JPH09241566A - Ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition which can provide coating films having excellent properties and excellent specular gloss by mixing a polyurethane resin binder with an aminated polyester base polymer dispersant, a pigment and a solvent. SOLUTION: A high-molecular-weight diol obtained by mixing 20-80wt.% polyether base doil having a molecular weight of 700-2,500 with 80-20wt.% polyester type diol having a molecular weight of 700-2,500 is reacted with a diisocyanate and a chain extender to produce a polyurethane resin. This resin is mixed as a binder with an aminated polyester type polymer dispersant, a pigment and a solvent to obtain an ink composition. The polymer dispersant can be produced by, for example, reacting a polymepoxy compound with a compound having a carboxyl group at either end and a number-average molecular weight of 500-50,000 and a compound having one sec. amino group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ink composition containing a polyurethane resin as a binder and a polyester-based polymer dispersant having an amino group.

[0002]

2. Description of the Related Art Pigment dispersants are used in the manufacture of paints and inks for the purpose of improving dispersibility, manufacturing stability of paints and inks, preventing color separation, and improving coating film performance. For such a purpose, polyalkyleneimine-based polymer dispersants are disclosed in JP-A-48-79178 and JP-A-5-179178.
It is disclosed in JP-A-4-37082 and JP-A-61-174939. These pigment dispersants are currently used for general purposes, but although sufficient coating performance is obtained in the coating field, they are insufficient in the ink field. In particular, when the pigment dispersant as described above is used in the ink formulation using a polyurethane resin, it is difficult to use due to the compatibility problem, and crystallization or the like may occur at the time of forming the coating film, which may impair the appearance of the coating film. At present, among the coating film performances, it is the actual situation that satisfactory performance in terms of specular gloss is not obtained.

[0003]

An object of the present invention is to provide an ink composition which gives a sufficient specular gloss in an ink coating film.

[0004]

As a result of intensive studies to achieve the above object, the present inventor has blended a polyurethane resin as a binder and a polyester polymer dispersant having an amino group as a pigment dispersant in appropriate amounts. It was found that the above ink composition can meet this purpose, and the present invention has been completed based on this finding.

That is, the present invention is an ink composition containing a polyurethane polymer as a binder and a polyester polymer dispersant having an amino group.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The ink composition of the present invention comprises a polyurethane resin, a polyester-based polymeric pigment dispersant having an amino group, a pigment and a solvent. The pigment dispersant is 0.1 to 200% by weight in terms of solid content based on the pigment.
used. Further, the ink composition may be composed of a component obtained by adding additives such as a defoaming agent and a leveling agent.

Examples of applicable pigments include titanium dioxide, cadmium sulfide, calcium carbonate, barium carbonate,
Inorganic pigments such as barium sulfate, clay, talc, yellow lead and carbon black, azo series, diazo series, condensed azo series, thioindigo series, indanthrone series, quinacridone series, anthraquinone series, benzimidazolone series, perylene series, perinone Examples of organic pigments include phthalocyanine pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, anthrapyridine pigments, and dioxazine pigments. The pigment is 0.1 to 0.1 based on the total amount of the composition.
80% by weight is blended.

As the solvent, toluene, xylene, n-
Hexane, cyclohexane, n-heptane and other high boiling point petroleum hydrocarbons and other hydrocarbon solvents, methylene chloride, chloroform, dichloroethane and other halogenated hydrocarbon solvents, dioxane, tetrahydrofuran, butyl ether, butyl ethyl ether, diglyme and other ethers. Type solvent, ketone type solvent such as methyl isobutyl ketone, cyclohexanone, isophorone, ethyl acetate, butyl acetate,
Ester solvents such as ethylene glycol monoethyl ether acetate, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t
-Butyl alcohol, amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, cyclopentanol, cyclohexanol, alcohol solvents such as benzyl alcohol, p-tertiarybutylbenzyl alcohol , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 2-methoxypropyl acetate,
Examples thereof include amide solvents such as dimethylacetamide and dimethylformamide. These can be used alone or in combination of two or more.

The above ink composition is dispersed using a roll mill, a ball mill, a sand grind mill, a paint shaker, a kneader, a dissolver, an ultrasonic disperser or the like.

The suitable polyurethane resin used as the binder in the present invention is selected from those defined in the following (A) to (C).

(A) A polyurethane resin is produced from a high molecular weight diol, a diisocyanate and a chain extender, and the diol component of the polyurethane resin has a molecular weight of 700 to 250.
20-80% by weight of polyether type diol of 0 and polyester type diol 20-8 of molecular weight 700-2500
Polyurethane resin, which is a 0% by weight mixture.

(B) A polyurethane resin is produced from a high molecular weight polyol, a diisocyanate and a chain extender, and the polyol component of the polyurethane resin has a molecular weight of 500 to 3
A polyurethane resin which is a high molecular weight polyol having at least 50% by weight of poly (1,2-propylene adipate) glycol of 2,000 and having an amine value of 0.1 to 20 per gram of the polyurethane resin solids.

(C) The polyurethane resin is a high molecular weight polyol, polyisocyanate, and tin-based metal salt compound,
Manufactured from metal salt compounds other than tin, the polyisocyanate component of the polyurethane resin has an isocyanate group of 1
A polyurethane resin which is a polyisocyanate having an average of 2 or more in the molecule.

The above-mentioned polyurethane resins (A) to (C) are disclosed, for example, in JP-A-58-6754 and JP-B-5-80512.
It can be produced according to the method described in JP-A No. 62-288622.

The polyether type diol in the polyurethane resin (A) is an alkylene oxide adduct of two active hydrogen-containing compounds, specifically, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene. Examples thereof include polyoxyalkylene glycols such as propylene glycol and polyoxytetramethylene glycol, and alkylene oxide adducts such as ethylene oxide of bisphenol A, propylene oxide, and ethylene propylene oxide. Among them, the polyurethane resin synthesized from the polyether type diols derived from bisphenol A exhibits particularly excellent adhesiveness or blocking property to various films and low temperature stability. Therefore, for the purpose of the present invention, bisphenol is used. Polyether type diols derived from A are particularly preferred.

On the other hand, the polyester type diol is a dibasic acid such as adipic acid, phthalic anhydride, isophthalic acid, maleic acid, fumaric acid or succinic acid, and ethylene glycol, diethylene glycol, propylene glycol, 1.4 butanediol, Neopentyl glycol,
The one obtained by a condensation reaction with glycols such as 1.6 hexanediol. However, the molecular weights of these polyether type diols and polyester type diols are required to be in the range of 700 to 2500, preferably 1000 to 2000, and when the molecular weight is 700 or less, the polyurethane resin synthesized therefrom has a cohesive force between the resins. However, there is a drawback in that the adhesiveness and the suitability for laminating become poor, and the amount of residual liquid agent on the printed matter increases. The other 250
On the contrary, when the molecular weight is 0 or more, the cohesive force between the resins is insufficient and blocking is likely to occur.

Regarding the mixing ratio of the polyether type diol and the polyester type diol, the mixing ratio of the polyether type diol and the polyester type diol is from 80/20.
The optimum ratio is 20/80, and in the case of a polyurethane resin containing 20% by weight or less of polyester type diol, the adhesiveness to the polyester film or the suitability for laminating becomes insufficient, and the versatility which is the object of the present invention is not satisfied. Will be things. 20% by weight of polyether type diol
On the contrary, in the following cases, the suitability for a polypropylene film is deteriorated and the solubility of the resin is lowered, so that it is restricted in use.

Diisocyanates, which are other constituents of the polyurethane resin, are aromatic, aliphatic and alicyclic diisocyanates. For example, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,
3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Typical examples thereof are lysine diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and methylcyclohexane diisocyanate. From the standpoint that a resin having excellent solubility can be obtained, alicyclic diisocyanates such as isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate are preferable.

As the chain extender, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane, -4,4'-
Diamine can be mentioned. Further, diamines having a hydroxyl group in the molecule, for example, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2
-Hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine and the like can be used as well. Further, if necessary, a dialkylamine such as di-n can be used as a polymerization terminator.
-Butylamine can also be used.

As a method for producing the polyurethane resin (A), first, a diol component and a diisocyanate are reacted under an isocyanate excess condition to prepare a prepolymer having isocyanate groups at both ends, and the prepolymer is chained with a diamine in a suitable solvent. Obtained by extending.

