JP2003201436A - Polyolefin wax for coating material and printing ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wax of ethylene (co)polymer for use in an additive for coating materials, especially for printing inks, simultaneously improving both abrasion resistance and blocking resistance, and to provide a printing ink composition containing the wax. <P>SOLUTION: The wax (A) for use as an additive for coating materials consists of an ethylene (co)polymer, has a volume-average particle size of 0.3-20 μm, and meets the relationship: a/b≤4 (wherein, (a) is such one that the weight proportion of the larger particle sizes is 10% and b is such one that the weight proportion of the smaller particle sizes is 10%, in the particle size distribution by weight). The printing ink composition is obtained by incorporating 0.1-10 wt.% of the wax A in a printing ink. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin wax for a coating material and a printing ink composition, for example, a polyolefin wax suitable for a printing ink and a printing ink composition containing the polyolefin wax.

[0002]

BACKGROUND OF THE INVENTION In general, a coating material such as a printing ink contains a wax as an additive for improving abrasion resistance of a printing film, reducing tackiness, preventing blocking, imparting water resistance and water repellency. ing. Here, the wax is a general term for organic compounds mainly composed of an aliphatic component which is a solid at room temperature but melts when heated to become a low-viscosity fluid.

Carnauba wax, beeswax, paraffin wax, microcrystalline wax, polyethylene wax, polypropylene wax, fatty acid amide, and polytetrafluoro are conventionally used as waxes for printing inks such as lithographic printing and offset printing inks. Ethylene and the like are known. When wax is used as the printing ink, the abrasion resistance is improved by the action of the wax particles existing on the surface of the printing film formed from the printing ink. This is because the wax, a part of which protrudes from the ink surface to the outside, is crushed by the external physical pressure, spreads thinly on the ink coating film on paper and various film substrates, and protects the ink surface. .

The wax blended in the printing ink needs to be blended uniformly in the printing ink.
Known methods include a method of using pulverized wax, a method of kneading and mixing a solid wax, and a method of dispersing in solid oil or water. However, with the conventional solid wax, the unevenness of the surface of the printing ink containing the wax becomes large and a clear printed image cannot be obtained, and the desired effect cannot be obtained unless the printing ink contains a large amount of the wax. There was a problem.

[0005]

OBJECT OF THE INVENTION The present invention is a polyolefin wax for a coating material, particularly a polyolefin wax which is preferably used as an additive for a printing ink and which can simultaneously improve abrasion resistance and anti-blocking property, and such a wax. An object of the present invention is to provide a printing ink composition containing

[0006]

SUMMARY OF THE INVENTION The present invention provides the following polyolefin waxes for coating materials and printing ink compositions. (1) It is composed of an ethylene (co) polymer, has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, and a volume average particle diameter of 0.3 μm to 20 μm. Particle size a in which the weight ratio on the large particle size side in the weight particle size distribution is 10%.
(Μm) and the weight ratio on the small particle size side in the weight particle size distribution is 10
% Of the particle size b (μm) satisfies the following formula (I) a / b ≦ 4 (I), and the crystallization temperature (Tc (° C.) and the temperature decrease are measured by a differential scanning calorimeter (DSC). At a speed of 2 ° C./min.) And the density (D (kg / m 3)) measured by the density gradient tube method is expressed by the following formula (II) 0.501 × D-366 ≧ Tc (II) Polyolefin wax (A) for coating material to fill. (2) The ethylene (co) polymer is an ethylene / α-olefin copolymer obtained from ethylene and propylene and / or 1-butene, and has a density of 850 kg.
/ M ^{3 to} 980 kg / m ³ The polyolefin wax (A) for a coating material according to (1) above, which is in the range. (3) The polyolefin wax (A) for a coating material according to any of (1) or (2) above, wherein the ethylene (co) polymer is produced with a vanadium catalyst or a metallocene catalyst. (4) A printing ink composition, wherein the printing ink contains 0.1 to 10% by weight of the polyolefin wax (A) for a coating material according to any of (1) to (3) above.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The polyolefin wax for a coating material and the printing ink composition according to the present invention will be specifically described below. Polyolefin Wax for Coating Material The polyolefin wax (A) for coating material according to the present invention comprises a specific ethylene (co) polymer.

The ethylene (co) polymer used in the present invention is an ethylene homopolymer or a copolymer of ethylene and α-olefin. Here, the α-olefin includes propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, 1-pentene having 5 carbon atoms, and 1 having 6 carbon atoms.
-Hexene, 4-methyl-1-pentene, 8 carbon atoms
1-octene and the like, and preferably propylene, 1-butene, 1-hexene and 4-methyl-1-pentene.

The ethylene (co) polymer has a volume average particle diameter of 0.3 μm to 20 μm, preferably 0.3 to 15 μm,
It is more preferably in the range of 1 to 5 μm. When the volume average particle diameter of the ethylene (co) polymer is within the above range, the ink printed surface after ink coating is protected by adding a few% of the ethylene (co) polymer to the ink, It tends to show excellent wear resistance to frictional forces.

The ethylene (co) polymer has a particle size a (μm) such that the weight ratio on the large particle size side is 10% in the weight particle size distribution.
And the particle size b (μm) at which the weight ratio on the small particle size side is 10% in the weight particle size distribution, the following formula (I) a / b ≦ 4 (I) is preferred. a / b ≦ 3.5 (Ia) More preferably, the following formula (Ib) satisfies a / b ≦ 3.0 (Ib).

