JP2006131674A - New polymer and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer having polyolefin segments and a controlled structure and to provide applications of the polymer having such a controlled structure. <P>SOLUTION: The polymer has a structural unit represented by general formula (I) or general formula (VI). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel polymer having a (poly) alkylene ether structure having a polyolefin having a number average molecular weight of 400 to 5000 in the side chain, and a resin composition and use thereof using the same.

  Ethylene polymers or α-olefin polymers are excellent in cost and mechanical properties, and are most widely used as raw materials for various resin products. However, since the molecular structure is nonpolar and the affinity with other substances is poor, attempts have been made to introduce various functional groups.

Among them, polymers or oligomers that can be polymerized by the introduced functional groups are collectively referred to as macromonomers, and polymers such as controlled comb polymers having high functions can be obtained by copolymerizing with other monomers. It has been known. Many examples of polymers containing polyolefin-based macromonomers are known, but polyolefin-based macromers having polymerizable unsaturated groups have a small amount of polar groups and are used in terms of modification of polyolefins. It is hard to do. As other compounds having a polymerizable functional group, those having a hydroxyl group at the terminal (Patent Document 1) and those having an epoxy group in a polyolefin chain (Patent Document 2) are known. Furthermore, in order to be able to polymerize by reacting with tetracarboxylic acid, the polymer obtained using this macromer has a limited structure. In the latter, since there are a plurality of alkylene oxides having a statistical distribution in one polyolefin chain, problems such as cross-linking occur in the reaction of alkylene oxide. Therefore, the latter is effectively utilized and controlled as a macromer. It was difficult to obtain a polymer having a structure having a polyolefin skeleton and a skeleton composed of polar groups.
Japanese Patent Laid-Open No. 9-3173 JP-A-4-55403

An object of the present invention is to provide a polymer having a polyolefin segment and a controlled structure. Furthermore, it is providing the use of the polymer of such a controlled structure.

  That is, the present invention relates to the general formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, and i represents an integer of 1 or more).

The present invention is also a polymer (II) having hydroxyl groups at both ends of the polymer.

The present invention also provides a compound of general formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, i represents an integer of 1 or more),
Formula (III)

(III)
(Wherein R ² is a polymer having as a repeating unit a structural unit represented by R ² is a divalent hydrocarbon residue having 1 to 20 carbon atoms which may have a hetero atom).

The present invention also provides a compound of general formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, i represents an integer of 1 or more),
Formula (IV)

(IV)
(Wherein X represents an oxygen atom or an NH group, and R ³ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) as a repeating unit. It is a polymer having.

The present invention also provides a compound of general formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, i represents an integer of 1 or more) and a general formula (V)

(V)
(Wherein R ⁴ represents a C 1-20 divalent hydrocarbon residue which may contain a hetero atom) and a polymer having a repeating unit as a repeating unit.

The present invention further includes the use of a composition comprising the above-described polymer, a printing ink additive, a printing ink solvent dispersion, a printing ink, a resin composition, an adhesive, a coating composition, a molded article, and the like. is there.

  According to the present invention, various novel polymers having polyolefin segments can be provided. The polyolefin-based macromonomer that is the base of the polymer is advantageous in terms of economy because it does not use expensive monomer raw materials.

Moreover, the novel polymer of the present invention can provide materials suitable for printing ink additives, printing ink solvent dispersions, printing inks, resin compositions, adhesives, coating compositions, and molded articles.

  Hereinafter, embodiments of the present invention will be described.

  The polymer of the present invention has the general formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, and i represents an integer of 1 or more).

Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned, preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, particularly preferably. Propylene, 1-butene, 1-hexene and 4-methyl-1-pentene.

  Examples of dienes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene; 2-methyl-1,4-hexadiene, 2- Examples include methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene, and the like.

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

  The polyolefin contains 0.01 to 10.0 mol%, preferably 0.1 to 5.0 mol%, more preferably 0.5 to 3.0% of a structural unit derived from a diene. desirable.

  In general formula (I), the number average molecular weight (Mn) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the group represented by A is 400 to 5000, preferably 500 to 4500. More preferably, it is 600-4000. Here, Mn is a polystyrene equivalent value.

  In the general formula (I), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC of the group represented by A, that is, the molecular weight distribution (Mw / Mn) is not particularly limited. Although there are 0.0 to several tens of products, 4.0 or less, particularly 3.5 or less may be preferable in terms of uniformity of physical properties.

  The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the group represented by A can be measured under the following conditions using, for example, GPC-150 manufactured by Millipore.

Separation column: TSK GNH HT (column size: diameter 7.5 mm, length: 300 mm)
Column temperature: 140 ° C
Mobile phase: Orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.)
Antioxidant: Butylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) 0.025% by mass
Movement speed: 1.0 ml / min Sample concentration: 0.1% by mass
Sample injection amount: 500 microliters Detector: As a differential refractometer, it can be measured by measuring the molecular weight of a polyolefin having an unsaturated group at one end, which will be described later, and removing the molecular weight equivalent at the end.

  R is hydrogen or a hydrocarbon residue having 1 to 18 carbon atoms bonded to the double bond of the olefin constituting A, and includes hydrogen, a methyl group, an ethyl group, a propyl group, and the like.

  In general formula (VII), the groups represented by A2 and A3 are a copolymer comprising a hydrogen atom or an olefin having 2 to 20 carbon atoms and a diene.

  In the general formula (VII), the number average molecular weight (Mn) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the groups represented by A2 and A3 is 400 to 5000, preferably 500 to 4500. More preferably, it is 600-4000. Here, Mn is a polystyrene equivalent value.

  In the general formula (VII), the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC of the groups represented by A2 and A3, that is, the molecular weight distribution (Mw / Mn) is not particularly limited. 1.0 to several tens, but 4.0 or less, particularly 3.5 or less may be preferable in terms of uniformity of physical properties.

  The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the groups represented by A2 and A3 can be measured by the method described above.

  R is hydrogen or a hydrocarbon residue having 1 to 18 carbon atoms bonded to the double bond of the olefin constituting A2 and A3, such as hydrogen, methyl group, ethyl group, propyl group, etc. .

  In the polymer of the present invention, the content of the structural unit represented by the general formula (I) is not limited as long as it contains the structural unit represented by the general formula (I), and a preferable range varies depending on the use of the polymer. The same applies to the case where the polymer is a polymer having hydroxyl groups at both ends represented by the general formula (II).