Poly (1,2-propylene adipate) glycol in the polyurethane resin (B) is
A polyester diol obtained by dehydration condensation of 1,2-propanediol and adipic acid.

The constituents of the polyurethane resin which is the binder of the present invention are as follows. First, poly (1,2) having a molecular weight of 500 to 3000 is used as a high molecular weight polyol component.
-Propylene adipate) glycol is more preferably of molecular weight 700-2500. Moreover, the ratio of the glycol in the polymer polyol component is 50.
It is necessary that the content be at least wt%, more preferably at least 81 wt%.

The proportion of the poly (1,2) is less than 50% by weight.
Examples of the high molecular weight polyol that can be used in combination with (propylene adipate) glycol include polyether polyols of polymers or copolymers of ethylene oxide, propylene oxide, tetrahydrofuran and the like; ethylene glycol, 1,3
-Propanediol, 1,3-butanediol, 1,4
-Butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, 1,
Saturated and unsaturated low molecular weight glycols such as 4-butynediol, diethylene glycol, triethylene glycol and dipropylene glycol, and adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, shiyu Polyester polyols obtained by dehydration condensation of dibasic acids such as acids, malonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or acid anhydrides corresponding thereto;
Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds; other polycarbonate polyols, polybutadiene glycols, glycols obtained by adding ethylene oxide or propylene oxide to bisphenol A, etc., which are generally used in the production of polyurethane Known high molecular weight polyols are exemplified. still,
Of the above, in the case of a high molecular weight polyol obtained from a glycol and a dibasic acid, 5 mol% of the glycol component
Can be replaced by the following various polyols. That is, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, pentaerythritol, sorbitol and the like can be exemplified. The molecular weights of the various polymer polyols described above are determined in consideration of printability, drying property, etc., as in the case of the poly (1,2-propylene adipate) glycol.
Those within the range of up to 3000 are preferable.

Further, a part of the high molecular weight polyol component may be replaced with a low molecular weight polyol within a range not deviating from the binder performance of the polyurethane resin, and it is usually 10% by weight or less. . The low molecular weight polyols include poly (1,2-propylene adipate)
Examples of the above-mentioned various low-molecular polyols that can be used in the production of glycols or high-molecular-weight polyols that can be used in combination with the glycols.

When the polyurethane resin of the present invention is produced, the amino groups in the chain extender and / or the polymerization terminator must be present in excess with respect to the free isocyanate groups at both ends of the prepolymer. By doing so, a polyurethane resin having an amine value of 0.1 to 20, preferably 1 to 10 can be obtained. These ratios are such that the total equivalent of amino groups in the chain extender and / or the polymerization terminator is 1.01 to 1.30 equivalents when the isocyanate groups present at both ends of the prepolymer are 1 equivalent. To be inside. When the amino groups are in excess of 1.30 equivalents, the chain extender and / or the polymerization terminator remain unreacted, which adversely affects the printed matter in terms of odor, which is not preferable. When the amount is less than 01 equivalent, the adhesion to the film is hardly improved, which is not preferable.

The polyurethane resin (B) may be produced according to the above-mentioned method for producing the polyurethane resin (A).

In the production of the polyurethane resin (C),
The polyisocyanate component having an average of two or more isocyanate groups in one molecule is, for example, 2,4-triene diisocyanate, 2,6-toluene diisocyanate,
4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate, crude MDI
Known as aromatic polyisocyanate compounds such as polyphenylene polyisocyanate and xylylene diisocyanate; butane-1,4-diisocyanate, hexane-1,6-diisocyanate, lysine diisocyanate and other aliphatic polyisocyanate compounds; cyclohexane-1,4- Alicyclic polyisocyanate compounds such as diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methyldicyclohexylene diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate;
Monomers such as polyisocyanate compounds and / or those having high molecular weight by the reaction of hydroxyl group, amino acid group, carboxylic acid group, thiol group, and water, or high molecular weight by cyclopolymerization reaction of isocyanate group It can also be a converted product.

The tin-based metal salt compound component used in the production of the polyurethane resin (C) is an inorganic tin salt such as stannous chloride, stannic chloride, tin nitrate, tin sulfate, tin hydroxide or tin oxide. A compound and tetra-n-butyltin,
Organic substances such as n-butyltin trichloride, di-n-butyltin chloride, dimethyltin dichloride, trimethyltin hydroxide, dibutyltin dilaurate, dibutyltin-di-2-ethylhexoate, dibutyltin diacetate, dibutyltin fumarate, etc. Examples of the tin-based compound include organic tin compounds, and organic compounds are generally preferred because they have higher catalytic activity and excellent solubility in organic solvents.

The metal salt compound components other than tin include inorganic compounds and organic compounds, but in general, from the viewpoint of catalytic activity and solubility in organic solvents, organic metal salt compounds other than tin are generally used. Is preferred. Preferred examples are copper, lead,
Zinc, cobalt, nickel, manganese, calcium,
Iron, zirconium, barium, aluminum, cerium, magnesium, lithium, silver, mercury, cadmium,
There are inorganic compounds and organic compounds of metals such as molybdenum. Examples of these inorganic compounds include halides, hydroxides, oxides, nitrides, nitrogen oxides, sulfides and sulfates. As the organic compound, naphthenate,
There are octylate, neoate, oleate, stearate, tall oil fatty acid salt, palmitate salt, versatic acid salt, linseed oil fatty acid salt, abietic acid (rosin) salt and the like.

The compounding ratio of the tin-based metal salt compound and the metal salt compound component other than tin is 95/5 to 5/95% by weight, preferably 30/70 to 70/30% by weight. When the tin-based metal salt compound is 95% by weight or more, the reactivity is too high, so that the pot life is too short or the storage stability is deteriorated. Further, if the tin-based metal salt compound is 5% by weight or less, the reactivity is low, and the acceleration of curing cannot be improved. Further, the compounding ratio of these metal salt compounds to polyisocyanate is 5 ppm to 5% in terms of solid content, and in the case of having an aromatic isocyanate group, the reaction of the isocyanate group is high, and therefore may be about 5 ppm to 2000 ppm. In the case of having a content of 1%, the reactivity of the isocyanate group is low, so that it is preferably used in the range of 100 ppm to 5%.

As a method for producing the polyurethane resin (C), first, a diol component and a diisocyanate are reacted to prepare a prepolymer having an isocyanate group, and a tin-based metal salt compound and a metal salt compound other than tin are mixed therein. It is obtained by

In the present invention, a polyester-based polymer dispersant having an amino group, which is preferably used as a pigment dispersant in combination with a polyurethane resin as a binder, includes the following (D) to
It is selected from those defined in (F).

(D) The polyester polymer dispersant having an amino group is a polyepoxy compound, and the number average molecular weight is 50.
A polyester having an amine value of 5 to 200 mgKOH / g and a number average molecular weight of 1,000 to 100,000 obtained by reacting a compound having a carboxyl group at one end of 0 to 50,000 and a compound having one secondary amino group.

(E) The polyester polymer dispersant having an amino group has an amine value of 10 to 10 obtained by reacting an acrylic polymer having a tertiary amino group and / or a nitrogen-containing heterocycle showing basicity with a polyester. 200 mg KOH
/ G, polyester having a number average molecular weight of 1,000 to 100,000

(F) A polyester-based polymer dispersant having an amino group is reacted with a polyester having one hydroxyl group by reacting a part of the polyisocyanate having an isocyanate group of 2.5 to 6.0 on average. A polyester having a number average molecular weight of 1300 to 84000 obtained by reacting an unreacted isocyanate group of isocyanate with a compound having a substituent having active hydrogen in the molecule and a tertiary amino group.

The amino group-containing polyester polymer dispersants (D) to (F) are described in, for example, Japanese Patent Application No. 7-2509.
It can be manufactured by the methods described in JP-A No. 53-52, JP-A No. 4-227774 and JP-B No. 2-19844.

The polyepoxy compound which is a raw material for producing the polyester type polymer dispersant (D) having an amino group (hereinafter referred to as "pigment dispersant (D)") is ethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether. , Propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
In addition to polyglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether, glycidyl (meth ) A glycidyl ester group-containing acrylic polymer obtained by copolymerizing an acrylate with another polymerizable vinyl monomer.