When a / b of the ethylene (co) polymer satisfies the above formula, the surface of the ink is uniformly coated with the ethylene (co) polymer, and the ink abrasion resistance and blocking resistance tend to be improved. The volume average particle size and the particle size a in which the weight ratio on the large particle size side is 10% and the particle size b on the small particle size side in the weight particle size distribution are 10% are the ethylene (co) polymer. The pulverized product is dispersed in Isoton (dispersion medium), the particle size distribution is measured using a Coulter counter (manufactured by Coulter Co.), and a and b are determined from the data.

The ethylene (co) polymer has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, preferably 1,000 to 4,000, more preferably 1 , 500-2,
In the range of 500, the crystallization temperature (Tc (° C) and the temperature decreasing rate of 2 ° C / min.) Measured by a differential scanning calorimeter (DSC) and the density (D (kg / m
³ )) has the following formula (II) 0.501 × D-366 ≧ Tc (II), more preferably the following formula (IIa) 0.501 × D-366.5 ≧ Tc (IIa). Preferably satisfies the following formula (IIb) 0.501 × D-367 ≧ Tc ... (IIb).

When the relationship between the crystallization temperature (Tc) and the density (D) in the ethylene (co) polymer satisfies the above formula,
As a result of making the comonomer composition of the ethylene (co) polymer more uniform, the sticky component of the ethylene (co) polymer is reduced and the blocking resistance tends to be improved. The ethylene (co) polymer is preferably an ethylene / α-olefin copolymer obtained from ethylene and propylene and / or 1-butene, and has a density of 850 to 980.
kg / m ^3, preferably 890~970kg / m ^3, more preferably it is preferably in the range of 900~950kg / m ^3.

The ethylene (co) polymer has a density (D (kg / m ³ )) measured by a density gradient tube method and an intrinsic viscosity ([η]).
(Dl / g)) (measured in decalin at 135 ° C.) and penetration (Y (dmm)) (measured by JIS K2270) preferably satisfy the following formula (III). Y ≦ −9.92 × 10 ⁻⁴ [η] ^−2.71 × D + [η] ^−2.68 (III) When the penetration satisfies the above relationship, the ink printed surface after ink coating is protected and externally applied. It tends to show excellent wear resistance to frictional forces.

The ethylene (co) polymer has an Mw / Mn of 4
It is preferably 2.9 or less, more preferably 2.8 or less. When Mw / Mn is within the above range, the low-tail component and the high-tail component are reduced, and a uniform dispersion tends to be formed. The polyolefin wax for a coating material according to the present invention comprises the ethylene (co) polymer as described above. This polyolefin wax is solid at room temperature and becomes a low-viscosity liquid at 80 to 120 ° C. or higher.

The coating material in which the polyolefin wax of the present invention is used includes, for example, printing inks, paints, surface coating materials, hot melt coating materials, etc., and printing inks are particularly preferable. The printing ink used in the present invention may be water-based, oil-based, or solvent, and is preferably oil-based ink or solvent ink.

Method for Producing Ethylene (Co) Polymer As a catalyst for obtaining the above-mentioned ethylene (co) polymer, a vanadium-based catalyst comprising a soluble vanadium compound and an organic aluminum compound, selected from Group 4 of the periodic table Homogeneous catalysts such as metallocene catalysts comprising a transition metal metallocene compound and an organoaluminum oxy compound and / or an ionized ionic compound. The vanadium-based catalyst and the metallocene-based catalyst are
It is known and is, for example, as follows.

(Soluble Vanadium Compound) Examples of the soluble vanadium compound forming the vanadium catalyst include vanadium compounds represented by the following formula (i) or (ii). VO in ^{_{(OR 1) a X 1 b}} ... (i) V (OR 1) c X 1 d ... (ii) formula, R ¹ is a hydrocarbon group, X ¹ is a halogen atom.

A, b, c and d are each 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d
It is a number that satisfies ≦ 4 and 3 ≦ c + d ≦ 4. As the soluble vanadium compound, an electron donor addition product of a soluble vanadium compound obtained by contacting an electron donor can also be used. (Organoaluminum compound) As the organoaluminum compound forming the vanadium-based catalyst, a compound having at least one Al-carbon bond in the molecule can be used.
Examples of such a compound include the following general formula (iii)
An organoaluminum compound represented by: (R ² ) _m Al (OR ³ ) _n H _p X ² _q (iii) (wherein R ² and R ³ may be the same or different from each other, It is usually a hydrocarbon group containing 1 to 15, preferably 1 to 4. X ² is a halogen atom.
Is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q
= 3. ) Examples thereof include complex alkylated products of a Group 1 metal represented by the following general formula (iv) and aluminum.

(M ¹ ) Al (R ² ) ... (iv) (wherein M ¹ is Li, Na or K, and R ² is the same as R ^{2 in the} general formula (iii)). Metallocene compound) The metallocene compound forming the metallocene catalyst is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specific examples thereof include compounds represented by the following general formula (v).

M ² Lx (v) where M ² is a transition metal selected from Group 4 of the periodic table, x
Is the valence of the transition metal M ² , and L is a ligand. Examples of the transition metal represented by M ² include zirconium, titanium and hafnium. L is a ligand that coordinates to the transition metal M ^2, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton, and a ligand having this cyclopentadienyl skeleton. The ligand may have a substituent.

The ligand L having a cyclopentadienyl skeleton is, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group,
n-, i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, etc. Alkyl- or cycloalkyl-substituted cyclopentadienyl groups; further examples include indenyl groups, 4,5,6,7-tetrahydroindenyl groups, fluorenyl groups and the like. The hydrogen of the group having a cyclopentadienyl skeleton may be substituted with a halogen atom or a trialkylsilyl group.

