Pigment dispersant for aromatic polymers

The present invention relates to a pigment dispersant for an aromatic polymer, which comprises a copolymer wax of ethylene and an aromatic vinyl compound.

[0002] Conventional Techniques As a method for coloring an aromatic polymer such as polystyrene, styrene / acrylonitrile copolymer (AS), styrene / acrylonitrile / butadiene copolymer (ABS), a dry color method or a color compound is used. The method or master batch method is mainly adopted. In any of these methods, a pigment dispersant is used to uniformly disperse the pigment.

[0003] As a pigment dispersant for styrene-based polymers, Japanese Patent Publication No. 60-19934 describes a pigment dispersant composed of a graft polyolefin wax obtained by grafting a styrene-based compound on a polyolefin wax. Although this pigment dispersant has excellent performance such as pigment dispersibility, its production requires two steps, a polyolefin synthesis step and a styrene compound grafting step, and has a problem of high manufacturing cost. Further, even better pigment dispersibility is also required.

[0004] [Problems to be Solved by the Invention] The problems of the present invention are excellent pigment dispersibility in aromatic polymers, excellent transparency and coloring stability of the composition after compounding, and no grafting step is required. It is an object of the present invention to provide a pigment dispersant for an aromatic polymer having a low production cost.

[Means for Solving the Problems] The present invention is the following pigment dispersant for aromatic polymers. (1) A wax composed of a random copolymer of ethylene and an aromatic vinyl compound, wherein the above-mentioned ethylene / aromatic vinyl compound copolymer wax is an ethylene and an aromatic vinyl compound in the presence of a metallocene catalyst (A). An ethylene / aromatic vinyl compound copolymer wax obtained by copolymerizing with, or a copolymer of ethylene and an aromatic vinyl compound obtained by polymerizing in the presence of a metallocene catalyst (A). It is an ethylene / aromatic vinyl compound copolymer wax obtained by heat reduction, and the content of structural units derived from ethylene is 99 to 10% by weight, and the content of structural units derived from aromatic vinyl compounds is 1 to ~. Consists of ethylene / aromatic vinyl compound copolymer wax with 90% by weight and ultimate viscosity of 0.04 to 0.6 dl / g<u style="single">For aromatic polymers</u>Pigment dispersant. (2) The above-mentioned (1), wherein the aromatic vinyl compound is styrene.<u style="single">For aromatic polymers</u>Pigment dispersant.

[0006] The pigment dispersant for aromatic polymers of the present invention is<u style="single">the above</u>A pigment dispersant composed of an ethylene / aromatic vinyl compound copolymer wax. The above-mentioned ethylene / aromatic vinyl compound copolymer wax is a wax composed of a random copolymer of ethylene and an aromatic vinyl compound, and has a content of structural units derived from ethylene (hereinafter, may be referred to as ethylene content). Is 99 to 10% by weight, preferably 96 to 40% by weight, and the content of structural units derived from the aromatic vinyl compound (hereinafter, may be referred to as aromatic vinyl compound content) is 1 to 90% by weight, preferably 4 to 4 to 90% by weight. It is an ethylene / aromatic vinyl compound copolymer wax having an intrinsic viscosity of 60% by weight and an ultimate viscosity of 0.04 to 0.6 dl / g, preferably 0.1 to 0.4 dl / g measured at 135 ° C. in decalin. In the present invention, the term wax has a weight average molecular weight (Mw) of 1000 to 20,00.<u style="single">0</u>It means a low molecular weight polymer.

[0007] Examples of the aromatic vinyl compound include styrene; mono- or polyalkyl styrene such as methyl styrene, dimethyl styrene, and ethyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, and hydroxy styrene. Functional group-containing styrene derivatives such as chlorostyrene and divinylbenzene; 3-phenylpropylene, 4-phenylbutene and the like can be mentioned. Of these, styrene is preferred. The aromatic vinyl compound may be used alone or in combination of two or more.

[0008] In addition to ethylene and aromatic vinyl compounds, the ethylene / aromatic vinyl compound copolymer wax contains α-olefins having 3 to 20 carbon atoms, cycloolefins, and polarities as long as the object of the present invention is not impaired. Group-containing monomers, non-conjugated polyenes and the like may be copolymerized.

[0009] As the above-mentioned α-olefin,<u style="single">, Pu</u>Examples thereof include lopyrene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene. Examples of the cycloolefin include cyclobutene, cyclopentene, cyclohexene, cyclooctene and the like. Examples of the polar group-containing monomer include vinyl acetate, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, and maleic anhydride. Examples of the non-conjugated polyene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, etylidene norbornene and the like.

[0010] The ethylene / aromatic vinyl compound copolymer wax<u style="single">Is</u>Ethylene / aromatic vinyl compound copolymer wax produced using metallocene catalyst (A)<u style="single">And</u>Especially excellent in pigment dispersibility<u style="single">To.</u>[0011] In order to obtain an ethylene / aromatic vinyl compound copolymer wax using a metallocene catalyst (A), a method of copolymerizing ethylene and an aromatic vinyl compound in the presence of a metallocene catalyst (A), or metallocene. A method for heat-decomposing a copolymer of ethylene and an aromatic vinyl compound obtained by polymerization in the presence of a catalyst (A).<u style="single">Adopt</u>To.

[0012] When the ethylene / aromatic vinyl compound copolymer wax is used as a pigment dispersant, the ethylene / aromatic vinyl compound copolymer wax may be used alone or in combination of two or more. It can also be used.

Next, a method for producing an ethylene / aromatic vinyl compound copolymer wax by copolymerizing an ethylene and an aromatic vinyl compound in the presence of a metallocene catalyst (A) and the metallocene catalyst (A). Will be described.