The number average molecular weight of the compound having a carboxyl group at one end is preferably in the range of 500 to 50,000. When the number average molecular weight of this compound is less than 500, the polymer component of the pigment dispersant adsorbed to the pigment does not have a sufficient thickness as a steric repulsion layer and reaggregation of dispersed particles occurs, which is not preferable. Further, even if the number average molecular weight of the compound exceeds 50,000, it is difficult to produce the compound with good reproducibility, which is not preferable.

In the compound having a carboxyl group at one terminal used in the pigment dispersant (D), the compound represented by the general formula (I) is synthesized by using a monocarboxylic acid as a starting material, and the compound represented by the general formula (V) is used. It is obtained by subjecting the represented lactone to a ring-opening addition reaction.

[0040]

Embedded image (In the formula, R ¹ is a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, or 1 to 1 carbon atoms.
8 alkyl-substituted phenyl group, R ² has ² carbon atoms
~ 8 straight or branched alkylene group, m is 2
Indicates an integer of 200)

[0041]

Embedded image (R ⁹ represents a linear or branched alkylene group having 2 to 8 carbon atoms)

As the lactone represented by the general formula (V), for example, one or more compounds selected from ε-caprolactone, β-propiolactone, δ-valerolactone and the like can be used.

Examples of the monocarboxylic acid include aliphatic monocarboxylic acids such as acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isononanoic acid and arachidic acid. , Benzoic acid, aromatic monocarboxylic acids such as p-tert-butylbenzoic acid, and the like, and one or more compounds selected from them may be used as a starting material.

In the ring-opening polyreaction, a reaction catalyst can be used. Examples of such a catalyst include tertiary amines such as trimethylamine, triethylamine and dimethylbenzylamine, organotin compounds such as dibutyltin dilaurylate and trimethyl. Examples include organic aluminum compounds such as aluminum, triethylaluminum and trialkoxyaluminum, and organic titanate compounds such as tetraalkoxytitanate.

In the compound having a carboxyl group at one end used for the pigment dispersant (D), the compound represented by the general formula (II) is a ring-opening addition reaction of the above-mentioned lactone with a monohydric alcohol as a starting material. Then, a prepolymer having a hydroxyl group at one end is prepared, and then the cyclic acid anhydride represented by the general formula (VI) is subjected to ring-opening addition.

[0046]

Embedded image (In the formula, R ³ is a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, a benzyl group, or a C 1 to 18 carbon atom. Alkyl-substituted benzyl group, R ⁴ is a linear or branched alkylene group having 2 to 8 carbon atoms, X is a residue of an acid anhydride having 2 to 8 carbon atoms, and n is 2 to 20.
Indicates an integer of 0)

[0047]

Embedded image (X represents a residue of an acid anhydride having 2 to 8 carbon atoms)

As the monohydric alcohol, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, 2 -Saturated aliphatic alcohols such as ethylhexyl alcohol, lauryl alcohol and stearyl alcohol, alicyclic alcohols such as cyclopentanol and cyclohexal, and aromatic alcohols such as phenol, benzyl alcohol and p-tert-butylbenzyl alcohol. , And one or more compounds selected from them can be used.

Examples of the cyclic acid anhydride represented by the general formula (VI) include succinic anhydride, phthalic anhydride, maleic anhydride,
Dibasic acids such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrabrominated phthalic anhydride, tetrachlorinated phthalic anhydride, and het anhydride can be used.

In the compound having a carboxyl group at one terminal used in the pigment dispersant (D), the compound represented by the general formula (III) can be obtained by using the above-mentioned monovalent carboxylic acid as a starting material. Can be obtained by ring-opening copolymerization of the monoepoxy compound represented by A reaction catalyst can be used in this ring-opening copolymerization reaction.

[0051]

Embedded image [In the formula, R ⁵ is a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, or 1 to 1 carbon atoms.
8 phenyl group substituted with an alkyl group, R ⁶ is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, —CH ₂ Cl, —CH ₂ OR ′ or —
CH ₂ COR ″ (where R ′ is 1 to 1 carbon atoms)
8 linear or branched alkyl group, phenyl group,
Or an allyl group and R ″ has 1 to 1 carbon atoms
18 represents a linear or branched alkyl group, a phenyl group or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms), X is a residue of an intramolecular acid anhydride having 2 to 8 carbon atoms, p represents an integer of 2 to 200]

[0052]

[Chemical 6] (R ¹⁰ represents a linear or branched alkylene group having 2 to 8 carbon atoms)

Examples of the monoepoxy compound represented by the general formula (VII) include ethylene oxide, propylene oxide,
Aliphatic monoepoxy compounds such as 1-butene oxide and α-olefin oxide, glycidyl ether compounds such as methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether and phenyl glycidyl ether, lauric acid glycidyl ester, versatic acid glycidyl ester, In addition to glycidyl ester compounds such as p-tert-butylbenzoic acid glycidyl ester, one or more compounds selected from epichlorohydrin and the like can be used.

Examples of such a catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodo, tetrabutylammonium iodo, benzyltrimethylammonium chloride, benzyltrimethylammonium. Bromide, quaternary ammonium salts such as benzyltrimethylammonium iodide, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodo, benzyltrimethylphosphonium chloride, benzyltrimethyl Phosphonium bromide, In addition to quaternary phosphonium salts such as diltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and tetraphenylphosphonium iodo, phosphorus compounds such as triphenylphosphine, potassium acetate, sodium acetate, potassium benzoate, benzoic acid In addition to organic carboxylic acids such as sodium, sodium alcoholates, potassium alcoholates and the like, the above-mentioned tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride and the like can be mentioned.

In the compound having a carboxyl group at one end used in the pigment dispersant (D), the compound represented by the general formula (IV) is a monohydric alcohol as a starting material, and the monoepoxy compound and the acid anhydride are used as starting materials. It is obtained by subjecting and to ring-opening copolymerization. In this ring-opening copolymerization reaction, the reaction catalyst used in the general formula (III) can be used.

[0056]

Embedded image [R ⁷ is a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms, a benzyl group, or 1 carbon atom.
To 18 alkyl substituted benzyl group, R ⁸ is a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, -CH ₂ Cl, -CH ₂ OR 'or -CH ₂ COR ″ (wherein R ′ represents a linear or branched alkyl group having 1 to 18 carbon atoms, a phenyl group, or an allyl group, and R ″ represents a straight chain having 1 to 18 carbon atoms). A chain or branched alkyl group, a phenyl group or an alkyl group-substituted phenyl group having 1 to 18 carbon atoms), X is a residue of an intramolecular acid anhydride having 2 to 8 carbon atoms, and q is 2 ~ Indicates an integer of 200]

In the compound having a carboxyl group at one end used in the pigment dispersant (D), a radical chain transfer agent having one carboxyl group and one mercapto group in each molecule is used to radically polymerize the polymerizable vinyl group-containing monomer. The acrylic polymer obtained by polymerization will be described. First, a radical chain transfer agent and a polymerizable vinyl group-containing monomer are added in the presence of an initiator at 40 ° C to 180 ° C.
It is obtained by radical copolymerization with. As the copolymerization method, known methods such as solution polymerization, bulk polymerization and suspension polymerization can be applied, but solution polymerization is preferable.

Examples of the radical chain transfer agent having one carboxyl group and one mercapto group in one molecule include mercaptoacetic acid, 2-mercaptopropionic acid and 3-mercaptopropionic acid.

The polymerizable vinyl group-containing monomer is preferably one having one polymerizable vinyl group in the molecule, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl ( (Meth) acrylate, 2-ethylhexyl (meth)
(Meth) acrylic acid esters such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Hydroxyl group-containing (meth) acrylic acid esters such as hydroxypropyl (meth) acrylate, acrylamides such as (meth) acrylamide, dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N -Amino group-containing (meth) acrylic acid esters such as diethylaminoethyl (meth) acrylate, (meth) acrylic acid, styrene, styrenes such as α-methylstyrene, and the like,
One or more compounds selected from these can be used.

As the initiator, azo-based initiators such as azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile and 1,1'-azobiscyclohexane-1-carbonitrile, Organic peroxides such as benzoyl peroxide, lauroyl peroxide, tertiary butyl hydroperoxide, tertiary butyl peroxybenzoate, acetyl peroxide, methyl ethyl peroxide, dicumyl peroxide, di-n-propyl peroxydicarbonate A system initiator can be mentioned.