When the metallocene compound has two or more groups having a cyclopentadienyl skeleton as the ligand L, two groups having two cyclopentadienyl skeletons among them are ethylene, propylene, etc. A substituted alkylene group such as isopropylidene or diphenylmethylene; a silylene group or a dimethylsilylene group;
It may be bonded via a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Ligands other than those having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L are hydrocarbon groups having 1 to 12 carbon atoms,
Alkoxy group, aryloxy group, sulfonic acid-containing group (-
SO ₃ R ⁴ ), a halogen atom or a hydrogen atom (where R is
⁴ is 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 the like.

(Example-1 of metallocene compound) When the metallocene compound represented by the above general formula (v) has, for example, a transition metal valence of 4, more specifically, it is represented by the following general formula (vi). To be done. R ⁵ _k R ⁶ _l R ⁷ _m R ⁸ _n M ² (vi) where M ² is a transition metal selected from Group 4 of the periodic table, R ⁵
Is a group (ligand) having a cyclopentadienyl skeleton, R
⁶ , R ⁷ and R ⁸ are each independently a group (ligand) having or not having a cyclopentadienyl skeleton.
k is an integer of 1 or more, and k + l + m + n = 4.

Examples of the metallocene compound in which M ² is zirconium and at least two ligands having a cyclopentadienyl skeleton are included are shown below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl)
Zirconium dichloride, etc.

Among the above compounds, compounds in which the 1,3-position-substituted cyclopentadienyl group is replaced with a 1,2-position-substituted cyclopentadienyl group can also be used. Another example of the metallocene compound is the above general formula (vi)
In at least two of R ⁵ , R ⁶ , R ⁷ and R ⁸ ;
For example, R ⁵ and R ⁶ are groups (ligands) having a cyclopentadienyl skeleton, and these at least two groups are bound to each other via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. It is also possible to use a bridge type metallocene compound. At this time R
⁷ and R ⁸ are independently the same as the ligand L other than the above-mentioned ligand having a cyclopentadienyl skeleton.

Examples of such bridge-type metallocene compounds are ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium. Dichloride,
Methyl phenyl silylene bis (indenyl) zirconium dichloride etc. are mentioned.

(Example-2 of Metallocene Compound) As another example of the metallocene compound, a metallocene compound represented by the following general formula (vii) described in JP-A-4-268307 can be mentioned.

[0030]

[Chemical 1]

Here, M ² is a transition metal of Group 4 of the periodic table, and specific examples thereof include titanium, zirconium and hafnium. R ¹¹ and R ¹² may be the same or different and each is 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; a carbon atom. An aryloxy group having 6 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms; 7 to 40 carbon atoms
Or an arylalkenyl group having 8 to 40 carbon atoms; or a halogen atom, preferably a chlorine atom.

R ¹³ and R ¹⁴ may be the same or different and each is 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. _{^{; -N (R 20) 2,}} -SR 20,
-OSi (R ²⁰⁾ _3, a -Si (R ^{2 0)} ₃ or -P (R ²⁰⁾ ₂ group. Here, 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 for 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 carbon atom having 1 to 4 carbon atoms.
An alkyl group of, specifically, methyl, ethyl, propyl,
Examples thereof include isopropyl, butyl, isobutyl and trifluoromethyl, with methyl being particularly preferred.

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

[0035]

[Chemical 2]

= BR^{twenty one}, = AlR^{twenty one}, -Ge-, -Sn
-, -O-, -S-, = SO, = SO ₂, = NR^{twenty one}, =
CO, = PR^{twenty one}, = P (O) R^{twenty one}Such. M³Is silicon,
Germanium or tin, preferably silicon or germanium
It is Ni. Where R^{twenty one}, R^{twenty two}And R^{twenty three}Are each other
May be the same or different, hydrogen atom; halogen source
Child; alkyl group having 1 to 10 carbon atoms; 1 to carbon atom
10 fluoroalkyl groups; ants having 6 to 10 carbon atoms
Group; fluoroaryl group having 6 to 10 carbon atoms; charcoal
Alkoxy group having 1 to 10 elementary atoms; 2 to 10 carbon atoms
Alkenyl group of 7 to 40 carbon atoms arylalkyl
Group; arylalkenyl group having 8 to 40 carbon atoms;
Is an alkylaryl group having 7 to 40 carbon atoms.
"R^{twenty one}And R^{twenty two}Or "R^{twenty one}And R^{twenty three}Is each
May form a ring with the atoms to which they bind
Yes.

Further, R ¹⁷ is = CR ²¹ R ²² , = SiR ^{21
R 22, = GeR 21 R 22} , -O -, - S -, = SO, = P
R ²¹ or = P (O) R ²¹ is preferred. R ¹⁸
And R ¹⁹ may be the same or different from each other, and R ²¹
The same thing as is mentioned. m and n may be the same or different from each other and are 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

Metallocene represented by the above general formula (vii)
The following compounds are mentioned as an example of a compound. rac
-Ethylene (2-methyl-1-indenyl)²-Zirco
Nium-dichloride, rac-dimethylsilylene (2
-Methyl-1-indenyl) ²-Zirconium-dichloro
Ride etc. These metallocene compounds are, for example,
It can be produced by the method described in Kahei 4-268307.
You can

(Example-3 of Metallocene Compound) As the metallocene compound, a metallocene compound represented by the following general formula (viii) can also be used.

[0040]

[Chemical 3]

In the formula, M ³ represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium, hafnium or the like. R ²⁴ and R ²⁵ 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, a silicon-containing group, oxygen. A containing group, a sulfur containing group, a nitrogen containing group or a phosphorus containing group is shown.