  The polymer of the present invention may be any polymer as long as it has a structural unit of the general formula (I) that can be produced by reacting with a compound that reacts with a hydroxyl group or an epoxy group. For example, a polymer having an ether bond, an ester bond, a urethane bond, an amide bond, or a carbonate bond. Furthermore, a block copolymer reacted with siloxane is specifically exemplified.

  Such a polymer can be obtained by ring-opening polymerization or copolymerization of an epoxy compound obtained by epoxidizing a polyolefin having an unsaturated group at one end, which will be described later. If water or a diol is used as the initiator, a polymer having both hydroxyl groups can be obtained.

  The polymer comprises a structural unit represented by the above general formula (I) and a general formula (III)

(III)
(In the formula, R ² is a polymer having a structural unit represented by R ^{2 as a} divalent hydrocarbon residue having 1 to 20 carbon atoms which may have a hetero atom). .
In the general formula (III), the hydrocarbon residue of R ² is not particularly limited, but is an arylene such as an alkylene group such as a methylene group or an ethylene group, a cycloalkylene group such as a cyclohexylene group, a phenylene group or a xylylene group. And a group in which a part of these hydrogen atoms is substituted with a hydrocarbon residue or a hetero atom or a hydrocarbon residue substituted with a hetero atom, and the polymer has a dicarboxylic acid having a corresponding structure as a monomer unit. It can be produced by condensation with a diol having a structural unit of the general formula (I). In this case, other polymerization components such as hydroxycarboxylic acid or other diols or dicarboxylic acids having different structures may be copolymerized.

  The weight average molecular weight of the polymer is not particularly limited, and the preferred range varies depending on the use, but is generally 1,000 to 1,000,000. If used as a molding material, 10,000 to 500,000, an additive for printing ink In general, it is set to about 1000 to 20000. Is generally.

  Another embodiment of the polymer of the present invention has the structural unit represented by the above general formula (I) and has the general formula (IV).

(IV)
(Wherein X represents an oxygen atom or an NH group, and R ³ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) as a repeating unit. It is a polymer.

In general formula (IV), as the hydrocarbon residue of R ³ , the same hydrocarbon residues as those of R ² in general formula (III) described above can be exemplified, and the polymer is a diisocyanate. It can be produced by condensation with a diol having a structural unit of the general formula (I) as a monomer unit. In this case, other polymerization components such as other diols or diisocyanates having different structures can be copolymerized.

  The weight average molecular weight of the polymer is not particularly limited, and the preferred range varies depending on the use, but is generally 1,000 to 1,000,000. If used as a molding material, 10,000 to 500,000, for printing ink If it is used as an additive, it is generally about 1000 to 20000.

  Another aspect of the polymer of the present invention is the structural unit represented by the general formula (I) and the general formula (V).

(V)
(Wherein R ⁴ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom), and is a polymer having a repeating unit as a repeating unit.

In general formula (V), the hydrocarbon residue of R ⁴ is not particularly limited, but is an alkylene group such as a methylene group, an ethylene group, a butylene group or a hexylene group, a cycloalkylene group such as a cyclohexylene group, or a phenylene group. And an arylene group such as a xylylene group and a biphenylene group, and a group in which some of these hydrogens are substituted with a hydrocarbon residue or a heteroatom or a hydrocarbon residue substituted with a heteroatom. An epoxy obtained by epoxidizing a polyolefin having an unsaturated group at one end described later, which is a methylene group that is a polymer of ethylene group, propylene group, and formaldehyde formed by polymerizing alkylene oxide such as ethylene oxide and propylene oxide By ring-opening polymerization of the compound and alkylene oxide It may be a structure that can be manufactured and copolymerized at the same time and randomly copolymerized, or a structure obtained by sequentially polymerizing block copolymers.

  As is clear from the gist of the invention, the ratio may be any ratio as long as both are contained.

  Although there is no restriction | limiting also as a weight average molecular weight of the whole, Generally, in order to use it as 1,000-1,000,000, a compatibilizing agent, etc., it utilizes as an additive for printing inks. In some cases, the weight average molecular weight is generally about 1000 to 20000.

  The polymer of the present invention can be produced by the following method.

  First, as a monomer corresponding to the structure represented by the general formula (I) in the target polymer, the general formula (VIII)

(VIII)
(In the formula, A represents a copolymer comprising an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The polyolefin having a double bond represented by

This polyolefin can be produced by the following method.
(1) A polymerization method using a titanium-based catalyst comprising a titanium compound and an organoaluminum compound.
(2) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(3) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane).

Among the above methods (1) to (3), particularly according to the method (3), the polyolefin can be produced with high yield. In the method (3), for example, in the presence of the following metallocene catalyst comprising a metallocene compound of a transition metal selected from Group 4 of the periodic table and an organoaluminum oxy compound and / or an ionized ionic compound, The polyolefin having the above double bond can be produced by copolymerizing the olefin and the diene.

(polymerization)
The polyolefin used in the present invention can be obtained by homopolymerizing ethylene usually in a liquid phase or copolymerizing ethylene and olefin in the presence of a metallocene catalyst. At this time, a hydrocarbon solvent is generally used, but an olefin may be used as a solvent. The monomers used here are as described above.

  Polymerization methods include suspension polymerization in which the polyolefin is present as particles in a solvent such as hexane, gas phase polymerization in which the solvent is not used, and polymerization at a temperature of 140 ° C. or higher. Solution polymerization that polymerizes in a melted state is possible, and among them, solution polymerization is preferable in terms of both economy and quality.

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

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

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

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

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

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

  In the polymerization, ethylene and olefin used as necessary are supplied to the polymerization system in such an amount ratio that a polyolefin having the specific composition described above can be obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.

  When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, so that a polyolefin can be obtained by treatment by a conventional method.

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

The unsaturated group content in the polyolefin is measured as follows. ^{By 13} C-NMR, it is obtained by comparing the peak area of carbon in the unsaturated portion with the peak area of all carbon. Thereby, the number M of unsaturated groups per 1,000 carbons can be obtained. The unsaturated group content per molecule can be obtained by Mn × M / 14,000. The number M of unsaturated groups per 1,000 carbons is 1.4 to 105, preferably 2.8 to 70, and more preferably 4 to 35.

