JP2008144032A - Inkjet ink and color filter substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide inkjet ink of stable injection by an inkjet method, and a color filter substrate formed using the ink by the inkjet method. <P>SOLUTION: The inkjet ink comprises a solvent comprising an ester derivative of a trihydric or higher-hydric alcohol, a pigment, a pigment derivative, a dispersing resin and a thermally reactive compound. The inkjet ink that comprises triacetin as the ester derivative of the trihydric or higher-hydric alcohol is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

 The present invention relates to an inkjet ink and a color filter substrate. The ink-jet ink of the present invention can be suitably used, for example, for producing a color filter substrate for a liquid crystal display panel.

 A liquid crystal display panel used for a thin television or the like includes a color filter substrate, a liquid crystal cell substrate, and a backlight unit as main components. The backlight unit is a light source provided on the back surface of the liquid crystal cell substrate. The liquid crystal of the liquid crystal cell substrate is filled between the TFT (thin film transistor) array substrate and the color filter substrate. On the color filter substrate, a repeating pattern of three primary colors (red, green, blue; RGB) is formed at a position facing each pixel of the TFT array substrate. A transparent electrode is provided on the entire surface of the color filter substrate, and the direction of the liquid crystal is controlled by the voltage with the pixel electrode of the TFT array substrate, and the amount of transmitted light is controlled.

 Specifically, the color filter substrate is formed by arranging three or more kinds of fine stripe-shaped filter segments of different colors in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine mosaic shape. The filter segments are arranged in a constant arrangement. A light shielding region (black matrix) having a certain width is provided between the filter segments in order to increase the display contrast of the color filter substrate. The width of the stripes constituting the color filter substrate and the length of one side of the mosaic are as fine as about 70 μm, and are arranged in a predetermined order for each hue. Moreover, the film thickness of a normal color filter substrate is 0.8 to 1.5 μm, and the pigment occupies 25 to 45% by weight in the filter segment.

Conventionally, a color filter substrate is manufactured by applying a photoresist solution in which a pigment is dispersed on a transparent substrate, and then repeating processes such as drying, exposure, development, and curing. Therefore, productivity is low and the demand for cost reduction is high. In particular, with the increase in size of liquid crystal display panels, a technique for replacing photoresist has been demanded. In accordance with these requirements, manufacturing methods and manufacturing facilities have been reviewed, and the manufacture of color filter substrates by the inkjet method has attracted attention. The inkjet method is particularly advantageous in that the manufacturing apparatus can be easily downsized and the productivity is high. Furthermore, in recent years, due to the advancement of technology relating to printer heads and inks, pigment-based inks have begun to be used in the ink jet method, and as a result, light resistance and fastness have also been improved. Also from this point, various proposals have been made, in which it is advantageous to apply the ink jet method to color filter substrate applications (for example, Patent Documents 1 to 3).
JP-A-1-217302 Japanese Patent Laid-Open No. 7-174915 JP-A-8-75916

  The formation of the filter segment by the ink jet method is performed by providing a black matrix on a transparent substrate in advance and filling the region divided by the black matrix with the ink by the ink jet method. At this time, if the solid content of the ink is low and / or the pigment concentration is low, in the process of creating a color filter having a desired color density, the ink overflows beyond the black matrix and the ink is mixed into the adjacent area. In addition, the hue of the filter segment may be impaired. Therefore, the ink used for the color filter is required to have a high solid differentiation and a high pigment concentration.

  However, high solidification and high pigment concentration reduces the amount of solvent in the ink and makes it easy to dry. As a result, the ink viscosity increases at the nozzle part of the inkjet head, making the discharge unstable, and the vicinity of the nozzle The solid matter adheres to the surface of the nozzle and the flight direction of the droplet is bent. In some cases, the solid matter is deposited inside the nozzle and non-ejection occurs, which adversely affects the ejection.

  Accordingly, an object of the present invention is to provide an inkjet ink that can be stably ejected by an inkjet method. Another object of the present invention is to provide a color filter substrate formed by an ink jet method using the above ink.

  According to the present invention, the above-described problems can be solved by an inkjet ink containing at least an ester derivative of a trihydric or higher polyhydric alcohol, a pigment, a pigment derivative, a dispersion resin, and a thermally reactive compound.

  In a further preferred embodiment of the inkjet ink according to the present invention, the ester derivative of the trihydric or higher polyhydric alcohol is triacetin.

  In still another preferred embodiment of the inkjet ink according to the present invention, the solvent used in combination with the ester derivative of the trihydric or higher polyhydric alcohol has a boiling point of 200 ° C. or higher, and a dialkylene glycol monoalkyl ether compound, or Trialkylene glycol monoalkyl ether compound.

In a preferred embodiment of the inkjet ink according to the present invention, the proportion of the ester derivative of the trihydric or higher polyhydric alcohol is 3 to 50% by weight based on the total amount of the solvent.
As a preferred form of the inkjet ink according to the present invention, the pigment derivative is represented by the general formula (1):
General formula (1)
G ¹ -eq
(In the formula, G ¹ is a q-valent chromogenic compound residue, e is a basic substituent, an acidic substituent, or a neutral substituent, and q is an integer of 1 to 4)
It is a compound represented by these.

  In a preferred embodiment of the inkjet ink according to the present invention, the pigment derivative comprises a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. It contains at least one basic derivative selected from the group.

 As a preferable form of the ink-jet ink according to the present invention, the dispersion resin is one or more of the following (a) to (e).

(A) a dispersion resin containing one or more phosphoric acid groups or a dispersion resin containing a monomer represented by the general formula (2) as a polymerization component,
(B) a polyester-based dispersion resin represented by the general formula (3),
(C) a vinyl-based dispersion resin containing the carboxyl group-containing unit (G) represented by the general formula (4) in an average amount of 0.3 to 3.0 per molecule of the vinyl polymer;
(D) Terminal obtained by reacting polyisocyanate (da) having three or more isocyanate groups with monoalcohol (db) at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. For isocyanate compounds,
A compound (dc) having one or more acidic groups and two or more hydroxyl groups;
A condition in which a polyol compound containing an acrylic resin (dd) and / or a siloxane resin (de) having two or more hydroxyl groups present with 1 to 30 atoms sandwiched therebetween is excessive in hydroxyl groups A dispersion resin obtained by polymerization with
Branched urethane-based dispersion resin (A) in which the proportion derived from polyisocyanate (da) in the nonvolatile component is 25% to 60% by weight,
(E) Terminal obtained by reacting polyisocyanate (ea) having three or more isocyanate groups with monoalcohol (eb) at a molar ratio of NCO / OH = 3/2 to 3 / 0.5 For isocyanate compounds,
A polyol compound containing an acrylic resin (ed) and / or a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms sandwiched between them under the condition that the hydroxyl group is excessive. A hydroxyl group in a terminal hydroxyl group compound obtained by polymerization;
A dispersion resin obtained by reacting an acid anhydride group in a compound having an acid anhydride group (eg),
Branched urethane type dispersion resin (B) whose ratio derived from the polyisocyanate (ea) in a non-volatile component is 25 to 60 weight%.

General formula (2):

(In General Formula (2), R ¹ represents hydrogen or a methyl group.
R ² represents an alkylene group.
m represents an integer of 1 to 20. )

General formula (3):
(HOOC-) _e -R ^a1 -(-COO-[-R ^a3 -COO-] _f -R ^a2 ) _g
(In the general formula (3), R ^a1 is a tetravalent tetracarboxylic acid compound residue,
R ^a2 is a monoalcohol residue,
R ^a3 is a lactone residue,
e represents an integer of 2 or 3, f represents an integer of 1 to 50, and g represents (4-e). )

General formula (4):

(In general formula (4),
R ^b1 is a hydrogen atom or a methyl group,
X ¹ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—;
X ² is a group represented by the following general formula (23),
X ³ is a group represented by the following general formula (24),
Y ¹ is a group represented by the general formula (5) or a group represented by the general formula (6). )

Formula (23)
-(-R ^b2 -O-) _m1-
(In General Formula (23), R ^b2 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m1 is an integer of 1 to 50. is there.)