[0014] As the metallocene catalyst (A), a metallocene-based catalyst conventionally used as a single-site catalyst and a metallocene-based catalyst similar thereto are used without limitation, and a metallocene compound (transition metal compound) of a transition metal is particularly used. ) (B) and a catalyst composed of an organic aluminum oxy compound (C) and / or an ionized ionic compound (D) are preferably used.

[0015] As the metallocene compound (B), a transition metal metallocene selected from Group 4 of the Periodic Table of Elements (Long Periodic Type) represented by Group Numbers 1 to 18 according to the revised version of the IUPAC Inorganic Chemistry Naming Method (1989). Examples of the compound, specifically, a metallocene compound represented by the following general formula (1). MLx ... (1) In Eq. (1), M is a transition metal selected from Group 4 of the periodic table, specifically zirconium, titanium or hafnium, and x is the valence of the transition metal.

[0016] L is a ligand that coordinates with the transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton and has this cyclopentadienyl skeleton. The ligand may have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, and the like. n-, i-, sec-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclo Pentazienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadi Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as enyl group, ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and indenyl group, 4,5,6,7- Examples thereof include a tetrahydroindenyl group and a fluorenyl group.

[0018] These groups may be substituted with a halogen atom, a trialkylsilyl group, or the like. Of these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

[0019] When the metallocene compound (B) represented by the formula (1) has two or more groups having a cyclopentadienyl skeleton as the ligand L, a group having two cyclopentadienyl skeletons among them. They are bonded to each other via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a substituted silylene group such as methylphenylsilylene group. May be good.

[0020] Examples of L other than the ligand having a cyclopentadienyl skeleton include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, and a sulfonic acid-containing group (-SO).₃R¹), Halogen atom or hydrogen atom (where R¹Is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group. ) And so on.

[0021] Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and more specifically, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group and other cycloalkyl groups, Examples thereof include an aryl group such as a phenyl group and a trill group, and an aralkyl group such as a benzyl group and a neofil group.

[0022] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. The group etc. can be mentioned. Examples of the allyloxy group include a phenoxy group.

[0023] Sulfonic acid-containing group (-SO₃R¹) Examples include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonate group, and a p-chlorobenzenesulfonato group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0024] The metallocene compound (B) represented by the above formula (1) is more specifically represented by the following general formula (2) when the valence of the transition metal is 4, for example. R²_kR³_lR⁴_mR⁵_nM ... (2) [0025] In Eq. (2), M is a transition metal similar to the transition metal of Eq. (1), preferably zirconium or titanium, and R.²Is a group (ligand) having a cyclopentadienyl skeleton, and R³, R⁴And R⁵Is the same as L other than a group having a cyclopentadienyl skeleton independently or a ligand having a cyclopentadienyl skeleton in the general formula (1). k is an integer greater than or equal to 1 and k + l + m + n = 4.

[0026] Hereinafter, a metallocene compound (B) in which M is zirconium and contains at least two ligands having a cyclopentadienyl skeleton will be illustrated. Bis (Cyclopentadienyl) Zirconium Monohydrate Monohydride, Bis (Cyclopentadienyl) Zirconium Dichloride, Bis (Cyclopentadienyl) Methyl Zirconium Monolide, Bis (Cyclopentadienyl) Zirconium Phenoxy Monolide, Bis (Methyl) Cyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) Zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclo Examples thereof include pentadienyl) zirconium dichloride, bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, and the like.

[0027] In the present invention, a metallocene compound (B) in which the above-mentioned 1,3-position-substituted cyclopentadienyl group is replaced with a 1,2-position-substituted cyclopentadienyl group can also be used. Further, in the above equation (2), R², R³, R⁴And R⁵At least 2 of²And R³Is a group (ligand) having a cyclopentadienyl skeleton, and at least two of these groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like, a bridge-type metallocene compound. (B) can also be exemplified. At this time R⁴And R⁵Are the same as L other than the ligand having the cyclopentadienyl skeleton independently described in the equation (1).

[0028] Examples of such a bridge-type metallocene compound (B) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato) isopropyridenebis ( Indenyl) Zirconium dichloride and the like.

[0029] In the present invention, it is desirable to use the metallocene compound represented by the following general formula (3) as the bridge-type metallocene compound (B).

[Chemical 1]<img file="JP3858397B2_D0001.tif" />[0030] In equation (3), M¹Indicates the transition metal atoms of groups 4, 5 and 6 of the periodic table, specifically titanium, zirconium, hafnium and the like. R⁶And R⁷Are independently hydrogen atoms, halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, halogenated hydrocarbon groups with 1 to 20 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or Indicates a phosphorus-containing group, specifically a halogen atom such as fluorine, chlorine, bromine, iodine; an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, an alkenyl group such as vinyl, propenyl, cyclohexenyl, etc. A hydrocarbon group having 1 to 20 carbon atoms such as an arylalkyl group such as benzyl, phenylethyl and phenylpropyl, and an aryl group such as phenyl, trill, dimethylphenyl, naphthyl and methylnaphthyl; the hydrocarbon group is substituted with a halogen atom. Halogenized hydrocarbon groups; [0031] Monohydrosulfide-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, tri-hydrocarbon-substituted silyls such as trimethylsilyl and triethylsilyl, trimethylsilyl ether and the like. Cyril ether of hydrocarbon-substituted silyl, Silicon-substituted alkyl groups such as trimethylsilylmethyl, silicon-substituted aryl groups such as trimethylsilylphenyl, and silicon-containing groups; alkoxy groups such as hydrooxy groups, methoxy, ethoxy, and ants such as phenoxy and methylphenoxy.<u style="single">-</u>Oxygen-containing groups such as roxy groups, arylalkoxy groups such as phenylmethoxy and phenylethoxy; sulfur-containing groups such as substituents in which the oxygen of the oxygen-containing group is substituted with sulfur; alkylaminos such as amino groups, methylamino and dimethylamino A group, an arylamino group such as phenylamino, methylphenylamino or a nitrogen-containing group such as an alkylarylamino group; a phosphorus-containing group such as a phosphino group such as dimethylphosphino.

