JP2009241063A - Dispersant having active energy ray-curable unsaturated group, pigment dispersion composition, active energy ray-curable ink and active energy ray-curable coating material - Google Patents

Abstract

Disclosed is a dispersant having an active energy ray-curable unsaturated group that provides a cured film having high dispersion performance and excellent chemical resistance and gloss.
[Solution]
(A) one or more polar groups or polar molecular chains selected from acidic functional groups, neutralized bases of acidic functional groups, basic functional groups, neutralized bases of basic functional groups, and nonionic polar molecular chains; B) Molecular chain having an alkyl group or alkenyl group derived from oil or fat, molecular chain having an alkyl group or alkenyl group having 6 or more carbon atoms, molecular chain having a molecular unit having 4 or more carbon atoms as a repeating unit, and rosin skeleton or water An active energy ray-curable unsaturated group comprising a resin containing one or more low-polarity molecular chains selected from molecular chains containing an rosin skeleton and (C) an active energy ray-curable unsaturated group It is a dispersing agent which has.
[Selection figure] None

Description

  The present invention relates to a dispersant having an active energy ray-curable unsaturated group, a pigment dispersion composition, an active energy ray-curable ink, and an active energy ray-curable coating material.

  Active energy ray curable inks and paints do not require a long heat oven line and are not required to cure by instantly irradiating high energy active energy rays, compared to thermosetting inks and paints. Since it is a solvent, it does not release a large amount of organic solvent that can cause air pollution. Conventional thermosetting inks and paints require a large organic solvent vapor recovery device, and the organic solvent vapor is usually incinerated by a gas burner in a combustion device called an afterburner. It will be released into the atmosphere. Active energy ray-curable inks and paints are excellent paints that do not cause deformation even in printed materials such as plastics having low heat resistance and materials to be coated because they are not heated. In this way, active energy ray-curable inks and paints are becoming popular because they are excellent in terms of energy saving, resource saving and low environmental load.

  In addition, active energy beam irradiation devices such as electron beam (EB), which is a high energy beam, have appeared as miniaturized products and low-priced products. There is a limit to the cost reduction. On the other hand, since UV (ultraviolet) irradiation devices are easy to miniaturize, UV curable inks and paints that can be UV-cured have become widespread.

  Active energy ray curable inks and paints include vinyl or (meth) acryloyl group-containing monomers or oligomers, photoinitiators and other ink or paint raw material development and application research, lamps, lamp houses, power supplies, etc. Due to the improvement of the whole related field, such as the increase in irradiation intensity through research and development of irradiation equipment, it has now achieved the same performance as conventional thermosetting paints and inks. Replacement with curable inks and paints is progressing.

  Active energy ray-curable inks and paints are specially applied to the fields that require short-time curing and the application or printing of plastic products that are susceptible to thermal deformation because of their extremely short curing time and the ability to cure at low temperatures. Has been. In particular, UV curable ink-jet inks that can be printed on demand are applicable to electronic materials such as printing on plastic films, mobile phones, and liquid crystal display color filters because they do not choose to be coated or printed.

  Active energy ray-curable inks and paints are prepared with pigments that are colorants and vehicle (generic name for resins, solvents, etc.) added to inks with a viscosity suitable for printing and paints with a viscosity suitable for coating. The In particular, UV curable inkjet inks and spray coating inks are required to have a low viscosity. Therefore, it is required that the ink in which the pigment is dispersed has no viscosity change, the pigment is well dispersed with respect to the low-viscosity monomer, and has a low viscosity. In addition, it is also required that the cured film has the same homogeneity as the thermosetting ink or paint, in particular, excellent chemical resistance and gloss.

  Regarding the former low viscosity, it is empirically known that the pigment dispersion composition in which the pigment is uniformly dispersed has a low viscosity. Therefore, in the pigment dispersion composition used for the production of active energy ray-curable ink or paint, when the ink or paint is prepared, the pigment contains active energy such as a low viscosity vinyl group or (meth) acryloyl group. It is required to disperse well with respect to a monofunctional or polyfunctional monomer having linear curability.

  Regarding the homogeneity of the latter cured film, in the case of heat curing, the film is homogenized by the heat of molecular motion and the crosslinking reaction occurs relatively slowly, so there is little bias in the crosslinked structure, and the coating film shrinks due to the crosslinking reaction. Since internal distortion is easily relieved, there is little structural bias or strength bias. However, in the case of active energy ray curing, since it cures instantaneously, the cross-linked structure is biased, and distortion inside the coating such as shrinkage due to the cross-linking reaction is difficult to be alleviated, resulting in structural bias and strength bias. It has been reported.

  This distortion and structural deviation cause a decrease in adhesion to the object to be coated or the object to be printed, and a decrease in coating film strength or chemical resistance. For this reason, various methods have been taken such as adding oligomers having a high molecular weight and polymers having a flexible structure to alleviate structural bias and distortion. However, the addition of such a polymer compound increases the viscosity of the composition.

  For example, in Patent Document 1, an acidic surface is treated with a synergist, and high dispersibility is obtained with a basic polymer dispersant. Although high dispersibility of the pigment can be obtained by such a method, the basic polymer dispersant itself used here does not contribute to UV curing at all, and thus the uniformity of the coating film cannot be improved. Further, depending on the dispersing agent bleed from the cured coating film, it becomes a factor to deteriorate the coating film performance.

JP 2003-253155 A (Claims)

  Accordingly, an object of the present invention is to provide a dispersant having an active energy ray-curable unsaturated group that provides a cured film having high pigment dispersion performance and excellent chemical resistance and gloss, and a pigment dispersion composition using the same It is to provide an active energy ray curable ink and an active energy ray curable coating.

  As a result of intensive studies to solve the above-described problems in the prior art, the present inventors have obtained (A) an acidic functional group, a neutralized base of an acidic functional group, a basic functional group, and a neutralized basic functional group. One or more polar groups or polar molecular chains selected from bases and nonionic polar molecular chains; and (B) a molecular chain having an alkyl group or alkenyl group derived from fats and oils; an alkyl group or alkenyl group having 6 or more carbon atoms (C) active energy ray curing, one or more low-polarity molecular chains selected from a molecular chain, a molecular chain having a molecular unit having 4 or more carbon atoms as a repeating unit, and a molecular chain including a rosin skeleton or a hydrogenated rosin skeleton A dispersant having an active energy ray-curable unsaturated group made of a resin containing a polymerizable unsaturated group achieves both high dispersibility with coloring materials such as pigments and dyes and excellent chemical resistance of the cured film. Fool who can Or, also found that it is possible to improve the gloss of the cured film, thereby completing the present invention.

That is, the present invention
(1) (A) One or more polar groups or polar molecular chains selected from acidic functional groups, neutralized bases of acidic functional groups, basic functional groups, neutralized bases of basic functional groups, and nonionic polar molecular chains And (B) a molecular chain having an alkyl or alkenyl group derived from fats and oils, a molecular chain having an alkyl group or alkenyl group having 6 or more carbon atoms, a molecular chain having a molecular unit having 4 or more carbon atoms as a repeating unit, and rosin One or more low-polar molecular chains selected from molecular chains containing a skeleton or a hydrogenated rosin skeleton;
(C) A dispersant having an active energy ray-curable unsaturated group, comprising a resin containing an active energy ray-curable unsaturated group,
(2) The dispersant having an active energy ray-curable unsaturated group according to (1), wherein the resin is a polyurethane resin,
(3) All or part of the polar group or polar molecular chain (A), the low polar molecular chain (B) and the active energy ray-curable unsaturated group (C) are included in the side chain of the resin. A dispersant having an active energy ray-curable unsaturated group according to (1) or (2),
(4) Any one of the above (1) to (3), wherein all or part of the polar group or polar molecular chain (A) is a basic functional group or a neutralized base of a basic functional group. A dispersant having an active energy ray-curable unsaturated group of
(5) The nonionic polar molecular chain is a polyoxyethylene ether molecular chain having three or more oxyethylene ether repeating units and constitutes the main chain of the resin or is bonded to the main chain of the resin or the terminal thereof. The dispersing agent having an active energy ray-curable unsaturated group according to any one of the above (1) to (4), which is a side chain, (6) of the active energy ray-curable unsaturated group (C) All or a part is an acryloyl group or a methacryloyl group, and the concentration of the acryloyl group or methacryloyl group is 0.2 to 3.0 mol / kg, according to any one of (1) to (5) above Dispersants having active energy ray-curable unsaturated groups as described,
(7) The resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom,
At least a part of the bifunctional compound having a hydroxyl group or an active hydrogen atom is a side chain of a polar group or polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C). Is comprised of
A polar group or polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C) is used as a side chain with respect to the total number of moles of the bifunctional compound having a hydroxyl group or an active hydrogen atom. The active energy ray-curable non-setting property according to any one of the above (1) to (6), wherein the ratio of the total number of moles of the bifunctional compound having a hydroxyl group or an active hydrogen atom is 20 to 100 mol%. A dispersant having a saturated group,
(8) The resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom,
At least a part of the bifunctional compound having a hydroxyl group or an active hydrogen atom is
The following general formula (I):

(In the general formula (I), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ and R 2 ^At least one of ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ¹ and R ² may be the same or different, and R ³ is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these. )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (IV):

(In the general formula (IV), ^{R 4} and ^{R _5,} -C _p H _{2p -OH,} a _{-C q H 2q -COO-C r} H 2r -OH or an active hydrogen atom, and, ^{R 4} and R at least one of the ^five _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer from 1 to 4, R ⁴ and R ⁵ may be the same or different, and R ⁶ is
The following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (6), s is an integer of 5-30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a group containing a low-polar molecular chain represented by
Or a group containing a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units,
A group containing a polyether having two or more molecular units having 4 or more carbon atoms as repeating units,
It is a group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as repeating units, or a group containing a polycaprolactone having two or more molecular units having 4 or more carbon atoms as repeating units. )
A dispersant having an active energy ray-curable unsaturated group according to any one of the above (1) to (7), which is a compound having a hydroxyl group or an active hydrogen atom represented by:
(9) The resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom,
At least a part of the bifunctional compound having a hydroxyl group or an active hydrogen atom is
The following general formula (IX):

(In General Formula (IX), R ⁷ and R ⁸ are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ⁷ and R 8 ^At least one of ⁸ is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ⁷ and R ⁸ may be the same or different, and R ⁹ is represented by the following general formula (X):

(In general formula (X), d is an integer of 1-4, and e is an integer of 5-30.)
A nonionic polar molecular chain-containing group represented by )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (XI):

(In General Formula (XI), R ¹⁰ and R ¹¹ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ¹⁰ and R 11 at least one of the ¹¹ _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, and R ⁴ and R ⁵ may be the same or different, and R ¹² represents the following general formula (XII):

(In general formula (XII), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
It is a low polar molecular chain containing group represented by these. )
A dispersant having an active energy ray-curable unsaturated group according to any one of the above (1) to (8), which is a compound having a hydroxyl group or an active hydrogen atom represented by:
(10) A pigment dispersion composition comprising a pigment and a dispersant having an active energy ray-curable unsaturated group described in any one of (1) to (9) above, (11) An active energy ray-curable ink comprising a pigment and a dispersant having an active energy ray-curable unsaturated group described in any one of (1) to (9) above, and (12) An active energy ray-curable coating composition comprising a pigment and a dispersant having an active energy ray-curable unsaturated group described in any one of (1) to (9) above is provided. is there.

  According to the present invention, a dispersant having an active energy ray-curable unsaturated group that gives a cured film having high pigment dispersion performance and excellent chemical resistance and gloss, a pigment dispersion composition using the same, Active energy ray-curable inks and paints can be provided.