Examples of the organic amino compound having one secondary amino group in the molecule used as the raw material for producing the pigment dispersant (D) include, for example, dimethylamine, diethylamine, diisopropylamine, di-n-butylamine and diisobutylamine. , Di-2-ethylhexylbutylamine, N
-Methylethanolamine, N-ethylethanolamine, N-ethylethanolamine, pyrrolidine, piperidine, N-methylpiperazine, morpholine, 2-piperoline, 3-piperoline, 4-piperoline and the like cyclic amines.

As the method for producing the pigment dispersant (D), first, a compound having a carboxyl group at one end is prepared and then reacted with a polyepoxy compound at 80 to 140 ° C. Then, it is obtained by reacting an organic amino compound having one secondary amino group in the molecule at 60 ° C to 140 ° C.

The number average molecular weight of the pigment dispersant (D) is 1,
It is preferably in the range of 000 to 100,000.
When the number average molecular weight of the pigment dispersant is less than 1,000, the polymer component of the pigment dispersant adsorbed on the pigment is not sufficient as a steric repulsion layer and reaggregation of dispersed particles occurs, which is not preferable. Further, the number average molecular weight of the pigment dispersant is 10
Even if it exceeds 10,000, it is difficult to produce it with good reproducibility, and the number average molecular weight of the pigment dispersant is 10 or less.
If it exceeds 50,000, it may act as a flocculant, which is not preferable.

The amine value of the pigment dispersant (D) is 5 to 200 m.
Desirably in gKOH / g. When the amine value of the pigment dispersant is less than 5 mgKOH / g, the adsorbing power to the pigment surface is insufficient and the pigment dispersant is likely to be desorbed from the pigment surface, resulting in deterioration of pigment dispersion stability, which is not preferable. In addition, the amine value of the pigment dispersant is 200 mgKO
If it exceeds H / g, the ratio of the steric repulsion layer to the adsorbed components of the pigment dispersant adsorbed on the pigment surface becomes too small, and sufficient pigment dispersion stability cannot be obtained, and the water resistance and weather resistance of the coating film, etc. It is not preferable because it may cause deterioration in performance such as properties and adhesion.

There are the following two methods for obtaining the polyester as a raw material for producing the polyester-based polymer dispersant (E) having an amino group [hereinafter referred to as "pigment dispersant (E)"]. As the first production method, first, the above-mentioned monocarboxylic acid, for example, acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isononanoic acid, 2-ethylhexanoic acid. , Arachidic acid or aromatic monocarboxylic acids such as benzoic acid, p-tertiarybutylbenzoic acid, etc. having one or more compounds selected as a starting material and having a monoepoxy compound such as a phenyl group. Styrene oxide; a phenyl glycidyl ether having a glycidyl ether group containing an alkyl group or an aromatic group having 4 to 19 carbon atoms, p-tolyl glycidyl ether,
n-butyl glycidyl ether, dibromocresyl glycidyl ether; lauric acid glycidyl ester, stearic acid glycidyl ester, versatic acid glycidyl ester, p having a glycidyl ester group containing an alkyl group or an aromatic group having 3 to 17 carbon atoms, p -Tert-butyl benzoic acid glycidyl ester; one or more compounds selected from α-olefin oxides having an alkyl group having 5 to 10 carbon atoms, and further represented by the general formula (VI) Cyclic acid anhydrides such as phthalic anhydride, succinic anhydride, hexahydrogenated phthalic anhydride, tetrabrominated phthalic anhydride, tetrachlorophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, maleic anhydride, anhydrous het One or more compounds selected from acids and the like and the above general formula (V) Displayed lactones such as ε-
One or two or more compounds selected from caprolactone, β-propionolactone, δ-parerolactone, etc., at 100 ° C to 200 ° C, preferably 120 ° C to 1
A ring-opening addition reaction is carried out at 60 ° C. to obtain a polyester polymer compound having one hydroxyl group at the molecular end.

In this production method, a monocarboxylic acid is first used as a starting material, a monoepoxy compound is subjected to a ring-opening polymerization of an acid anhydride, and then a lactone is subjected to a ring-opening addition reaction, and / or Any method of random structure obtained by randomly reacting a monoepoxy compound, an acid anhydride and a lactone with a monocarboxylic acid as a starting material can be used. The reaction solvent in the above reaction is not particularly limited,
For example, toluene, xylene, ethylbenzene, Solvesso # 100 (registered trademark of Exxon Chemical Co., Ltd.), Solvesso # 150 (registered trademark of Exxon Chemical Co., Ltd.), turpentine oil, aromatic hydrocarbon solvent such as tetralin, n-hexane. , Cyclohexane, methylcyclohexane, n-heptane, n-octane, n-decane, mineral spirits, isooctane, nonane, trimethylhexane, solvent naphtha, Isobar (registered trademark of Exxon Chemical Co., Ltd.), New Sol Deluxe ) Registered trademark)
Such as aliphatic hydrocarbon solvents, ester solvents such as methyl acetate, ethyl acetate, -n-butyl acetate, isobutyl acetate, ether solvents such as ethyl ether, tetrahydrofuran, dioxane, diglyme, acetone, methyl ethyl ketone, methyl isobutyl ketone , Methylamyl ketone, cyclohexanone, isophorone and other ketone solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether and other cellosolve solvents And its esters, methylene chloride, trichloroethylene, perchlorethylene, orthodichlorobenzene, etc. Chlorinated hydrocarbon solvents, dimethylformamide, a mixture of one or more solvents such as dimethylsulfoxide can be used.

In the above reaction, in the absence of a catalyst or, if necessary, tertiary amines such as triethylamine and dimethylbenzylamine, quaternary amine salts such as tetramethylammonium chloride, tetrabutoxy titanate and dibutyltin dilaurate. Organometallic salts such as, phosphorus compounds such as triphenylphosphine,
Known catalysts such as organic carboxylate such as potassium benzoate and sodium benzoate, and inorganic salts such as potassium iodide can be used. Similarly, monohydric alcohols, for example, saturated aliphatic methyl alcohol having 1 to 18 carbon atoms, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Isobutyl alcohol, t-butyl alcohol, amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, 2-ethylhexyl alcohol, lauryl alcohol, stearyl alcohol, alicyclic cyclopentanol, cyclohexanol, aromatic benzyl alcohol, p -One or more compounds selected from tertiary butylbenzyl alcohol as a starting material, and one or more compounds of the cyclic acid anhydride represented by the general formula (VI), and the above monoepoxy compound. 1 or 2 or more and 1 or 2 or more of the lactones represented by the general formula (V) are subjected to a ring-opening addition reaction according to the method described above, and have a desired molecular weight, A polymer compound of polyester having one hydroxyl group at the terminal is obtained.

Also in this production method, a monoepoxy compound is first used as a starting material, a monoepoxy compound and an acid anhydride are subjected to ring-opening polymerization, and then a lactone is subjected to a ring-opening addition reaction. / Or, firstly using a monohydric alcohol as a starting material, ring-opening addition reaction of lactones, and then a block structure obtained by ring-opening polymerization of a monoepoxy compound and an acid anhydride, and / or monohydric alcohol As a starting material, any method of a random structure obtained by subjecting a monoepoxy compound, an acid anhydride, and a lactone to a random addition reaction can be used. Also,
As the reaction solvent and the catalyst in this production method, those described above can be used. Further, using a monohydric alcohol as a starting material, one or more of the above lactones and one or more of the above monoepoxy compounds are subjected to a ring-opening addition reaction to have a desired molecular weight and a hydroxyl group at the molecular end. 1
To obtain a polymer compound of polyester polyether.

