

[Example 3]
To a 300 ml glass flask, 15 g of a low molecular weight ethylene polymer and 2.7 g of maleic anhydride were added and reacted at 200 ° C. for 6 hours in a nitrogen atmosphere. Excess unreacted maleic anhydride was removed under reduced pressure (10 mmHg) in 1 hour to obtain a maleic anhydride low molecular weight ethylene polymer (B-3).

[Example 4]
A 300 ml glass flask was charged with 5 g of a low molecular weight ethylene polymer (A-1), 100 ml of xylene, 1.47 g of sulfuric acid and 3.79 g of acetic anhydride, and reacted at 100 ° C. for 3 hours. After the reaction, the product was added to 800 ml of methanol to precipitate the product. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. A sulfonated low molecular weight ethylene polymer (B-4) was obtained.

[Example 5]
250 ml of dimethylene and 4.5 g of low molecular weight ethylene polymer (A-1) were added to a glass reactor with an internal volume of 500 ml that had been sufficiently purged with nitrogen, and the temperature was raised to 140 ° C. at normal pressure while circulating ethylene at 100 L / hr. Warm up. Thereafter, methylaluminoxane was converted to 2.5 mmol in terms of aluminum atom, and dimethylsilyl (1- (2-methyl-4,5-benzindenyl)) (9- (2,7-ditertbutylfluorenyl) zirconium dichloride was reduced to 0.0. Polymerization was started by adding 005 mmol, and after 15 minutes, a small amount of isobutanol was added to stop the reaction, and the product was added to 2,000 ml of methanol to precipitate the product. The obtained polymer was 10.5 g, and according to ¹³ C-NMR analysis, it contained 1.10 long-chain branches in 1,000 carbons.

[Comparative Example 1]
Polymerization was carried out in the same manner as in Example 5 except that 4.5 g of the low molecular weight ethylene polymer (A-1) was not used. The obtained polymer was 4.9 g, and according to ¹³ C-NMR analysis, no long chain branching in 1,000 carbons was contained.

The modified low molecular weight ethylene polymer (B) of the present invention can impart any functional group to the unsaturated group of the low molecular weight ethylene polymer (A) by various modification techniques. Such a modified low molecular weight ethylene polymer (B) is useful as a toner release agent because it has excellent high-temperature release properties and excellent low-temperature fixability. Further, the modified low molecular weight ethylene polymer (B) is excellent in pigment dispersibility, and is therefore useful as a pigment dispersant and a lubricant for polyvinyl chloride resin because of excellent initial lubricity. . Furthermore, many useful uses such as paint modifiers and polishes can be provided.

Claims (20)

Modified low molecular weight ethylene polymer having a hetero atom-containing group obtained by treating an unsaturated group of the low molecular weight ethylene polymer (A) defined by (i) to (vi) below with a modifier. (B).
(I) a copolymer obtained by copolymerizing ethylene and at least one diene, or at least one olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene Is a copolymer obtained by copolymerizing
(Ii) 0.1 to 4.0 unsaturated group content per molecule (iii) density of 870 to 980 kg / m ³
(Iv) Melting point is 70-130 ° C
(V) A number average molecular weight of 400 to 5,000
(Vi) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less The modifying agent according to claim 1, wherein the modifying agent is at least one compound selected from an oxidizing agent, a sulfonating agent, maleic anhydride and derivatives thereof, a hydroborating agent, an organoaluminizing agent, and a halogenating agent. Molecular weight ethylene polymer (B). The modified low molecular weight ethylene polymer (B) according to claim 1, wherein the heteroatom-containing group is an oxygen-containing group, a sulfur-containing group, a metal-containing group or a halogen-containing group. The low molecular weight ethylene polymer (A) is a copolymer obtained by copolymerizing (i) ethylene and vinyl norbornene (5-vinylbicyclo [2,2,1] hept-2-ene), or ethylene The modified low molecular weight ethylene polymer (B) according to claim 1, which is a copolymer obtained by copolymerizing at least one olefin selected from α-olefins having 3 to 12 carbon atoms and vinyl norbornene. The low molecular weight ethylene polymer (A) and / or the modified low molecular weight ethylene polymer (B) according to claim 1 is used as a macromonomer, polymerized alone, or from ethylene and an α-olefin having 3 to 10 carbon atoms. A low molecular weight ethylene polymer (C) obtained by copolymerization with at least one selected olefin. A resin composition comprising the low molecular weight ethylene polymer (C) according to claim 5. A paint modifier comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A polishing agent comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A mold release agent for resin molding comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A rubber processing aid comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A paper quality improver comprising the modified low molecular weight ethylene polymer (B) according to claim 1. An abrasion resistance improver for ink comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A fiber processing aid comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A hot melt additive comprising the modified low molecular weight ethylene polymer (B) according to claim 1. An electrical insulating agent comprising the modified low molecular weight ethylene polymer (B) according to claim 1. The compounding agent for natural waxes containing the modified low molecular weight ethylene polymer (B) of Claim 1. An antifogging agent for polyolefin film comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A release agent for a toner comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A pigment dispersant comprising the modified low molecular weight ethylene polymer (B) according to claim 1. A lubricant for vinyl chloride resin comprising the modified low molecular weight ethylene polymer (B) according to claim 1.