  According to the present invention, in particular, a carbon black pigment whose surface is treated with a synergist such as phthalocyanine sulfonic acid, a carbon black pigment in which an acidic group is introduced on the surface by diazo coupling, a phenolic hydroxyl group on the surface by oxidation, A dispersant capable of suitably dispersing a carbon black pigment having an acidic group such as a carboxyl group dispersed in a solvent, a resin monomer, or the like can be provided.

The dispersant having an active energy ray-curable unsaturated group of the present invention (hereinafter also referred to as the dispersant of the present invention) is:
(A) one or more polar groups or polar molecular chains selected from acidic functional groups, neutralized bases of acidic functional groups, basic functional groups, neutralized bases of basic functional groups, and nonionic polar molecular chains;
(B) a molecular chain having an alkyl group or an alkenyl group derived from fats and oils, a molecular chain having an alkyl group or alkenyl group having 6 or more carbon atoms, a molecular chain having a molecular unit having 4 or more carbon atoms as a repeating unit, and a rosin skeleton or water One or more low-polar molecular chains selected from molecular chains containing an rosin skeleton;
(C) It consists of resin containing an active energy ray hardening unsaturated group, It is characterized by the above-mentioned.

  That is, the dispersant of the present invention is a resin having, as essential components, a polar group or polar molecular chain (A), a low polar molecular chain (B), and an active energy ray-curable unsaturated group (C) in one molecule. It is characterized by comprising.

  The resin constituting the dispersant of the present invention includes, as a polar group or polar molecular chain (A), an acidic functional group, a neutralized base of an acidic functional group, a basic functional group, a neutralized base of a basic functional group, a nonionic series One or more types selected from polar molecular chains are included, and in this specification, the polar group or polar molecular chain (A) includes reaction residues of the above groups or molecular chains.

Although the acidic functional group is not particularly limited, for example, a carboxyl group (—COOH), a hydroxyl group (—OH), a sulfonic acid group (—SO ₃ H), a phosphate ester group (phosphate monoester, phosphate diester, Including a phosphate triester group).

The neutralized base of the acidic functional group is not particularly limited. For example, the acidic functional group is a group neutralized with a basic compound such as sodium hydroxide or ammonium hydroxide. For example, when the acidic functional group is a carboxyl group, -COONa, -COONH _{4 and the} like can be mentioned.

  Although it does not restrict | limit especially as said basic functional group, For example, basic nitrogen-containing functional groups, such as an aliphatic amine group, an alicyclic amine group, a hetero alicyclic amine group, an aromatic amine group, etc. are mentioned.

  The neutralized base of the basic functional group is not particularly limited, and examples thereof include a group in which the basic functional group is neutralized with an acidic compound such as hydrochloric acid or sulfuric acid.

  Examples of the nonionic polar molecular chain include nonionic polar molecular chains such as a polyoxyalkylene ether molecular chain or a polyoxypropylene ether molecular chain, or a molecular chain of a copolymer thereof. The nonionic polar molecular chain is a polyoxyethylene ether molecular chain having three or more oxyethylene ether repeating units and constitutes the main chain of the resin or is bonded to the main chain of the resin or the terminal thereof. A side chain is preferred. The number of repeating oxyethylene ether units in the polyoxyethylene ether molecular chain is more preferably 4 or more, and even more preferably 5 or more.

  The nonionic polar molecular chain is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
The nonionic polar molecular chain represented by is preferable in that the dispersibility of the pigment is increased.

  d is more preferably an integer of 1 to 3. Moreover, e is more preferably an integer of 8 to 30.

  It is more preferable that f is an integer of 1 to 3. Moreover, it is more preferable that g is an integer of 8-30. h is more preferably an integer of 1 to 10, and further preferably an integer of 1 to 6.

  In the dispersant of the present invention, the acidic functional group, the neutralized base of the acidic functional group, the basic functional group, and the neutralized base of the basic functional group may be bonded to the main chain of the resin, and the side chain. May be bonded to. In the dispersant of the present invention, the nonionic polar molecular chain may be bonded to the main chain of the resin or the terminal thereof, or may be bonded to the side chain of the resin, or the above You may comprise the principal chain of resin.

  The resin constituting the dispersant of the present invention includes, as the low polar molecular chain (B), a molecular chain having an oil or fat-derived alkyl group or alkenyl group, a molecular chain having an alkyl group or alkenyl group having 6 or more carbon atoms, or a carbon number. It contains at least one selected from a molecular chain having 4 or more molecular units as a repeating unit, or a molecular chain containing a rosin skeleton or a hydrogenated rosin skeleton. In the present specification, the low polar molecular chain (B) includes reaction residues of the respective low polar molecular chains.

  The alkyl group or alkenyl group having 6 or more carbon atoms may be linear, branched or cyclic. Further, the molecular chain having the above-mentioned molecular unit having 4 or more carbon atoms as a repeating unit may have any of linear, branched or cyclic molecular units.

  In addition, when the dispersing agent of the present invention includes a molecular unit having 4 or more carbon atoms, for example, a molecular unit having 6 carbon atoms, the molecular unit includes, in addition to an alkylene group having 6 carbon atoms, a carbon number. Examples include those in which a methyl group is bonded to an alkylene group of 5, and those in which a butoxy group is bonded to an ethylene group having 2 carbon atoms. That is, it means that the number of carbon atoms in one molecular unit is 6.

  Moreover, as a low polarity molecular chain (B), following general formula (V)

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a low-polar molecular chain represented by the following general formula (VI):

(In general formula (6), s is an integer of 5-30.)
Or a low-polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a low-polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a group containing a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units, or 2 having 2 or more molecular units having 4 or more carbon units as repeating units. It is a group containing a polyether having the above, a group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as repeating units, or two or more molecular units having 4 or more carbon atoms as repeating units A group containing polycaprolactone is preferable in that the dispersibility of the pigment is increased.

  i is more preferably an integer of 6 to 30. Further, j is more preferably an integer of 0-4.

  More preferably, s is an integer of 8-30. T is more preferably an integer of 8 to 30. u is more preferably an integer of 8 to 30.

  In the dispersant of the present invention, the low polarity molecular chain (B) may be bonded to the main chain of the resin or the terminal thereof, or may be bonded to the side chain of the resin, or the above You may comprise the principal chain of resin.

  The resin constituting the dispersant of the present invention has an active energy ray-curable unsaturated group (C).

  In this specification, the active energy ray-curable unsaturated group (C) is a group that cures a resin composition containing a pigment dispersant by irradiating active energy rays such as UV light. Examples of the energy ray-curable unsaturated group (C) include unsaturated group-containing groups such as vinyl groups, acryloyl groups, and methacryloyl groups. In the present specification, the active energy ray-curable unsaturated group (C) includes a reaction residue of an active energy ray-curable unsaturated group.

  In the dispersant of the present invention, the active energy ray-curable unsaturated group may be bonded to the main chain of the resin skeleton constituting the dispersant or the terminal thereof, or to the side chain of the resin skeleton. Alternatively, it may constitute the main chain of the resin skeleton.

  In the dispersant of the present invention, when all or part of the active energy ray-curable unsaturated group (C) is an acryloyl group or a methacryloyl group, the concentration of the acryloyl group or the methacryloyl group is 0.2 to 3. It is preferably 0 mol / kg, more preferably 0.2 to 2.5 mol / kg, further preferably 0.3 to 2.5 mol / kg, and 0.3 to 2.0 mol / kg. It is particularly preferred that

  If the concentration of the acryloyl group or methacryloyl group is less than 0.2 mol / kg, sufficient chemical resistance (solvent resistance) cannot be obtained. If the concentration exceeds 3.0 mol / kg, the unsaturated group concentration is too high. If it becomes too high, the cross-linking of the cured coating film will increase, and the workability and adhesion will decrease.

  As the dispersant of the present invention, all or part of the polar group or polar molecular chain (A), the low polar molecular chain (B) and the active energy ray-curable unsaturated group (C) are present in the side chain of the resin. What is contained is preferable.

  Examples of the resin constituting the dispersant of the present invention include a polyurethane resin, an acrylic copolymer resin, a polyester resin, a polyether resin, and an epoxy resin, and among these resins, a polyurethane resin is more preferable.

  In the dispersant of the present invention, the main chain includes the polar group or polar molecular chain (A), the low polar molecular chain (B) and the active energy ray-curable unsaturated group (C) with the resin skeleton as the main chain. As a side chain, in a side chain bonded to the main chain, or as a group or molecular chain constituting the main chain.

  As the dispersant of the present invention, the resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom, and at least of the bifunctional compound having a hydroxyl group or an active hydrogen atom. A part contains a polar group or polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C) in its side chain, and the hydroxyl group or active hydrogen A hydroxyl group comprising a polar group or a polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C) in the side chain with respect to the total number of moles of the bifunctional compound having atoms; The ratio of the total number of moles of the bifunctional compound Y having an active hydrogen atom is preferably 20 to 100 mol% of the entire bifunctional compound in order to increase the dispersibility of the pigment. From the viewpoint of enhancing the dispersibility of the pigment, the total number of moles of the bifunctional compound Y is more preferably 25 to 80 mol%.

  A bifunctional compound having a hydroxyl group or an active hydrogen atom comprising a polar group or a polar molecular chain (A) in the side chain and a low polar molecular chain (with respect to the total number of moles of the bifunctional compound having a hydroxyl group or an active hydrogen atom) B) or the ratio of the total number of moles with the bifunctional compound having a hydroxyl group or active hydrogen atom comprising the active energy ray-curable unsaturated group (C) in the side chain is 20 to 100 mol% of the entire bifunctional compound And a dispersing agent in which a polar group or polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C) extends as a side chain in a comb tooth shape is obtained, Since the affinity for the organic solvent can be improved by the polar group or the polar molecular chain (A) and the affinity for the pigment can be improved by the low polar molecular chain (B), the pigment can be suitably dispersed. .

  A bifunctional compound having a hydroxyl group or an active hydrogen atom containing a polar group or polar molecular chain (A) in the side chain, and a hydroxyl group or an active hydrogen atom containing a low polarity molecular chain (B) in the side chain The ratio of the total number of moles with the functional compound is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, more preferably 30 to 80 mol% of the entire bifunctional compound having a hydroxyl group or an active hydrogen atom. More preferably, it is mol%.

  Moreover, the hydroxyl group which contains the said polar group or polar molecular chain (A) in the side chain with respect to the mole number of the bifunctional compound which has the hydroxyl group or active hydrogen atom which comprises the said low polarity molecular chain (B) in a side chain Or the ratio of the number of moles of a bifunctional compound having an active hydrogen atom (the number of moles of a bifunctional compound having a hydroxyl group or an active hydrogen atom comprising a polar group or polar molecular chain (A) in the side chain / low polarity molecular chain ( The number of moles of the bifunctional compound having a hydroxyl group or an active hydrogen atom comprising B) in the side chain is preferably 2/8 to 8/2, more preferably 3/7 to 7/3. Preferably, it is 4/6 to 6/4.

  The total amount of the bifunctional compound having a hydroxyl group or active hydrogen atom comprising the active energy ray-curable unsaturated group (C) in the side chain is such that the active energy ray-curable unsaturated group concentration of the entire resin is 0. The amount is preferably 3 to 3.0 equivalents / kg, more preferably 0.4 to 2.5 equivalents / kg, and 0.5 to 2.0 equivalents / kg. More preferably, the amount.