  Next, the polyolefin is epoxidized, that is, the double bond at the terminal of the polyolefin is oxidized to obtain a polymer containing an epoxy group at the terminal represented by the general formula (IX).

(IX)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Represents
Although the epoxidation method is not particularly limited, the following methods can be exemplified.
(1) Oxidation with peracids such as performic acid, peracetic acid, perbenzoic acid (2) Oxidation with titanosilicate and hydrogen peroxide (3) Oxidation with rhenium oxide catalyst such as methyltrioxorhenium and hydrogen peroxide ( 4) Oxidation with a porphyrin complex catalyst such as manganese porphyrin or iron porphyrin and hydrogen peroxide or hypochlorite (5) Salen complex such as manganese Salen and oxidation with hydrogen peroxide or hypochlorite (6) Manganese- Oxidation with a TACN complex such as a triazacyclononane (TACN) complex and hydrogen peroxide (7) Oxidation with hydrogen peroxide in the presence of a group VI transition metal catalyst such as a tungsten compound and a phase transfer catalyst The above (1) to (7) Among these methods, the methods (1) and (7) are particularly preferable in terms of the active surface.

The epoxy content in the total unsaturated groups of the epoxy group-containing polymer is determined by ¹ H-NMR. For example, in the case of an epoxy group-containing polymer obtained by epoxidizing an unsaturated group-containing polymer composed of ethylene and vinyl norbornene, the peak (D) for the three protons at the base of the epoxy group is 2.25 to 2 per proton. It is observed at .50 ppm, 2.65 to 2.77 ppm, and 2.80 to 3.15 ppm. When epoxy modification is not sufficient, a peak (E) corresponding to 3 protons of a double bond is observed at 2 protons at 4.80 to 5.10 ppm and 1 proton at 5.70 to 5.97 ppm. If the peak areas of the peaks (D) and (E) are _SD and S _E , respectively, the epoxy group content (Ep (%)) is calculated by the following formula.

Ep (%) = S _D × 100 / (S _D + S _E )

The epoxy group-containing polymer obtained by the above method can be subjected to ring-opening polymerization to produce a polymer having a structural unit of the general formula (I). For the catalyst, polymerization conditions, etc., known ring-opening polymerization methods of alkylene oxide can be used. For example, Takayuki Otsu, “Chemistry of Revised Polymer Synthesis”, Kagaku Dojin, January 1971, p. . 172-180 discloses an example in which a polyol is obtained by polymerizing various monomers. Catalysts used for ring-opening polymerization include Lewis acids such as AlCl3, SbCl5, BF3, and FeCl3 for cationic polymerization, alkali metal hydroxides or alkoxides for anionic polymerization, and amines, as disclosed in the above documents. Alkali earth metal oxides, carbonates, alkoxides or alkoxides such as Al, Zn, Fe, etc. can be used for phosphazene catalysts and coordination anionic polymerization. Here, as the phosphazene catalyst, for example, an anion of a compound disclosed in JP-A-10-77289, specifically, a commercially available tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium chloride is alkalinized. The thing made into the alkoxy anion using the metal alkoxide etc. can be utilized.

  Using the active hydrogen compound such as water, amines, diols, and polyols as an initiator in the presence of the above catalyst, the polymer (e) is homopolymerized by ring-opening polymerization of only the terminal epoxy group-containing polymer. A copolymer is obtained, and a copolymer can be obtained by ring-opening polymerization of the terminal epoxy group-containing polymer (e) and another alkylene oxide.

  As the reaction solvent, an epoxy group-containing polymer, an inert solvent for alkylene oxide can be used, alicyclic hydrocarbons such as n-hexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, dioxane, and the like. And halogenated hydrocarbons such as dichlorobenzene.

Except for the phosphazene catalyst, the catalyst is used in an amount of preferably 0.05 to 5 moles, more preferably 0.1 to 3 moles per mole of the starting epoxy group-containing polymer (e). The amount of the phosphazene catalyst used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol, more preferably 1 mol with respect to 1 mol of the epoxy group-containing polymer (e), from the viewpoint of polymerization rate, economy and the like. 5 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol.

  The reaction temperature is usually 25 to 150 ° C., preferably 50 to 110 ° C., and the reaction time varies depending on the reaction conditions such as the amount of catalyst used, the reaction temperature, and the reactivity of olefins, but is usually several minutes to 50 hours. .

  By using water or diols as the initiator, a polymer (II) having hydroxyl groups at both ends can be obtained. In addition, when a polyether polyol having a specific molecular weight obtained by polymerizing alkylene oxide in advance is used as an initiator, it becomes possible to introduce a hydrophilic unit having a predetermined molecular weight and has hydroxyl groups at both ends having desired physical properties. Manufacture of a block copolymer becomes easy.

  Examples of the polyether polyol include polyethylene glycol, propylene glycol, polytetraethylene glycol and the like. Among these, polyethylene glycol and polypropylene glycol are preferable.

  It has a structural unit represented by the above general formula (I) and has the general formula (III)

(III)
Wherein R ² is a polymer having a structural unit represented by a repeating unit (hereinafter referred to as polymer (b)) and R ² is a hydrocarbon residue having 1 to 20 carbon atoms which may have a divalent hetero atom. Can be produced by the following method.
(1) Reaction of a polymer having hydroxyl groups at both ends represented by the general formula (II) with a dicarboxylic acid corresponding to the general formula (III).
(2) Reaction of epoxy group-containing polymer with dicarboxylic acid corresponding to general formula (II).
(3) Reaction of polyester polyol obtained by condensation reaction of dicarboxylic acid corresponding to general formula (III) and diols and an epoxy group-containing polymer.

  Here, general diols in (1) and (2) may coexist.

  The dicarboxylic acid is as described above, and more specifically, various commercially available dicarboxylic acids such as oxalic acid, maleic acid, phthalic acid, isophthalic acid, and terephthalic acid can be used as they are.

  Examples of the diol include aliphatic diols such as ethylene glycol, propylene glycol, and butanediol, and aromatic diols such as biphenol and bisphenol A. In some cases, glycerin having a trifunctional hydroxyl group can also be used. These diols can be obtained alone or in admixture of two or more.