General formula (24)
-(-CO-R ^b3 -O-) _m2-
(In the general formula (24), R ^b3 is a linear or branched alkylene group having 4 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is an integer of 0 to 20. is there.)

General formula (5)

(In general formula (5),
A combination in which ^{one of} A ^{1 to} A ³ is a hydrogen atom and the other two are —COOH;
A one is -COOR ^c1 of the A ¹ to A ^3, a or the other two are combined is -COOH, or three of A ¹ to A ³ is -COOH, k is 1 or 2 It is.
R ^c1 is an alkyl group having 1 to 18 carbon atoms. )

General formula (6)

(In general formula (6),
A combination in which one of A ^{5 to} A ⁷ is a hydrogen atom and the other two are —COOH;
One of A ^{5 to} A ⁷ is —COOR ^d2 and the other two are combinations that are —COOH, or three of A ^{5 to} A ⁷ are —COOH.
However, ^Rd2 is a C1-C18 alkyl group.
R ^d1 is a group represented by a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, formula (25), or a formula It is group represented by (26). )

  In a preferred embodiment of the inkjet ink according to the present invention, the thermally reactive compound is selected from the group consisting of a melamine compound, a benzoguanamine compound, an epoxy compound, a phenol compound, a blocked isocyanate compound, an acrylate monomer, and a silane coupling agent. 1 type or 2 types or more of compounds.

  In a preferred embodiment of the ink-jet ink according to the present invention, a binder resin is further included.

 In a preferred embodiment of the inkjet ink according to the present invention, the solid content is 3 to 60% by weight based on the total weight of the ink composition.

  In a preferred embodiment of the inkjet ink according to the present invention, the content of the pigment is 1 to 30% by weight based on the total weight of the ink composition.

  In a preferred embodiment of the inkjet ink according to the present invention, the weight ratio of the pigment to the dispersion resin is 100: 3 to 100: 150.

  In a preferred embodiment of the inkjet ink according to the present invention, the viscosity at 25 ° C. is 2 to 40 mPa · s.

  The present invention also relates to a color filter substrate carrying a printing layer made of inkjet ink.

  The inkjet ink of the present invention contains a pigment, a pigment derivative, a dispersion resin, a heat-reactive compound, and an ester derivative of a trihydric or higher polyhydric alcohol as a solvent, so that it has a high solid content and a high pigment concentration. Excellent stability and ejection properties. Therefore, when a color filter is produced using the ink composition for ink jet recording of the present invention, non-ejection and flying bending are unlikely to occur, and the yield can be improved.

[Solvent]
The inkjet ink of the present invention is characterized by containing an ester derivative of a trihydric or higher polyhydric alcohol as a solvent.

    In general, it is known to suppress ink evaporation as a method for improving ejection stability, and a solvent having a high boiling point and a low vapor pressure such as a solvent having a hydroxyl group is used. However, when a solvent having a large proportion of hydroxyl groups in the molecule is used, the polarity of the solvent is increased and the pigment dispersion stability is lowered, which causes an increase in ink viscosity over time. Therefore, as an improvement measure, it is conceivable to improve the dispersion stability by reducing the proportion of hydroxyl groups in the solvent molecule, such as acetylation of hydroxyl groups. An ester derivative of an alcohol is suitable.

  Examples of the trihydric or higher polyhydric alcohol that can be used in the present invention include trivalent polyhydric alcohols such as glycerin, butanetriol, pentanetriol, trimethylolethane, and trimethylolpropane, and tetravalent polyhydric alcohols such as diglycerin and pentaerythritol. And polyhydric alcohols having a valence of 4 or more, such as polyhydric alcohols, sorbitol and dipentaerythritol. Among them, a trivalent polyhydric alcohol is preferable to give an appropriate boiling point, and glycerin is particularly preferable among them.

  Examples of ester derivatives of trihydric or higher polyhydric alcohols that can be used in the present invention include triacetin.

  In the present invention, an organic solvent usually used in ink-jet inks can be used as a solvent used in combination with an ester derivative of a trihydric or higher polyhydric alcohol.

  As a solvent used in combination with an ester derivative of a trihydric or higher polyhydric alcohol, a (di / tri) alkylene glycol monoalkylene ether compound having a boiling point of 200 ° C. or higher is particularly preferable.

Specifically, dialkylene glycol monoalkylene such as ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether Ether compounds,
Examples include trialkylene glycol monoalkylene ether compounds such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether.

  Among these, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate can be particularly preferably used.

  In the inkjet ink of the present invention, the ester derivative of the trihydric or higher polyhydric alcohol is preferably blended in an amount of 3 to 50% by weight, more preferably 5 to 30% by weight, based on the total weight of the solvent. Yes. If the blending amount is less than 3% by weight, the ejection performance may be significantly deteriorated due to ink drying in the ink jet head portion. If the blending amount is more than 50% by weight, the drying process after landing of the ink on the base material becomes long. As a result, production efficiency may decrease.

[About pigments]
The pigment constituting the ink-jet ink of the present invention is colored in a desired hue, and is preferably excellent in heat resistance, chemical resistance, liquid crystal resistance, and light resistance.

 As the pigment, for example, an organic pigment, an inorganic pigment, or carbon black (for example, acetylene black, channel black, furnace black, etc.) can be used, and two or more kinds of pigments can be mixed and used.

  Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments (eg, azo, disazo, polyazo, etc.), phthalocyanine pigments (eg, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc.), anthraquinone type Pigment (for example, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, violanthrone, etc.), quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, iso Examples thereof include indoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red rose, and molybdenum. Red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, bitumen, cobalt blue, cerulean Blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, and the like can be given.

  In the following, pigments that can be used in the ink-jet ink of the present invention are indicated by color index (CI) numbers.

  Examples of red inkjet ink include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, Red pigments such as 272 can be used. A yellow pigment or an orange pigment can be used in combination with the red inkjet ink.

  Examples of yellow inkjet ink include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 It can be used yellow pigments such 177,179,180,181,182,185,187,188,193,194,199.

  Examples of the orange inkjet ink include C.I. I. Orange pigments such as CI Pigment Orange 36, 43, 51, 55, 59, and 61 can be used.

  Examples of green inkjet ink include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green inkjet ink.

  Examples of blue inkjet ink include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. For blue inkjet ink, C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  These pigments can be used in combination of two or more.

  The particle diameter of the pigment is preferably sufficiently small with respect to the wavelength of visible light from the viewpoint of the absorption coefficient of visible light (appropriate spectrum) and transparency. That is, the pigment preferably has an average primary particle size of 10 nm to 300 nm, particularly 10 nm to 100 nm. The primary particle diameter refers to the diameter of the smallest unit pigment particle, and is measured with an electron microscope.

  The primary particle diameter of the pigment can be controlled within an appropriate range using a known dispersing device such as a sand mill, a kneader, or a two roll.

[About pigment derivatives]
As a pigment derivative used for this invention, what is shown by following General formula (1) can be used, for example.

General formula (1)
G ¹ -eq
(In the formula, G ¹ is a q-valent chromogenic compound residue,
e is a basic substituent, an acidic substituent, or a neutral substituent;
q is an integer of 1 to 4. )

  As a basic substituent, the substituent shown by following General formula (8), General formula (9), General formula (10), or General formula (11) is mentioned, for example.