  As the dispersant of the present invention, the resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom, and at least of the bifunctional compound having a hydroxyl group or an active hydrogen atom. Some of the following general formula (I):

(In the general formula (I), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ And at least one of R ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, and b is an integer of 1 to 3. , C is an integer of 1 to 4, R ¹ and R ² may be the same or different, and R ³ is a group containing a nonionic polar molecular chain described later.)
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (IV):

(Wherein, ^{R 4} and ^{R _5,} -C _p H _{2p -OH,} a _{-C q H 2q -COO-C r} H 2r -OH or an active hydrogen atom, and at least one of ^{R 4} and ^{R 5} one _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is 1 to 6 integer, q is an integer of 1 to 3, r is 1 to 4 It is an integer, and R ⁴ and R ⁵ may be the same or different, and R ⁶ is a group containing a low-polarity molecular chain described later.)
And a compound having a hydroxyl group or an active hydrogen atom represented by the formula:

  In the present specification, the group having an active hydrogen atom means a group other than a hydroxyl group having an active hydrogen atom that reacts with an isocyanate compound, and examples thereof include an amino group.

  When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (I) and the general formula (IV) is used as the dispersant, the isocyanate compound is all difunctional. It may be only an isocyanate compound, or a combination of a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound or a monofunctional isocyanate compound.

Further, when a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (I) and the general formula (IV) is used as a dispersant, the general formula (I) and the general formula A monofunctional compound having one hydroxyl group or one active hydrogen atom that reacts with an isocyanate compound may be used together with the bifunctional compound represented by the formula (IV). In this case, the monofunctional compound having one hydroxyl group or one active hydrogen atom that reacts with the isocyanate compound forms the terminal portion of the main chain of the polyurethane resin.
General formula (I)

And R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ and R ² At least one of R ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH. Therefore, either one or both of R ¹ and R ² have a hydroxyl group. a is an integer of 1 to 6, b is an integer of 1 to 3, c is an integer of 1 to 4, and R ¹ and R ² may be the same or different.

  More preferably, a is an integer of 2-4. Moreover, b is more preferably an integer of 1 to 2. Furthermore, c is more preferably an integer of 1 to 3.

In the compound represented by the general formula (I), R ³ represents the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these.

  More preferable ranges and further preferable ranges of d, e, f, g, and h are the same as the above-described ranges.

  In addition, the above general formula (IV)

In the bifunctional compound represented by R ⁴ and R ⁵ , —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ⁴ and At least one of R ⁵ is —C _p H _2p —OH or —C _q H _2q —COO—C _r H _2r —OH. Therefore, either one or both of R ⁴ and R ⁵ have a hydroxyl group. p is an integer of 1 to 6, q is an integer of 1 to 3, r is an integer of 1 to ^4, and R ⁴ and R ⁵ may be the same or different.

  p is more preferably an integer of 2 to 6, and further preferably an integer of 2 to 4. Further, q is more preferably an integer of 2 to 3. Furthermore, r is more preferably an integer of 2 to 4, and further preferably an integer of 2 to 3.

In the general formula (IV), R ⁶ represents the following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a group containing a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units, or 2 having 2 or more molecular units having 4 or more carbon units as repeating units. A group containing a polyether having the above, a group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as repeating units, or a poly having two or more molecular units having 4 or more carbon atoms as repeating units It is a group containing caprolactone.

  More preferable ranges and further preferable ranges of i, j, s, t, and u are the same as the above-described ranges.

  The dispersant of the present invention comprises a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (I) and the bifunctional compound represented by the general formula (IV). In this case, the ratio of the structural unit derived from the general formula (I) to the structural unit derived from the general formula (IV) in the polyurethane resin (the structural unit derived from the general formula (I): derived from the general formula (IV) The structural unit) is preferably 1: 0.1 to 0.1: 1, more preferably 1: 0.3 to 0.3: 1, and 1: 0.5 to 0.5. More preferably, the ratio is 1.

  When the dispersant of the present invention is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound represented by the above general formula and a bifunctional compound represented by the general formula (IV), In the polyurethane resin, the bifunctional compound represented by the general formula (I) gives a nonionic polar molecular chain represented by the general formulas (II) to (III), and is represented by the general formula (IV). The compound to be added imparts a low polar molecular chain represented by the general formulas (V) to (VIII). For this reason, in the polyurethane resin formed by reacting the isocyanate compound with the bifunctional compound represented by the general formula (I) and the general formula (IV), the general formula (I) and the general formula (IV) By the bifunctional compound represented, the polar molecular chain (A) and the low polar molecular chain (B) will be provided, and the polar molecular chain (A) and the low polar molecular chain (B) respectively give an organic solvent. By improving the affinity and the affinity for the pigment, and having a comb-like structure having a large number of polar molecular chains (A) and low-polar molecular chains (B) as side chains with respect to the main chain of the molecular chain, It is considered that the above-mentioned affinity can be effectively exhibited and the pigment can be suitably dispersed. In addition, the amino group or amide group contained in the structural unit derived from the general formula (I) or the structural unit derived from the general formula (IV) exhibits weak ionic affinity with the acidic functional group on the pigment surface. Therefore, it is considered that the pigment can be suitably dispersed.

  A polyurethane resin obtained by reacting the bifunctional compound represented by the general formula (I) and the bifunctional compound represented by the general formula (IV) can be produced by a method described later.

  As the dispersant of the present invention, the resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom, and at least of the bifunctional compound having a hydroxyl group or an active hydrogen atom. Some of the following general formula (IX):

(In General Formula (IX), R ⁷ and R ⁸ are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ⁷ and R 8 ^At least one of ⁸ is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ⁷ and R ⁸ may be the same or different, and R ⁹ is represented by the following general formula (X):

(In general formula (X), d is an integer of 1-4, and e is an integer of 5-30.)
A nonionic polar molecular chain-containing group represented by )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (XI):

(In General Formula (XI), R ¹⁰ and R ¹¹ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ¹⁰ and R 11 at least one of the ¹¹ _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, and R ⁴ and R ⁵ may be the same or different, and R ¹² represents the following general formula (XII):

(In general formula (XII), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
It is a low polar molecular chain containing group represented by these. )
What is a compound which has a hydroxyl group or an active hydrogen atom represented by these is preferable.

  Preferred ranges and more preferred ranges for a, b, c, d, e, p, q, r, i, and j are the same as those described above.

  The dispersant of the present invention comprises a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI). In this case, the ratio of the structural unit derived from the general formula (IX) to the structural unit derived from the general formula (XI) in the polyurethane resin (the structural unit derived from the general formula (IX): derived from the general formula (XI) The structural unit is preferably 1: 0.2 to 0.2: 1, more preferably 1: 0.3 to 0.3: 1, and 1: 0.5 to 0.5. More preferably, the ratio is 1.

  When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the general formula (XI) is used as the dispersant, the isocyanate compound is all difunctional. It may be only an isocyanate compound, or a combination of a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound or a monofunctional isocyanate compound.

  When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the general formula (XI) is used as a dispersant, the general formula (IX) and the general formula A monofunctional compound having one hydroxyl group or one active hydrogen atom that reacts with an isocyanate compound may be used together with the bifunctional compound represented by the formula (XI). In this case, the monofunctional compound having one hydroxyl group or one active hydrogen atom that reacts with the isocyanate compound forms the terminal portion of the main chain of the polyurethane resin.

  When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI) is used as the dispersant, this polyurethane resin is used. Is a compound in which the bifunctional compound represented by the general formula (IX) imparts a nonionic polar molecular chain-containing group represented by the general formula (X), and the compound represented by the general formula (XI) is And a low polar molecular chain-containing group represented by the general formula (XII).

  For this reason, in the polyurethane resin formed by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI), the above general formula (IX) is used. And the bifunctional compound represented by the general formula (XI) gives the polar molecular chain (A) and the low-polar molecular chain (B).

  The polyurethane resin obtained by reacting the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI) can be prepared by a method described later.

  Furthermore, in place of part or all of the bifunctional compound represented by the general formula (I) and the bifunctional compound represented by the general formula (IV), a nonionic polar molecular chain (A) and A side chain diol having a low polar molecular chain (B) has a pigment dispersing effect and can be used. Examples of such a compound include the following general formula (I ′)

(In the general formula (I ′), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ And at least one of R ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, and b is an integer of 1 to 3. , C is an integer of 1 to 4, R ¹ and R ² may be the same or different, and R ^{3 ′} is represented by the following general formula (II ′):

(In general formula (II '), d' is an integer of 6-30, and e is an integer of 5-30.)
Or a nonionic polar molecular chain represented by the following general formula (III ′):

(In general formula (III ′), f ′ is an integer of 6 to 30, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
Or a nonionic polar molecular chain represented by
Or the following general formula (V '):

(In general formula (V '), i' is an integer of 6-30, and j is an integer of 5-30.)
Is a nonionic polar molecular chain represented by )
Can be mentioned.

  A polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the above general formula (I) and the bifunctional compound represented by the general formula (IV) includes the above general formula (I) together with the isocyanate compound. And a bifunctional compound represented by the above general formula (IV) are used, and therefore the pigment dispersant has an amino group. Similarly, a polyurethane resin obtained by reacting the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI) is, together with the isocyanate compound, represented by the general formula (IX). Since the bifunctional compound represented and the bifunctional compound represented by the general formula (XI) are used, the pigment dispersant has an amino group. And, when a pigment having an acidic functional group is used as the pigment, the amino group in the pigment dispersant exhibits ionic affinity with the acidic functional group in the pigment, so that the dispersibility of the pigment is increased. Can do.

  In addition, a part or all of the bifunctional compound represented by the general formula (I) and the bifunctional compound represented by the general formula (IV) or the bifunctional compound represented by the general formula (IX) and the general formula (XI) The same effect can be obtained when a bifunctional compound represented by the general formula (I ′) is used in place of a part or all of the bifunctional compound represented by

  The dispersant of the present invention can be suitably used as a dispersant for dispersing a pigment in a photocurable resin composition such as a pigment dispersion composition or a photoresist composition. By using the dispersant of the present invention, a cured film having high pigment dispersion performance, high developability with an alkaline developer, and excellent chemical resistance can be provided.

  The dispersant of the present invention includes, for example, the diol (a) having the polar group or polar molecular chain (A) described above, the diol (b) having the low polar molecular chain (B) described above, and the active energy ray described above. It can be obtained by reacting a curable unsaturated group (C) and a compound (c) having a hydroxyl group with a bifunctional or higher isocyanate compound (d).

  In this method, the diol (a) having the polar molecular chain (A) and the diol (b) having a low polar molecular chain (B) are connected in a block manner via a bifunctional or higher functional isocyanate compound (d). It is preferable in that it can be performed. Further, in this method, as the diol (b), a dispersant in which the low polarity molecular chain (B) extends as a side chain in the comb tooth shape by using a diol (b) having a low polarity molecular chain (B) in the side chain. Is preferable in that

  And the acidic functional group in the diol (a), the neutralized base of the acidic functional group, the basic functional group, the neutralized base of the basic functional group, the nonionic polar molecular chain is the polar group of the dispersant of the present invention or It corresponds to a polar molecular chain (A). Moreover, the low polar molecular chain in the diol (b) corresponds to the low polar molecular chain (B) of the dispersant of the present invention. Moreover, the active energy ray-curable unsaturated group in the compound (c) corresponds to the active energy ray-curable unsaturated group (C) of the dispersant of the present invention.

  As the diol (a) having a polar group or polar molecular chain (A), a polyol compound (a1) having an acidic functional group, a polyol compound (a2) having a basic functional group, or a polyol compound having a nonionic polar molecular chain (A3) is mentioned.