  A method of forming an ester bond from an alcohol and a carboxylic acid is well known, and a method of removing water in the presence of a dehydration catalyst. There is no particular limitation on the method of reacting carboxylic acid in the presence of alkali such as amine after anhydride or acid chloride. Also, as a method of directly reacting an epoxide and a carboxylic acid, a known method such as a reaction in the presence of an alkali metal salt of carboxylic acid or the like can be disclosed.

  It has a structural unit represented by the above general formula (I) and has the general formula (IV)

(IV)
(In the formula, X represents an oxygen atom or an NH group, and R ³ represents a hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom). Hereinafter, the polymer (c) can be produced by the following method.
(1) Reaction of the epoxy group-containing polymer with a diisocyanate corresponding to the general formula (IV).
(2) Reaction of the polymer (II) with a diisocyanate corresponding to the general formula (IV).
(3) Reaction of the polymer (b) with a diisocyanate corresponding to the general formula (IV).

  Examples of the diisocyanate that can be used for the production of the polymer (c) include, for example, Matsudaira Nobutaka et al., “Polyurethane”, Tsuji Shoten, 1964, p. Among those disclosed in 13-18, those having 3 to 23 carbon atoms can be used, and among them, diisocyanate is usually selected. Specifically, hexamethylene diisocyanate, xylylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and the like can be used, but they may be used alone or in combination.

  Further, a small amount of polyisocyanate such as monoisocyanate or triisocyanate can be used in combination.

  As for the reaction methods of both, many methods are known as disclosed in the above-mentioned literature, and a known method such as heating in the presence of a catalyst such as a tin salt or an amine can be employed.

  Structural unit represented by general formula (I) and general formula (V)

(V)
(Wherein R ⁴ represents a hydrocarbon residue having 1 to 20 carbon atoms that may contain a hetero atom), a polymer having a structural unit represented by a repeating unit (hereinafter referred to as polymer (d)), Although it can manufacture by various methods as mentioned above, it is common to superpose | polymerize by the method similar to the polymerization method of a corresponding epoxide and the said epoxy group containing polymer.

The polymer of the present invention described above, the composition containing the polymer, the resin composition containing the polymer and other thermoplastic resins, and the polymer are used for printing ink additives, adhesives, and coatings. It is useful as a composition and has excellent performance as an additive for printing ink.

(Polyolefin micronization method)
When adding polyolefin to printing ink, it is common to use polyolefin in the form of fine powder, an additive comprising fine powder, or a solvent dispersion (dispersion). It is preferable that the volume average particle diameter of the fine particles contained in the fine powder, the additive composed of the fine powder, or the solvent dispersion system is in the range of 0.3 μm to 10 μm, more preferably 0.5 μm to 5 μm. It is a range. When the volume average particle diameter of the polyolefin particles is within this range, the balance between the abrasion resistance and gloss of the printing ink surface is excellent. The method for obtaining such a polyolefin fine powder is not particularly limited as long as it is a method capable of micronizing polyolefin, and examples thereof include a method of pulverizing using a jet mill, a ball mill or the like. In order to produce a fine polyolefin powder, it is desirable to prepare particles having a volume average particle size of 500 μm or less by preliminary pulverization using a pulverizer such as a pin mill, screen mill, or tube mill. In the preliminary pulverization, a granulation method other than pulverization such as a crystallization method using a solvent or spray granulation can be used.

(Production method of polyolefin solvent dispersion)
As the method for producing the polyolefin solvent dispersion of the present invention, a method using a wet ball mill is preferred. The polyolefin is preferably made into particles having a volume average particle diameter of 500 μm or less in advance by the method described above. Solvents for dissolving polyolefin include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, p-xylene, cumene, and cymene; chain hydrocarbons such as hexane, heptane, octane, nonane, and decane; cyclohexane, Alicyclic hydrocarbons such as methylcyclohexane, decalin and methyldecalin; alcohols such as hexanol, heptanol, octanol, nonanol and denanol; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve and butyl cellosolve Ketones such as methyl ethyl ketone, isobutyl ketone, cyclohexanone, and the like. These can be used alone or in combination of two or more.

(Printing ink composition)
Examples of printing ink compositions using non-aromatic solvents to which polyolefin fine particles (fine powder) used in the present invention or solvent dispersions thereof are added include polyurethane resins or polyurethane polyurea resins. 1 type of solvent such as ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, etc. The printing ink composition used individually or in combination of 2 or more types is mentioned. In addition, the resin solid content concentration of the binder in the printing ink composition is appropriately determined in consideration of workability at the time of printing, printing effect, and the like, and is not particularly limited, but is 3 to 50% by weight. It is preferable to adjust to.

  The additive comprising the polyolefin of the present invention or its solvent dispersion is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight of the polyolefin, based on the total amount of the printing ink composition. Added to contain. The said polyolefin can be used individually by 1 type or in combination of 2 or more types.

  When the content of the polyolefin is within the above range, the printing ink is excellent in the balance of abrasion resistance and blocking resistance.

  As a method for adding polyolefin, it can be added at any step in the conventional printing ink production process. In other words, the pigment and polyolefin both dispersed in the varnish and kneaded may be converted into an ink, or after being subjected to the dispersion and kneading process, an additive made of polyolefin or a solvent dispersion system thereof is mixed into an ink. Also good.

  Here, the amount of the polymer of the present invention contained in the composition, resin composition, printing ink additive, adhesive and coating composition is preferably 0.5 to 20% by mass, In particular, it is preferably 1.0 to 10% by mass.

  Examples of other thermoplastic resins in the resin composition include polyolefin resins such as polyethylene and polypropylene, polystyrene resins such as polystyrene and acrylonitrile / butadiene / styrene copolymers (ABS resins), polymethyl methacrylate, and polyacrylic acid. Acrylic resins such as butyl, rubbery (co) polymers such as polybutadiene and polyisoprene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyacetal resins, polycarbonate resins, thermoplastic polyurethane resins, fluorine resins, etc. Or a mixture of two or more thereof.

  The composition or the resin composition may contain at least one selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant, and a polymer antistatic agent.