[0032] Among these, R⁶Is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms of methyl, ethyl, and propyl. Also R⁷Is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms of methyl, ethyl and propyl.

[0033] R⁸, R⁹, R¹⁰And R¹¹Independently indicate a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms, among which a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group is indicated. It is preferably a hydrogen group. R⁸And R⁹, R⁹And R¹⁰, R¹⁰And R¹¹At least one set of them may be combined with the carbon atoms to which they are bonded to form a monocyclic aromatic ring.

[0034] Further, the group other than the group forming the aromatic ring may be cyclic by bonding with each other when there are two or more kinds of hydrocarbon groups or halogenated hydrocarbon groups. R¹¹When is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms include the above R.⁶And R⁷The same as the above can be exemplified.

[0036] X¹And X²Independently indicate 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, or a sulfur-containing group. Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the halogenated hydrocarbon group having 1 to 20 carbon atoms, and the oxygen-containing group include the above-mentioned R.⁶And R⁷The same as the above can be exemplified.

[0037] Further, as the sulfur-containing group, the above-mentioned R⁶, R⁷Groups similar to, and methyl sulfonate, trifluoromethane sulphonate, phenyl sulphonate, benzyl sulphonate, p-toluene sulphonate, trimethyl benzene sulphonate, triisobutyl benzene sulphonate, p-chlorobenzene sul. Sulfonate groups such as phonate and pentafluorobenzene sulphonate, methyl sulphinate, phenyl sulphinate, benzene sulphinate, p-toluene sulphate, trimethylbenzene sulphinate, pentafluorobenzene sulphinate and the like. A sulfinate group can be exemplified.

[0038] Y¹Is 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, and a divalent tin-containing group. , -O-, -CO-, -S-, -SO-, -SO₂-, -NR¹²-, -P (R)¹²)-, -P (O) (R¹²)-,-BR¹²-Or-AlR¹²-(However, R¹²Indicates a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms).

[0039] Y¹Specific examples of the above are methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4. -A divalent hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group such as cyclohexylene and an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene; the above 1 to 20-2 carbon atoms such as chloromethylene. Halogenated hydrocarbon groups obtained by halogenating valent hydrocarbon groups; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, Alkyl silylenes such as diphenylcilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylcyrylene groups, tetramethyl-1,2-disilylene, tetraphenyl-1,2-dicilylene, etc. A divalent silicon-containing group such as an alkyldicyrylene, an alkylaryldicilylene, or an aryldisilylene group; a divalent germanium-containing group in which the silicon of the divalent silicon-containing group is replaced with germanium; the divalent silicon-containing group described above. It is a divalent tin-containing group substituent in which silicon is replaced with tin.¹²Is the above R⁶, R⁷Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, and halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0040] Among these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is preferable, and among them, an alkyl is particularly preferable. It is preferably silylene, alkylaryl silylene, or aryl silylene.

[0041] A specific example of the metallocene compound (B) represented by the above formula (3) is shown below. rac-dimethylmethylenebis (indenyl) zirconium dichloride, rac-dimethylmethylenebis (2-methyl-1-indenyl) zirconium dichloride, rac-diphenylmethylenebis (2-methyl-1-indenyl) zirconium dichloride, rac-ethylenebis (2-methyl-1-indenyl) 2-Methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-1-indenyl) zirconium dimethyl, 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, 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-anthracenyl) -1-indenyl) zirconium dichloride and the like.

[0042] Further, in the present invention, the metallocene compound represented by the following general formula (4) can also be used as the metallocene compound (B). L¹M²Z₂ ... (4) (M in the formula²Is a Group 4 or Lantanide series metal in the Periodic Table, L¹Is a derivative of the delocalized π-bonding group, metal M²It imparts a constrained geometry to the active sites, where Z is a hydrocarbon group, a silyl group or a germanium group, each independently containing a hydrogen atom, a halogen atom or 20 or less carbon, silicon or germanium. ) [0043] Among the metallocene compounds (B) represented by the formula (4), the metallocene compound represented by the following general formula (5) is preferable.

[Chemical 2]<img file="JP3858397B2_D0002.tif" />[0044] In equation (5), M³Is titanium, zirconium or hafnium, and Z is similar to the above. Cp is M³To η⁵It is a cyclopentadienyl group, a substituted cyclopentadienyl group, or a derivative thereof, which is π-bonded in a binding manner.

[0045] W¹Is an element of Oxygen, Sulfur, Boron or Group 14 of the Periodic Table, or a group containing these elements, V¹Is a ligand containing nitrogen, phosphorus, oxygen or sulfur. W¹And V¹A fused ring may be formed with. Also Cp and W¹A fused ring may be formed with.

[0046] Preferred examples of the group represented by Cp of the general formula (5) include a cyclopentadienyl group, an indenyl group, a fluorenyl group and saturated derivatives thereof, and these are metal atoms (M).³) To form a ring. Each carbon atom in the cyclopentadienyl group is a halogen, a hydrocarbyl group, a substituted hydrocarbyl group (one or more hydrogen atoms in this group are substituted with halogen), and a hydrocarbyl-substituted metalloid group (metalloid of this group). May be substituted with the same or different groups selected from the group consisting of (selected from Group 14 of the Periodic Table of the Elements). In addition, one or more substituents may be combined to form an associative algebra. Preferred hydrocarbyls and substituted hydrocarbyl groups capable of substituting at least one hydrogen atom in the cyclopentadienyl group contain 1 to 20 carbon atoms and are linear or branched alkyl groups, cyclic hydrocarbon groups, alkyl substituteds. Includes cyclic hydrocarbon groups, aromatic groups and alkyl-substituted aromatic groups. Preferred organic metalloid groups include mono-, di- and tri-substituted organic metalloid groups of Group 14 elements, each of which contains 1 to 20 carbon atoms. Specific preferred organic metalloid groups include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl, triphenyljarmill and trimethyljarmil.