As the polyol compound (a1) having an acidic functional group, a carboxyl group (—COOH), a hydroxyl group (—OH), a sulfonic acid group (—SO ₃ H), a phosphoric acid ester group (phosphoric acid monoester group, phosphoric acid diester) And a polyol compound having one or more selected from an acidic functional group such as a sulfate group and a group obtained by neutralizing them with a basic compound.

  Examples of the polyol compound (a2) having a basic functional group include compounds having a hydroxyl group and a basic nitrogen-containing group such as dialkanolamines.

  Examples of the polyol compound (a3) having a nonionic polar molecular chain include polyol compounds having a nonionic polar molecular chain such as a polyoxyethylene ether chain and a polyoxyethylene ether-polyoxypropylene ether glycol copolymer molecular chain.

  Examples of the polyol compound (a1) having an acidic functional group include trimethylolpropane monophosphate ester, trimethylolpropane monosulfate ester, polyester diol in which at least a part of the dibasic acid component is sodium sulfosuccinic acid or sodium sulfoisophthalic acid, Diaminocarboxylic acids such as lysine, cystine and 3,5-diaminocarboxylic acid, 2,6-dihydroxybenzoic acid, 3,5 dihydroxybenzoic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2, 2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, carboxyl group-containing polycaprolactone diol, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (Hydroxyp Pills) propionic acid, 2,2-bis (dihydroxy alkanoic acids such as hydroxymethyl) butanoic acid, caprolactone adducts of dihydroxy alkanoic acids and the like.

Examples of the polyol compound (a2) having a basic functional group include N-monoalkyl dialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine and N-methylpropanolamine, N, N-dihydroxyethylglycine, N, Cationic diols such as N-bis (2-hydroxyethyl) -3-carboxy-propionamide;
Michael addition reaction product of dimethylaminoethyl acrylate and dialkanolamine such as diethanolamine and dipropanolamine;
Michael addition reaction of monoalkylamines such as ethylamine and butylamine and hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate;
Diamine consisting of tertiary amine and primary amine such as dimethylaminoethylamine, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, etc. and primary amine, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Michael addition reaction products of hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate;
Compounds consisting of heterocyclic amines and primary amines such as N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethyl-4-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine and 2 -Michael addition reaction products of hydroxyalkyl acrylates such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate.

As the polyol compound (a3) having a nonionic polar molecular chain, a polybasic acid, a polyoxyethylene ether diol having 3 or more polyoxyethylene ether repeating units by adding ethylene oxide to a diol;
A block copolymer diol in which the polyoxyethylene ether chain occupies 60 mol% or more of the block copolymer diol of polyoxypropylene ether glycol or polyoxybutylene ether glycol and polyoxyethylene ether;
A block copolymer diol polymer diol in which the polyoxyethylene ether chain occupies 60 mol% or more, a block copolymer diol of polyoxyethylene ether, and the like are typical diols having a polar group in the molecular main chain.

  Moreover, as a polyol compound (a3) which has a nonionic polar molecular chain, following formula

^{(Wherein, R 13} is an alkyl group of 4-27 carbon atoms, w, x is a positive integer, w + x is 5-50.)
The diol represented by these is mentioned.

  Examples of the polyol compound (a3) having a nonionic polar molecular chain include alkoxypolyoxyethylene ether acrylates such as methoxypolyoxyethylene ether acrylate having 3 or more polyoxyethylene ether repeating units, and diethanolamine or dipropanolamine. A diol obtained by Michael addition reaction with a dialkanolamine is a representative diol having a polar molecular chain in the molecular side chain.

  As such a polyol compound (a3) having a nonionic polar molecular chain, the following general formula (I):

(Where R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and at least one of R ¹ and R ² one _is -C _a H 2a -OH or _{-C b H 2b -COO-C c} H 2c -OH, a is an integer from 1 to 6, b is an integer of 1 to 3, c is 1 to 4 And R ¹ and R ² may be the same or different, and R ³ is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these. )
The bifunctional compound represented by these can be mentioned.

  The more preferable ranges and further preferable ranges of the above a, b, c, d, e, f, g, and h are the same as the above-described ranges.

  Moreover, as a polyol compound (a3) which has a nonionic polar molecular chain, following general formula (IX):

(In General Formula (IX), R ⁷ and R ⁸ are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ⁷ and R 8 ^At least one of ⁸ is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ⁷ and R ⁸ may be the same or different, and R ⁹ is represented by the following general formula (X):

(In general formula (X), d is an integer of 1-4, and e is an integer of 5-30.)
A nonionic polar molecular chain-containing group represented by )
And a bifunctional compound represented by the formula:

  The more preferable ranges and further preferable ranges of the above a, b, c, d, and e are the same as the above-described ranges.

  As described above, the compound represented by the general formula (I) and the compound represented by the above (IX) are, for example, methoxy polyoxyethylene ether acrylate having 5 to 30 polyoxyethylene ether repeating units, It can be prepared by Michael addition reaction with dialkanolamine such as diethanolamine and dipropanolamine.

  Examples of the diol (b) having a low polar molecular chain (B) include a diol (b) having an alkyl group or an alkenyl group derived from an oil or fat, and a diol (b) having an alkyl group or an alkenyl group derived from an oil or fat. Examples thereof include long-chain polyols derived from fats and oils such as castor oil-modified diol and castor oil-modified polyol; glycerin fatty acid monoesters such as glycerin lauric acid monoester, glycerin stearic acid monoester, and glycerin oleic acid monoester.

  Examples of the diol (b) having a low polar molecular chain (B) include a polyol (b) having an alkyl group or alkenyl group having 6 or more carbon atoms, and having an alkyl group or alkenyl group having 6 or more carbon atoms. Examples of the polyol (b) include cyclohexane-1,4-dimethanol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, and 2-butyl-2. -Diols having hydroxyl groups at both ends, such as ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, etc., long-chain alkyl groups via ester groups in the side chains Or diols having an alkenyl, diols having a long-chain alkyl group or an alkenyl group via an ester group in the side chain, etc. That.

  Examples of the polyol (b) having an alkyl group or alkenyl group having 6 or more carbon atoms include the following formula:

(However, R ¹⁴ is an alkyl group or alkenyl group having 6 or more carbon atoms.)
A diol represented by
Diol having an alkyl group or alkenyl group having 6 or more carbon atoms via an ether group as a side chain, such as the following formula

(However, R ¹⁴ is an alkyl group or alkenyl group having 6 or more carbon atoms.)
A diol represented by
Following formula:

(However, v is an integer of 4 to 27, and is preferably any of 11, 17, and 21.)
The diol represented by these can be mentioned.

  Examples of the diol (b) having a low polar molecular chain (B) include a polymer polyol (b) having two or more molecular units having 4 or more carbon atoms as repeating units. Examples of (b) include polyester polyols and polyether polyols. Examples of the polymer polyol (b) include polymer diols such as polyester diol, polycarbonate diol, polylactone diol, and butadiene diol. Furthermore, examples of the polymer polyol (b) include polymer diols of compounds having a rosin skeleton or a hydrogenated rosin skeleton.

  The polymer polyol (b) preferably has a number average molecular weight in the range of 300 to 5,000.

  The polymer polyol (b) preferably has repeating molecular units in which each molecular unit has 4 or more carbon atoms, and the average number of carbon atoms of 2 or more molecular units is 4 or more, preferably 6 or more. It has two or more units.

  As the polyester polyol (b), one or more of the following polyols and polyol synergistic components and one or more of polybasic acids and anhydrides thereof undergo a condensation reaction. Can be obtained.

  The polyol having 4 or more carbon atoms in the molecular unit, which is a raw material for the polyester polyol (b), is cyclohexane-1,4-dimethanol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1, Examples include 8-octanediol, 1,9-nonanediol, cyclohexyldimethanol, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, castor oil-modified diol, and castor oil-modified polyol.

  Polyol polyol (b), which is a raw material for polyol, includes, but is not limited to, alkyl monoglycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, decyl glycidyl ether and stearyl glycidyl ether, and alkyl glycidyl esters. One type or two or more types of monoepoxy compounds such as (product name Cardura E10: manufactured by Shell Japan Co., Ltd.) may be mentioned.

  Polybasic acids and their anhydrides that are raw materials for the polyester polyol (b) include aliphatic dibasic acids such as adipic acid, azelaic acid, sebacic acid and dimer acid, and anhydrides thereof, dodecenyl succinic anhydride, Aromatic polybasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride, and anhydrides thereof, alicyclic polybasic acids such as hydrophthalic anhydride and dimethyl-1,4-cyclohexanedicarboxylic acid, and the like The anhydride of these is mentioned.

  There are also polyester polyols obtained by ring-opening addition polymerization of monomers having a lactone ring such as ε-caprolactone and β-methyl-δ-valerolactone starting from a hydroxyl-terminated compound such as the above-mentioned polyol and the above-mentioned polyester polyol (b). As an example of polyester polyol (b).

  Examples of the polycarbonate diol (b) include 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, and 2-butyl-2-ethyl-1,3-propanediol. Polycarbonate diols using diols such as 1,9-nonanediol and 2-methyl-1,8-octanediol as raw materials.

  Examples of the polyether polyol (b) include polyether polyols in which propylene oxide, tetrahydrofuran, or butylene oxide is added using bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, or the like as starting materials.

  The polylactone diol is obtained by ring-opening addition polymerization of a monomer having a lactone ring such as ε-caprolactone or β-methyl-δ-valerolactone, starting from a hydroxyl-terminated compound such as glycol or polyester polyol. Is mentioned.

  As polybutadiene diol, the following formula:

(However, k = 0.2, l = 0.2, m = 0.6, and n is a positive integer.)
Polybutadiene diols Poly bdR-15HT, R-45HT (made by Idemitsu Kosan Co., Ltd.), polyisoprene diol Poly ip (made by Idemitsu Kosan Co., Ltd.),
Following formula:

(In the formula, n represents a positive integer.)
Α, ω-polybutadiene glycol G-1000, G-2000, G-3000 (manufactured by Nippon Soda Co., Ltd.) and the like represented by

  Examples of the polymer diol (b) of a compound having a rosin skeleton or a hydrogenated rosin skeleton include Pine Crystal D-6011 and D-6240 (manufactured by Arakawa Chemical Industries).

  Moreover, as diol (b) which has a low polar molecular chain (B), following general formula (IV)

In the bifunctional compound represented by R ⁴ and R ⁵ , —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ⁴ and At least one of R ⁵ is —C _p H _2p —OH or —C _q H _2q —COO—C _r H _2r —OH, p is an integer of 1 to 6, q is an integer of 1 to 3, r is an integer of 1 to 4, R ⁴ and R ⁵ may be the same or different, and R ⁶ is represented by the following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a group containing a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units, or 2 having 2 or more molecular units having 4 or more carbon units as repeating units. A group containing a polyether having the above, a group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as repeating units, or a poly having two or more molecular units having 4 or more carbon atoms as repeating units It is a group containing caprolactone. )
The bifunctional compound represented by these can be mentioned.

  More preferable ranges and further preferable ranges of p, q, r, i, j, s, t, and u are the same as those described above.

  Moreover, as diol (b) which has a low polar molecular chain (B), following general formula (XI):

(In General Formula (XI), R ¹⁰ and R ¹¹ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ¹⁰ and R 11 at least one of the ¹¹ _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, and R ⁴ and R ⁵ may be the same or different, and R ¹² represents the following general formula (XII):

(In general formula (XII), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
It is a low polar molecular chain containing group represented by these. )
And a bifunctional compound represented by the formula:

  More preferable ranges and further preferable ranges of p, q, r, i, and j are the same as those described above.

  The compound represented by the general formula (IV) or the compound represented by the above (XI) is obtained by reacting, for example, an alkylphenyl polyoxyethylene ether acrylate with a dialkanolamine such as diethanolamine or dipropanolamine. Can be produced.