General formula (8):

(In general formula (8),
_{X: -SO 2 -, - CO} -, - CH 2 NHCOCH 2 -, - CH 2 -, or a direct bond.
n represents an integer of 1 to 10.
R ³ and R ⁴ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ³ and R ⁴ Represents an optionally substituted heterocycle containing a nitrogen, oxygen, or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. )

General formula (9):

(In general formula (9),
R ⁵ and R ⁶ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ⁵ and R ⁶ Represents an optionally substituted heterocycle containing a nitrogen, oxygen, or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. )

General formula (10):

(In the general formula (10),
_{X: -SO 2 -, - CO} -, - CH 2 NHCOCH 2 -, - CH 2 -, or a direct bond.
R ⁷ : represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred. )

General formula (11):

(In general formula (11),
_{X: -SO 2 -, - CO} -, - CH 2 NHCOCH 2 -, - CH 2 -, or a direct bond.
Y: represents —NR ¹² —Z—NR ¹³ — or a direct bond.
R ¹² and R ¹³ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
Z: represents an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.
P: A substituent represented by the following general formula (12) or a substituent represented by the following general formula (13).
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the general formula (9), or a substituent represented by the general formula (10). )

Formula (12):

(In general formula (12),
n2 represents an integer of 1 to 10.
R ¹⁴ and R ¹⁵ each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ¹⁴ and R ¹⁵ together. Represents an optionally substituted heterocycle containing a nitrogen, oxygen, or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable. )

General formula (13):

(In general formula (13),
R ^{16 represents} an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred. )
As an acidic or neutral substituent, the substituent shown by following General formula (14), General formula (15), or General formula (16) is mentioned, for example.

General formula (14)

(In general formula (14),
M: represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom.
l: represents the valence of M. )

General formula (15)

(In the general formula (15),
R ²¹ , R ²² , R ²³ , R ²⁴ : each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (except when all are hydrogen atoms). )

General formula (16)

(In general formula (16),
A: A hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ , or SO ₃ H is represented.
k ₁ represents an integer of _{1 to} 4. )
The chromogenic compound refers to a compound having a generally known dye skeleton and a compound having a skeleton similar to the dye skeleton, which hardly absorbs in the visible light region.

  Examples of the chromogenic compound residue include a diketopyrrolopyrrole dye residue, an azo dye residue (eg, azo, disazo, polyazo, etc.), a phthalocyanine dye residue, and an anthraquinone dye residue (eg, diamino). Dianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, etc.), quinacridone dye residue, dioxazine dye residue, perinone dye residue, perylene dye residue, thioindigo dye residue , Isoindoline dye residues, isoindolinone dye residues, quinophthalone dye residues, selenium dye residues, metal complex dye residues, anthraquinone residues, or triazine residues.

  Moreover, as an anthraquinone derivative, the anthraquinone which has the said basic, acidic, or neutral substituent can be used. Examples of triazine derivatives include alkyl groups (eg, methyl group, ethyl group), amino groups, alkylamino groups (eg, dimethylamino group, diethylamino group, dibutylamino group), nitro groups, hydroxyl groups, alkoxy groups. A group (for example, methoxy group, ethoxy group, butoxy group, etc.), or a halogen (for example, chlorine, etc.); a phenyl group optionally substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group, or the like; Alternatively, it may have a substituent such as a phenylamino group which may be substituted with a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group, a dimethylamino group, a diethylamino group, a nitro group, or a hydroxyl group. Use a derivative in which the above basic, acidic, or neutral substituent is introduced into 1,3,5-triazine. It can be.

  Among the pigment derivatives, particularly preferably, a basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. Including at least one species. By using a pigment derivative having basicity, the adsorptivity with a dispersion resin having an acidic group is remarkably improved, and not only the viscosity of the ink-jet ink of the present invention is lowered but also the dischargeability is improved.

[About dispersion resin]
In the ink-jet ink of the present invention, a known dispersion resin can be used, but it is preferable to use one or more of the following dispersion resins.

(A) Dispersion resin containing phosphoric acid group (b) Polyester dispersion resin represented by general formula (3) (c) Vinyl dispersion resin represented by general formula (4) (d) Branched urethane dispersion Resin A
(E) Branched urethane dispersion resin B
(A) Dispersion resin containing phosphoric acid group The dispersion resin containing a phosphoric acid group of the present invention has its chemical structure and production method as long as the dispersion resin has one or more phosphate groups. Is not particularly limited.

 Particularly limited phosphate groups include, for example, alkali metals (eg, sodium, potassium, lithium, etc.), polyvalent metals (eg, calcium, magnesium, aluminum, zinc, etc.), ammonia, or organic amines (eg, ethylamine, dibutylamine). , Triethanolamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, stearylamine, oleylamine, distearylamine, etc.) and a salt.

  The phosphate group contained in the resin having a phosphate group can be, for example, a monovalent phosphate group represented by the formula (17) or a divalent phosphate group represented by the formula (18). There can also be.

  As a resin having a phosphoric acid group, a vinyl containing a monomer represented by the following general formula (2) (for example, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, or propylene glycol acrylate phosphate) as a polymerization component. System polymers.

General formula (2):

(In General Formula (2), R ¹ represents hydrogen or a methyl group.
R ² represents an alkylene group.
m represents an integer of 1 to 20. )

Although the specific example of the monomer which has a phosphoric acid group is shown below, it is not restricted to this.
These monomers having a phosphate group can be produced, for example, by the methods described in JP-B-50-22536 and JP-A-58-128393. Examples of commercially available products include Phosmer M, Phosmer CL, Phosmer PE, Phosmer MH (manufactured by Unichemical Co., Ltd.), Light Ester P-1M (Kyoeisha Chemical Co., Ltd.), JAMP-514 (Johoku Chemical Co., Ltd.), Examples thereof include KAYAMER PM-2 and KAYAMERPM-21 (manufactured by Nippon Kayaku Co., Ltd.).

  These monomers having a phosphate group can be used alone or in combination of two or more. Further, the copolymerization ratio of the monomer having a phosphate group in the copolymer is preferably 0.1 to 30 parts by weight or less, and 0.1 to 5 parts by weight or less with respect to 100 parts by weight of all monomers. More preferably.

  The resin preferably further contains a hydroxyl group and a carboxyl group. The hydroxyl group and carboxyl group are not only slowly crosslinked by the esterification reaction, but also cause a crosslinking reaction with the melamine compound, so that the resistance is remarkably improved. Examples of the method for obtaining a resin having a hydroxyl group or a carboxyl group include, but are not limited to, a method obtained by copolymerizing a monomer having a hydroxyl group or a monomer having a carboxyl group and another acrylic monomer.

  Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl ( (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin (meth) acrylate, polyethylene glycol mono (meth) acrylate (n = 2 to 50), polycaprolactone-modified hydroxyethyl (meth) acrylate (repetition number of caprolactone = 1) -6), epoxy (meth) acrylate, hydroxyl-terminated urethane (meth) acrylate, N-methylolacrylamide, allyl alcohol, polyethylene glycol monomethacrylate, polyethylene glycol Monoacrylate, hydroxypropyl methacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, poly (ethylene glycol-propylene glycol) monomethacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, poly (ethylene glycol- Tetramethylene glycol) monomethacrylate, poly (ethylene glycol-tetramethylene glycol) monoacrylate, poly (propylene glycol-tetramethylene glycol) monomethacrylate, poly (propylene glycol-tetramethylene glycol) monoacrylate, propylene glycol polybutylene Glycol monomethacrylate, or propylene glycol polybutylene glycol mono acrylate.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-carboxyethyl acrylate, ω-carboxy-polycaprolactone monoacrylate, and phthalic acid monohydroxy. Examples include ethyl acrylate, glutaconic acid, or tetrahydrophthalic acid.

  Moreover, in order to make adsorption | suction with a pigment or a pigment derivative stronger, it is preferable that an aromatic ring is further included in the said resin.

  Examples of the monomer having an aromatic ring include benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, bisphenol F ethylene oxide-modified diacrylate, nonylphenoxypolyethylene glycol monoacrylate, nonylphenoxypolyethylene glycol-polypropylene glycol monomethacrylate. Nonylphenoxy polypropylene glycol-polyethylene glycol monomethacrylate, nonylphenoxy poly (ethylene glycol-propylene glycol) monoacrylate, phenol ethylene oxide modified acrylate, nonyl phenol ethylene oxide modified acrylate, and the like.

  Moreover, the monomer shown by the following general formula (19) or general formula (20) is also mentioned.