Also in this production method, a ring structure and / or a mono-epoxy compound is firstly subjected to a ring-opening addition reaction with a monohydric alcohol as a starting material and then a monoepoxy compound is subjected to a ring-opening addition reaction. A block structure obtained by subjecting a monoepoxy compound to a ring-opening addition reaction with a monohydric alcohol as a starting material, and then performing a ring-opening addition reaction with a lactone, and / or with a monohydric alcohol as a starting material,
Any method of a random structure obtained by ring-opening copolymerization of a lactone and a monoepoxy compound can be used. As the reaction solvent in this production method, the above-mentioned one can be used. The ring-opening addition reaction for obtaining the polymer compound of the polyester polyether includes polymerization methods such as anion polymerization, coordination anion polymerization, and cation polymerization shown below. In the case of the anionic polymerization method, L
10 to 200 ° C. by using known catalysts such as alkali metals such as i, Na and K, metal alcoholates and tertiary amines
At 1 to 15 hours for anionic polymerization. In the case of the coordinated anionic polymerization method, Al (R) ₃ , Zn (R) ₂ , (R) ₂ Al
Coordination anionic polymerization is carried out at 10 to 200 ° C. for 1 to 15 hours using a known catalyst such as (OR ′), Al (OR ′) ₃ and Ti (OR ′) ₄ . Incidentally, R'represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R represents a halogen atom or an alkyl group having 1 to 18 carbon atoms. In the case of the cationic polymerization method, a known catalyst such as a metal halide such as AlCl ₃ or p-toluenesulfonic acid or phosphoric acid is used.
Cationic polymerize at ˜200 ° C. for 1 to 15 hours.

Next, one or a combination of two or more polymer compounds of polyester or polyester polyether having one hydroxyl group at one of the molecular ends obtained by the above-mentioned method is combined, and a diisocyanate compound such as tolylene diisocyanate, Isophorone diisocyanate,
4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate,
Methylcyclohexane 2,4 (2,6) diisocyanate, 4,4′-methylenebis (cyclohexylisocyanate), 1,3- (isocyanatomethyl) cyclohexane, trimethylhexamethylenediisocyanate,
One or more selected from dimer acid diisocyanate and the like, and the molar ratio of the polymer compound of the polyester having one hydroxyl group at one of the molecular ends to the diisocyanate compound is 0.7 to 1.3, preferably 0.9 to 1. .1 is reacted with one isocyanate group of the diisocyanate compound at 0 ° C. to 80 ° C. for 0.5 to 6 hours to obtain a polymer compound of polyester and / or polyester polyether having one isocyanate group at the molecular end.

Next, the acrylic polymer component which is another raw material in the production of the pigment dispersant (E) will be described.
Polyester compound having one isocyanate group at the molecular end and / or polymer compound of polyester polyether and hydroxyl group-containing copolymerizable monomer, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, Alternatively, N-methylol acrylamide, N-methylol methacrylamide, allyl alcohol, ε-caprolactone modified hydroxyalkyl (meth) acrylate (for example, Praxel FM-
2, FM-4, manufactured by Daicel Chemical Industries, Ltd., etc., and / or active methylene group-containing copolymerizable monomers such as acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl acrylate, From acetoacetoxypropyl methacrylate or allyl acetoacetate,
Polymer compound of polyester and / or polyester polyether containing isocyanate group at the molecular end and hydroxyl group-containing copolymerizable monomer and / or active methylene group-containing copolymerizable monomer in combination of one kind or two or more kinds The molar ratio of the body is 0.7 to 1.5, preferably 0.8
.About.1.2 and reacted at 0.degree. C. to 140.degree. C. for 1 to 10 hours to obtain a macromer having a vinyl group or an isopropenyl group at the molecular end. This macromerization reaction is without catalyst,
Alternatively, if necessary, known catalysts such as tertiary amines such as triethylamine and dimethylbenzylamine, dibutyltin dilaurate, organic metal salts such as zinc naphthenate and zinc octylate can be used.

Further, the above-mentioned cyclic acid anhydride is added to a polymer compound of polyester and / or polyester polyether having one hydroxyl group at the molecular end at 100 ° C. to 200 ° C.
The ring-opening addition reaction is carried out at a temperature of 120 ° C., preferably 120 ° C. to 160 ° C. to obtain a polymer compound of polyester and / or polyester polyether having one carboxyl group at the molecular end. Next, this polymer compound and a glycidyl group-containing copolymerizable monomer such as glycidyl (meth) acrylate and allyl glycidyl ether are used in a molar ratio of 0.
7 to 1.5, preferably 0.9 to 1.1, and 100
2 to 2 at ℃ to 200 ℃, preferably 120 to 160 ℃
The reaction is performed for 0 hours to obtain a macromer having a vinyl group or an isopropenyl group at the molecular end. At the time of this macromerization reaction, it is desirable to add a polymerization inhibitor such as hanoderoquinone or 4-methoxyphenol.

The general formula (VIII) thus obtained

[0074]

Embedded image (R ₁₁ is a hydrogen atom or a methyl group, A is an organic bonding group, and Y is a polyester compound residue), and a macromer of the polyester and / or polyester polyether compound represented by the general formula (IX)

[0075]

Embedded image (R ₁₁ is a hydrogen atom or a methyl group, X is an imidazole group,
A tertiary amino group-containing copolymerizable monomer represented by a tertiary amino group represented by a pyridine group, a carbazole group, a quinoline group, or an N-alkylpiperidine group and / or a nitrogen-containing heterocyclic group exhibiting basicity) Copolymerizable monomer having a nitrogen-containing heterocycle showing a monomer and / or basicity, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N -Dimethylaminopropyl (meth) acrylate, N, N-
Diethylaminopropyl (meth) acrylate, N, N
-Dimethylaminobutyl (meth) acrylate, N, N
-Diethylaminobutyl (meth) acrylate, N, N
-Dimethylaminohexyl (meth) acrylate, N,
Aminoalkyl (meth) acrylates such as N-diethylaminohexyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-
Diethylaminoethyl (meth) acrylamide, N, N
-Dimethylaminopropyl (meth) acrylamide,
Aminoalkyl (meth) acrylamides such as N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide,
N, N-dimethylaminoethyl vinyl ether, N, N
-Diethylaminoethyl vinyl ether, N, N-dipropylaminoethyltyl vinyl ether, N, N-dibutylaminoethyl vinyl ether, N, N-dimethylaminopropyl vinyl ether, N, N-diethylaminopropyl vinyl ether, N, N-dipropylaminopropyl Vinyl ether, N, N-dimethylaminobutyl vinyl ether, N, N-diethylaminobutyl vinyl ether, N, N-dipropylaminobutyl vinyl ether, N, N-dibutylaminobutyl vinyl ether,
N, N-dimethylaminobenzyl vinyl ether, N,
N-diethylaminobenzyl vinyl ether, N, N-
Dibromopyraminobenzyl vinyl ether, N, N-dimethylaminohexyl vinyl ether, N, N-diethylaminohexyl vinyl ether, N, N-dipropylaminohexyl vinyl ether, N, N-dibutylaminohexyl vinyl ether, N, N-dimethylamino Aminoalkyl vinyl ethers such as octyl vinyl ether and N, N-diethylaminooctyl vinyl ether, vinyl pyridines such as 2-vinyl pyridine, 4-vinyl pyridine and 5-ethyl-2-vinyl pyridine, 1
1 selected from vinylimidazoles such as -vinylimidazole and 1-vinyl-2-methylimidazole, vinylquinolines such as 2-vinylquinoline, vinylpiperidines such as N-methyl-3-vinylpiperidine
One or more compounds and, if desired, the general formula (X)

[0076]

Embedded image (R ₁₂ represents an alkyl group having 1 to 4 carbon atoms, Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, a phenyl group or a nitrile group), for example, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl
(Meth) acrylate, alkyl esters of (meth) acrylic acid such as benzyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, etc. Alkoxyalkyl esters of (meth) acrylamide, N
-Methyl (meth) acrylamide, N-ethyl (meth)
Acrylamide, N-butyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethoxymethyl (meth) acrylamide,
N-butoxymethyl (meth) acrylamide, N, N-
(Meta) such as dimethylaminopropyl acrylamide
Acrylamide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy (meth) acrylates such as Praxel FM-2 and Praxel FM-4, vinyl fragrance such as styrene, α-methylstyrene and vinyltoluene Α, β ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, tert-butyl cyclohexyl vinyl ether, 2-chloroethyl vinyl ether, n-propyl Vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, tert-butyl vinyl ether, n-
Alkyl vinyl ethers such as pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether and 2-ethylhexyl vinyl ether, alicyclic vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether and methyl cyclohexyl vinyl ether, aromatic vinyl ethers such as benzyl vinyl ether, hydroxy Ethyl vinyl ether, hydroxypropyl vinyl ether, hydroxyisopropyl vinyl ether, didroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether,
Hydroxyalkyl vinyl ethers such as 2-hydroxypropyl vinyl ether, and one or more compounds selected from vinyl acetate, vinyl chloride, acrylonitrile and allyl ethers in the presence of a polymerization initiator at 40 ° C to 180 ° C. It can be produced by copolymerizing at 0 ° C. for 3 to 20 hours in the above-mentioned synthetic solvent. As the polymerization initiator, any one can be used as long as it can be used in ordinary vinyl type polymerization, and examples thereof include azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, and 1 , 1'-azobiscyclohexane-1-carbonitrile, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroctoate, cumene hydroperoxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, etc. Is mentioned.