  Examples of the compound (c) having an active energy ray-curable unsaturated group (C) and a hydroxyl group include compounds having an active energy ray-curable vinyl group or (meth) acryloyl group and a hydroxyl group.

  Examples of the compound (c) having a vinyl group and a hydroxyl group include monohydroxyethyl vinyl ether, monohydroxybutyl vinyl ether, cyclohexanedimethanol monohydroxylovinyl ether, diethylene glycol monovinyl ether and the like.

  Examples of the compound (c) having a (meth) acryloyl group and a hydroxyl group include monohydroxyacryl methacrylate, monohydroxytriacrylate, monohydroxypentaacrylate, and dihydroxymono (meth) acrylate.

  Further, a compound obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or ε-caprolactone may be used.

  As monohydroxyacryl methacrylate relating to the compound (c) having a (meth) acryloyl group and a hydroxyl group, monohydroxy such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate Examples include mono (meth) acrylate, N-hydroxyethylacrylamide, light ester G-201P (manufactured by Kyoeisha Chemical Co., Ltd.), light ester G-101 (manufactured by Kyoeisha Chemical Co., Ltd.), glycerin di (meth) acrylate, and the like.

  Examples of the monohydroxytriacrylate according to the compound (c) having a (meth) acryloyl group and a hydroxyl group include pentaerythritol triacrylate.

  Examples of the monohydroxypentaacrylate according to the compound (c) having a (meth) acryloyl group and a hydroxyl group include dipentaerythritol pentaacrylate.

  Examples of the dihydroxy mono (meth) acrylate according to the compound (c) having a (meth) acryloyl group and a hydroxyl group include glycerin mono (meth) acrylate.

  Furthermore, as the compound (c) having a (meth) acryloyl group and a hydroxyl group, a compound having a (meth) acryloyl group and an isocyanate group is reacted with a dialkanolamine such as diethanolamine or dipropanolamine at a low temperature of 40 ° C. or lower. A diol compound having one (meth) acryloyl group and two hydroxyl groups in the same molecule is obtained, and when this compound is used, a (meth) acryloyl group can be introduced into the molecular side chain.

  Examples of the bifunctional or higher functional isocyanate compound (d) include aliphatic diisocyanates such as 1,6 hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate; trimers of the aliphatic diisocyanate; low Aliphatic polyisocyanates such as adducts of molecular triols and aliphatic isocyanates, or isophorone diisocyanate, hydrogenated MDI, hydrogenated tolylene diisocyanate, methylcyclohexylene diisocyanate, isopropylidenecyclohexyl-4,4′-diisocyanate and norbornene Alicyclic diisocyanates such as diisocyanates; trimers of the alicyclic diisocyanates; alicyclic polyisocyanates such as adducts of low-molecular triols and the alicyclic isocyanates Or araliphatic diisocyanates such as xylylene diisocyanate; trimers of xylylene diisocyanate; aromatic cycloaliphatic polyisocyanates such as adducts of low molecular triols and the araliphatic isocyanate, or 4, 4 '-Diphenylmethane diisocyanate, aromatic diisocyanates such as tolylene diisocyanate; triphenylmethane triisocyanate; trimers of the aromatic diisocyanate; aromatic polyisocyanates such as adducts of low molecular triols and the aromatic isocyanate, or Trifunctional or higher polyisocyanate such as polymethylene polyphenyl isocyanate, or Cosmonate LL (Mitsui Chemicals, Inc .: carbodiimidized 4,4′-diphenylmethane diisocyanate and 4, '- a mixture of diphenylmethane diisocyanate) and, or, Carbodilite V-05 (Nisshinbo Industries, Ltd.: terminal aliphatic having polycarbodiimide group polyisocyanate compound) polyisocyanate compounds having carbodiimide groups, such as and the like. Moreover, these may use 2 or more types together.

  Below, one or more polar groups or polar molecular chains (A) selected from acidic functional groups, neutralized bases of acidic functional groups, basic functional groups, neutralized bases of basic functional groups, and nonionic polar molecular chains A diol (a) having a low molecular weight chain (B), a compound (c) having an active energy ray-curable unsaturated group (C) and a hydroxyl group, and a bifunctional or higher functional isocyanate compound A method for producing the dispersant of the present invention by reaction with (d) is exemplified.

  Diol (a) having a polar group or polar molecular chain (A), diol (b) having a low polar molecular chain (B), an active energy ray-curable unsaturated group (C) and a compound having a hydroxyl group (c ) And the bifunctional or higher functional isocyanate compound (d) are [a], [b], [c], and [d], respectively, according to the following methods (1) to (3): The dispersant of the present invention can be obtained.

  That is, (1) a first-stage reaction in which a diol (a) having a polar group or polar molecular chain, a diol (b) having a low polar molecular chain (B), and a bifunctional or higher isocyanate compound (d) are reacted. To obtain an isocyanate group-terminated polyurethane resin.

First stage reaction conditions: {([a] + [b]) / [d]} ≦ 1
Then, in the second stage reaction, the obtained isocyanate group-terminated urethane resin and active energy ray-curable unsaturated groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, etc. And the compound (c) having a hydroxyl group can be reacted to obtain the dispersant of the present invention having an active energy linear unsaturated group at the side chain and terminal.

  In addition, (2) ([a] + [b] + [c]) / [d] ≧ 1 and a hydroxyl-terminated polyurethane resin can be obtained by a one-step reaction.

Further, (3) in the first stage reaction, the reaction was carried out as ([a] + [b] + [c]) / [d] ≦ 1, and once the isocyanate group-terminated polyurethane resin was obtained, As a step reaction,
(3-1) Any one selected from a diol (a) having a polar group or a polar molecular chain (A) and a diol (b) having a low polar molecular chain (B) in the isocyanate group of the polyurethane resin at the isocyanate group terminal. React with any diol to obtain a hydroxyl-terminated polyurethane resin,
(3-2) One or more active energy ray-curable unsaturated groups as the compound (c) having an active energy ray-curable unsaturated group (C) and a hydroxyl group on the isocyanate group of the isocyanate group-terminated polyurethane resin; An active energy ray-curable unsaturated group-terminated polyurethane resin is obtained by reacting a compound containing one hydroxyl group,
(3-3) An isocyanate-terminated polyurethane resin can be obtained by reacting the isocyanate group of the isocyanate-terminated polyurethane resin with an N, N′-dialkylalkanolamine such as N, N′-dimethylethanolamine. .

  Moreover, in the method shown to said (1)-(3), the polyol which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, is used with diol (b) which has a low polar molecular chain (B). Thus, an unsaturated group can also be introduced into the molecular chain.

  Further, if necessary, the isocyanate group-terminated polyurethane resin can be reacted with diol, amine, amino alcohol, or the like to extend the molecular chain.

  The reactions (1) to (3) are carried out in the absence of a solvent or in an organic solvent. Examples of the reaction solvent include known arbitrary solvents that do not react with an isocyanate group, and a solvent having few impurities such as moisture, base, and strong acid is preferable. The reaction temperature is preferably 40 to 120 ° C. If the reaction temperature is too low, the reaction time becomes long, and if the reaction temperature is too high, the isocyanate may increase in quantity.

  In the above reaction, any known catalyst can be used as necessary. Examples of the catalyst include tin-based catalysts such as dibutyltin disuccinate, dibutyltin dilaurate, and stannous octylate, and amine-based urethane catalysts such as triethylenediamine, diazabicycloundecene (DBU), and DBU salts.

  As a method for producing the dispersant of the present invention, one or more polarities selected from an acidic functional group, a neutralized base of an acidic functional group, a basic functional group, a neutralized base of a basic functional group, and a nonionic polar molecular chain are used. A (meth) acrylic monomer or macromer having a group or polar molecular chain (A) and a (meth) acrylic monomer or macromer having a low polar molecular chain (B) are copolymerized with an initiator having a functional group in the molecule. To obtain a polymer having a functional group at the terminal, and then reacting the obtained polymer with a compound having an active energy ray-curable unsaturated group and a functional group that reacts with the terminal functional group. Examples thereof include a method for producing a dispersant having a (meth) acrylic resin skeleton.

  In addition, as a method for producing the dispersant of the present invention, one or more selected from an acidic functional group, a neutralized base of an acidic functional group, a basic functional group, a neutralized base of a basic functional group, and a nonionic polar molecular chain A diol (or dibasic acid) having a polar group or polar molecular chain (A) and a dibasic acid (or diol) having a low polar molecular chain (B) are reacted to obtain a polyester, and then obtained. And a method of preparing a dispersant having a polyester resin skeleton by reacting the obtained polyester with a compound having an active energy ray-curable unsaturated group (C) and a functional group that reacts with an acid or a hydroxyl group. .

  In addition, as a method for producing the dispersant of the present invention, one or more selected from an acidic functional group, a neutralized base of an acidic functional group, a basic functional group, a neutralized base of a basic functional group, and a nonionic polar molecular chain The diol having a polar group or polar molecular chain (A), the diol having a low polar molecular chain (B), and a difunctional or higher isocyanate compound are reacted to obtain an isocyanate group-terminated polyurethane resin, and then obtained. A method of preparing a dispersant for a polyurethane resin skeleton having an active energy ray-unsaturated group terminal by reacting a polyurethane resin having an isocyanate group end with a compound having an active energy ray-curable unsaturated group (C) and a hydroxyl group. Can be mentioned.

  The dispersant of the present invention can be suitably used as a dispersant for dispersing a dispersion such as a pigment or a dye in a pigment dispersion composition, active energy ray-curable ink or paint. The dispersant of the present invention can provide a cured film having high dispersion performance of the dispersion and excellent chemical resistance and gloss.

  Next, the pigment dispersion composition of the present invention will be described.

  The pigment dispersion composition of the present invention contains the pigment and the dispersant having an active energy ray unsaturated group of the present invention.

  The pigment dispersion composition of the present invention is obtained by dispersing a pigment with the dispersant of the present invention, and may contain a dye together with the pigment.

  Examples of the pigment contained in the pigment dispersion composition of the present invention include inorganic pigments such as carbon black, titanium oxide, and iron oxide, insoluble azo pigments, soluble azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, isoindoline pigments, and benzimidazo. Organic pigments such as Ron pigments, pyranthrone pigments, thioindigo pigments, and quinophthalone pigments, or surface modified pigments that have been surface modified by bonding acidic functional groups or neutralizing bases of acidic functional groups to the surface of these pigments Can be mentioned.

  Among the above pigments, carbon black includes carbon black produced by a contact method called channel black, roller black, and disk black, carbon black produced by a furnace method called gas furnace black, and oil furnace black, and thermal black. And carbon black produced by a thermal method called acetylene black, and among these, furnace black excellent in productivity is more preferable.

  The surface-modified pigment according to the pigment dispersion composition of the present invention is preferably a pigment whose surface is modified with an acidic functional group or a neutralized base of an acidic functional group. In other words, the surface-modified pigment is preferably one having an acidic functional group on the surface, or one obtained by neutralizing all or part of the acidic functional group with a basic compound.

  The acidic functional group or the neutralized base of the acidic functional group bonded to the surface-modified pigment is the same as the acidic functional group or the neutralized base of the acidic functional group according to the dispersant of the present invention. Among these, the acidic functional group relating to the surface-modified pigment is preferably a combination of a carboxyl group and a hydroxyl group.

  As an example of the surface modified pigment, a surface modified pigment whose pigment is carbon black will be described below.