[In General Formula (19) and General Formula (20), R ²⁵ and R ²⁷ represent a hydrogen atom or a methyl group, R ²⁶ and R ²⁸ represent an alkylene group having 1 to 4 carbon atoms, and n ₃ represents 1 to Represents an integer of 100]
Examples of the monomer represented by the general formula (19) or the general formula (20) include paracumylphenol ethylene oxide modified acrylate, ethylene oxide modified bisphenol A dimethacrylate, ethylene oxide modified bisphenol A diacrylate, and propylene oxide modified bisphenol A. Dimethacrylate, propylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, ethylene oxide-propylene oxide modified bisphenol A diacrylate, propylene oxide ethylene oxide (block type) modified bisphenol A dimethacrylate, propylene oxide tetra Methylene oxide modified bisphenol A di Methacrylate, or and propylene oxide tetramethylene oxide-modified bisphenol A diacrylate.

  Examples of the monomer other than the monomer including a hydroxyl group, a carboxyl group, and / or an aromatic ring include, for example, (meth) acrylic acid alkyl esters [for example, methoxypolyethylene glycol monomethacrylate, methoxypolyethyleneglycol monoacrylate, octoxypolyethyleneglycol. Monoacrylate, octoxy polyethylene glycol polypropylene glycol monomethacrylate, octoxy polyethylene glycol polypropylene glycol monoacrylate, lauroxy polyethylene glycol monoacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate, stearoxy polyethylene glycol-polypropylene glycol mono Acrylate Allyloxy polyethylene glycol-polypropylene glycol monomethacrylate, allyloxy polyethylene glycol-polypropylene glycol monoacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, poly Tetramethylene glycol dimethacrylate, polytetramethylene glycol diacrylate, poly (ethylene glycol-tetramethylene glycol) dimethacrylate, poly (ethylene glycol-tetramethylene glycol) diacrylate, poly (propylene glycol-tetramethylene glycol) Dimethacrylate, poly (propylene glycol-tetramethylene glycol) diacrylate, polyethylene glycol-polypropylene glycol-polyethylene glycol diacrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc.], amino group-containing acrylic monomer [eg, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate etc.] or vinyl acetate etc. may be mentioned, but not limited thereto. Moreover, the monomer generally used for the synthesis | combination of an acrylic resin, such as the alkyl (meth) acrylate by which one part or all part of the hydrogen atom of the alkyl group is substituted by the heterocyclic ring or the halogen atom, can also be used.

  The weight average molecular weight (Mw) of the resin having a phosphate group is preferably 1000 to 50000, more preferably 2000 to 30000.

  Synthesis of a resin having a phosphoric acid group is performed in the presence of a polymerization initiator in an inert gas stream at 50 to 150 ° C. over 2 to 10 hours. If necessary, it may be performed in the presence of a solvent. Examples of the polymerization initiator include organic peroxides (for example, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate, etc. ) Or an azo compound (for example, 2,2′-azobisisobutyronitrile and the like). The polymerization initiator is preferably used in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the monomer.

  Examples of the solvent used at the time of resin synthesis include acetate solvents (eg, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate), ketone solvents (eg, cyclohexanone, methyl isobutyl ketone, etc.), xylene, or Examples include ethylbenzene.

  A commercially available resin can also be used as the resin having a phosphate group. Examples of commercially available resins include Dispers BYK110, 111, and 180 manufactured by Big Chemie, and SOLPERSE 26000 and 36600 manufactured by Avicia.

(B) Polyester-based dispersion resin As long as the (b) polyester-based dispersion resin that can be used in the present invention has a structure represented by the following general formula (3), its chemical structure and production method are particularly limited. is not. The production method includes, for example, a first step of producing a polyester having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, a polyester having a hydroxyl group at one end, and a tetracarboxylic acid. A method comprising a second step of reacting dianhydride is preferred.

General formula (3):
(HOOC-) _e -R ^a1 -(-COO-[-R ^a3 -COO-] _f -R ^a2 ) _g
(In the general formula (3), R ^a1 is a tetravalent tetracarboxylic acid compound residue,
R ^a2 is a monoalcohol residue,
R ^a3 is a lactone residue,
e represents an integer of 2 or 3, f represents an integer of 1 to 50, and g represents (4-e). )

  The monoalcohol that can be used for the production of the (b) polyester-based dispersion resin is not particularly limited as long as it is a compound having one hydroxyl group. The aliphatic monoalcohol is, for example, preferably a linear or branched substituted or unsubstituted saturated aliphatic monoalcohol having 1 to 30 carbon atoms (more preferably 1 to 25 carbon atoms), or a carbon atom. Examples thereof include substituted or unsubstituted saturated alicyclic monoalcohols having 1 to 30 (more preferably 1 to 25 carbon atoms). Examples of the substituent of the saturated aliphatic monoalcohol or saturated alicyclic monoalcohol include a carboxyl group.

  Examples of aliphatic monoalcohols are methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, 4-methyl-2-pentanol. 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2- Examples include octyl decanol, 2-octyl decanol, 2-hexyl decanol, behenyl alcohol, and oleyl alcohol. Examples of the alicyclic monoalcohol include cyclohexanol.

  As the aliphatic monoalcohol, a branched aliphatic monoalcohol is preferable. For example, the number of carbon atoms is 8 to 20 such as 2-ethylhexanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, or 2-hexyldecanol. Are preferred.

  As the monoalcohol, a substituted or unsubstituted aromatic monoalcohol having 6 to 30 carbon atoms (more preferably 6 to 25 carbon atoms), for example, phenol or cumylphenol can be used. A saturated aliphatic monoalcohol having an aliphatic group having 1 to 6 carbon atoms and substituted with an aromatic group having 6 to 10 carbon atoms, such as benzyl alcohol, can also be used.

  Furthermore, as the monoalcohol, monoalkylene glycol monoether having a hydroxyl group at one end or polyalkylene glycol monoether having a hydroxyl group at one end can be used. As these monoalkylene glycol monoethers or polyalkylene glycol monoethers, preferably, mono or polyethylene glycol or mono or polypropylene glycol alkyl monoethers having 1 to 8 carbon atoms can be mentioned. Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene Glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, trie Lenglycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, triethylene glycol Propylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetra Ethylene glycol monob Chill ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl Mention may be made of alkylene glycol monoalkyl ethers such as ether, tetrapropylene glycol mono-2-ethylhexyl ether and tetradiethylene glycol monomethyl ether.

  Furthermore, examples of the monoalcohol that can be used for the production of the (b) polyester-based dispersion resin include monoalcohols having one or more ethylenically unsaturated double bonds. Examples of the ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group, and a (meth) acryloyl group is preferable. These can be compounds having different types of double bonds in one compound.

  As the monoalcohol having an ethylenically unsaturated double bond, for example, an unsaturated monoalcohol compound having one, two, or three or more ethylenically unsaturated double bonds can be used. Examples of monoalcohols having one ethylenically unsaturated double bond include hydroxyalkyl esters of (meth) acrylic acid having 1 to 8 carbon atoms, such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2 -Hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, and the like can be mentioned.

  Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate or glycerin di (meth) acrylate. Examples of the monoalcohol having three ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having five ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate. be able to.

  Alcohols obtained by addition polymerization of alkylene oxide starting from the hydroxyl group of the aliphatic monoalcohol, aromatic monoalcohol, and monoalcohol having an ethylenically unsaturated double bond exemplified above, that is, one end is ether Polyalkylene glycols that have been converted to or esterified can also be used in the production of (b) polyester-based dispersion resins. As the alkylene oxide used for the addition polymerization, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, or a mixture of two or more thereof is used. be able to. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. The addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, and particularly preferably 5 to 100 in one molecule.

The addition of alkylene oxide can be carried out by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. Commercially available products of the addition polymerization product thus obtained include Nippon Oil & Fats Uniox series or Nippon Oil & Fats Bremer series.
Specifically, UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP-1000, PP -500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET series, 30PPT -800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, or 10APB-500B.

  The monoalcohol that can be used in the production of the (b) polyester-based dispersion resin is not limited to the above examples, and any compound can be used as long as it is a compound having one hydroxyl group. Also, two or more types can be used in combination.