As the copolymerization method, known methods such as solution polymerization, bulk polymerization and suspension polymerization can be applied, but the solution polymerization method is preferable. Next, as the second production method, the above-mentioned method is used in advance. The tertiary amino group-containing copolymerizable monomer represented by the formula (IX) and / or the basicity-containing copolymerizable monomer having a nitrogen-containing heterocycle is obtained by converting the above-mentioned hydroxyl group-containing copolymerizable monomer. , And / or one or more compounds of an active methylene group-containing copolymerizable monomer, and, if desired,
An acrylic polymer is obtained by copolymerizing the copolymerizable monomer represented by the formula (X) with a polymerization initiator at 40 to 180 ° C. for 3 to 10 hours in the above-mentioned synthetic solvent. . Then, this acrylic polymer is produced by reacting a polyester and / or polyester polyether compound having one isocyanate group at the molecular end obtained in the same manner as in the first production method at 30 to 100 ° C. for 3 to 20 hours. can do.

Next, as a method for producing the pigment dispersant (E), the above-mentioned hydroxyl group-containing copolymerizable monomer or carboxyl group-containing copolymerizable monomer such as (meth) acrylic acid is used. Starting from one or more compounds selected from the above, one or more of the above monoepoxy compounds and one or two of the above cyclic acid anhydrides.
And at least one of the above-mentioned lactones are subjected to a ring-opening addition reaction in the presence of the above-mentioned polymerization inhibitor according to the above-mentioned first production method, and have a desired molecular weight A macromer of a polyester compound having a hydroxyl group at the other end and a vinyl group or an isopropenyl group at the other end is obtained. In this production method, first, a hydroxyl group-containing copolymerizable monomer or a carboxyl group-containing copolymerizable monomer is used as a starting material, and a monoepoxy compound and a cyclic acid anhydride are subjected to ring-opening copolymerization, followed by lactone. Structure obtained by subjecting compounds to a ring-opening addition reaction, and / or after first subjecting a lactone to a ring-opening addition reaction using a hydroxyl group-containing copolymerizable monomer as a starting material, a monoepoxy compound and a cyclic acid anhydride Block structure obtained by ring-opening copolymerization of
And / or a random structure obtained by randomly adding and reacting a monoepoxy compound, a cyclic acid anhydride and a lactone with a hydroxyl group-containing copolymerizable monomer or a carboxyl group-containing copolymerizable monomer as a starting material. Any method of obtaining can be used. Further, using the above-mentioned hydroxyl group-containing copolymerizable monomer as a starting material, one or more kinds of the above-mentioned lactones and one or more kinds of the above-mentioned monoepoxy compounds are used to inhibit the above-mentioned polymerization. In the presence of an agent, a ring-opening addition reaction is carried out according to the above-mentioned first production method,
A macromer of a polyester polyether compound having a desired molecular weight, having a hydroxyl group at the terminal and having a vinyl group or an isopropenyl group at the other terminal is obtained. In this production method, first, a hydroxyl group-containing copolymerizable monomer is used as a starting material to cause a ring-opening addition reaction of lactones, and then a block structure obtained by ring-opening copolymerization of a monoepoxy compound, and / Alternatively, a block structure and / or a hydroxyl group-containing compound obtained by ring-opening copolymerization of a lactone with a ring-opening copolymerization of a monoepoxy compound using a hydroxyl group-containing copolymerizable monomer as a starting material Any method of a random structure obtained by randomly adding and reacting a monoepoxy compound and a lactone with a copolymerizable monomer as a starting material can be used.

Next, the general formula (X
I)

[0080]

Embedded image (R ₁₁ is a hydrogen atom or a methyl group, B is an organic bonding group, Q is a polyester compound residue), and a macromer of a polyester or polyester polyether compound, and a tertiary amino group represented by the above formula (IX). One or more compounds selected from the group-containing copolymerizable monomer and / or the copolymerizable monomer having a basic nitrogen-containing heterocycle, and, if necessary, the above The compound (1) or two or more compounds selected from the copolymerizable monomers represented by the formula (X) at 40 to 180 ° C. in the presence of a polymerization initiator in the same manner as in the above method. It can be produced by copolymerizing for 3 to 20 hours.

The number average molecular weight of the pigment dispersant (E) is 1,0.
When it is less than 00, the polymer component of the pigment dispersant adsorbed on the surface of the pigment cannot exert a sufficient effect as a three-dimensional repulsion layer, causing a phenomenon such as re-aggregation of dispersed particles or caking, and It is not preferable because it causes a remarkable decrease. In addition, the number average molecular weight of the pigment dispersant is 100,
It is difficult to produce it with good reproducibility even if it is set to 000 or more, and the number average molecular weight of the pigment dispersant is 10 or less.
On the other hand, if it exceeds 50,000, it may act as a flocculant, which is not preferable. Therefore, in the pigment dispersant of the present invention, it is necessary to design the number average molecular weight in the range of 1,000 to 100,000. Further, when the amine value of the pigment dispersant (E) is less than 10 mgKOH / g, the adsorption power to the pigment surface is insufficient, and the resin added as a coating film component and the pigment dispersant have good affinity, It is not preferable because the dispersion stability of the pigment is deteriorated such that the pigment dispersant is desorbed from the surface of the pigment. Furthermore, when the amine value of the pigment dispersant exceeds 200 mgKOH / g, the ratio of the steric repulsion layer to the adsorbed portion of the pigment dispersant adsorbed on the pigment surface becomes too small, and sufficient pigment dispersion stability cannot be obtained. It is not preferable because it causes deterioration of coating film performance such as water resistance, weather resistance and adhesion of the coating film. Therefore, the amine value of the pigment dispersant of the present invention is 10 to 2
It needs to be designed to fall within the range of 00 mgKOH / g.

Polyisocyanate having an average functionality of 2.5 to 6, which is one of the raw materials for producing the polyester-based polymer dispersant (F) having an amino group (hereinafter referred to as "pigment dispersant (F)"). Examples of are as follows.

"Desmodur L" (registered trademark) represented by the formula (XII) obtained by adding diisocyanate to polyol

[0084]

Embedded image

"Desmodur N" (registered trademark) represented by the formula (XIII) obtained from the diisocyanate by the Biuret reaction

[0086]

Embedded image "Desmodur HL" (registered trademark) represented by the formula (XIV) having an isocyanurate structure formed by ring formation of diisocyanate

[0087]

Embedded image

The "death module I" represented by the formula (XV)
L "(registered trademark)

[0089]

Embedded image

"Porlen KC" represented by the formula (XVI)
(Registered trademark)

[0091]

Embedded image

"Porlen HR" represented by the formula (XVII)
(Registered trademark)

[0093]

Embedded image

Tolylene diisocyanate-isophorone diisocyanate represented by the formula (XVIII)

[0095]

Embedded image

Trimec isophorone diisocyanate "isocyanurate T1890" represented by the formula (XIX)

[0097]

Embedded image

These compounds mentioned above are commercial products, often a mixture of compounds having certain similar structures, rather than the pure form of the compounds of the above formulae.
"Average functionality" means that the product has a constant functionality of 2.5-6 with respect to the isocyanate groups, preferably 3-6. For example, "trifunctional" means that one molecule has a statistical average of three free isocyanate groups. The average functionality is the average molecular weight M
It can be determined experimentally by determining n. First, determine the number of isocyanate groups, and from this number, 1
Calculate the molecular weight per isocyanate group. Average functionality is the quotient of the average molecular weight divided by the molecular weight per isocyanate group.