[0047] Z of the general formula (5)¹Specific examples of the above include hydrides, halos, alkyls, silyls, germils, aryls, amides, aryloxys, alkoxys, phosphides, sulfates, acyls, pseudohalides such as cyanides, azides, acetylacetonates or mixtures thereof. It may be the same or different.

[0048] Among the metallocene compounds (B) represented by the general formula (5), the metallocene compound represented by the following general formula (6) is preferable.

[Chemical 3]<img file="JP3858397B2_D0003.tif" />[0049] In equation (6), M⁴Is the above M³Is the same as V²Is -O-, -S-, -NR¹⁷-,-PR¹⁷-Or¹⁷, SR¹⁷, N (R)¹⁷)₂Or P (R)¹⁷)₂It is a neutral two-electron donor ligand selected from the group consisting of. Here R¹⁷Is a hydrogen atom, or an alkyl, aryl, silyl, alkyl halide or aryl halide group with up to 20 non-hydrogen atoms, or two Rs.¹⁷Or R described later¹⁸A fused ring may be formed with and.

[0050] In equation (6), W²Is Si (R¹⁸)₂, C (R)¹⁸)₂, Si (R)¹⁸)₂Si (R¹⁸)₂, C (R)¹⁸)₂C (R¹⁸)₂, CR¹⁸= CR¹⁸, C (R)¹⁸)₂Si (R¹⁸)₂, Ge (R¹⁸)₂, BR¹⁸, B (R)¹⁸)₂Is. Here R¹⁸Is the above R¹⁷Is the same as. In equation (6), R¹³~ R¹⁶Are independently hydrogen atoms, or alkyl, aryl, silyl, jarmil, cyano, halo and combinations thereof (eg, alkalil, aralkyl, silyl-substituted alkyl, silyl-substituted aryl, cyanoalkyl) with up to 20 non-hydrogen atoms. , Cyanoaryl, haloalkyl, halosilyl, etc.) or R¹³~ R¹⁶Adjacent pairs of may form a hydrocarbyl ring condensed on the cyclopentadienyl moiety.

[0051] In equation (6), Z²Are hydrides in each case, or have up to 20 non-hydrogen atoms such as halo, alkyl, arylsilyl, jarmil, aryloxy, alkoxy, amide, silyloxy and combinations thereof (eg, alkalil, aralkyl, silyl). , Substituted alkyl, silyl substituted aryl, aryloxyalkyl, aryloxyaryl, alkoxyalkyl, alkoxyaryl, amidealkyl, amidearyl, syroxyalkyl, syroxyaryl, amide syroxyalkyl, haloalkyl, haloaryl, etc.), and up to 20 hydrogens. It is a group selected from the group consisting of neutral Lewis bases having atoms other than.

[0052] In the metallocene compound (B) represented by the general formula (6), V²When is a neutral two-electron donor ligand, M⁴And V²The bond between and is more precisely a bond called a coordination covalent bond. Also, the complex can exist as a dimer or higher oligomer.

[0053] In the metallocene compound (B) represented by the general formula (6), R¹³~ R¹⁶, Z², R¹⁷Or R¹⁸At least one of is preferably an electron donating part, especially V²Is-NR¹⁹-Or-PR¹⁹-(However, R¹⁹Is preferably an amide or phosphide group corresponding to (is an alkyl having 1 to 10 carbon atoms or an aryl having 6 to 10 carbon atoms).

[0054] Among the metallocene compounds (B) represented by the general formula (6), the amide silane or amide alkanediyl compound represented by the following general formula (7) is preferable.

[Chemical 4]<img file="JP3858397B2_D0004.tif" />[0055] In equation (7), M⁵Is η on the cyclopentadienyl group⁵Titanium, zirconium or hafnium bonded in a bonding mode, R²⁰~ R²⁵Is a group selected from the group consisting of silyl, alkyl, aryl and combinations thereof, each independently having a hydrogen atom or up to 10 carbons, or R.²²~ R²⁵Adjacent pairs of may form a hydrocarbyl ring that condenses with the cyclopentadienyl moiety. In equation (7), W³Is silicon or carbon, Z³Are hydrides, halos, alkyls of up to 10 carbons, aryls, aryloxys or alkoxys in each case.

[0056] In the metallocene compound (B) represented by the general formula (7), R²⁰Are methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl, etc.²²~ R²⁵Are independently hydrogen atoms, methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, etc., and Z³Preferably metallocene compounds such as chloro, bromo, iodo, methyl, ethyl, propyl, butyl, pentyl, hexyl (including isomers), norbornyl, benzyl, phenyl and the like. Also R²²~ R²⁵Also preferred is a metallocene compound in which the cyclopentadienyl moiety forms a fused ring and the cyclopentadienyl moiety is an indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl ring or the like.

[0057] Specific examples of the metallocene compound (B) represented by the general formula (7) include (t-butyramide) dimethyl (tetramethyl-η).⁵-Cyclopentadienyl) Silane Titanium Dichloride, (t-Butylamide) (Tetramethyl-η)⁵-Cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (t-butyramide) (tetramethyl-η)⁵-Cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamide) (tetramethyl-η)⁵-Cyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (tetramethyl-η)⁵-Cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (ethylamide) (tetramethyl-η)⁵-Cyclopentadienyl) -methylene titanium dichloride, (t-butyramide) dimethyl (tetramethyl-η)⁵-Cyclopentadienyl) silane Zirconium dibenzyl, (benzylamide) dimethyl (tetramethyl-η)⁵-Cyclopentadienyl) Silane Titanium Dichloride, (Phenylphosphide) Dimethyl (Tetramethyl-η)⁵-Cyclopentadienyl) Silane Zirconium Dibenzyl and the like.