  Examples of the alkali metal or alkaline earth metal salt include monocarboxylic acid or dicarboxylic acid having 1 to 20 carbon atoms (for example, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), and sulfonic acid having 1 to 20 carbon atoms (for example, Methanesulfonic acid, p-toluenesulfonic acid, etc.), alkali metals, alkaline earth metals and salts of organic acids such as thiocyanic acid, hydrohalic acids (eg hydrochloric acid, hydrobromic acid, etc.), hydrobromic acid, peroxy Preferred examples include salts of inorganic acids such as chloric acid, sulfuric acid and phosphoric acid. Among these, halides such as lithium chloride, sodium chloride and potassium chloride, acetates such as potassium acetate, and perchlorates such as potassium perchlorate are preferable.

  The content of the alkali metal or alkaline earth metal salt in the composition or resin composition is usually 0.001 to 3% by mass, preferably 0.01 to 2% by mass, based on the total amount of the polymer / resin. is there.

  As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used. Examples of nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide, Examples include fatty acid esters of glycerin, fatty acids of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines, anionic Surfactants include, for example, carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates; Examples of cationic surfactants include alkyltrimethylammonium salts, sulfonic acid salts such as rubenzene sulfonate, alkyl sulfonate, and paraffin sulfonate; and phosphate esters such as higher alcohol phosphates. And the like, and the like. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines, which can be used alone or Two or more types can be used in combination.

  Among the surfactants, anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable.

  Content of surfactant in the said composition or resin composition is 0.001-5 mass% normally with respect to a polymer and resin whole quantity, Preferably it is 0.01-3 mass%.

  As the polymer antistatic agent, for example, a polymer type antistatic agent such as a known polyether ester amide can be used. Examples of the known polyether ester amide are described in, for example, JP-A-7-10989. And polyether ester amides composed of polyoxyalkylene adducts of bisphenol A.

  As the other polymer antistatic agent, a block polymer having a repeating structure in which the unit of bonding between the polyolefin block and the hydrophilic polymer block is 2 to 50 can be used, and examples thereof include a block polymer described in US6552131. .

  The content of the polymer antistatic agent in the composition or resin composition is generally 0 to 40% by mass, preferably 5 to 20% by mass, based on the total amount of the polymer / resin.

  Moreover, a compatibilizer may be contained in the composition or the resin composition. According to the compatibilizing agent, the compatibility between the polymer of the present invention and another thermoplastic resin can be improved. Examples of the compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group, such as And a polymer described in JP-A-258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin portion and an aromatic vinyl polymer portion.

  Content of the compatibilizing agent in the said composition or resin composition is 0.1-15 mass% normally with respect to a polymer and resin whole quantity, Preferably it is 1-10 mass%.

  Other additives for resin can be arbitrarily added to the above composition or resin composition within a range that does not impair the effect of the polymer of the present invention, depending on the application. Examples of such additives for resin include pigments, dyes, fillers, glass fibers, carbon fibers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, and the like.

  A molded body formed by molding the resin composition has good paintability and printability. Examples of the molding method of the resin composition include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.). Depending on the method, it can be formed by any method.

  Examples of the method for coating the molded body include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating. Examples of the paint that can be used include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. Although a coating film thickness can be suitably selected according to the objective, it is 10-50 micrometers (dry film thickness) normally.

The method for printing on the molded body may be any printing method that is generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, offset printing, and the like. Is mentioned. As the ink in these printings, those usually used for plastic printing can be used.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
(Synthesis example 1 of polyether resin)
Into a stainless steel autoclave with an internal volume of 2 liters sufficiently purged with nitrogen, 940 ml of hexane, 20 ml of propylene, 50 ml of vinylnorbornene (5-vinylbicyclo [2,2,1] hept-2-ene) were charged, and hydrogen was supplied at 0.3 MPa ( It was introduced until the gauge pressure was reached. Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and vinyl norbornene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure.

As described above, the unsaturated group content per 1,000 carbons is 11.8, and the vinyl norbornene content is 10.3% by weight (unsaturated group content (average) = 1.1 / molecule). The density is 937 kg / m ³ , the melting point is 106 ° C., the penetration is 3, Mn is 1,300, Mw is 3,700, and Mw / Mn is 2.8. A molecular weight ethylene polymer (A-1) was obtained.

In a 500 ml separable flask, 100 g of the unsaturated group-containing ethylene polymer (A-1) (vinyl group 84.3 mmol), toluene 300 g, Na ₂ WO ₄ 0.85 g (2.6 mmol), CH ₃ (nC ₈ H) ₁₇ ) ₃ NHSO ₄ 0.60 g (1.3 mmol) and phosphoric acid 0.11 g (1.3 mmol) were charged, and the mixture was heated to reflux with stirring for 30 minutes to completely melt the polymer. After the internal temperature was set to 90 ° C., 37 g (326 mmol) of 30% hydrogen peroxide solution was added dropwise over 3 hours, and the mixture was stirred at an internal temperature of 90 to 92 ° C. for 3 hours. Thereafter, 34.4 g (54.4 mmol) of a 25% aqueous sodium thiosulfate solution was added while maintaining the temperature at 90 ° C., and the mixture was stirred for 30 minutes. The peroxide in the reaction system was completely decomposed with the peroxide test paper. It was confirmed. Subsequently, 200 g of dioxane was added at an internal temperature of 90 ° C. to crystallize the product, and the solid was collected by filtration and washed with dioxane. The obtained solid was stirred in a 50% aqueous methanol solution at room temperature, and the solid was collected by filtration and washed with methanol. Further, the solid was stirred in 400 g of methanol, collected by filtration and washed with methanol. By drying at room temperature under reduced pressure of 1 to 2 hPa, the density is 965 kg / m ³ , the melting point is 106 ° C., the penetration is 2, Mn is 1,500, and Mw is 5,000. A low molecular weight ethylene polymer (A-1) having Mw / Mn of 3.3 was obtained. 96.3 g of a white solid of terminal epoxy group-containing polymer (B-1) was obtained (99% yield, olefin conversion rate 100%).

The ¹ H-NMR measurement results and physical properties of this epoxy group-containing polymer (B-1) were as follows.
¹ H-NMR: δ (C2D2Cl4) 0.88 (t, 3H, J = 5.94 Hz), 0.25-2.25 (m,), 2.28-2.50 (m, 1H,), 2.57-2.78 (m, 1H,) 2.80- 3.15 (m, 1H)
Using this epoxy group-containing polymer (B-1), a polyether was produced as follows.