As an example of the polyester to be reacted with the above polyisocyanate, a compound having one hydroxyl group is used as a starting constituent component, and propiolactone, valerolactone, caprolactone or a substituted derivative thereof obtained by polymerizing a lactone is used. Can be given. The starting components are n-butanol; propargyl alcohol, olein alcohol, lineelloyl.
yl) relatively long chain saturated and unsaturated alcohols such as alcohols, oxoalcohols, cyclohexanols, phenylethanols or neopentylalcohols; or 4-30 carbon atoms, such as fluorinated versions of higher alcohols, preferably 4 to 14 monohydric alcohols are used. The above alcohols, substituted phenols and unsubstituted phenols are polyoxyalkylene ethers, monoalkyl ethers, aryl ethers, by known methods of alkoxylation with ethylene oxide and / or propylene oxide.
It may be replaced by an aralkyl ether or a cycloalkyl ether, and these monohydroxy polyethers can be used by the above-mentioned method as a starting constituent for lactone polymerization. Mixtures of the above compounds can be used in any case.

This lactone polymerization is carried out by a known method.
At a temperature of about 100 to 180 [deg.] C., for example, p-toluenesulfonic acid or dibutyltin dilaurate is used as an initiator and proceeds as follows.

[0101]

Embedded image

These polyesters have a molecular weight of about 350.
It is suitable that it is ˜8000, preferably 500 to 5000, and more preferably the compound obtained by the lactone polymerization of the above formula. The alcohol used as the starting constituent is preferably a saturated monohydric alcohol having 4 to 18 carbon atoms.

As another example of polyester, a hydroxyl group is 1
Examples thereof include those obtained by condensation of glycol and dibasic acid in the presence of a compound having C. The formation of the dihydroxy polyester can be suppressed by using an appropriate stoichiometric amount of the compound having one above-mentioned hydroxyl group. The reaction further proceeds by a mechanism as shown in the following example.

[0104]

[Chemical 21]

These polyesters have an average molecular weight of 4
Suitably it is between 00 and 2500, preferably between 800 and 1500.

Further examples of the polyester include those obtained by condensing an oxycarboxylic acid in the presence of a compound having one above-mentioned hydroxyl group for controlling the molecular weight. The reaction proceeds, for example, by the mechanism shown by the following formula.

[0107]

Embedded image

In this case, the average molecular weight of the polyester is 6
The range of 00 to 3000 is suitable, and the range of 800 to 1500 is preferable.

The pigment dispersant (F) can be produced by reacting the above-mentioned polyisocyanate, a compound having one hydroxyl group, and a polyester compound polymerized with a lactone in the presence of a catalyst such as dibutyltin dilaurate, which is usually used, at a reaction temperature of 20 to N of the polyisocyanate at 70 ° C
It is reacted with 15 to 50% of CO groups, preferably 20 to 35%, and then the compound having a substituent having an active hydrogen and a tertiary amino group is further added to 15 to 45%, preferably 20 to 45% of NCO groups of polyisocyanate. React with ~ 35%. This reaction can also be carried out in the presence of a suitable solvent that does not interfere with the reaction, for example, xylene, an ether containing dioxane, dimethylformamide and the like. The obtained dispersant has a number average molecular weight of 1300 to 8400.
It is obtained in the range of 0.

Examples of the compound having a substituent having active hydrogen and a tertiary amino group in the molecule include those having 2 to 12 carbon atoms.
Individual diols, triols, diamines, dialkanolamines and monoalkanolamines, also N, N-diethyl-1,4-butanediamine, 1- (2-aminoethyl) -piperazine, 2- (1-pyrrolidyl)- Ethylamine, 4-amino-2-methoxy-pyrimidine, 2-
Dimethylaminoethanol, further N, N-dimethyl-1,3-propanediamine, 4- (2-aminoethyl) -pyridine, 2-amino-6-methoxybenzothiazole, 4- (aminomethyl) -pyridine, 3 -Amino-1,2,4-triazole and 1- (3-aminopropyl) -imidazole are particularly preferred.

Next, Production Examples 1 to 3 of the polyurethane resin used as the binder in the present invention will be shown.

Production Example 1 Synthesis was carried out based on the polyurethane resin production example described in JP-B-58-6754.

In a flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, 120 parts of a propylene oxide adduct of bisphenol A having an average molecular weight of 1900 and an average molecular weight of 10 were added.
100 parts of polyester diol produced from 00 butylene glycol and adipic acid and 85 parts of isophorone diisocyanate were charged, and 120 ° C. under a nitrogen gas flow,
The reaction was carried out for 5 hours to obtain a polyurethane prepolymer having a free isocyanate value of 3.45%. Then, a mixture of 400 parts of ethyl acetate, 30 parts of isophoronediamine, and 116 parts of isopropyl alcohol was added thereto to carry out chain extension.
The polyurethane resin solution 1 thus obtained had a resin solid content of 35% and a viscosity of 1000 cps (25 ° C.).

Production Example 2 Synthesis was carried out based on the polyurethane resin production example described in JP-B-5-80512.

By the same operation as in Production Example 1, an average molecular weight of 20 was obtained.
200 parts of poly (1,2-propylene adipate) glycol of 00 and 45 parts of isophorone diisocyanate were charged to obtain a polyurethane prepolymer having a free isocyanate value of 3.28%. Then methyl ethyl ketone 405
Chain, 14 parts of isophoronediamine, 2.5 parts of diethylenetriamine and 202 parts of isopropyl alcohol were added for chain extension. The polyurethane resin solution 2 thus obtained had a resin solid content of 30% and a viscosity of 890 cps.
(25 ° C).

Production Example 3 Synthesis was carried out based on the polyurethane resin production example described in JP-A-62-288622.

220 parts of toluene diisocyanate and 450 parts of ethyl acetate are charged in the same apparatus as in Production Example 1, and the temperature is raised to 70 ° C. under nitrogen gas flow. 80 parts of polypropylene glycol and 16 parts of polypropylene triol
0 part was charged and reacted at 80 ° C. for 6 hours to obtain a polyurethane prepolymer having a free isocyanate value of 5.20%. Then, a polyurethane resin solution 3 obtained by adding 25 ppm of dibutyl tin malate and 25 ppm of copper oleate had a resin solid content of 40% and a viscosity of 100 cps (25
° C).

Next, Reference Examples 1 to 4 relating to the production of the raw material polymer for the polyester polymer dispersant having an amino group, which is used as the pigment dispersant in the present invention, will be shown.

Reference Example 1 Production of Polyester Having Carboxyl Group at One Terminal In a flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen gas inlet tube, 150.0 parts of xylene, 0.3 part of tetrabutoxy titanate, octylic acid. 44.0 parts and ε-caprolactone 556.0 parts were charged and the temperature was raised to 140 to 160 ° C. Then, the reaction is carried out at 160 ° C, and the solid content is 79%.
The reaction was terminated when the reaction became. After cooling to room temperature,
249.7 parts of xylene was added to obtain a polyester A having a carboxyl group at one end. The resulting polyester A had a number average molecular weight of 2,100, a solid content of 60.0%, and an acid value of 29.0 mgKOH / g.

Reference Example 2 Production of Polyepoxy Compound 300.0 parts of xylene was charged into a flask equipped with a stirrer, a reflux tube, a thermometer and a nitrogen gas inlet tube, and 130 to 135 were charged.
The temperature was raised to ° C. Glycidyl methacrylate 390.
0 parts, 210.0 parts butyl methacrylate and tertiary butyl peroxy-2-ethyl hexaate 3
After dropwise adding 6.0 parts of the mixed solution over 2 hours, the temperature was 135 ° C.
For 1 hour. Then 3.0 parts of tertiary butyl peroxy-2-ethylhexaate was added to 10.
A mixed solution dissolved in 0 part was added, and a polymerization reaction was further performed at 120 ° C. for 5 hours. After cooling to room temperature, xylene 5
1.0 part was added to obtain a polyepoxy compound. The obtained polyepoxy compound had a solid content of 62.0%, a number average molecular weight of 4100, and an epoxy value of 250.0 mgKOH /
g.

Reference Example 3 Production of Acrylic Polymer Synthesis was carried out based on the production example described in JP-A-4-227774.