[0058] Further, in the present invention, the following metallocene compound can also be used as the metallocene compound (B). Ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconide dichloride, ethylene {2-methyl-4 (9-phenanthril) -1-indenyl} (2,7-dimethyl-9) -Fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthril) -1-indenyl} (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5 -Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconide, ethylene (2-methyl) -4,5-Benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaft-1-indenyl) (9-fluorenyl) zirconium dichloride , Ethylene (2-methyl-α-acenaft-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconide dichloride, ethylene (2-methyl-α-acenaft-1-indenyl) (2,7-di- t-Butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconide dichloride, etc.

[0059] In addition, among the above zirconium compounds, a compound in which zirconium is replaced with titanium or hafnium can be exemplified. A method for producing the metallocene compound (B) is described in, for example, Japanese Patent Application Laid-Open No. 3-163088.

[0060] As the metallocene compound (B) used in the present invention, the metallocene compound represented by the general formula (4) is particularly preferable from the viewpoint of polymerization activity and pigment dispersibility. The metallocene compound (B) described above may be used alone or in combination of two or more. The metallocene compound (B) used in the present invention may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

Next, the organoaluminum oxy compound (C) and the ionized ionic compound (D) used in forming the metallocene catalyst (A) will be described.

[0062] The organoaluminum oxy compound (C) used in the present invention may be a conventionally known aluminooxane (C), or is benzene-insoluble as exemplified in JP-A-2-78687. It may be an organoaluminum oxy compound (C).

[0063] Such a conventionally known aluminoxane (C) is specifically represented by the following general formula (8) or (9).

[Chemical 5]<img file="JP3858397B2_D0005.tif" />[In equation (8) or (9), R²⁶Is 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 an integer of 2 or more, preferably 5 to 40. .. ] [0064] Here, this aluminooxane (C) is given by the formula (OAl (R).²⁷)) Alkyloxyaluminum unit and formula (OAl (R)²⁸)) Alkyloxyaluminum unit (where R²⁷And R²⁸Is R²⁶Hydrocarbon groups similar to R²⁷And R²⁸May represent a mixed alkyloxyaluminum unit consisting of (representing different groups).

[0065] Aluminoxane (C) is produced by, for example, the following method, and is usually recovered as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to a suspended aromatic hydrocarbon solvent and reacted to recover the solution as a solution of the aromatic hydrocarbon solvent. (2) A method in which water (water, ice or water vapor) is directly allowed to act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a hydrocarbon medium such as decane, benzene or toluene.

[0066] Examples of the solvent used in the preparation of aluminoxane (C) include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and simen; pentane, hexane, heptane, octane, decane, dodecane and hexadecane. Aliphatic hydrocarbons such as octadecane; Aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane; ethers such as ethyl ether and tetrahydrofuran; petroleum distillates such as gasoline, kerosene, and light oil; Examples thereof include hydrocarbon solvents such as group hydrocarbons, aliphatic hydrocarbons, and halides of alicyclic hydrocarbons, such as chlorinated compounds and brominated compounds. Among these solvents, aromatic hydrocarbons are particularly preferable.

[0067] Examples of the ionized ionic compound (D) include Lewis acid, an ionic compound, a borane compound, and a carborane compound. These ionized ionic compounds (D) are described in JP-A No. 1-501950, JP-A No. 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703. It is described in Japanese Patent Application Laid-Open No. 3-207704, USP-5321106, and the like.

[0068] As a Lewis acid used as an ionized ionic compound (D), BR₃(Here, R is the same or different, and is a phenyl group or fluorine which may have a substituent such as a fluorine, a methyl group, or a trifluoromethyl group.) Examples thereof include trifluoro. Examples thereof include boron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, and tris (pentafluorophenyl) boron.

[0069] The ionic compound used as the ionized ionic compound (D) is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the metallocene compound (B) by reacting with the metallocene compound (B) and stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include organoboron compound anions, organoarsenic compound anions, organoaluminum compound anions, and the like, and those that are relatively bulky and stabilize transition metal cation species are preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, there are triphenylcarbenium cations, tributylammonium cations, N, N-dimethylammonium cations, ferrosenium cations and the like.

[0070] Of these, an ionic compound containing a boron compound as an anion is preferable, and specifically, the ionic compound includes a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a tria. Lillephosphonium salt and the like can be given.

Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). ) Boron and the like.

[0072] Examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron and the like.

[0073] Examples of the dialkylammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

[0074] Examples of the triarylphosphonium salt include triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, and tri (dimethylphenyl) phosphonium tetra (phenyl). ) Boron and the like.

[0075] Further, as the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate and the like can be used. You can also give it.

[0076] Examples of the borane compound used as the ionized ionic compound (D) include the following compounds. Decabolan (14); Anionic salts such as bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decabolate; and tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobalt Examples thereof include salts of metal borane anions such as acid salt (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III).

[0077] Examples of the carborane compound used as the ionized ionic compound (D) include anionic salts such as 4-carbanonaborane (14) and 1,3-dicarbanonaborane (13); and tri (n-butyl) ammonium bis. (Nonahydride-1,3-dicarbanonabolate) Cobalate (III), Tri (n-butyl) ammonium bis (Undecahydride-7,8-dicarbabounecarbolate) Tartrate (III), etc. Examples include salts of metal carborane anions. The above-mentioned ionized ionic compound (D) may be used in combination of two or more.

[0078] The metallocene catalyst (A) used in the present invention may further contain the following organoaluminum compound (E) in addition to the above-mentioned components, if necessary. Examples of the organoaluminum compound (E) used as necessary in the present invention include organoaluminum compounds represented by the following general formula (10).