  Among the above monoalcohols, for example, 4-methyl-2-pentanol, isopentanol, isooctanol, 2-ethylhexanol, isononanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, or 2- By using a branched aliphatic monoalcohol such as hexyldecanol, or a polyalkylene glycol having a hydroxyl group at one end, the crystallinity is lowered and may become liquid at room temperature. It is preferable in terms of compatibility.

  By performing ring-opening polymerization of a lactone using the monoalcohol as an initiator, a polyester having a hydroxyl group at one end and usable for the production of the (b) polyester-based dispersion resin can be obtained. The lactone that can be used in the ring-opening polymerization is preferably a 4-membered to 10-membered ring, more preferably a 5-membered to 7-membered lactone, and the ring-constituting carbon atom is substituted or unsubstituted. Can be. Examples of the substituent of the ring-constituting carbon atom include an alkyl group having 1 to 4 carbon atoms. Also, an unsaturated lactone containing one or more ethylene bonds in the ring, or a condensed lactone with an aromatic compound (for example, benzene) can be used.

  Specific examples of suitable lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone. Of these, δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone is preferably used from the viewpoint of ring-opening polymerizability. Examples of the alkyl substituent include an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group, and can be substituted with one or more of these alkyl substituents. .

  The lactone can be used without being limited to the above examples, and can be used alone or in combination of two or more. When two or more types are used in combination, the crystallinity is lowered and may become liquid at room temperature, which is preferable in terms of workability and compatibility with other resins.

  The ring-opening polymerization of the monoalcohol and the lactone can be carried out in a known manner, for example, by charging the monoalcohol, the lactone, and the polymerization catalyst in a reactor connected to a dehydrating tube and a condenser and under a nitrogen stream. . When a low-boiling monoalcohol is used as the monoalcohol, it can be reacted under pressure using an autoclave. Moreover, when using the compound which has an ethylenically unsaturated double bond as said monoalcohol, it is preferable to add a polymerization inhibitor and to react under a dry air flow.

  The number of moles of the lactone added per mole of the monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles. When the added mole number is less than 1 mole, the effect as a dispersant cannot be obtained. When the added mole number is more than 50 moles, the molecular weight of the dispersant becomes too large, resulting in a decrease in dispersibility and fluidity.

  Examples of the polymerization catalyst for the ring-opening polymerization include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethyl. Quaternary ammonium salts such as ammonium bromide or benzyltrimethylammonium iodide, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, Benzyltrimethylphosphonium bromide In addition to quaternary phosphonium salts such as benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, or tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, potassium acetate, sodium acetate, potassium benzoate, or benzoic acid In addition to organic carboxylates such as sodium acid salt, alkali metal alcoholates such as sodium alcoholate or potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride, etc. be able to. The catalyst is used in an amount of 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When the amount of the catalyst is 3000 ppm or more, the (b) polyester-based dispersion resin is intensely colored, which adversely affects the stability of the product. On the contrary, if the amount of the catalyst used is 0.1 ppm or less, the rate of ring-opening polymerization of the cyclic ester is extremely slow, which is not preferable.

  The ring-opening polymerization reaction can be carried out without a solvent, or a suitable dehydrated organic solvent can be used. The solvent used in the ring-opening polymerization reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as it is as a part of the ink composition for ink jet recording.

  The ring-opening polymerization reaction is preferably performed in the range of 100 ° C. to 220 ° C., more preferably 110 ° C. to 210 ° C. If the reaction temperature is less than 100 ° C, the reaction rate is very slow, and if it exceeds 210 ° C, side reactions other than the addition reaction of lactone, such as decomposition of lactone adducts into lactone monomers, formation of cyclic lactone dimers and trimers, etc. are likely to occur. .

  As a polymerization inhibitor used when using a monoalcohol having an ethylenically unsaturated double bond, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, Alternatively, phenothiazine or the like is preferable, and these can be used alone or in combination, and the amount used is preferably 0.01% to 6%, more preferably 0.05% to 1.0%.

  The (b) polyester-based dispersion resin used in the present invention reacts a hydroxyl group of a polyester having a hydroxyl group at one end obtained in the first step with a tetracarboxylic dianhydride (second step). ) Is preferably obtained.

  Examples of tetracarboxylic dianhydrides used in the second step include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and heterocyclic tetracarboxylic acids. An acid dianhydride or a polycyclic tetracarboxylic dianhydride can be mentioned.

  Specifically, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride, or 1,2,3,4-cyclobutanetetracarboxylic dianhydride, , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride Product, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, or bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Of alicyclic tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, or 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene It can be mentioned heterocyclic tetracarboxylic acid anhydrides such as down-1,2-dicarboxylic acid anhydride.

  Further, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4 , 4′-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dica Boxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide Anhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride Bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene Anhydrides, or aromatic tetracarboxylic dianhydrides such as 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, or 3,4-dicarboxy-1,2 , 3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Mention may be made of the formula tetracarboxylic dianhydride.

  As the aromatic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride having two or more aromatic rings is particularly preferable, and in particular, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride. Product, ethylene glycol ditrimellitic anhydride ester, or 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride.

  The tetracarboxylic dianhydride that can be used in the production of the (b) polyester-based dispersion resin is not limited to the compounds exemplified above, and any structure having two carboxylic acid anhydrides may be used. It doesn't matter. These may be used alone or in combination. Furthermore, the tetracarboxylic dianhydride that can be suitably used for the production of the polyester-based dispersion resin (b) is an aromatic tetracarboxylic dianhydride from the viewpoint of reducing the viscosity of the pigment dispersion. A tetracarboxylic dianhydride having two or more aromatic rings (especially 2 to 4) is preferable.

  The reaction ratio in the second step is the ratio of the number of moles <N> of the anhydrous ring of the tetracarboxylic anhydride to the number of moles <H> of the hydroxyl group of the polyester having a hydroxyl group at one end [<H> / <N >] Is preferably 0.5 << H> / <N> <1.2, more preferably 0.7 << H> / <N> <1.1, and most preferably <H> / <N. > = 1. When the reaction is performed with <H> / <N> <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.

  A catalyst may be used in the second step. Examples of the catalyst include tertiary amine compounds such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, , 5-diazabicyclo- [4.3.0] -5-nonene.

  Both the first step and the second step may be performed without a solvent, or an appropriate dehydrated organic solvent may be used. The solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

  The reaction temperature is 80 ° C to 180 ° C, preferably 90 ° C to 160 ° C. When the reaction temperature is 80 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the half-esterified product again forms a cyclic anhydride, making it difficult to complete the reaction.

In the general formula (3), f is preferably an integer of 1 to 30, more preferably an integer of 2 to 20. In the general formula (3), when at least one of e and f is 2 or more, the plurality of R ^a3 present in the general formula (3) are all the same group, Groups can be included.

Preferably, R ^{a1 in the} general formula (3) is represented by the following formulas (27) to (29).

（式中、Ａは、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ₂ＣＨ₂ＯＣＯ−、−ＳＯ₂−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、式（３０）または式（３１）である。）

(In the formula, A represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, (It is (30) or Formula (31).)

Preferably, R ^{a2 in the} general formula (3) is an aliphatic alkyl group having 8 to 20 carbon atoms, or a terminal ether or ester polyoxyalkylene having a molecular weight of 200 to 1500 (the number of carbon atoms in the alkylene moiety is 2 to 2). 4) a group, R ³ is a hexamethylene group, a pentamethylene group, or an alkyl-substituted hexamethylene group, e is 2 or 3, f is an integer from 3 to 20, and g is ( 4-e) is a resin-type dispersant represented by the general formula (3).

  The ink composition for ink jet recording of the present invention may contain one or more (b) polyester-based dispersion resins represented by the general formula (3). In the ink composition for ink jet recording of the present invention, the (b) polyester-based dispersion resin represented by the general formula (3) is preferably 0.02 to 20% by weight based on the weight of the entire composition. It is preferably contained in an amount of 0.1 to 10% by weight. When the content of the resin-type dispersant is less than 0.02% by weight, the viscosity of the ink composition is not lowered, and when it exceeds 20% by weight, the film forming property of the ink may be lowered.