  17.9 g (44.8 mmol) of PEG400 (Mn = 400) and 6.7 g (35.8 mmol) of 30 wt% KOH aqueous solution were collectively inserted into a flask equipped with a thermometer, a stirring rod, a nitrogen introduction tube and a condenser. Then, the temperature was raised to 100 ° C. to perform dehydration. After dehydration, the temperature was raised to 120 ° C., 40.5 g (27 mmol) of the epoxy group-containing polymer (B-1) (Mn = 1500) was added, the reaction was performed for 18 hours, and then the reaction product was taken out and cooled at 120 ° C. .

After cooling, 100 ml of distilled water was added to the obtained solid, and hydrochloric acid was added dropwise for neutralization. After neutralization, filtration was performed, and the filtrate was washed with distilled water and dried to obtain 39.8 g of a copolymer (1) as a white solid. This copolymer (1) was subjected to ¹ H-NMR measurement. As a result, the integration value of the terminal methyl group (shift value: 0.88 ppm) of the epoxy group-containing polymer A and the alkylene group of PEG400 (shift value: 3.52 to 3.70). From the comparison with the integrated value of (ppm), it was found that the epoxy group-containing polymer A: PEG400 = 1 mol: a polymer having a composition of 2 mol. Further, it was found by atomic absorption analysis that the K content was 1.3% by weight.

The analysis result of ¹ H-NMR is shown below.
¹ H-NMR: δ (C2D2Cl4) 0.88 (t, 6H, J = 6.6 Hz), 0.9-1.6 (m,), 3.20-3.40 (m, 2H, α-position of oxygen atom), 3.45-3.72 (m, (Α position of oxygen atom, methylene group of PEG)

[Example 2]
(Synthesis Example 2 of Polyether Resin)
In a flask equipped with a thermometer, a stir bar, a nitrogen introducing tube and a condenser, PEG 600 (Mn = 598) 6.13 g (10.25 mmol), epoxy group-containing polymer (B-1) (Mn = 1500) 26.4 g (17.6 mmol) and 69 g of toluene were collectively inserted, the temperature was raised to 130 ° C., and azeotropic dehydration was performed while distilling toluene. After 19 g of toluene was distilled off, the temperature was lowered to 110 ° C., 0.56 g (3.9 mmol) of boron trifluoride diethyl ether complex was added, and the reaction was performed for 7.5 hours, and then the reaction solution was dropped into 158 g of methanol. As a result, a white solid was precipitated.

This white solid was filtered, and the residue was washed with methanol and dried to obtain 23.1 g of copolymer (2). The copolymer (2) was subjected to ¹ H-NMR measurement in the same manner as in Example 1. As a result, it was found that the polymer had a composition of epoxy group-containing polymer A: PEG600 = 4 mol: 1 mol.

Example 3
(Polyether resin synthesis example 3)
17.9 g (17.9 mmol) of PEG1000 (Mn = 1000) and 6.7 g (35.8 mmol) of 30 wt% KOH aqueous solution were collectively inserted into a flask equipped with a thermometer, a stirring bar, a nitrogen introduction tube and a condenser. Then, the temperature was raised to 100 ° C. to perform dehydration. After dehydration, the temperature was raised to 120 ° C., 40.5 g (27 mmol) of the epoxy group-containing polymer (B-1) (Mn = 1500) was added, the reaction was performed for 18 hours, and then the reaction product was taken out and cooled at 120 ° C. .

After cooling, 100 ml of distilled water was added to the obtained solid, and hydrochloric acid was added dropwise for neutralization. After neutralization, filtration was performed, and the filtrate was washed with distilled water and dried to obtain 39.8 g of a copolymer (3) as a white solid. The copolymer (3) was subjected to ¹ H-NMR measurement in the same manner as in Example 1. As a result, it was found that the polymer had a composition of epoxy group-containing polymer A: PEG1000 = 4 mol: 1 mol. Further, it was found by atomic absorption analysis that the K content was 1.3% by weight.

Example 4
(Synthesis of polyurethane resin)
In a flask equipped with a thermometer, a stir bar, a nitrogen introducing tube and a condenser, 5.03 g (8.36 mmol) of PEG600 (Mn = 598), 4.5 g (ca 0.7 mmol) of copolymer (2) ( Mn = ca 6500) and 40 g of toluene were collectively inserted, the temperature was raised to 130 ° C., and azeotropic dehydration was performed while distilling toluene. After distilling off 13 g of toluene, the temperature was lowered to 110 ° C., 1.58 g (9.4 mmol) of hexamethylene diisocyanate and 0.01 g of dibutyltin dilaurate as a catalyst were added, and the reaction was carried out for 3.5 hours. When concentrated, 9.81 g of copolymer (4) was obtained. This copolymer (4) was a thermoplastic polyurethane resin. This copolymer (4) was subjected to ¹ H-NMR measurement. As a result, the integration value of the terminal methyl group (shift value: 0.86 ppm) of the epoxy group-containing polymer A and the methylene group adjacent to the nitrogen atom of the carbamate bond ( Compared with the integrated value of shift value: 3.12 ppm), and the integrated value of terminal methyl group (shift value: 0.86 ppm) of epoxy group-containing polymer (B-1) and methylene group adjacent to the oxygen atom of carbamate bond ( Comparison with the integrated value of shift value: 4.16 ppm) revealed that the polymer had a composition of copolymer (2): hexamethylene diisocyanate: PEG600 = 1 mol: 13 mol: 12 mol.

The analysis result of ¹ H-NMR is shown below.
¹ H-NMR: δ (C2D2Cl4) 0.86 (t,, J = 6.6 Hz), 1.05-1.4 (m,), 1.47 (t,, J = 5.6 Hz), 3.10 (t, J = 5.6 Hz), 3.4 -3.74 (m,), 4.16 (t,, J = 5.6Hz)
Melting point (Tm) 112 ° C

Example 5
(Production Example 1 of Solvent Dispersion System)
Copolymer (1) having a volume average particle size of about 150 μm by preliminary pulverization by a pulverizer and 40 parts by weight of a solvent (20 parts by weight of isopropyl alcohol and 20 parts by weight of ethyl acetate) are made of 1 liter of chromium steel. After sealing in a ball mill, it was pulverized by rotation for 24 hours. Thereafter, 35 parts by weight of the solvent having the above composition was added to dilute the solid content to 25% by weight. The volume average particle diameter of the solvent dispersion (Dispersion 1) thus obtained was measured with Microtrac (Honeywell: HRA) and found to be 4.5 μm.