[0079] (R²⁹)_nAlX_3-n ... (10) In equation (10), R²⁹Is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3 carbon atoms.

[0080] Examples of such a hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group, and an allyl group, and specifically, a methyl group, an ethyl group, an n-propyl group, and the like. Examples thereof include an isopropyl group and an isobutyl group.

[0081] Specific examples of such organoaluminum compounds include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butylaluminum, general formula (iC)₄H₉) xAly (C₅H₁₀) Z (in the equation, x, y, z are positive numbers and z 2x), alkenyl aluminum such as isoprenyl aluminum, dialkylaluminum halide such as dimethylaluminum chloride, diisobutylaluminum chloride, diisobutyl Examples thereof include dialkylaluminum hydride such as aluminum hydride, dialkylaluminum alkoxide such as dimethylaluminum methoxyde, and dialkylaluminum allyloxide such as diethylaluminum phenoxide.

[0082] Further, as the organoaluminum compound (E), a compound represented by the following formula (11) can also be used. (R³¹)_nAl (R³⁰)_3-n ... (11) (in the formula, R³¹Is the above R²⁹Similar to R³⁰Is -OR³²Moto, -OSi (R³³)₃Group, -OAl (R³⁴)₂Group, -N (R)³⁵)₂Group, -Si (R)³⁶)₃Group or -N (R)³⁷) Al (R)³⁸)₂Group, n is 1-2, R³², R³³, R³⁴And R³⁸Is a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc.³⁵Is a hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc.³⁶And R³⁷Is a methyl group, an ethyl group, or the like. ) [0083] Specific examples of such an organoaluminum compound (E) include the following compounds. (C₂H₅)₂Al (OSi (CH)₃)₃), (Iso-C₄H₉)₂Al (OSi (CH)₃)₃), (C₂H₅)₂Al (OAl (C)₂H₅)₂), (CH₃)₂Al (N (C)₂H₅)₂), (C₂H₅)₂Al (NH (CH)₃)), (Iso-C₄H₉)₂Al [N (Si (CH)₃)₃)₂]Such.

[0084] In the metallocene catalyst (A) used in the present invention, at least one of the above-mentioned component (B), component (C), component (D) and component (E) is supported on a fine particle carrier. It may be a solid catalyst.

[0085] Further, the metallocene catalyst (A) includes a fine particle carrier, a component (B), a component (C) (or a component (D)), a polymer or a copolymer produced by prepolymerization, and if necessary, a component. It may be a prepolymerization catalyst composed of (E).

[0086] The fine particle carrier used in the solid catalyst and the prepolymerization catalyst is an inorganic or organic compound, and is a granular or fine particle solid having a particle size of 10 to 300 μm, preferably 20 to 200 μm.

[0087] Of these, the inorganic carrier is preferably a porous oxide, specifically, SiO.₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂And so on, or a mixture of these, such as SiO₂-MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO etc. can be exemplified. Among these, SiO₂And Al₂O₃It is preferable that the main component is at least one component selected from the group consisting of.

[0088] In addition, a small amount of Na is added to the above-mentioned inorganic oxide.₂CO₃, K₂CO₃, CaCO₃, MgCO₃, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg (NO)₃)₂, Al (NO)₃)₃, Na₂OK₂O, Li₂It does not matter if it contains carbonates such as O, sulfates, nitrates, and oxide components.

[0089] Although the properties of such a fine particle carrier differ depending on the type and manufacturing method, the specific surface area is 50 to 1000 m.²/ g, preferably 100-700m²/ g, pore volume 0.3-2.5 cm³It is desirable to be / g. The fine particle carrier is used by firing at a temperature of 100 to 1000 ° C, preferably 150 to 700 ° C, if necessary.

[0090] Further, as the fine particle carrier, a granular or fine particle solid of an organic compound having a particle size of 10 to 300 μm can be mentioned. Examples of such organic compounds include (co) polymers or vinylcyclohexanes produced mainly of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene. Examples of polymers or copolymers produced containing styrene as a main component can be exemplified.

[0091] In order to produce the ethylene / aromatic vinyl compound copolymer wax used in the present invention using the metallocene catalyst (A), ethylene and an aromatic vinyl compound are usually used in the presence of the metallocene catalyst (A). Copolymerize by solution polymerization or slurry polymerization in the liquid phase.

[0092] Examples of such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof; alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and its halogen derivatives; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and chlorobenzene and their halogen derivatives are used. These solvents may be used in combination.

[0093] Ethylene and the aromatic vinyl compound may be copolymerized by either a batch method or a continuous method. When the copolymerization is carried out by the continuous method, the metallocene catalyst (A) is used at the following concentrations.

That is, the concentration of the metallocene compound (B) 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 (C) is supplied in an amount of 0.1 to 10000, preferably 1 to 5000, in terms of the ratio of aluminum atoms (Al / transition metal) to the metallocene compound (B) in the polymerization system.

[0095] The ionized ionic compound (D) has a molar ratio of the ionized ionic compound (D) to the metallocene compound (B) in the polymerization system (ionized ionic compound (D) / metallocene compound (B)) of 0.1 to It is supplied in an amount of 20, preferably 1-10.

[0096] When the organoaluminum compound (E) is used, it is usually used in an amount of about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.

[0097] In the copolymerization reaction for producing an ethylene / aromatic vinyl compound copolymer wax, the normal temperature is -30 to + 250 ° C, preferably 0 to 200 ° C, and the pressure exceeds 0 to 80 Kg. /cm²(Gauge pressure), preferably above 0 ~ 50Kg / cm²It is performed under the condition of (gauge pressure).

[0098] The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to. 1.5 hours. The ultimate viscosity and molecular weight of the ethylene / aromatic vinyl compound copolymer wax can be adjusted by a method such as adjusting the hydrogen supply rate in the supply of ethylene at a constant rate.