(C) Vinyl-based dispersion resin The (c) vinyl-based dispersion resin that can be used in the present invention includes a carboxyl group-containing unit (G) represented by the general formula (4) in the vinyl polymer main chain. The chemical structure and the production method are not particularly limited as long as the vinyl polymer has a structure containing an average amount of 0.3 to 3.0 per molecule of the vinyl polymer.

In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance between these two functional parts. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important. In the carboxyl group-containing unit (G) represented by the general formula (4), Y ¹ represented by the general formula (4) is two carboxyl groups directly bonded to the ring-constituting carbon atom of the aromatic ring or A plurality of carboxyl groups that are directly bonded to the ring-constituting carbon atoms of this aromatic ring are the adsorption sites of the pigment. However, when Y ¹ has only one carboxyl group (outside the scope of the present invention), high dispersibility, fluidity, and storage stability are not exhibited, which is not preferable.

  The (c) vinyl dispersion resin used in the present invention has an average of 0.3 to 3.0 carboxyl group-containing units (G) represented by the general formula (4) per molecule of the vinyl polymer. It is important to include: More preferably, it is 0.35 or more and 2.0 or less, and most preferably 0.4 or more and 1.5 or less. When the number is less than 0.3, the number of sites adsorbed on the pigment is small, and as a result, the dispersibility is lowered. On the other hand, when the number is more than 3.0, there are too many sites to be adsorbed to the pigment, and conversely, the dispersibility may be lowered.

In general formula (4), X ¹ is preferably —COO— from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability, and R ^b2 is a hydrocarbon group having 1 to 4 carbon atoms ( For example, a methylene group, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group is preferable, and m1 is preferably 1 to 10 (more preferably 1 to 3). ), R ^b3 is preferably a pentamethylene group, and m2 is preferably 0 to 5 (more preferably 0 to 3). In particular, Y ¹ is preferably a group represented by General Formula (5), and more preferably, in General Formula (5), all of A ^{1 to} A ³ are —COOH, and k is 1. Or a combination in which one of A ^{1 to} A ³ is a hydrogen atom, the other two are —COOH, and k is 1. Y ¹ can also be a group represented by the general formula (6). In this case, R ^d1 is represented by —COOCH ₂ CH ₂ OCO—, or a formula (25) or a formula (26). It is preferably a group.

One of A ^{5 to} A ⁷ is —COOR ^d2 (where R ^d is a linear or branched alkyl group having 6 to 10 carbon atoms), and the other two are —COOH. A combination is preferred.

  As the (c) vinyl-based dispersion resin used in the present invention, the general formula (21):

[In general formula (21),
G represents a carboxyl group-containing unit (G) represented by the general formula (4) according to claim 1,
R ²⁹ represents a hydrogen atom or a methyl group,
R ³⁰ represents a hydrogen atom or a methyl group,
R ³¹ is an aromatic group, or —CO—X ⁷ —R ³³ (where X ⁷ is —O— or —NH—, and R ³² is a hydrogen atom or a straight chain having 1 to 18 carbon atoms) A branched or branched alkyl group, and R ³² may have an aromatic group as a substituent),
X ⁴ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—;
X ⁵ is the formula:
-(-R ^b4 -O-) _m3- ,
(Wherein R ^b4 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m3 is an integer of 1 to 50)
A group represented by
X ⁶ is the formula:
-(-CO-R ^b5 -O-) _m4-
(Wherein R ^b5 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20)
A group represented by

Including the carboxyl group-containing unit (G) in the general formula (21), a hydroxyl group-containing unit (J) containing —X ⁴ —X ⁵ —X ⁶ —H, and —C (R ⁵ ) (R ⁶ ) —. The main chain structural unit (K) can be included in a random type or a block type,
When the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain constituent unit (K) contained in the general formula (21) are plural, And p1, p2, and p3 represent the average number of each structural unit per molecule of (c) vinyl-based dispersion resin, and p1 is 0.3 or more and 3.0 or less, p2 is 0 or more and 180 or less, and p3 is 6 or more and 250 or less]
A carboxyl group-containing unit (G) represented by general formula (21j)

〔一般式（２１ｊ）中、Ｒ⁴、Ｘ⁴、Ｘ⁵、及びＸ⁶は、前記と同じ意味である〕
で表される水酸基含有単位（Ｊ）と、一般式（２１ｋ）：

[In the general formula (21j), R ⁴ , X ⁴ , X ⁵ , and X ⁶ have the same meaning as described above.]
A hydroxyl group-containing unit (J) represented by the general formula (21k):

〔一般式（２１ｋ）中、Ｒ³⁰及びＲ³¹は、前記と同じ意味である〕
で表される主鎖構成単位（Ｋ）との各構成単位からなるブロック共重合体又はランダム共重合体を挙げることができる。

[In the general formula (21k), R ³⁰ and R ³¹ have the same meaning as described above.]
The block copolymer or random copolymer which consists of each structural unit with the main chain structural unit (K) represented by these can be mentioned.

Therefore, the preferred (c) vinyl-based dispersion resin used in the present invention is the general formula (21) or the general formula (21a):
-[G] p1- [J] p2- [K] p3- (21a)
It is a copolymer represented by these. Here, G is a carboxyl group-containing unit represented by the general formula (4), J is a hydroxyl group-containing unit represented by the general formula (21j), and K is the general formula (21k). ), P1 is 0.3 or more and 3.0 or less (preferably 0.35 or more and 2.0 or less, more preferably 0.4 or more and 1.5 or less), and p2 is 0. 180 or less (preferably 0.05 or more and 50 or less), and p3 is 6 or more and 250 or less (preferably 10 or more and 100 or less). In the general formula (21a), the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain constituent unit (K) each exist in a block copolymerization format or a random copolymerization format. Can do. Furthermore, the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain structural unit (K) can each be present in plural in the general formula (4a). In this case, each unit can be the same or different from each other. For example, the main chain structural unit (K) can include structural units having two or more structures.

In the hydroxyl group-containing unit (J) contained in the vinyl dispersion resin (c) used in the present invention represented by the general formula (21) or the general formula (21a), X ⁴ may be —COO—. R ^b4 is preferably a hydrocarbon group having 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a linear or branched propylene group or a linear or branched butylene group), m3 is preferably 1 to 10 (more preferably 1 to 3), R ^b5 is preferably a pentamethylene group, and m4 is preferably 0 to 5 (more preferably 0 to 3). .

In the vinyl dispersion resin (c) used in the present invention represented by the general formula (21) or the general formula (21a), R ³⁰ is a methyl group as the main chain constituent unit (K), and R ³¹ Preferably contains a main chain structural unit (K1) which is —CO—O—CH ₂ —Ar (wherein Ar is an aromatic group, particularly a phenyl group). The main chain structural unit (K1) preferably has an average amount of 1 or more and 100 or less per molecule of the vinyl polymer, and the (c) vinyl-based dispersion resin of this embodiment is excellent in dispersion ability. .

Further, in the vinyl-based dispersion resin used in the present invention represented by the general formula (21) or the general formula (21a), R ³⁰ is a methyl group as the main chain constituent unit (K), R ³¹ preferably contains a main chain structural unit (K2) in which —CO—O—R ³² (wherein R ³² is a linear or branched alkyl group having 2 to 10 carbon atoms). More preferably, the main chain structural unit (K2) coexists with the main chain structural unit (K1) in the vinyl-based dispersion resin (c).

Furthermore, in the (c) vinyl-based dispersion resin used in the present invention represented by the general formula (21) or the general formula (21a), R ⁵ is a methyl group as the main chain structural unit (K). , R ⁶ is an aromatic group (particularly a phenyl group), the main chain structural unit (K3) alone or in combination with the main chain structural unit (K1) and / or the main chain structural unit (K2). It is preferable to include. Furthermore, as the main chain structural unit (K), a main chain structural unit (K4) in which R ⁵ is a hydrogen atom and R ⁶ is a carboxyl group is converted into the main chain structural unit (K1), main chain structural unit ( K2) and / or the main chain structural unit (K3) can be included together.