R ²⁴ is preferably a hydrocarbon group,
Especially methyl, ethyl or propyl having 1 to 3 carbon atoms
Is preferably an alkyl group of R ²⁵ is preferably hydrogen or a hydrocarbon group, particularly a hydrogen atom, or methyl,
It is preferably an alkyl group having 1 to 3 carbon atoms such as ethyl or propyl. R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹
Are the same or different and each represents 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, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. Even if at least one set of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ is combined with the carbon atom to which they are bonded to form a monocyclic aromatic ring. Good. When two or more kinds of hydrocarbon groups or halogenated hydrocarbon groups are present, the groups other than the group forming an aromatic ring 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 ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon number of 1 to 2.
Y representing a hydrocarbon group of 0, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group is a divalent hydrocarbon group of 1 to 20 carbon atoms, or 1 to 12 carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,
O -, - CO -, - S -, - SO -, - SO 2 -, - N
^{R 30 -, - P (R} 30) -, - P (O) (R 30) -, - BR 30 -
Or -AlR ³⁰ - (provided that, R ³⁰ 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.

In the above formula, R ²⁶ and R ²⁷ , R ²⁷ and R
²⁸ , R ²⁸ and R ²⁹ include a monocyclic aromatic ring formed by bonding at least one pair to each other, and examples of the ligand coordinated to M ³ include those represented by the following formulae. To be

[0045]

[Chemical 4]

(In the formula, Y is the same as that shown in the above formula.) (Example-4 of metallocene compound) As the metallocene compound, a metallocene compound represented by the following general formula (ix) is used. You can also

[0047]

[Chemical 5]

In the formula, M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R
²⁸ and R ²⁹ are the same as those used in the above general formula (viii). R of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹
It is preferred that the two groups including ²⁶ are alkyl groups,
R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. Further, this alkyl group may be substituted with a halogen atom or a silicon-containing group, and examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ²⁴ and R ²⁵ .

Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , groups other than the alkyl group are preferably hydrogen atoms. Two groups selected from R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. Examples of the halogen atom include those similar to the above R ²⁴ and R ²⁵ .

Examples of X ³ , X ⁴ and Y are the same as above. Specific examples of the metallocene compound represented by the above general formula (ix) 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, a transition metal compound 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 R type or S type can also be used. (Example-5 of metallocene compound) As the metallocene compound, a metallocene compound represented by the following general formula (x) can also be used.

[0052]

[Chemical 6]

In the formula, M ³ , R ²⁴ , X ³ , X ⁴ and Y are
The same atom or group as described in the general formula (viii) above can be mentioned. R ²⁴ is preferably a hydrocarbon group, and 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 ³ and X ⁴ 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 (x) 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, etc. Further, in these compounds, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

(Example-6 of Metallocene Compound) As the metallocene compound, a metallocene compound represented by the following general formula (xi) can also be used. _{^{LaM 4 X 5 2 ... (xi}} ) where, M ⁴ is a metal of Group 4 of the periodic table or lanthanum series. La is a derivative of the delocalized π-bonding group, and is a group that imparts a constrained geometry to the metal M ⁴ active site. X ^{5 s} may be the same or different, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms,
It is a silyl group containing 20 or less silicon or a germanyl group containing 20 or less germanium.

Among these compounds, the compound represented by the following formula is preferable.

[0057]

[Chemical 7]

M ⁴ is titanium, zirconium or hafnium. X ⁵ is the same as that described in the general formula (xi). Cp is a substituted cyclopentadienyl group which is π-bonded to M ⁴ and has a substituent Z. Z is oxygen, sulfur, boron or an element of Group 4 of the periodic table (eg 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 such a formula are shown below. (Dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamido) (tetramethyl-η ⁵
-Cyclopentadienyl) -1,2-ethanediyl) titanium dichloride and the like. In addition, in this metallocene compound, a compound in which titanium is replaced with zirconium or hafnium can be given.

(Example-7 of Metallocene Compound) As the metallocene compound, a metallocene compound represented by the following general formula (xiii) can also be used.

[0061]

[Chemical 8]

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, or 1 carbon atom.
3-40 arylalkenyl groups, 12-4 carbon atoms
0 alkylaryl group or silicon-containing group,
Alternatively, at least two groups adjacent to each other among the groups represented by R ³¹ form a single or plural aromatic ring or aliphatic ring together with the carbon atom to which they are bonded. In this case, the ring formed by R ³¹ has 4 to 20 carbon atoms in all including carbon atoms to which R ³¹ is bonded.

Aryl group, arylalkyl group, arylalkenyl group, alkylaryl group and aromatic ring,
R ³¹ other than R ³¹ that forms an aliphatic ring is a hydrogen atom,
It is a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group. R ^{32 s} may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, or a carbon number of 1 to 1.
0 alkyl group, C 6-20 aryl group, C 2-10 alkenyl group, C 7-40
Is an arylalkyl group, 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.

Further, at least two adjacent groups of the groups represented by R ³² may form a single or plural aromatic ring or aliphatic ring together with the carbon atom to which they are bonded. In this case, the ring formed by R ³² is R
R having a total of 4 to 20 carbon atoms including carbon atoms to which ³² is bonded and forming an aromatic ring or an aliphatic ring.
R ³² other than ³² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group.

In the group constituted by the two groups represented by R ³² by forming one or more aromatic rings or aliphatic rings, a fluorenyl group has a structure represented by the following formula. included.

[0066]

[Chemical 9]

R ³² is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or methyl, ethyl,
It is preferably a hydrocarbon group having 1 to 3 carbon atoms of propyl. A preferable example of the fluorenyl group having R ³² as the substituent is a 2,7-dialkyl-fluorenyl group, and the alkyl group of the 2,7-dialkyl in this case has 1 to 1 carbon atoms. And the alkyl group of 5. R ³¹ and R ³² may be the same or different from each other.