36.8 parts of xylene was placed in a flask equipped with a stirrer, a reflux tube, a thermometer, a nitrogen gas introducing tube, and a dropping tank.
1.0 part of decanol and 0.1 part of sodium methylate were charged, and the temperature was raised to 130 to 140 ° C. under nitrogen flow. In a reflux state, 35.7 parts of ε-caprolactone was dropped from the dropping tank over 1 hour. The mixture is further stirred under reflux for 4 hours, and the solid content after heating and drying at 140 ° C for 30 minutes is 45
%, Butyl glycidyl ether 1
5.5 parts was dropped from the dropping tank over 1 hour. 4.5 parts of tolylene diisocyanate was added and stirred at 30 ° C for 2 hours, and it was confirmed that 50% of the isocyanate groups had reacted.
-1.5 parts of hydroxyethylmethacrylate were added. The temperature was raised to 60 ° C., the reaction was carried out for 3 hours, and the reaction was terminated when 100% of the isocyanate groups had reacted.
The resultant is designated as Macromer A.

Reference Example 4 Production of Polyester Synthesis was carried out based on the production example described in JP-B-2-19844.

A flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 2.1 parts of commercially available heptadecafluorodecanol having an average molecular weight of 445, 5.9 parts of 2-ethylhexanol and 92 parts of valerolactone. C., and mixed under nitrogen gas flow, 0.004 parts of dibutyltin dilaurate was added, and the mixture was heated to 180.degree. C. for 1 hour. The reaction was terminated when the solid content reached 98%. A colorless to slightly yellowish solid product was obtained at room temperature, and a polyester B having a melting point of 60 to 70 ° C. was obtained.

Next, Production Examples 4 to 7 of the pigment dispersant of the present invention and Comparative Example 1 (production of polyester pigment dispersant) will be shown.

Production Example 4 35.7 parts of xylene and 45.1 parts of the polyester A obtained in Reference Example 1 and a reference example 2 were placed in a flask equipped with a stirrer, a reflux tube, a thermometer and a nitrogen gas introducing tube. Then, 15.7 parts of the polyepoxy compound was charged and the temperature was raised to 120 ° C. to carry out the reaction. When the acid value became 1 mgKOH / g or less, the mixture was cooled to 60 ° C., and di-n-butylamine 3.5.
Parts were added and the temperature was raised to 100 ° C. The reaction was carried out at 100 ° C. for 4 to 5 hours to obtain Pigment Dispersant 1. The obtained pigment dispersant 1 has a solid content of 40.1% and a number average molecular weight of 10500.
The amine value was 38.5 mgKOH / g.

Production Example 5 39.0 parts of xylene was charged in the same apparatus as in Reference Example 1 and the temperature was raised to 85 ° C., and the macromer A obtained in Reference Example 3 and dimethylaminopropylacrylamide 1.0 were added thereto.
Part and a 20% solution of 0.8 parts of 2,2′-azobis (2,4dimethylvaleronitrile) were added dropwise from separate dropping tanks over 2 hours. After the dropping, the mixture was reacted at 85 ° C. for 2 hours to obtain pigment dispersant 2. The obtained pigment dispersant 2 has a solid content of 4
0%, number average molecular weight 3100, amine value 45 mgK
OH / g.

Production Example 6 In a device similar to that of Reference Example 1, "Desmodur HL" (6% in butyl acetate) was prepared as an aromatic-aliphatic polyisocyanate.
0%) 10.7 parts, xylene 15.7 parts, and the polyester B obtained in Reference Example 4 were mixed, dibutyltin laurate 0.001 part was added, and the reaction was carried out at 50 ° C. After the reaction was completed, the reaction mixture was diluted with 20 parts of ethyl acetate cellosolve, and 0.3 part of 1,4-butanediamine dissolved in 20 parts of xylene was added. Immediately after 55% of the NCO groups had reacted, 2.1 parts of 2-amino-6-methoxybenzothiazole dissolved in 15 parts of N-methylpyrrolidone were added to stop the slightly exothermic reaction. The reaction mixture was
Heat to 0 ° C. and stir for 1 hour. The pigment dispersant 3 thus obtained was slightly viscous and yellow, and had a number average molecular weight of 7,400 as a transparent solution.

Comparative Example 1 330 parts of 12-hydroxystearic acid and 34 parts of xylene were mixed in a flask equipped with a stirrer, a reflux tube, a thermometer and a nitrogen gas introducing tube, and the temperature was raised to 190 to 200 ° C. and the reaction was carried out for 22 hours. Excess water is removed, and the obtained liquid is designated as polyester C. Next, in a similar device, a molecular weight of about 5000
75 parts of polyethyleneimine (33% aqueous solution) and 22 parts of toluene are stirred and boiled under nitrogen flow to remove water, then 50 parts of the polyester C and 22 parts of toluene are added, and the mixture is heated to 150 ° C. and stirred for 3 hours. . The obtained pigment dispersant 4 was brown and had an acid value of 17.0 mgKOH / g.

The present invention will be specifically described below with reference to examples.

[0131]

EXAMPLES Using polyurethane resins and various pigment dispersants, the raw materials were uniformly mixed according to the ink mill base formulation shown in Table 1, and dispersed with a paint shaker (manufactured by Red Devil Co., USA) to obtain ink mill base examples 1-9. . Similarly, Comparative Examples were manufactured to obtain Comparative Examples 2 to 4. The viscosity characteristics and coating film performance of these mill bases were evaluated, and the results are shown in Table 1.

The ink mill base viscosity characteristics were measured by using a B type viscometer (manufactured by Tokimec Co.) for the ink mill base 2
The viscosity at 0 ° C. and 60 rpm was measured. In addition, the specular glossiness is based on the ink mill base bar coater No. 40 was used to prepare a coating film, and the specular glossiness of the obtained coating film was measured using a gloss meter (manufactured by Minolta). The glossiness was measured at 60 °.

[0133]

[Table 1]

From Table 1, it was found that the ink composition of the present invention gave a coating film having high specular gloss.

[0135]

The ink composition of the present invention has good coating performance and gives a coating having excellent specular gloss.

Claims (8)

[Claims] 1. An ink composition comprising a polyurethane polymer as a binder, a polyester polymer dispersant having an amino group, a pigment, and a solvent. 2. The polyurethane resin and the polyester polymer dispersant having an amino group are 0.1 to 200% by weight and 0.1 to 200% by weight, respectively, in terms of solid content based on the pigment.
The ink composition according to claim 1, which contains 3. The polyurethane resin is a high molecular weight diol,
A diol component of the polyurethane resin, which is produced from diisocyanate and a chain extender, is 20 to 80% by weight of a polyether type diol having a molecular weight of 700 to 2500 and a molecular weight of 7
The ink composition according to claim 1, which is a mixture of 20 to 80% by weight of a polyester type diol of 00 to 2500. 4. A polyurethane resin is produced from a high molecular weight polyol, a diisocyanate and a chain extender, and the polyol component of the polyurethane resin has a molecular weight of 500 to 30.
The ink composition according to claim 1, having at least 50% by weight of poly (1,2-propylene adipate) glycol of 00 and having an amine value of 0.1 to 20 per gram of the solid content of the polyurethane resin. 5. A polyurethane resin is produced from a high molecular weight polyol, a polyisocyanate and a tin-based metal salt compound, and a metal salt compound other than tin, and the polyisocyanate component of the polyurethane resin has an average of two or more isocyanate groups in one molecule. The ink composition according to claim 1, which is a polyisocyanate. 6. A polyester-based polymer dispersant having an amino group is a polyepoxy compound and has a number average molecular weight of 500 to
The amine value obtained by reacting a compound having a carboxyl group at one end with 50,000 and a compound having one secondary amino group is 5 to 200 mgKOH / g, and the number average molecular weight is in the range of 1,000 to 100,000. Ink composition described in 7. A polyester polymer dispersant having an amino group having an amine value of 10 to 200 mgKOH obtained by reacting an acrylic polymer having a tertiary amino group and / or a nitrogen-containing heterocycle having basicity with a polyester. /
The ink composition according to claim 1, wherein g and the number average molecular weight are in the range of 1,000 to 100,000. 8. A polyester-based polymer dispersant having an amino group reacts a part of polyisocyanate having an isocyanate group of 2.5 to 6.0 on average with a polyester having one hydroxyl group, and then polyisocyanate. The ink composition according to claim 1, which is a compound obtained by reacting the unreacted isocyanate group with a compound having a substituent having active hydrogen in the molecule and a tertiary amino group.