(Example 1 of storage stability evaluation of solvent dispersion)
Dispersion 1 was placed in a test tube (30φ × 200 mm) and allowed to stand at room temperature for 10 days, and then the height of the solvent layer produced by sedimentation of the solid content was evaluated. The lower this height, the better the storage stability. The results are shown in Table 1.

(Printing ink production example 1)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 1000 parts of polyester diol having a number average molecular weight of 2000 obtained from adipic acid and 3-methyl-1,5-pentanediol, and isophorone 222 parts of diisocyanate was charged and reacted at 90 ° C. for 6 hours under a nitrogen stream. Next, 82 parts of isophorone diamine, 7.8 parts of di-n-butylamine, 2143 parts of ethyl acetate and 918 parts of isopropyl alcohol were added and allowed to react at 50 ° C. for 3 hours with stirring. A polyurethane resin solution (A) having 600 mPa · s and a number average molecular weight of 45,000 was obtained.

  Next, 50 parts by weight of the polyurethane resin solution (A), 10 parts by weight of the pigment, 22 parts by weight of ethyl acetate, 5 parts by weight of isopropyl alcohol, 10 parts by weight of propylene glycol monomethyl ether, 3 parts by weight of pure water, and After mixing the above dispersion 1 at a ratio of 3 parts by weight, the mixture was stirred and mixed, and the pigment was dispersed by a conventional method using a sand mill to obtain a printing ink composition (ink 1). Disazo yellow (“Lionol Yellow 1405G” manufactured by Toyo Ink Co., Ltd.) was used as the pigment.

(Printing ink printing example 1)
Evaluation of printing was carried out by diluting ink 1 with a diluting solvent (composition: ethyl acetate / isopropyl alcohol = 60 parts by weight / 40 parts by weight), adjusting the viscosity to 15 seconds with Zahn Cup # 3 manufactured by Koiso Co., Ltd. By printing on a treated OPP film (“P-2161” manufactured by Toyobo Co., Ltd., thickness 20 μ). As the gravure plate, one having an imposition of a gradation portion (5 μ to 40 μ) and a 35 μ solid portion was used.

(Abrasion resistance and blocking resistance evaluation example 1)
According to the following method, the abrasion resistance and the blocking resistance of the film on which the ink 1 was printed were evaluated. The results are shown in Table 1.

Abrasion resistance evaluation method [1] Use of Gakushin type friction tester type II (Tester Sangyo Co., Ltd.) Friction paper CRC cardboard Load / friction frequency 200g x 1000 times [2] Evaluation: Ink printed surface is a friction element A four-step evaluation is performed based on the degree of ink transfer to the cardboard.

(Good) 4-3-2-1 (Evil)

4: Excellent wear resistance, ink hardly adheres to cardboard
3: Although excellent in abrasion resistance, it is recognized that the ink slightly adheres to the cardboard.

            2: Adhesion of ink to cardboard is clearly observed.

            1: Adhesion of ink to cardboard is remarkable.

Blocking resistance evaluation method [1] Two coated layers of the above ink-printed film are stacked on the inside, sandwiched by a lath plate, and a weight is placed on a smooth table so that the load is 10 g / cm ² . This is left in a constant temperature and humidity (25 ° C., 50%) for 24 hours, and then the situation when the two sheets of paper are pulled apart is evaluated in four stages.

(Good) 4-3-2-1 (Evil)

4: The printed surface is not damaged at all.

        3: Slight cohesive failure is observed in the ink on the peeled surface, and a light force is required at the time of peeling.

        2: Clear cohesive failure is observed in the ink on the peeled surface, and a strong force is required at the time of peeling.

1: Interfacial peeling between ink and paper is observed at the time of peeling.

Example 6
(Production Example 2 of Solvent Dispersion System)
The copolymer (2) obtained above was coarsely pulverized into 2 mm squares using a desktop power mill (Dalton). Further, the copolymer (2) was pulverized under the following conditions.
1) Equipment / Jet Mill: Supersonic Jet Crusher LABO JET (manufactured by Nippon Pneumatic Industry Co., Ltd.)
2) Grinding conditions-All samples used were immersed in a liquid nitrogen solution for 1 minute or more immediately before grinding.

Sample feed rate: 1 g / min to 50 g / min (adjusted according to the particle size)
・ Air primary pressure: 6kg / cm ² G
・ Gas amount: 0.4 Nm ³ / min ・ Louvre type: Three types of large, medium, and small are used, and the particle size is adjusted in balance with the clearance with the classification zone. (The louver diameter is small, the classification clearance is large, and the particle size is small.)
Gas amount: 0.4 Nm ³ / min The volume average particle diameter of the fine powder obtained by the above method was 5.2 μm as measured by Microtrac (Honeywell: HRA). Further, 25 parts by weight of the fine powder and 40 parts by weight of the solvent (20 parts by weight of isopropyl alcohol and 20 parts by weight of ethyl acetate) were placed in a 1 liter chrome steel ball mill and sealed by rotation for 10 hours. Thereafter, 35 parts by weight of a solvent having the above composition was added to dilute the polyethylene wax solid content to 25% by weight. The volume average particle size of the solvent dispersion (Dispersion 2) thus obtained was 4.3 μm when measured by Microtrac (Honeywell: HRA).

(Example 2 of storage stability evaluation of solvent dispersion)
The storage stability of the dispersion 2 described in Example 5 was evaluated in the same manner as in Example 1 to evaluate the storage stability of the dispersion 2. The results are shown in Table 1.

(Printing ink production example 2)
A printing ink composition (ink 2) was obtained in the same manner as in the printing ink production example 1 described in Example 5, except that the dispersion 1 was changed to the dispersion 2.

(Printing ink printing example 2)
Ink 2 was printed in the same manner as printing ink printing example 1 described in Example 5.

(Abrasion resistance and blocking resistance evaluation example 2)
Abrasion Resistance and Blocking Resistance Evaluation Example 1 described in Example 5 was evaluated for abrasion resistance and blocking resistance of the film on which ink 2 was printed. The results are shown in Table 1.
Example 7
A solvent dispersion (dispersion 3) was obtained in the same manner as in Example 5 except that the copolymer (1) was changed to the copolymer (3). The volume average particle size of Dispersion 3 was 6.5 μm as measured by Microtrac (Honeywell: HRA). Using dispersion 3, a printing ink composition (ink 3) was obtained in the same manner as in Example 5. The evaluation results are shown in Table 1.