R ³³ and R ³⁴ may be the same or different from each other, and are the same as the above hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, and carbon atom. Alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, and 8 carbon atoms
40 arylalkenyl groups, C 7-40 alkylaryl groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups. At least one of R ³³ and R ³⁴ is preferably an alkyl group having 1 to 3 carbon atoms.

X ³ and X ^{4, which} may be the same or different, are each a hydrogen atom, a halogen atom, or a carbon number of 1 to 2.
It is a hydrocarbon group of 0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, or a conjugated diene residue formed from X ³ and X ⁴ . The conjugated diene residue formed from X ³ and X ⁴ is preferably a residue of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-diphenylbutadiene. , These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms.

X ³ and X ⁴ 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, carbon atom 1-2
A hydrocarbon group of 0 and a halogenated hydrocarbon group of 1 to 20 carbon atoms).

Among these divalent groups, those in which the shortest connecting portion of --Y-- is composed of 1 or 2 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, and an alkyl group. Particularly preferred is silylene, alkylarylsilylene or arylsilylene.

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

[0073]

[Chemical 10]

In the formula, 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 or different from each other, and are 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, a silicon-containing group, It is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a 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, and particularly, a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl, phenyl, It is preferably an aryl group such as α-naphthyl or β-naphthyl, or a hydrogen atom. R ^{37 s} may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 2 to 2 carbon atoms.
An alkenyl group having 10 carbon atoms, 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. 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 1 to 1 carbon atoms of methyl, ethyl, n-propyl, i-propyl, n-butyl or tert-butyl. It is preferably a hydrocarbon group of 4. Further, 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.

Of these, one of R ³⁸ and R ³⁹ has 1 carbon atom such as methyl, ethyl or propyl.
It is preferable that it is an alkyl group of ~ 3 and the other is a hydrogen atom. X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon atom number of 1 to 20.
Hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing group, sulfur-containing group or nitrogen-containing group,
Alternatively, it is a conjugated diene residue formed from X ³ and X ⁴ . Of these, halogen atoms or carbon atoms of 1 to
It is preferably 20 hydrocarbon groups.

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,
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 represents 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).

Of these, Y is 2 having 1 to 5 carbon atoms.
It is preferably a divalent hydrocarbon group, a divalent silicon-containing group or a divalent germanium-containing group, more preferably a divalent silicon-containing group, and an alkylsilylene, an alkylarylsilylene or an arylsilylene. Is particularly preferable. The metallocene compounds described above may be used alone or in combination of two or more. The metallocene compound may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

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

[0081]

[Chemical 11]

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 an integer of 2 or more, preferably 5 to 40. Aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ′)) and an alkyloxyaluminum unit represented by the formula (OAl (R ″)) (here, R ′).
And R ″ can exemplify the same hydrocarbon group as R, and R ′ and R ″ represent different groups. ) May be formed from a mixed alkyloxyaluminum unit. The organoaluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum.

(Ionized Ionic Compound) Examples of the ionized ionic compound (sometimes referred to as ionic ionized compound or ionic compound) include Lewis acids, ionic compounds, borane compounds and carborane compounds. it can. Examples of the Lewis acid include compounds represented by BR ₃ (R is fluorine, a phenyl group which may have a substituent such as a methyl group or a trifluoromethyl group, or fluorine.). 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) Examples include boron.

Examples of the ionic compounds 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, tri (n-butyl) ammonium tetra (phenyl) boron and the like. Examples of the dialkyl ammonium salt as the ionic compound include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) is used.
Examples thereof include borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate. As the borane compound, decaborane (9); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium]
Examples thereof include salts of metal borane anions such as decaborate and bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III).

Examples of the carborane compound include 4-carbanonaborane (9), 1,3-dicarbanonaborane (8), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate). ) Salts of metal carborane anions such as nickelate (IV). Such ionized ionic compounds may be used alone or in combination of two or more. The organoaluminum oxy compound and the ionized ionic compound can also be used by supporting them on the carrier compound.

When forming the metallocene catalyst, the above-mentioned organoaluminum compound may be used together with the organoaluminum oxy compound and / or the ionizable ionic compound. (Polymerization) The ethylene (co) polymer used in the present invention is
In the presence of the vanadium-based catalyst or the metallocene-based catalyst, ethylene is usually homopolymerized in a liquid phase, or ethylene, α-olefin and, if necessary, other copolymerizable monomers are copolymerized. At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. The respective monomers used here are as described above.

Polymerization methods include suspension polymerization in which an ethylene (co) polymer is polymerized in the presence of particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and 1
Solution polymerization in which an ethylene (co) polymer coexists with a solvent or alone in a molten state at a polymerization temperature of 40 ° C. or higher is possible. Among them, solution polymerization is preferable in terms of economy and quality.

The polymerization reaction may be carried out by either a batch method or a continuous method. When carrying out the polymerization batchwise, the catalyst components are used in the concentrations described below. When a vanadium-based catalyst is used, the concentration of soluble vanadium compound in the polymerization system is usually 0.01.
.About.5 mmol / liter (polymerization volume), preferably 0.1.
It is 05 to 3 mmol / liter. It is desirable that the soluble vanadium compound is supplied at a concentration of 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system. The organoaluminum compound has a molar ratio of aluminum atoms to vanadium atoms in the polymerization system (Al / V),
2 or more, preferably 2 to 50, more preferably 3 to 2
Supplied in an amount of 0.