[0099] When producing an ethylene / aromatic vinyl compound copolymer wax, ethylene and an aromatic vinyl compound are supplied to the polymerization system in an amount such that a copolymer having a specific composition as described above can be obtained. To.

[0100] When the ethylene and the aromatic vinyl compound are copolymerized as described above, the ethylene / aromatic vinyl compound copolymer wax is usually obtained as a polymerization solution containing the same. This polymerization solution is treated by a conventional method to obtain an ethylene / aromatic vinyl compound copolymer wax.

[0101] As a method for producing an ethylene / aromatic vinyl compound copolymer wax by heating and reducing it, a high amount obtained by copolymerizing ethylene and an aromatic vinyl compound in the presence of a metallocene catalyst (A). A method in which a molecular weight ethylene / aromatic vinyl compound copolymer is supplied to a single-screw or double-screw extruder and extruded while being melt-kneaded, and high-molecular-weight ethylene is used in a tubular reactor, a tank reactor, etc. -A method in which an aromatic vinyl compound copolymer is directly supplied and heat-decomposed, or a high-molecular-weight ethylene / aromatic vinyl compound copolymer is supplied to an extruder and continuously extruded while being melt-kneaded to form a tube type. Examples thereof include a method of supplying to a reactor and heating and reducing it. The heating temperature in the extruder or reactor is 300-450 ° C, preferably 350-400 ° C. Among these methods, a method in which a high molecular weight ethylene / aromatic vinyl compound copolymer is supplied to an extruder, continuously extruded while being melt-kneaded, and supplied to a tubular reactor to be heat-decomposed is preferable. .. Further, the heating reduction is preferably carried out in an inert atmosphere such as nitrogen.

[0102] The high molecular weight ethylene / aromatic vinyl compound copolymer used for heat reduction can be produced by using the metallocene catalyst (A) in the same manner as the ethylene / aromatic vinyl compound copolymer wax. it can. However, by adjusting the hydrogen supply rate, a copolymer having a large ultimate viscosity and a large molecular weight can be produced.

[0103] The pigment dispersant of the present invention is used as a pigment dispersant for aromatic polymers. Here, specifically, the aromatic polymer contains styrene-based compound component units such as polystyrene, polyα-methylstyrene, styrene / acrylonitrile copolymer (AS), and styrene / acrylonitrile / butadiene copolymer (ABS). Styrene-based polymers; polyesters; polycarbonates; polyphenylene ethers and the like can be exemplified. Among these aromatic polymers, it is preferable to use the pigment dispersant of the present invention for coloring styrene-based polymers, especially polystyrene.

[0104] When dispersing the pigment in the aromatic polymer, only the pigment dispersant of the present invention can be used, or a known pigment dispersant can be used in combination.

[0105] The pigment dispersant of the present invention can be used for either inorganic or organic pigments conventionally known for coloring polymers. Specific examples of the above-mentioned inorganic pigments include metals such as aluminum, silver and gold; carbonates such as calcium carbonate and barium carbonate; ZnO and TiO.₂, Al₂O₃ NH₂O, Fe₂O₃ NH₂Oxides such as O; CaSO₄, BaSO₄Sulfates such as; Bi (OH)₂NO₃Nitrate such as; PbCl₂ Pb (OH)₂Chloride such as; CaCrO₄, BaCrO₄Chromate such as; CoCr₂O₄Subchromates, manganates and permanganates such as Cu (BO)₂Borates such as; Na₂U₂O₇ 6H₂Uranate such as O; K₃CO (NO)₂)₆ 3H₂Nitrite such as O; SiO₂Silicates such as CuAsO₃ Cu (OH)₂Arsenates and arsenates such as Cu (C)₂H₃O₂)₂ Cu (OH)₂Acetates such as; (NH₄)₂MnO₂(P₂O₇)₂Phosphates such as: Aluminates, Molybdenates, Zincates, Stinates, Antimonates, Tungsates, Serenes, Titanates, Iron Cyanides, Phyllates and Others; , ZuS, CdS and other sulfides.

Specific examples of organic pigments include natural organic pigments such as cochineal lake and madder lake; nitroso pigments such as naphthol green Y and naphthol green B; naphthol yellow S, pigment chlorin 2G and the like. Nitro pigments; Azo pigments such as Permanent Red 4R, Hansa Yellow, Brilliant Carmine 6B, Scarlet 2R; Basic dye lakes such as Malakine Green and Rhodamine B; Acid dye lakes such as Acid Green Lake and Eosin Lake; Mediation dye lakes such as Alizarin Lake and Purpurin Lake; Tian dye pigments such as Thio Indigo Red B and Intenslen Orange; Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.

[0107] The proportion of the pigment dispersant of the present invention used is usually 50 to 150 parts by weight, preferably 80 to 120 parts by weight, based on 100 parts by weight of the pigment.

[0108] The present invention<u style="single">For aromatic polymers</u>The pigment dispersant can be used for coloring of aromatic polymers by any method, such as coloring by a dry color method, coloring by a color compound method, or coloring by a masterbatch method. For example, in coloring by the dry color method or coloring by the color compound method, a mixture consisting of a pigment and the pigment dispersant of the present invention is finely powdered to prepare a powdery or beaded dry color, which is then pelletized into the aroma. Weigh and mix with group polymers in a tumbler or suitable mixer, evenly sprinkle dry color on the surface of the resin pellets, and use a shear force to knead the resin melted with a screw through an extruder or a molding machine. Is dispersed and colored, and this is molded. Further, the colored pellets obtained by extruding the melt-colored resin from the extruder in the above step and cutting the resin are the color compound.