  As an example of the pigment having an acidic group on the surface, carbon black is cited. Carbon black having an acidic group such as a sulfonic acid group, a phosphoric acid group, or a carboxylic acid group introduced by a coupling reaction of a diazonium salt, Examples thereof include acidic carbon black obtained by oxidizing the surface of carbon black with an oxidizing agent, and among these, carbon black in which the acidic functional group is a carboxyl group and a hydroxyl group is preferable.

In order to obtain a carbon black into which an acidic functional group has been introduced by introducing an acidic functional group into the carbon black before the introduction of the functional group, that is, to obtain a surface-modified pigment, the carbon black before the introduction of the functional group is obtained at a high temperature. A method of oxidizing by contacting with free oxygen at a temperature, a method of oxidizing with an oxidizing agent such as ozone or NO ₂ , a method of treating under normal pressure or pressure with bromine and water, or an oxidizing solution such as nitric acid or sulfuric acid And a method of introducing a carboxyl group or a hydroxyl group into carbon black before introduction of a functional group by an oxidation method such as a combination of these methods or an oxidation method such as a method of oxidation with hydrogen peroxide. It is done. Moreover, as a method of introducing an acidic functional group such as a carboxyl group, a sulfone group, and a phosphoric acid group into carbon black before the introduction of a functional group other than the oxidation method, a diazo coupling method can be mentioned. As carbon black in which an acidic functional group is introduced or carbon black in which part or all of the acidic functional group is neutralized with a basic compound, CAB-O-JET200, CAB-O-JET300 manufactured by Cabot Specialty, Examples thereof include water dispersible carbon black such as CAB-O-JET400.

  And as a pigment dispersion composition of this invention, the said pigment is disperse | distributed with the dispersing agent of this invention in the organic solvent can be mentioned. Further, as the pigment dispersion composition of the present invention, an active energy ray-curable low-viscosity monomer such as a vinyl monomer or a (meth) acrylate monomer, a (meth) acrylate oligomer, and a known arbitrary resin as necessary are added. In addition, there may be mentioned those in which the pigment is dispersed by the dispersant of the present invention. Furthermore, examples of the pigment dispersion composition of the present invention include those in which the pigment is dispersed in an organic solvent and a monomer by the dispersant of the present invention.

  Examples of the active energy ray-curable low-viscosity monomer include known vinyl monomers and (meth) acrylate monomers. The active energy ray-curable low-viscosity monomer is appropriately selected depending on the application, and examples thereof include monomers listed in Technonet “Photo-curing Technology Data Book”, Material Nos. A-101 to A-360. Acrylate monomers, methacrylate monomers listed in M-101 to M305, vinyl monomers listed in C-01 to C-24 and T-10, allyl monomers, vinyl groups, allyl groups, acrylic groups Or the monomer which has a methacryl group is mentioned.

  Examples of the organic solvent include ester solvents such as ethyl acetate, propyl acetate, butyl acetate and isoamyl acetate, and ester ethers such as methyl glycol ether acetate, ethyl glycol ether acetate, butyl glycol ether acetate and propylene glycol methyl ether acetate. , Ketones such as acetone, methyl ethyl ketone, and isobutyl ketone, and known organic solvents such as tetrahydrofuran and N-methylpyrrolidone.

  The pigment dispersion composition of the present invention may contain a polymerization inhibitor, and examples of the polymerization inhibitor include hydroquinone, methoquinone, P-methoxyphenol, nitrosamine salts and the like.

  In the pigment dispersion composition of the present invention, the pigment dispersion composition in which the pigment is dispersed in an organic solvent is preferably used for an active energy ray-curable liquid ink or paint, and has a low active energy ray curability. A pigment dispersion composition in which the above pigment is dispersed in a monomer having a viscosity is preferably used for an ultraviolet curable inkjet ink.

  A pigment dispersion composition in which the pigment is dispersed in an active energy ray-curable low-viscosity monomer can be suitably used as a liquid ink, a paint, particularly an ultraviolet curable inkjet ink.

  Among the pigment dispersion compositions of the present invention, a pigment dispersion composition in which a pigment is dispersed in an organic solvent is an active energy ray curable liquid by adding an active energy ray curable monomer or oligomer as necessary. It can be used for the production of inks or paints. In the case of a pigment dispersion composition in which a pigment is dispersed in an active energy ray-curable low-viscosity monomer, it can be used for producing an ultraviolet curable inkjet ink.

  In the pigment dispersion composition of the present invention, the pigment content is appropriately selected, but is preferably 5 to 35% by weight, and more preferably 7 to 15% by weight. In the pigment dispersion composition of the present invention, the content of the dispersant of the present invention is appropriately selected depending on the pigment content.

  In the pigment dispersion composition of the present invention, an active energy ray-curable compound such as a vinyl monomer or (meth) acrylate monomer, or a polymerization inhibitor is added as necessary with the dispersant of the present invention and the pigment as essential components. Above, it can obtain by disperse | distributing with well-known arbitrary dispersers, such as a homogenizer apparatus including a bead mill. Moreover, when obtaining the pigment dispersion composition of this invention, you may mix dye with the said pigment.

  The pigment dispersion composition of the present invention is used as an active energy ray curable ink and a pigment dispersion composition (mill base) for producing an active energy ray curable coating, particularly as a pigment dispersion composition (mill base) for producing an ultraviolet curable ink jet ink. ) Is preferably used.

  Next, the active energy ray curable ink and the active energy ray curable paint of the present invention will be described.

  The active energy ray curable ink of the present invention contains a pigment and the dispersant of the present invention.

  In particular, the active energy ray curable ink of the present invention is suitable as an ultraviolet curable inkjet ink. Moreover, the active energy ray-curable ink of the present invention can contain a dye together with the pigment.

  The active energy ray-curable coating material of the present invention contains a pigment and the dispersant of the present invention. The active energy ray-curable coating material of the present invention can contain a dye together with the pigment.

  The active energy ray-curable ink of the present invention and the active energy ray-curable paint of the present invention have many similar points. Ink (paint) ".

  The active energy ray-curable ink (paint) of the present invention preferably contains an active energy ray-curable compound and a photopolymerization initiator in addition to the pigment and the dispersant of the present invention. In addition, the active energy ray-curable ink (paint) of the present invention can be used depending on the application, such as a coating film smoothing aid, an adhesive aid, an auxiliary agent such as a polymerization inhibitor, or a surface tension adjustment or coating. A resin or an additive can be contained for the purpose of adjusting the adhesion to the printing material.

  The pigment according to the active energy ray-curable ink (paint) of the present invention is the same as the pigment according to the pigment dispersion composition of the present invention.

  The active energy ray-curable compound according to the active energy ray-curable ink (paint) of the present invention is particularly a resin, monomer, or oligomer that is cured by irradiation with infrared rays, ultraviolet rays, electron beams, X-rays, or the like. Without limitation, compounds that are normally used as active energy ray-curable resins, monomers, or oligomers of active energy ray-curable inks (paints) can be mentioned.

  Examples of the active energy ray-curable compound include a resin, monomer or oligomer having a (meth) acryloyl group, or a resin, monomer or oligomer having a vinyl group. Specifically, examples of the active energy ray-curable compound include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and the like as (meth) acrylate oligomers. You may use the above together.

  Examples of the active energy ray-curable compound include monofunctional (meth) acrylates such as methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxy. (Meth) acrylate having a substituent such as ethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl; N -Vinylpyrrolidone; N-vinylcaprolactam; N-methyl morpholine etc. may be mentioned, and two or more of these may be used in combination.

  Examples of the active energy ray-curable compound include polyfunctional (meth) acrylates such as 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol , Di (meth) acrylate such as polypropylene glycol, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, and 4 mol or more of ethylene oxide or propylene oxide added to 1 mol of neopentyl glycol Di (meth) acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, and 3 moles or more of ethylene oxide per mole of trimethylolpropane Alternatively, diol or tri (meth) acrylate of triol obtained by adding propylene oxide, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, poly (meth) acrylate of dipentaerythritol, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified alkyl Phosphoric acid (meth) acrylate and the like, which may be used in combination of two or more.

  Examples of the active energy ray-curable compounds include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and the like as (meth) acrylate oligomers. Also good. When the active energy curable ink (paint) of the present invention is an ultraviolet curable inkjet ink, the content of the (meth) acrylate oligomer is low from the viewpoint of suppressing the viscosity of the inkjet ink or obtaining suitable curability. It is preferable that it is 0-20 mass% with respect to the total amount of ultraviolet curable inkjet ink.

  The photopolymerization initiator according to the active energy ray-curable ink (paint) of the present invention is not particularly limited as long as it is a photopolymerization initiator usually used in an active energy ray-curable ink (paint), but is a molecular cleavage type. Alternatively, a hydrogen abstraction type is preferable.

  Examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylethoxy. Phosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methyl- Benzyl) -1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morofolinopropan-1-one, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphine oxide , Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are preferably used, and other molecular cleavage types include 1-hydroxycyclohexyl phenyl ketone and benzoin ethyl ether. , Benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one or the like may be used in combination, and further, a hydrogen abstraction type photopolymerization initiator, benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl- 4'-methyl-diphenyl sulfide may be used in combination .

  In addition, as a sensitizer for the photopolymerization initiator, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, You may use together amines which do not raise | generate an addition reaction with active energy ray hardening compounds, such as N-dimethylbenzylamine and 4,4'-bis (diethylamino) benzophenone. Of course, it is preferable that the photopolymerization initiator and the sensitizer are excellent in solubility in the active energy ray-curable compound and do not inhibit the transmittance of the active energy ray.

  The polymerization inhibitor according to the active energy ray-curable ink (paint) of the present invention is not particularly limited, and examples thereof include hydroquinone, methoquinone, p-methoxyphenol, nitrosamine salts and the like. In the active energy ray-curable ink (paint) of the present invention, the content of the polymerization inhibitor is preferably 0.01 to 0.5% by weight.

  In the active energy ray-curable ink (paint) of the present invention, the content of each compound is appropriately selected depending on the application, but is generally as follows.

  When using a pigment such as carbon black, the content of the pigment is preferably 1.5 to 30% by weight, preferably 2 to 30% by weight in the active energy ray-curable ink (paint) of the present invention. More preferably, it is 3 to 25% by weight, more preferably 3 to 20% by weight. Moreover, when using titanium white (titanium dioxide) as a pigment, it is preferable that content of a pigment is 1.5 to 60 weight% in the active energy ray hardening-type ink (paint) of this invention.

  The content of the dispersant of the present invention is preferably 1 to 30% by weight, more preferably 2 to 20% by weight in the active energy ray-curable ink (paint) of the present invention, and a pigment. It is suitable that it is 20-200 weight part with respect to 100 weight part. The content of the active energy ray-curable compound is preferably 20 to 95% by weight, more preferably 45 to 95% by weight in the active energy ray-curable ink (paint) of the present invention, and pigment 100. It is suitable that it is 20-200 weight part with respect to a weight part. The content of the photopolymerization initiator is preferably 2 to 20% by weight, more preferably 4 to 15% by weight, and 100 parts by weight of pigment in the active energy ray-curable ink (paint) of the present invention. 1 to 20 parts by weight is appropriate.

  And when the active energy ray curable ink (paint) of this invention is a ultraviolet curable inkjet ink, it is preferable that content of each compound in an ultraviolet curable inkjet ink is as follows.

  That is, the content of the pigment (dye) is 1.5 to 20 in the ultraviolet curable ink-jet ink in that when a pigment such as carbon black is used, a sufficient image density and light resistance of the printed image can be obtained. % By weight is preferable, 2 to 20% by weight is more preferable, and 2 to 10% by weight is further preferable. Moreover, when using titanium white (titanium dioxide) as a pigment, it is preferable that content of a pigment is 1.5 to 35 weight% in the active energy ray hardening-type ink (paint) of this invention.