The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the hydrocarbon solvent and / or the liquid monomer. At this time, the soluble vanadium compound is preferably diluted to the above concentration, but the organoaluminum compound may be supplied to the polymerization system after being adjusted to an arbitrary concentration, for example, 50 times or less the concentration in the polymerization system. desirable.

When a metallocene catalyst is used, the concentration of the metallocene compound in the polymerization system is usually 0.0
It is 0005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter. The organoaluminum oxy compound has a molar ratio of aluminum atom to transition metal in the metallocene compound in the polymerization system (Al / transition metal) of 1 to 10,000,
It is preferably supplied in an amount of 10 to 5000.

The ionized ionic compound is expressed in the molar ratio of the ionized ionic compound to the metallocene compound in the polymerization system (ionized ionic compound / metallocene compound) in an amount of 0.5 to 20, preferably 1 to 10. Supplied. When an organoaluminum compound 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.

When the polymerization is carried out in the presence of the vanadium catalyst, the polymerization reaction is usually carried out at a temperature of -50 to +100.
℃, preferably -30 to +80 ℃, more preferably-
At 20 to + 60 ° C, the pressure exceeds 4.9 MPa (5
0 kgf / cm ² , gauge pressure) or less, preferably more than 0 and 2.0 MPa (20 kgf / cm ² , gauge pressure) or less.

When the polymerization is carried out in the presence of the metallocene catalyst, the polymerization reaction is usually carried out at a temperature of -20 to +150.
℃, preferably 0 to 120 ℃, more preferably 0 to 1
At 00 ° C, the pressure exceeds 0 to 7.8 MPa (80 kgf
/ Cm ² , gauge pressure) or less, preferably more than 0.
It is carried out under the conditions of 9 MPa (50 kgf / cm ² , gauge pressure) or less.

During the polymerization, ethylene and optionally an α-olefin are supplied to the polymerization system in such an amount ratio that an ethylene (co) polymer having the above-mentioned specific composition can be obtained. A molecular weight modifier such as hydrogen may be added during the polymerization. When the polymerization is carried out in this way, the produced polymer is usually obtained as a polymerization liquid containing the polymer. Therefore, the ethylene (co) polymer according to the present invention can be obtained by treating the polymer by a conventional method.

The polymerization reaction can be carried out with the above-mentioned various catalyst systems. Among them, the use of metallocene catalysts, particularly the catalysts containing the metallocene compound shown in (Example 6 of metallocene compound) are preferable. Further in the present invention,
It is preferable to produce an ethylene / α-olefin copolymer using a metallocene catalyst. The ethylene / α-olefin copolymer synthesized with a metallocene catalyst has a crystal part in a solid state, which is microscopically smaller than that of the ethylene / α-olefin copolymer with a conventional Ziegler catalyst. There is a report that it is thin and uniform (Tetsuya Harada, next-generation polymer industrialization technology using metallocene catalysts, 1995 Interresearch), and the yield is improved by pulverizing ethylene / α-olefin copolymers synthesized with metallocene catalysts. Fine particles with good particle size distribution and narrow particle size distribution can be obtained.

(Method for pulverizing ethylene (co) polymer) The method for obtaining fine powder of ethylene (co) polymer is not particularly limited as long as it is a method capable of pulverizing the ethylene (co) polymer. For example, jet mill , A vibrating ball mill, a stirring mill, a planetary mill or the like. In order to produce a fine powder of ethylene (co) polymer, it is desirable to preliminarily pulverize it to a diameter of about 1 mm or less with a pulverizer such as a ball mill, a pin mill, a screen mill or a tube mill.

A specific example of the method for pulverizing an ethylene (co) polymer will be described by taking a method using an air jet mill as a pulverizer as an example. 1mm ethylene (co) polymer in advance
Coarsely pulverize to about the diameter. Freeze this,
It is supplied to the air jet mill body by a table feeder at a certain speed. The resulting fine powder of ethylene (co) polymer is supplied to an air classifier to remove low-particle-size components and achieve a desired particle size distribution. The original pressure of the air,
By optimizing the amount of gas in the circulating gas and the suction degree of the fine powder recovery line, the recovery efficiency of the fine powder can be improved, and the particle size distribution can be adjusted by the gas amount and supply rate.

In the preliminary pulverization and fine pulverization, granulation methods other than pulverization such as a crystallization method using a solvent, a spray granulation method and an emulsion dispersion method in water can be used together with the pulverization method. The coating material is usually 0.1-100μ on various substrates.
It is used as a coating film having a thickness of m. The polyolefin wax powder satisfying the above formula (I) is obtained by classifying a pulverized product of ethylene (co) polymer as described above,
If the pulverized product is not classified, a polyolefin wax powder satisfying the formula (I) cannot be obtained. The ethylene (co) polymer satisfying the above formula (II) is a homogeneous catalyst as described above,
In particular, it can be obtained by using a metallocene catalyst,
It cannot be obtained with the conventional Ziegler type catalyst (see Comparative Example below). The ethylene (co) polymer satisfying the above formula (III) can be obtained by using a metallocene catalyst, but is particularly suitable when ethylene and propylene are copolymerized by using the above-mentioned "Example 6 of metallocene compound". And an ethylene / propylene copolymer having a density of 940 kg / m ³ or less is produced.

Printing Ink Composition The printing ink composition according to the present invention has a polyolefin wax (ethylene (co) polymer) content of 0.1 to 10% by weight, preferably 0.1% by weight, based on the total amount of the printing ink composition.
It is contained in an amount of 5 to 5% by weight. The said polyolefin wax can be used individually by 1 type or in combination of 2 or more types.