  When the main chain structural unit (K1) and the main chain structural unit (K2) coexist, their ratio (K1 / K2) is, for example, 0.01 to 100, preferably 0.1 to 10. be able to. Further, when the main chain structural unit (K3) coexists with the main chain structural unit (K1) and / or the main chain structural unit (K2), the ratio [K3 / (K1 + K2)] is, for example, 0. It can be 01-10, preferably 0.05-2. Furthermore, when the main chain structural unit (K4) is allowed to coexist with the other main chain structural units (K), the ratio [K4 / K] is, for example, 0 to 0.1, preferably 0 to 0. .01.

  The end of the main chain of the vinyl-based dispersion resin (c) represented by the general formula (21) is derived from a known polymerization method of an ethylenically unsaturated monomer or a structure considered in the polymerization process, for example, a polymerization initiator It may have a chemical structure derived from a chain transfer agent, a solvent, or an ethylenically unsaturated monomer.

In the vinyl-based dispersion resin (c) used in the present invention, the main chain structural unit (K) in which R ⁶ is a carboxyl group (—COOH) in the general formula (21) is at least a part of the main chain structural unit (K). Can be included as However, when the content of the carboxyl group-containing main chain constituent unit (K) is too large, the dispersion performance is lowered. Therefore, the amount of the carboxyl group-containing main chain constituent unit (K) is the amount of the carboxyl group-containing unit (G). The number is preferably 0 to 4 times, more preferably 0 to 2 times the number.

  The number average molecular weight of the (c) vinyl-based dispersion resin used in the present invention is preferably 500 or more and 20000 or less, more preferably 1000 or more and 10,000 or less, and most preferably 1500 or more and 8000 or less. Even if the number average molecular weight is less than 500 or more than 20000, the dispersibility or fluidity may be lowered.

  The (c) vinyl-based dispersion resin used in the present invention can be prepared by the production method used in the present invention. According to the production method used in the present invention described later, not only the (c) vinyl-based dispersion resin but also (c) a vinyl-based dispersion resin having a wide structure including the (c) vinyl-based dispersion resin is produced. be able to. That is, the (c) vinyl-based dispersion resin used in the present invention can be prepared by selecting a specific starting material in the production method used in the present invention described later.

Examples of the method for producing (c) the vinyl-based dispersion resin used in the present invention include the following production methods 1 to 3.
Manufacturing method 1:
(A) A step of producing an ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4). ,
(B) It comprises a step of copolymerizing the ethylenically unsaturated monomer with another ethylenically unsaturated monomer.
Manufacturing method 2:
(C) a step of copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer,
The process comprises a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) with the hydroxyl group of the copolymer.
Manufacturing method 3:
While copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer, a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) is simultaneously added to the hydroxyl group. Let it react.

  As the ethylenically unsaturated monomer (h) having a hydroxyl group used in the above production method, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. Specifically, (meth) acrylate monomers having a hydroxyl group, for example, 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) ) -Hydroxybutyl (meth) acrylate and hydroxyalkyl (meth) acrylate such as cyclohexanedimethanol mono (meth) acrylate, or a (meth) acrylamide monomer having a hydroxyl group, such as N- (2-hydroxyethyl) ( (Meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydro) N- (hydroxyalkyl) (meth) acrylamide such as (cibutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2 -Hydroxyalkyl vinyl ethers such as-(or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, And hydroxyalkyl allyl ethers such as 2- (or 3- or 4-) hydroxybutyl allyl ether.

  In addition, an ethylenically unsaturated monomer obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether Can also be used as an ethylenically unsaturated monomer (h) having a hydroxyl group in the production method used in the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

  Examples of the tricarboxylic acid anhydride (M3) include aliphatic tricarboxylic acid anhydrides, aromatic tricarboxylic acid anhydrides, and polycyclic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride), etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides.

  Moreover, in the manufacturing method used by this invention, in tetracarboxylic dianhydride (M4) mentioned later with respect to tetracarboxylic dianhydride which has two acid anhydrides per molecule, it is 1 of 1 molecule. An acid anhydride is an alcohol having 1 to 18 carbon atoms or a cycloalcohol having 5 to 18 carbon atoms (for example, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or Branched pentanol or cyclopentanol, linear or branched hexanol or cyclohexanol, linear or branched heptanol or cycloheptanol, linear or branched octanol or cyclooctanol, linear Or branched nonanol or cyclononanol, linear Or branched decanol or cyclodecanol, linear or branched dodecanol or cyclododecanol, linear or branched myristyl alcohol or cyclomyristyl alcohol, linear or branched cetyl alcohol or cyclocetyl The tetracarboxylic anhydride monoester monoanhydride ring-opened with alcohol, linear or branched stearyl alcohol or cyclostearyl alcohol) is also used in the production method used in the present invention. ). In the present specification, an aliphatic tetracarboxylic acid monoester monoanhydride is an aliphatic tricarboxylic acid anhydride, an aromatic tetracarboxylic acid monoester monoanhydride is an aromatic tricarboxylic acid anhydride, a polycyclic tetracarboxylic acid anhydride. The monoester monoanhydride is described as a polycyclic tricarboxylic acid anhydride. Specific examples of these tetracarboxylic acid anhydride monoester monoanhydrides are obvious to those skilled in the art from the tetracarboxylic acid anhydrides described below.

  Examples of the tetracarboxylic acid anhydride (M4) include aliphatic tetracarboxylic acid anhydrides, aromatic tetracarboxylic acid anhydrides, and polycyclic tetracarboxylic acid anhydrides.

  Examples of the aliphatic tetracarboxylic acid anhydride include 1,2,3,4-butanetetracarboxylic acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5,6-tricarboxy Norbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic anhydride and the like can be mentioned.

  Examples of the aromatic tetracarboxylic anhydride include pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride, 2,3,6 , 7-Naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-Tetraphenylsilanetetracarboxylic anhydride, 1,2,3,4-furantetracarboxylic acid Water, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, Bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4 '-Diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane anhydride, 9,9-bis (3,4-dicar Kishifeniru) fluorene anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene anhydride, and the like.

  Examples of the polycyclic tetracarboxylic acid anhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid anhydride and 3,4-dicarboxy-1,2,3. , 4-tetrahydro-6-methyl-1-naphthalene succinic anhydride and the like.

  The tetracarboxylic acid anhydride may be either monoanhydride or dianhydride.

  Among the above, it is preferable to use an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride, more preferably trimellitic acid anhydride, pyromellitic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride. 2,3,6,7-naphthalenetetracarboxylic acid anhydride is preferable, and trimellitic acid anhydride is more preferable.

  The production method 1 used in the present invention will be described in more detail.

  In the production method 1 used in the present invention, first, the step (c) -A of reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4). I do. This step (c) -A is preferably carried out at 80 ° C. to 150 ° C. by adding a polymerization inhibitor while allowing dry air to flow into the reactor so that the monomer will not thermally polymerize. . More preferably, it is 90 to 130 ° C. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

  In the step (c) -A, when the ethylenically unsaturated monomer (h) having a hydroxyl group and the tricarboxylic acid anhydride (M3) are reacted, the reaction ratio is “ethylenically unsaturated monomer having a hydroxyl group (h ) / Mol of tricarboxylic anhydride (M3) ”is preferably 0.8 or more and 10 or less. More preferably, it is 0.9 or more and 5 or less, and further preferably 0.95 or more and 2 or less. If it is less than 0.8, the tricarboxylic acid anhydride (M3) remains, which is not preferable. If it exceeds 10, a large amount of the ethylenically unsaturated monomer (h) having a hydroxyl group remains, and the amount of other ethylenically unsaturated monomers that can be copolymerized in the subsequent step (c) -B decreases, which is not preferable. .

  When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic anhydride (M4) are reacted in the step (c) -A, the reaction ratio is “ethylenically unsaturated monomer having a hydroxyl group ( The number of moles of h) / number of moles of tetracarboxylic anhydride (M4) ”is preferably 0.9 or more and 1.1 or less. More preferably 1. If it is less than 0.9, a large amount of tetracarboxylic acid anhydride (M4) remains, which is not preferable. When the ratio exceeds 1.1, a compound obtained by adding an ethylenically unsaturated monomer (h) having two hydroxyl groups to one tetracarboxylic anhydride (M4) is formed, and gelation is performed in step (c) -B. In some cases, it is not preferable.