  Further, the content of the dispersant of the present invention is preferably 1 to 30% by weight, more preferably 2 to 20% by weight in the ultraviolet curable inkjet ink, and with respect to 100 parts by weight of the pigment, It is suitable that it is 20-200 weight part. The content of the active energy ray-curable compound is preferably 20 to 95% by weight, more preferably 45 to 90% by weight, and more preferably 40 to 90% by weight in the ultraviolet curable inkjet ink. It is suitable that it is -95 weight part. The content of the photopolymerization initiator is preferably 2 to 20% by weight in the ultraviolet curable inkjet ink, more preferably 4 to 15% by weight, and 2 to 15% with respect to 100 parts by weight of the pigment. Appropriate parts are by weight.

  The active energy ray-curable ink (paint) of the present invention is printed with a solvent as required by appropriately selecting the type or content of each compound according to the application or usage situation. Or it is adjusted to a viscosity suitable for coating.

  The production method of the active energy ray-curable ink (paint) of the present invention is not particularly limited. For example, the active energy ray-curable compound (monomer or oligomer having active energy ray curability) is added to the pigment dispersion composition of the present invention. Or resin) and a photopolymerization initiator, and, if necessary, other coating smoothing aids, adhesion aids, polymerization inhibitors and other auxiliaries or additives, etc. The active energy ray-curable ink (paint) of the present invention can be produced by adjusting the content.

  In addition, the above active energy ray-curable compound or organic solvent is added to the mill base (high concentration pigment dispersion) comprising the pigment dispersion composition of the present invention so as to have a viscosity suitable for coating and printing. You can also.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention. In addition, the part in an Example and a comparative example and each component amount in a table | surface represent a weight part.

Example 1 <Synthesis Example of Dispersant 1>
(1) Synthesis of side chain PEG diol In a flask with stirring, dry nitrogen, blowing tube, and cooling tube, methoxypolyoxyethylene ether acrylate (Kyoeisha Chemical Co., Ltd., light acrylate 130A) 82, which is a nonionic polar molecular chain-imparting component And 18 parts of diethanolamine were charged at 40 ° C. or lower, heated to 60 ° C. and reacted for 3 hours to obtain a side chain PEG diol having a methoxypolyoxyethylene chain which is a nonionic polar molecular chain on the side chain with a molecular weight of 582. .
(2) Synthesis of polyurethane dispersant Agitated, dried air blowing tube, flask with cooling tube was charged with 250 parts of propyl acetate and 14.4 parts of diethanolamine. 21.2 parts of 2-methacryloyloxyethyl isocyanate (produced by Showa Denko KK, Karenz MOI) was gradually added. After reacting at 45 ° C. for 1 hour, at 40 ° C. or less, 58 parts of castor oil diol HS-2G-150R (manufactured by Toyokuni Oil Co., Ltd.) which is a low polar molecular chain imparting component, Kuraray polyester diol P- 1050 (number average molecular weight 994, manufactured by Kuraray Co., Ltd.) 85 parts, rosin-containing diol (Pine Crystal D-6250, manufactured by Arakawa Chemical Co., Ltd.) which is a low-polarity molecular chain-imparting component, side chain PEG obtained in (1) above 66 parts of diol, 38 parts of 1,6-hexamethylene diisocyanate, 76 parts of isophorone diisocyanate and 83 parts of methyl ethyl ketone were added and reacted at 70 ° C. for 5 hours. Furthermore, as an active energy ray-curable unsaturated group-providing component, 28 parts of light acrylate G-201P (manufactured by Kyoeisha Chemical Co., Ltd.) having a hydroxyl group and a (meth) acryloyl group in the molecule, and N-dimethylamino as an acidic functional group-providing component After adding 10 parts of ethanol and reacting at 70 ° C. for 1 hour, 0.3 parts of dibutyltin laurate, 0.3 part of methoquinone and 167 parts of methyl ethyl ketone were added, reacted at 70 ° C. for 5 hours, cooled to 40 ° C., Dispersant 1 comprising a polyurethane resin having an amino group at the end of the main chain having a (meth) acryloyl group concentration of 1 meq / g and an amine value of 23 mg / g was obtained.

Example 2 <Synthesis Example of Dispersant 2>
(1) Synthesis of side chain aminodiol Stirring, a dry nitrogen blowing tube, a flask with a cooling tube was charged with 214 parts of propyl acetate and 131 parts of N-dimethylpropylamine, and 369 parts of 4-hydroxybutyl acrylate was added dropwise at 35 ° C or lower. And propyl acetate was added dropwise. The temperature was raised to 60 ° C., and after 3 hours at 60 ° C., a side chain aminodiol having an amino group as a basic functional group in the molecular side chain was obtained.
(2) Synthesis of polyurethane dispersant In a flask with stirring, dry air blowing tube, and cooling tube, 250 parts of propyl acetate and 12.2 parts of diethanolamine are charged, and while stirring and cooling, an active energy ray-curable unsaturated group-providing component is added. Gradually add 18 parts of some 2-methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko). After reacting at 45 ° C. for 1 hour, 43 parts of castor oil diol HS-2G-150R (manufactured by Toyokuni Oil Co., Ltd.), which is a low-polarity molecular chain-imparting component at 40 ° C. or less, Kuraray polyester diol P-1010, which is a low-polarity molecular chain-imparting component 140 parts (number average molecular weight 994, manufactured by Kuraray Co., Ltd.), 33 parts of rosin-containing diol (Pine Crystal D-6011 manufactured by Arakawa Chemical Co., Ltd.) which is a low-polarity molecular chain-imparting component, and side chain aminodiol 136 obtained in (1) above Part, 1,6-hexamethylene diisocyanate 39 parts, isophorone diisocyanate 91 parts and methyl ethyl ketone 98 parts are added and reacted at 60 ° C. for 2 hours. Furthermore, 57 parts of light acrylate G-201P (manufactured by Kyoeisha Chemical Co., Ltd.) having a hydroxyl group and a (meth) acryloyl group in the molecule is added as an active energy ray-curable unsaturated group-providing component, and 0.3 part of dibutyltin laurate , 0.3 parts of methoquinone and 83 parts of methyl ethyl ketone, reacted at 70 ° C. for 5 hours, cooled to 40 ° C., and from a polyurethane resin having a (meth) acryloyl group concentration of 1.18 meq / g and an amine value of 20 mg / g Dispersant 2 was obtained.

Example 3 <Synthesis Example of Dispersant 3>
(1) Synthesis of side-chain polyethylene glycol (PEG) diol Methoxypolyoxyethylene ether acrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate), which is a nonionic polar molecular chain-imparting component, in a flask equipped with stirring, dry nitrogen, blowing tube, and cooling tube 130A, bromine number 34.9Br / 100g) and 18 parts of diethanolamine were charged at a temperature of 40 ° C. or lower and reacted at 60 ° C. for 3 hours. The molecular weight was 582 and the side chain was a nonionic polar molecular chain. A side chain polyethylene glycol (PEG) diol having a methoxypolyoxyethylene chain was obtained.
(2) Synthesis of low-chain side-chain diol Nonylphenyl polyoxyethylene ether acrylate (Kyoeisha Chemical Co., Ltd., Light acrylate NP-4EA), which is a low-polarity molecular chain-imparting component, in a flask equipped with stirring, dry nitrogen, blowing tube, and cooling tube ) 81 parts and 19 parts of diethanolamine were charged and reacted at 70 ° C. for 6 hours to obtain a side chain low-polar diol having a low-polarity group in the side chain having a molecular weight of 555.
(3) Synthesis of polyurethane resin 2-Methacryloyl, which is an active energy ray-curable unsaturated group-providing component, is charged with 250 parts of propyl acetate and 8 parts of diethanolamine in a flask equipped with a stirring, dry air blowing tube, and cooling tube, and stirred and cooled. 12 parts of oxyethyl isocyanate (Showa Denko, Karenz MOI) was gradually added. After reacting at 45 ° C. for 1 hour, at a temperature of 40 ° C. or less, 175 parts of a polyester diol (P-2050, number average molecular weight 2066, manufactured by Kuraray Co., Ltd.), which is a low polar molecular chain-imparting component, is a low polar molecular chain imparting component. 27 parts of rosin-containing diol (Arakawa Chemical Co., Ltd., Pine Crystal D-6011); 53 parts of the side chain polyethylene glycol (PEG) diol obtained in 1 above, 2. After adding 79 parts of the side-chain low-polar diol obtained in 1 above, 40 parts of 1,6-hexamethylene diisocyanate, 63 parts of isophorone diisocyanate, and 83 parts of methyl ethyl ketone, the mixture was reacted at 70 ° C. for 5 hours. Furthermore, 46 parts of a compound having a hydroxyl group and a (meth) acryloyl group (manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate G-201P) as an active energy ray-curable unsaturated group-imparting component was added and reacted at 70 ° C. for 1 hour. , 0.03 part of dibutyltin laurate, 0.03 part of methoquinone and 167 parts of methyl ethyl ketone were added, reacted at 70 ° C. for 5 hours, cooled to 40 ° C., (meth) acryloyl group concentration 0.92 meq / g, side chain Dispersant 3 comprising a polyurethane resin having a polar group and a low polar group was obtained.

Example 4 to Example 10 <Preparation Example of Surface Modified Carbon Black Dispersion Composition>
(1) Preparation of carbon black First, surface-modified carbon black-1 to surface-modified carbon black-3 were prepared by the following method.
<Synthesis of Surface Modified Carbon Black-1 (CB-1)>
Manufactured by Tokai Carbon Co. as carbon black ^{TOKABLACK # 8300 (N2SA: 244m 2} / g, DBP absorption 80 cm ^3/100 g) using a and the carbon black 150g was added to aqueous sodium persulfate solution 3000ml of concentration 2.0 N, the reaction Liquid phase oxidation was performed by reacting at a temperature of 60 ° C. and a stirring speed of 300 rpm for 10 hours. After the oxidation treatment, the carbon black dispersion was subjected to separation and purification of the salt remaining in the dispersion with an ultrafiltration membrane (AHP-1010 manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 50000) and concentrated to a carbon black concentration of 10 wt%. . The electric conductivity of the dispersion after concentration was 0.6 mS / cm. Thereafter, water was removed by evaporating the concentrated liquid with a dryer to obtain a dried carbon black, which was then pulverized with a cutter mixer to produce a carbon black powder that passed through a sieve having an opening of 300 μm. Thus, liquid phase oxidation was performed to obtain surface-modified carbon black (CB-1). The CB-1 carboxyl group amount 1450μmol / g, DBP absorption amount of 80cm ³ / 100g, STSA specific surface area was 240 m ² / g.
<Synthesis of surface modified carbon black-2 (CB-2)>
Manufactured by Tokai Carbon Co. as carbon black ^{TOKABLACK # 8300 (N2SA: 244m 2} / g, DBP absorption 80 cm ^3/100 g) using a ozone generator (manufactured by Yamato Scientific Co. CO-101) by the pressure 0.02 MPa, flow rate 5L / Ozone oxidation was performed for 8 hours under the condition of minutes. In this way, surface-modified carbon black (CB-2) was obtained. Carboxyl group amount of the CB-2 is 711μmol / g, DBP absorption amount of 80cm ³ / 100g, STSA specific surface area was 237m ² / g.
<Synthesis of Surface Modified Carbon Black-3 (CB-3)>
Cabot Jet 300 manufactured by Cabot Corporation was dried and pulverized with a mixer to obtain surface-modified carbon black (CB-3). Carboxyl group amount of the CB-3 is 684μmol / g, DBP absorption amount is 102cm ³ / 100g, STSA specific surface area was 244m ² / g.