When the content of the polyolefin wax is within the above range, the coating material tends to have an excellent balance of abrasion resistance and blocking resistance. As a method for adding the polyolefin wax, it can be added in any step in the conventional printing ink manufacturing step. That is, the pigment and the polyolefin wax may both be dispersed and kneaded in a varnish to be made into an ink, or the polyolefin wax may be mixed with the varnish which has been subjected to the dispersion and kneading steps to be made into an ink. The same effect can be obtained by mixing an anti-slip agent with the printing ink used as a product.

Any known kneading means may be used as a kneading means which can be used for producing the printing ink, but a twin-screw extruder, a single-screw extruder, a kneader and a Banbury mixer can be preferably exemplified. Further, the printing ink composition of the present invention, within the range of not impairing its performance, various auxiliary materials, for example, dispersants, emulsifiers, surfactants, stabilizers, wetting agents,
Thickener, foaming agent, defoaming agent, coagulant, gelling agent, anti-settling agent, antistatic agent, antistatic agent, antiaging agent, softening agent, plasticizer, filler, coloring agent, perfume agent. , An anti-adhesive agent, a release agent, etc. may be contained.

[0103]

By adding the polyolefin wax for coating material according to the present invention to the coating material, the abrasion resistance and the blocking resistance of the coating material can be simultaneously improved. The printing ink composition according to the present invention is simultaneously excellent in abrasion resistance and blocking resistance.

[0104]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0105]

[Production Example 1] Ethylene / α-olefin copolymer (WA
Production of X1) Using a metallocene catalyst, ethylene.α
An olefin copolymer was produced. 950 ml of hexane and 50 ml of propylene were charged into a stainless steel autoclave having an internal volume of 2 liters which had been sufficiently replaced with nitrogen.
Hydrogen was introduced until the pressure reached 1.0 kg / cm ² (gauge pressure). Next, after raising the temperature of the system to 150 ° C., 0.3 mmol of triisobutylaluminum and triphenylcarbenium tetrakis (pentafluorophenyl)
0.004 mmol borate, (t-butylamido) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl)
Silane titanium dichloride (manufactured by Sigma-Aldrich)
Polymerization was initiated by press-fitting 0.02 mmol with ethylene. Thereafter, the total pressure was maintained at 30 kg / cm ² (gauge pressure) by continuously supplying only ethylene, and polymerization was carried out at 150 ° C. for 20 minutes.

After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene and propylene were purged. The obtained polymer solution is heated to 100 ° C.
Dry under reduced pressure overnight. As a result, Mn was 2,050, propylene content was 7.3 mol% and density was 9
It was 20 kg / m ³ and 32.5 g of an ethylene / propylene copolymer having a crystallization temperature of 93 ° C. was obtained and designated as WAX1. The results are shown in Table 1.

[0107]

[Production Example 2] Ethylene / α-olefin copolymer (WA
Production of X2) In the polymerization of Production Example 1, 935 ml of hexane and 65 ml of 1-butene as the α-olefin component were charged,
Polymerization was performed in the same manner as in Production Example 1 except that hydrogen was introduced until the pressure reached 1.5 kg / cm ² (gauge pressure). Mn is 1,
900, the 1-butene content is 5.6 mol%,
37.5 g of ethylene / 1-butene copolymer having a density of 920 kg / m ³ and a crystallization temperature of 93 ° C. was obtained.
It was set to AX2. The results are shown in Table 1.

[0108]

[Production Example 3] Ethylene / α-olefin copolymer (WA
Production of X3) Polymerization was carried out in the same manner as in Production Example 1 except that 935 ml of hexane and hydrogen were introduced until the pressure became 1.0 kg / cm ² (gauge pressure) in Production Example 1. Mn is 2,
8,000, a density of 977 kg / m ³ and a crystallization temperature of 110 ° C., 38.8 g of an ethylene copolymer was obtained, which was designated as WAX3. The results are shown in Table 1.

[0109]

[Comparative Production Example 1] Preparation of catalyst In a glass autoclave having an internal volume of 1.5 liters, 25 g of commercially available anhydrous magnesium chloride was added to hexane 5
Suspended with 00 ml. While maintaining this at 30 ° C. and stirring, 92 ml of ethanol was added dropwise over 1 hour, and the reaction was further performed for 1 hour. After the reaction was completed, 93 ml of diethylaluminum monochloride was added dropwise over 1 hour, and the reaction was continued for another 1 hour. After completion of the reaction, 90 ml of titanium tetrachloride was added dropwise, the temperature of the reaction vessel was raised to 80 ° C., and the reaction was performed for 1 hour.

After the reaction was completed, the solid portion was decanted.
Wash with hexane until no more free titanium is detected
Clean Use this as a hexane suspension to increase the titanium concentration.
It quantified by titration and used for the following experiments.Production of ethylene / α-olefin copolymer (WAX4) Stainless steel with an internal volume of 2 liters that has been fully replaced with nitrogen
930 ml of hexane and 1-butene in the autoclave.
Charge 70 ml and add 20.0 kg / cm 2 hydrogen. ²(Game
It was introduced until Then, the temperature in the system is increased to 17
After heating to 0 ° C, 0.1 mm of triethylaluminum
Molar, ethyl aluminum sesquichloride 0.4 mm
Le, the titanium component obtained above is 0.008 mm in terms of atoms
Polymerization was initiated by pressurizing the moles with ethylene.
After that, by continuously supplying only ethylene,
Pressure is 40kg / cm²(Gauge pressure) at 170 ℃
Polymerization was carried out for 40 minutes.

After stopping the polymerization by adding a small amount of ethanol to the system, unreacted ethylene and 1-butene were purged. The obtained polymer solution is heated to 100 ° C.
Dry under reduced pressure overnight. As a result, as shown in Table 1, M
n is 2,000 and 1-butene content is 5.4 mol%
And the density is 917 kg / m ³ and the crystallization temperature is 101 ° C. 129 g of ethylene / 1-butene copolymer
To obtain WAX4. The results are shown in Table 1.