[0109] The pigment dispersant of the present invention is excellent in pigment dispersibility, can uniformly disperse the pigment in the aromatic polymer, and is also excellent in workability such as kneading workability in this case. In addition, the aromatic polymer composition in which the pigment is dispersed is also excellent in transparency and coloring stability. Further, the ethylene / aromatic vinyl compound copolymer wax can be easily produced by copolymerizing ethylene with an aromatic vinyl compound or by heating and reducing the ethylene / aromatic vinyl compound copolymer. , The manufacturing cost is low.

[Effect of the Invention] Since the pigment dispersant for an aromatic polymer of the present invention is composed of a specific ethylene / aromatic vinyl compound copolymer wax, it is excellent in pigment dispersibility in an aromatic polymer and is blended. The later aromatic polymer composition is excellent in transparency and coloring stability, and is easy to manufacture and low in manufacturing cost.

[Embodiments of the Invention] Next, examples of the present invention will be described. Example 1 &lt;&lt; Production of ethylene / aromatic vinyl compound copolymer wax &gt;&gt; After sufficiently replacing a 1-liter glass reactor equipped with a cooling tube and a stirrer with nitrogen, 494 ml of toluene and 6 ml of styrene were charged. It was saturated with ethylene with stirring. Next, the temperature inside the system was raised to 35 ° C, and methylaluminoxane (10 wt% toluene solution manufactured by Toso Axo) was added to 4.5 mM, [(C) so that the molar ratio of aluminum to the catalyst was 100.₅Me₄) SiMe₂(Nt-Bu)] TiCl₂[(T-Butylamide) Dimethyl (Tetramethyl-η)⁵-Cyclopentadienyl) silanedichloride] was added at 0.045 mM (0.01 mM toluene solution). Polymerization was carried out at 40 ° C. for 60 minutes while continuously supplying 7.0 N liter / hr of hydrogen and 100 N liter / hr of ethylene. After completion of the polymerization, 250 ml of isobutyl alcohol and 10 ml of hydrochloric acid water were added, and the mixture was heated and stirred at 80 ° C. for 30 minutes. The reaction solution containing isobutyl alcohol was transferred to a liquid separation funnel, washed twice with 250 ml of water, and separated into oil and water. The oil reservoir was then added to 3 L of methanol to precipitate the polymer. The precipitated polymer was vacuum dried at 130 ° C. for 12 hours to obtain an ethylene / styrene copolymer wax.

The ethylene content of the obtained ethylene / styrene copolymer wax was 90% by weight, the styrene content was 10% by weight, and the ultimate viscosity measured in 135 ° C decalin was 0.13 dl / g. Using this ethylene / styrene copolymer wax (hereinafter, sometimes abbreviated as ethylene / st wax) as a pigment dispersant, the performance was evaluated by the following method.

&lt;&lt; Performance Evaluation Method of Pigment Dispersant &gt;&gt; Micro-type fluoroscopic mixer (V type) manufactured by Tsutsui Chemicals Co., Ltd. in a ratio of 100 parts by weight of fine powder of pigment dispersant and 100 parts by weight of fine powder of phthalocyanine blue. A dry blend was prepared by mixing using a blender). This dry blend composition was supplied to a three-roll kneader at 130 ° C. and passed three times for kneading. This kneaded composition and polystyrene [manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name Toporex] are rotated at a speed of 50 r.pm at 160 ° C at a ratio such that the pigment concentration in the kneaded molded product is 1.3% by weight. It was supplied to the lavender kneader and kneaded for 5 minutes.

[0114] This kneaded product was pressed under the condition of a press temperature of 170 ° C. to obtain a masterbatch film having a thickness of 0.1 mm. The pigment dispersibility in this masterbatch film was evaluated on a scale of 5 to 1 below. The measurement was performed with a Lvzex 450 image processor manufactured by Toyo Ink Co., Ltd. The results are shown in Table 2. 5: The number of particles of 50 μm or more is 1.00 × 10³Pieces / cm³Less than 4: The number of particles of 50 μm or more is 1.00 × 10³Pieces / cm³More than 7 × 10³Pieces / cm³Less than 3: The number of particles of 50 μm or more is 7 × 10³Pieces / cm³More than 2.7 × 10⁴Pieces / cm³Less than 2: The number of particles of 50 μm or more is 2.7 × 10⁴Pieces / cm³More than 7.00 × 10⁴Pieces / cm³Less than 1: The number of particles of 50 μm or more is 7.00 × 10⁴Pieces / cm³[0115] Further, the degree of haze of the obtained film was measured as a film haze. The smaller this value, the better the transparency. In addition, it was investigated whether or not the dry blend composition was sticky and had an excessive motor load in the three-roll kneading step, and evaluated in the following three stages. The results are shown in Table 2. : Good : Normal ×: Bad [0116] Examples 2 to 5 Physical characteristics shown in Table 2 in the same manner as in Example 1 except that the amount of styrene used and the amount of hydrogen used are changed as shown in Table 2. An ethylene / styrene copolymer wax having the above was produced. Performance evaluation was carried out in the same manner as in Example 1 using this ethylene / styrene copolymer wax. The results are shown in Table 2.

[0117] Example 6 An ethylene / styrene copolymer wax was produced in the same manner as in Example 1 except that the catalyst was changed to isopropylidene-bis (indenyl) zirconium dichloride synthesized by a known method. Performance evaluation was carried out in the same manner as in Example 1 using this ethylene / styrene copolymer wax. The results are shown in Table 2.

Comparative Examples 1 and 2 Ethylene-styrene copolymer wax having the physical properties shown in Table 2 in the same manner as in Example 1 except that the amounts of styrene and hydrogen used were changed as shown in Table 1. Manufactured. Performance evaluation was carried out in the same manner as in Example 1 using this ethylene / styrene copolymer wax. The results are shown in Table 2.

[0119] [Table 1]<img file="JP3858397B2_D0006.tif" />[0120] [Table 2]<img file="JP3858397B2_D0007.tif" />