  The carboxyl group amount was measured by the following method.

About 2-5 g of carbon black was put in 50 ml of 0.976N sodium hydrogen carbonate aqueous solution, shaken for about 6 hours, carbon black was separated by filtration, and the titration test of the filtrate was performed to determine the carboxyl formed on the carbon black surface. The basis weight was measured.
(2) Preparation of Carbon Black Dispersion Composition Three types of dispersants 1 to 3 made of the polyurethane resin obtained in Examples 1 to 3 and the above three types of surface modified carbon blacks (CB-1 to CB) -3) was used to prepare a carbon black dispersion composition (CB mill base composition) having the composition shown in Table 1.

  That is, 10 parts (5 parts solids) of any of Dispersant 1 to Dispersant 3 made of polyurethane resin, 0.04 part of t-butylhydroquinone, and diacrylate of hydroxypivalate neopentyl glycol ester diol (manufactured by Kyoeisha Chemical Co., Ltd.) Light ester-HPPA) was blown into the air and reduced in pressure at 30 mbar, 50 ° C. for 1 hour to distill off the solvent of the polyurethane dispersant, and then the surface-modified carbon blacks CB-1 to CB-3 Any 8 parts, 11.2 parts of phenoxyethyl acrylate (Aronix M-101A manufactured by Toagosei Co., Ltd.), 5.6 parts of 2-methoxyethyl acrylate (2-MTA manufactured by Osaka Organic Chemical Co., Ltd.), 200 parts of 1 mm zirconia beads And dispersed in a paint shaker for 2 hours (5 hours in Example 10). 0% carbon black dispersion composition (CB mill base composition) was prepared.

  The viscosity of each CB mill base composition was measured by the following method. In Example 10, the particle size of the carbon black aggregate in the CB mill base was measured as follows. The results are listed in Table 1 along with the composition of each CB mill base.

In Table 1, each component amount is converted to a value when the weight of the surface-modified carbon black (CB-1 to CB-3) is 10 parts by weight, and the dispersant 1 is made of polyurethane resin. The amount of ~ dispersant 3) is a value in terms of solid content.
(viscosity)
The viscosity (mPa · s) at a temperature of 25 ° C. was measured using an E-type viscometer (TVE-20L manufactured by Toki Sangyo Co., Ltd.).
(Particle size)
It measured using the heterodyne laser Doppler system particle size distribution measuring apparatus (UPA model 9340 by Microtrac). The measurement was determined from the particle size distribution curve of the carbon black particle aggregate in the resin composition, with the value of 50% cumulative frequency being the average particle size and the value of 99% cumulative frequency being the maximum particle size. In the measurement, propylene glycol monomethyl ether acetate was used as a solvent for adjusting the viscosity.

Comparative Examples 1 to 6 <Preparation of Comparative Carbon Black Dispersion Composition>
Instead of using Dispersant 1 to Dispersant 3, Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Solspers 32000 (manufactured by Lubrizol Corp.), Solspers 39000 (manufactured by Lubrizol Corp.) are used as the dispersant. Each comparative carbon black dispersion composition (comparative CB mill base composition) having the composition shown in Table 2 was obtained in the same manner as in Examples 4 to 10 except that the solvent therein was not distilled off.

  The viscosity of each dispersion composition was measured in the same manner as in Examples 4 to 10. In Comparative Examples 1 to 3, the particle size of the carbon black aggregates in the dispersion composition was measured by the same method as in Examples 4 to 10. The results are listed in Table 2 along with the composition of each dispersion composition.

Example 11 to Example 17 <Preparation example of UV curable ink jet (UVIJ) ink>
As shown in Table 3, 35 parts of each CB mill base composition prepared in Examples 4 to 10, 17 parts of ethylene oxide-added trimethylolpropane triacrylate (Aronix M-350, manufactured by Toagosei Co., Ltd.), dipropylene glycol di Stir and filter 32 parts of acrylate (Shin Nakamura Chemical Co., Ltd. APG-100), 10 parts of 2-methoxyethyl acrylate (2-MTA made by Osaka Organic Chemical Co., Ltd.) and 6 parts of Irgacure 369 (Ciba Japan Co., Ltd.). Thus, UVIJ inks according to Examples 11 to 17 were obtained.

<Curing of UV curable ink jet (UVIJ) ink>
Using each of the UVIJ inks described above, the ink was applied to a 0.3 mm-thick untreated aluminum plate with a # 6 drawdown rod, and UV-cured by the UV irradiation tester manufactured by Eye Graphics under the following irradiation conditions. A coating film was formed.

(Irradiation conditions)
UV lamp: One metal halide lamp, condensing cold mirror
Irradiation distance: 150 mm
Lamp output: 160W
Conveyor speed: 10m
Peak illuminance: 845 mW / cm ²
Integrated light quantity: 550 mJ / cm ²
In addition, the blackness and gloss (%) of the obtained cured coating film are measured by the following methods, and the MEK rubbing test is performed by the following method as an index of curability and chemical resistance of the obtained cured coating film. did. The results are shown in Table 3.
(Blackness)
The reflection optical density (OD value) was measured using a Macbeth densitometer (RD-927 manufactured by Colmogen).
(Glossy)
Measurements were made with a BYK Gardner 60 degree gloss meter.
(MEK rubbing)
A cotton swab soaked in MEK so as to apply a load of about 200 g is pressed against the UV cured coating plate placed on the electronic balance, and the coating is rubbed by reciprocating the same part between 2 and 3 centimeters (rubbing) ), The number of reciprocating rubbing was measured when the coating film was peeled off and the ground was visible.

Comparative Example 7 to Comparative Example 12 <Preparation Example of Comparative UV Curing Inkjet (UVIJ) Ink>
Comparative UVIJ inks having the compositions shown in Table 4 were obtained in the same manner as in Examples 11 to 17 except that the comparative mill base prepared in Comparative Examples 1 to 6 was used as the CB mill base composition.

  Using each of the obtained comparative UVIJ inks, a UV cured coating film was formed on the aluminum plate in the same manner as in Examples 11 to 17, and curing obtained in the same manner as in Examples 11 to 17 The blackness, gloss (%), and MEK rubbing frequency of the coating film were measured. The results are shown in Table 4.

  From Table 1 and Table 2, it can be seen that a pigment dispersion composition having a low viscosity and a small particle size of pigment particle aggregates contained in the composition can be obtained by the dispersant of the present invention. This pigment dispersion composition It can be seen that by using as a mill base, the pigment can be dispersed with high dispersibility in a vehicle for UVIJ ink comprising a resin monomer or the like.

  Table 3 and Table 4 show that the UVIJ ink containing the dispersant of the present invention can provide a cured coating film having excellent blackness, gloss and rubbing resistance.

Claims (12)

(A) one or more polar groups or polar molecular chains selected from acidic functional groups, neutralized bases of acidic functional groups, basic functional groups, neutralized bases of basic functional groups, and nonionic polar molecular chains;
(B) a molecular chain having an alkyl or alkenyl group derived from fats and oils, a molecular chain having an alkyl group or alkenyl group having 6 or more carbon atoms, a molecular chain having a molecular unit having 4 or more carbon atoms as a repeating unit, and a rosin skeleton or One or more low-polar molecular chains selected from molecular chains containing a hydrogenated rosin skeleton,
(C) A dispersant having an active energy ray-curable unsaturated group, comprising a resin containing an active energy ray-curable unsaturated group.   The dispersant having an active energy ray-curable unsaturated group according to claim 1, wherein the resin is a polyurethane resin.   The all or part of the polar group or polar molecular chain (A), the low polar molecular chain (B) and the active energy ray-curable unsaturated group (C) are contained in the side chain of the resin. Or the dispersing agent which has an active energy ray hardening unsaturated group of Claim 2.   4. The active energy ray according to claim 1, wherein all or part of the polar group or polar molecular chain (A) is a basic functional group or a neutralized base of a basic functional group. 5. A dispersant having a curable unsaturated group.   The nonionic polar molecular chain is a polyoxyethylene ether molecular chain having three or more oxyethylene ether repeating units, and constitutes the main chain of the resin or a side chain bonded to the main chain of the resin or its terminal The dispersant having an active energy ray-curable unsaturated group according to any one of claims 1 to 4.   All or part of the active energy ray-curable unsaturated group (C) is an acryloyl group or a methacryloyl group, and the concentration of the acryloyl group or the methacryloyl group is 0.2 to 3.0 mol / kg. The dispersing agent which has an active energy ray-curable unsaturated group of any one of Claims 1-5. The resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom,
At least a part of the bifunctional compound having a hydroxyl group or an active hydrogen atom is a side chain of a polar group or polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C). Is comprised of
A polar group or polar molecular chain (A), a low polar molecular chain (B) or an active energy ray-curable unsaturated group (C) is used as a side chain with respect to the total number of moles of the bifunctional compound having a hydroxyl group or an active hydrogen atom. The ratio of the total number of moles of the bifunctional compound which has a hydroxyl group or an active hydrogen atom to comprise is 20-100 mol%, The active energy ray hardening unsaturated of any one of Claims 1-6 A dispersant having a group. The resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom,
At least a part of the bifunctional compound having a hydroxyl group or an active hydrogen atom is
The following general formula (I):

(In the general formula (I), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ and R 2 ^At least one of ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ¹ and R ² may be the same or different, and R ³ is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these. )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (IV):

(In the general formula (IV), ^{R 4} and ^{R _5,} -C _p H _{2p -OH,} a _{-C q H 2q -COO-C r} H 2r -OH or an active hydrogen atom, and, ^{R 4} and R at least one of the ^five _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer from 1 to 4, R ⁴ and R ⁵ may be the same or different, and R ⁶ is
The following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a group containing a low-polar molecular chain represented by
Or a group containing a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units,
A group containing a polyether having two or more molecular units having 4 or more carbon atoms as repeating units,
It is a group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as repeating units, or a group containing a polycaprolactone having two or more molecular units having 4 or more carbon atoms as repeating units. )
The dispersant having an active energy ray-curable unsaturated group according to any one of claims 1 to 7, which is a compound having a hydroxyl group or an active hydrogen atom represented by: The resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom,
At least a part of the bifunctional compound having a hydroxyl group or an active hydrogen atom is
The following general formula (IX):

(In General Formula (IX), R ⁷ and R ⁸ are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ⁷ and R 8 ^At least one of ⁸ is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ⁷ and R ⁸ may be the same or different, and R ⁹ is represented by the following general formula (X):

(In general formula (X), d is an integer of 1-4, and e is an integer of 5-30.)
A nonionic polar molecular chain-containing group represented by )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (XI):

(In General Formula (XI), R ¹⁰ and R ¹¹ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ¹⁰ and R 11 at least one of the ¹¹ _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, and R ⁴ and R ⁵ may be the same or different, and R ¹² represents the following general formula (XII):

(In general formula (XII), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
It is a low polar molecular chain containing group represented by these. )
The dispersant having an active energy ray-curable unsaturated group according to any one of claims 1 to 8, wherein the dispersant has a hydroxyl group or an active hydrogen atom.   A pigment dispersion composition comprising a pigment and a dispersant having an active energy ray-curable unsaturated group according to any one of claims 1 to 9.   An active energy ray-curable ink comprising a pigment and a dispersant having an active energy ray-curable unsaturated group according to any one of claims 1 to 9.   An active energy ray-curable coating material comprising a pigment and a dispersant having an active energy ray-curable unsaturated group according to any one of claims 1 to 9.