[0112]

[Table 1]

[0113]

[Production Examples 4 to 14] Except that in Production Example 1, the hydrogenation amount and the propylene addition amount were changed as shown in Table 2.
An ethylene / propylene copolymer was produced in the same manner as in Production Example 1. The results are shown in Table 2.

[0114]

Comparative Production Examples 2 to 10 An ethylene / propylene copolymer was prepared in the same manner as in Comparative Production Example 1 except that the hydrogenation amount was changed and propylene was used as a comonomer. Manufactured. The results are shown in Table 2.
Shown in.

[0115]

[Table 2]

Grinding of Ethylene Polymer All the samples obtained above were roughly crushed into squares of 2 mm square on a tabletop power mill (manufactured by Dalton). The milling of the ethylene polymer was carried out as follows. 1) Apparatus Jet mill: Supersonic jet crusher LABO JET (manufactured by Nippon Pneumatic Mfg. Co., Ltd.) 2) Grinding conditions-All samples were soaked in liquid nitrogen solution for 1 minute or more immediately before grinding. Sample feed rate: 1 g / min to 50 g / min (adjusted by the particle diameter commensurate) Air primary pressure: 6kg / cm ² G · Gas amount: 0.4 Nm ³ / min louver type; large, medium, small Using three types, the particle size is adjusted by balancing the clearance with the classification zone. (The louver diameter is small, the classification clearance is large, and the particle size is small.) 3) Secondary classification conditions (comparative fine powders 5 and 6 have not been implemented) ・ Gas amount: 0.4 Nm ³ / min The results are shown in Table 3. Show.

[0117]

[Table 3]

Preparation of printing ink Average degree of polymerization 45-55, nitrogen content 10.7-11.4
% By weight of nitrified cotton (manufactured by Asahi Kasei: LIG1 / 8 (N.V.
70%)), titanium acetylacetonate (Matsumoto Yakuhin Kogyo Co., Ltd .: Organix TC-100 (N.V.
75%)) 4 g, butyral resin (manufactured by Denki Kagaku Kogyo:
Denka butyral # 2000-L) 4 g, mixed solvent (ethyl acetate: IPA = 30: 70) 69 g, phthalocyanine bleu (Wako Pure Chemicals reagent special grade) 10 g, and wax fine powder 1 shown in Table 3 prepared above. 1 g was kneaded with an attritor for 1 hour to prepare a printing ink composition (A) having a nonvolatile content of 26.4%. Inks containing other fine powders and comparative fine powders were similarly prepared. Table 4 shows the blending amount (g) of each component of the prepared ink.

[0119]

[Table 4]

Abrasion resistance evaluation method: Ink is applied to the above base material so as to have a dry film thickness of 3 to 4 μm. Gakushin-type friction resistance tester Type II (Tester Sangyo Co., Ltd.) Friction paper CRC cardboard load / rubbing count 200g x 500 times Evaluation Ink is rubbed with a cardboard attached to a friction element, and the ink becomes cardboard. Four-level evaluation is performed according to the degree of transfer.

(Good) 4-3-2-1 (Poor) 4: Excellent abrasion resistance, ink hardly adheres to the cardboard 3: Excellent abrasion resistance, but ink slightly adheres to the cardboard Adherence is observed. 2: Adhesion of ink to cardboard is clearly recognized.

1: Adhesion of ink to cardboard is remarkable. Blocking resistance evaluation method After drying, two sheets of the ink-coated paper were stacked with the coated surface inside, sandwiched between lath plates, and the load was 10 g / cm ² on a smooth table.
Place the weight so that This is a constant temperature and humidity (25 ℃,
50%), after being left for 24 hours, the situation when two sheets of paper are separated is evaluated in four levels.

Status of printing surface (Good) 4-3-2-1
(Bad) 4: The printed surface was not damaged at all. 3: A slight cohesive failure was observed in the ink on the peeled surface, and a light force was required at the time of peeling. 2: Clearly cohesive failure was observed in the ink on the peeled surface, and a strong force was required at the time of peeling. 1: Interfacial peeling between the ink and paper is observed during peeling.

[0124]

[Table 5]

Claims (4)

[Claims] 1. An ethylene (co) polymer having a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000 and a volume average particle diameter of 0.3 μm. Particle size a (μm) in which the weight ratio on the large particle size side is 10% in the weight particle size distribution, and particle size b in which the weight ratio on the small particle size side is 10% in the weight particle size distribution. The relationship with (μm) satisfies the following formula (I) a / b ≦ 4 (I), and the crystallization temperature (Tc) measured by a differential scanning calorimeter (DSC).
(° C), measured at a cooling rate of 2 ° C / min. ) And the density (D (kg / m ³ )) measured by the density gradient tube method satisfy the following formula (II) 0.501 × D-366 ≧ Tc (II). Polyolefin wax (A) for materials. 2. The ethylene (co) polymer is an ethylene / α-olefin copolymer obtained from ethylene and propylene and / or 1-butene, and has a density of 8
Claim 1 is in the range of 50kg / m ³ ~980kg / m ³
Polyolefin wax (A) for coating materials as described in 1. 3. The polyolefin wax (A) for a coating material according to claim 1 or 2, wherein the ethylene (co) polymer is produced with a vanadium catalyst or a metallocene catalyst. 4. A printing ink composition, characterized in that the printing ink contains 0.1 to 10% by weight of the polyolefin wax (A) for a coating material according to any one of claims 1 to 3. .