Example 8
A solvent dispersion (dispersion 4) was obtained in the same manner as in Example 5 except that the copolymer (1) was changed to the copolymer (4). The volume average particle diameter of the dispersion 4 was 7.9 μm as measured by Microtrac (Honeywell: HRA). A printing ink composition (ink 4) was obtained using the dispersion 4 in the same manner as in Example 5. The evaluation results are shown in Table 1.

[Comparative Example 1]
(Comparative Production Example 1 of Solvent Dispersion System)
In Production Example 1 of the solvent dispersion of polyethylene wax described in Example 5, copolymer (1) was HW210MP (manufactured by Mitsui Chemicals, [η] = 0.13 dl / g, density was 940 kg / m ³ , Mw / Mn = 3.0, Mz / Mw = 2.4, penetration is 3 dmm, acid value is 1.0 KOH mg / g), and the solvent dispersion (dispersion 5) is obtained in exactly the same manner. It was. The volume average particle diameter of Dispersion 5 was 4.7 μm as measured by Microtrac (Honeywell: HRA).

(Storage stability comparative evaluation example 1 of solvent dispersion system)
The storage stability of the dispersion 5 described in Example 5 was evaluated in the same manner as in Example 1 to evaluate the storage stability of the dispersion 5. The results are shown in Table 1.

(Comparative production example 1 of printing ink)
A printing ink composition (ink 5) was obtained in the same manner except that the dispersion 1 was changed to the dispersion 5 in the manufacturing example 1 of the printing ink described in Example 5.

(Comparative printing example 1 of printing ink)
Ink 5 was printed in the same manner as printing ink printing example 1 described in Example 5.

(Abrasion resistance and blocking resistance comparative evaluation example 1)
Evaluation of abrasion resistance and blocking resistance described in Example 5 In the same manner as in Example 1, the abrasion resistance and blocking resistance of the film printed with ink 5 were evaluated. The results are shown in Table 2.

[Comparative Example 2]
In Example 6, the copolymer (2) was changed to HW410P (Mitsui Chemicals, [η] = 0.22 dl / g, density 950 kg / m ³ , Mw / Mn = 2.9, Mz / Mw = 2.1, A solvent dispersion (dispersion 6) was obtained in the same manner except that the penetration was changed to 1 dmm and the acid value was 0.0 KOH mg / g). The volume average particle size of the dispersion 6 was 4.3 μm.
A printing ink composition (ink 6) was obtained using the dispersion 6 in the same manner as in Example 5. The evaluation results are shown in Table 1.

  Table 1 shows the evaluation results of Examples and Comparative Examples.

The novel polymer according to the present invention and the composition containing the polymer are particularly useful as additives for printing ink, and the resin composition containing the polymer is a printing ink composition. It is useful for molded products that require good paintability or printability.

Claims (18)

Formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, and i represents an integer of 1 or more). The polymer (II) according to claim 1, which has hydroxyl groups at both ends. Formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, i represents an integer of 1 or more),
Formula (III)

(III)
(Wherein, R ² is a divalent hydrocarbon residue having 1 to 20 carbon atoms that may have a hetero atom) polymer having as a repeating unit a structural unit represented by. Formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, i represents an integer of 1 or more),
Formula (IV)

(IV)
(Wherein X represents an oxygen atom or an NH group, and R ³ represents a divalent hydrocarbon residue having 1 to 20 carbon atoms which may contain a hetero atom) as a repeating unit. Polymer. Formula (I)

i (I)
(In the formula, A represents a copolymer composed of an olefin and diene having 2 to 20 carbon atoms and a number average molecular weight of 400 to 5000, and R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. And i represents an integer of 1 or more), or
Formula (VI)

i (VI)
(In the formula, A2 and A3 represent a hydrogen atom or a copolymer consisting of an olefin having 2 to 20 carbon atoms and a diene and having a number average molecular weight of 5000 or less, and R is a hydrogen atom or 1 to 18 represents an alkyl group, i represents an integer of 1 or more) and a general formula (V)

(V)
(Wherein R ⁴ represents a C 1-20 divalent hydrocarbon residue which may contain a hetero atom), and a polymer having a repeating unit as a repeating unit. A composition comprising the polymer according to claim 1. The additive for printing ink according to claim 1, wherein the volume average particle diameter is in the range of 0.3 μm to 20 μm. 6. The printing according to claim 1, wherein the volume average particle size is in the form of fine particles having a range of 0.3 [mu] m to 10 [mu] m and is dispersed in a solvent at a ratio of 5 to 50% by weight. Ink solvent dispersion system. The solvent dispersion for printing ink according to claim 8, wherein the solvent is a non-aromatic solvent. The solvent dispersion for printing ink according to claim 9, wherein the non-aromatic solvent contains an alcohol solvent and / or an ester solvent in a proportion of 10% by weight or more. A printing ink comprising the polymer according to any one of claims 1 to 5 in the form of fine particles having a volume average particle size in the range of 0.3 to 10 µm in a proportion of 0.1 to 10% by weight. . A resin composition comprising at least one selected from the group consisting of the polymer according to claim 1 and an alkali metal or alkaline earth metal salt, a surfactant, a compatibilizing agent and a polymer antistatic agent. object. A resin composition comprising a polymer having the structural unit represented by formula (I) according to claim 1 and another thermoplastic resin. The polymer having the structural unit represented by the general formula (I) according to any one of claims 1 to 5, another thermoplastic resin, and an alkali metal or alkaline earth metal salt, a surfactant, a compatibilizing agent, and A resin composition comprising at least one selected from the group consisting of polymer antistatic agents other than the polymer. An adhesive comprising a polymer having a structural unit represented by formula (I) according to claim 1. A coating composition comprising a polymer having a structural unit represented by formula (I) according to claim 1. The molded article formed by shape | molding the composition formed by containing the polymer which has a structural unit represented by general formula (I) of Claims 1-5. A molded article obtained by coating or printing a molded article formed by molding a composition comprising a polymer having a structural unit represented by formula (I) according to claim 1.