  In step (c) -A, a catalyst may be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

  Furthermore, after reacting the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic acid anhydride (M4) at the above ratio, the acid anhydride remaining at this time is converted to water or carbon atoms of 1 to 18 carbon atoms. Ring opening with alcohol (step (c) -Aa), and removal of unnecessary tetracarboxylic anhydride (M4) can be facilitated.

  Then, in the manufacturing method 1, the process (c) -B which copolymerizes the ethylenically unsaturated monomer synthesize | combined by process (c) -A and another ethylenically unsaturated monomer is performed.

  As another ethylenically unsaturated monomer used in Step A, an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with an aromatic group, N-alkyl having 1 to 18 carbon atoms ( An ethylenically unsaturated monomer selected from (meth) acrylamide, styrene, and an ethylenically unsaturated monomer having a hydroxyl group (h) (including those remaining in step (c) -A) is copolymerized. Is preferred.

  Examples of unsubstituted alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, linear or branched propyl (meth) acrylate, linear or branched butyl (meth) acrylate, direct Linear or branched pentyl (meth) acrylate, cyclopentyl (meth) acrylate, linear or branched hexyl (meth) acrylate, cyclohexyl (meth) acrylate, linear or branched heptyl (meth) acrylate, Cycloheptyl (meth) acrylate, linear or branched octyl (meth) acrylate, cyclooctyl (meth) acrylate, linear or branched nonyl (meth) acrylate, cyclononyl (meth) acrylate, linear or Branched Desi (Meth) acrylate, cyclodecyl (meth) acrylate, linear or branched dodecyl (meth) acrylate, cyclododecyl (meth) acrylate, linear or branched myristyl (meth) acrylate, cyclomyristyl (meth) acrylate , Linear or branched cetyl (meth) acrylate, cyclocetyl (meth) acrylate, and linear or branched stearyl (meth) acrylate, or cyclostearyl (meth) acrylate. Examples of the alkyl (meth) acrylate substituted with an aromatic ring include benzyl (meth) acrylate.

  As unsubstituted N-alkyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, linear or branched N-propyl (meth) acrylamide, linear or branched N-butyl (meth) acrylamide, linear or branched N-pentyl (meth) acrylamide, N-cyclopentyl (meth) acrylamide, linear or branched N-hexyl (meth) acrylamide, N-cyclohexyl (Meth) acrylamide, linear or branched N-heptyl (meth) acrylamide, N-cycloheptyl (meth) acrylamide, linear or branched N-octyl (meth) acrylamide, N-cyclooctyl (meta ) Acrylamide, linear or branched N-nonyl (Meth) acrylamide, N-cyclooctyl (meth) acrylamide, linear or branched N-decyl (meth) acrylamide, N-cyclodecyl (meth) acrylamide, linear or branched N-dodecyl (meth) acrylamide N-cyclododecyl (meth) acrylamide, linear or branched N-myristyl (meth) acrylamide, N-cyclomyristyl (meth) acrylamide, linear or branched N-cetyl (meth) acrylamide, N -Cyclocetyl (meth) acrylamide, linear or branched N-stearyl (meth) acrylamide, or N-cyclostearyl (meth) acrylamide may be mentioned. Examples of the alkyl (meth) acrylate substituted with an aromatic ring include N-benzyl (meth) acrylamide. Here, (meth) acrylate refers to methacrylate or acrylate, and (meth) acrylamide refers to methacrylamide or acrylamide.

  In step (c) -B, it is preferable to perform polymerization at 50 ° C. to 150 ° C. using a polymerization initiator while replacing the reaction vessel with nitrogen. As the polymerization initiator, alkyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, isobutyl peroxide, laurolyl peroxide, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3, 3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate organic peroxides such as t-butylperoxyisobutyrate, 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisdiisobutyrate, 2,2′-azobis (2,4 -Azo compounds such as dimethylvaleronitrile) and 2,2-azobis (2-methylbutyronitrile). Of these, azo compounds are preferably used. The polymerization initiator is preferably used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total of ethylenically unsaturated monomers.

  In step (c) -B, a chain transfer agent can also be used. Chain transfer agents include methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate , Pentaerythritol tetrakisthioglycolate, methyl mercaptopropionate, methoxybutyl mercaptopropionate, octyl mercaptopropionate, tridecyl mercaptopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthio Examples include propionate and α-methylstyrene dimer.

  In step (c) -B, it is preferable to use a solvent. Solvents include acetates such as ethyl acetate, propyl acetate, butyl acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; aromatics such as xylene, toluene, and ethylbenzene Group hydrocarbons and the like can be used.

  When step (c) -Aa is not performed after step (c) -A, the acid anhydride remaining after step (c) -B is opened with water or an alcohol having 1 to 18 carbon atoms. (Step (c) -Bb). In step (c) -Aa or step (c) -Bb, the number of moles of water to be reacted or the alcohol having 1 to 18 carbon atoms is 0.9 times or more and 5 times the number of moles of the remaining acid anhydride. It is preferable that it is 2 times or less (preferably 1 to 2 times). If it is less than 0.9 times, many highly reactive anhydride rings remain, and if it exceeds 5 times, water or alcohol having 1 to 18 carbon atoms remains, anyway, when it is used for ink or paint, May be a problem. However, in the case where the water to be reacted or the alcohol having 1 to 18 carbon atoms is reacted more than 1 time with respect to the number of moles of the remaining acid anhydride, the water remaining after the reaction or having 1 to 18 carbon atoms is reacted. The alcohol can be removed by heating or under reduced pressure. The reaction step (c) -Aa or the step (c) -Bb is preferably performed at 80 to 150 ° C.

  Next, the production method 2 used in the present invention will be described in detail.

  In the manufacturing method 2 used by this invention, the process (c) -C which copolymerizes the ethylenically unsaturated monomer (h) which has a hydroxyl group with another ethylenically unsaturated monomer first is performed. As another ethylenically unsaturated monomer, an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with the aromatic ring exemplified in Step (c) -B of Production Method 1 or aromatic It is preferable that an N-alkyl (meth) acrylamide having 1 to 18 carbon atoms which may be substituted with a ring, and an ethylenically unsaturated monomer selected from styrene are copolymerized.

  The copolymerization ratio between the ethylenically unsaturated monomer (h) having a hydroxyl group and another ethylenically unsaturated monomer is such that one molecule after polymerization has an average of at least 0.3 to 177 hydroxyl groups. Decided to enter.

  The polymerization conditions such as the type of polymerization initiator, the type of chain transfer agent, the type of solvent, the amount and the reaction temperature in step (c) -C are the same as in step (c) -B of production method 1. Is preferred.

  Subsequently, in the production method 2, the step (c) -D in which the tricarboxylic acid anhydride (M3) or the tetracarboxylic acid anhydride (M4) is reacted with the hydroxyl group of the copolymer obtained in the step (c) -C. Do. In the step (c) -D, it is preferable to carry out at 80 ° C. to 150 ° C. while flowing nitrogen or dry air to the reaction vessel. Here, the catalyst exemplified in the step (c) -A of the production method 1 can also be used.

  In step (c) -D of production method 2, it is preferable to use tricarboxylic acid anhydride (M3) among tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4). When tetracarboxylic anhydride (M4) is used, it may gel. When tetracarboxylic anhydride (M4) is used and an anhydrous ring remains, the ring is opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in step (c) -Bb of production method 1. (Step (c) -Dd).

  Next, the production method 3 used in the present invention will be described in detail.

  In the production method 3 used in the present invention, an ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, and a tricarboxylic acid anhydride (M3) or tetra Carboxylic anhydride (M4) is reacted simultaneously. The reaction is preferably carried out at 80 ° C. to 150 ° C. while flowing nitrogen into the reaction vessel. As a catalyst for the reaction between the hydroxyl group and the acid anhydride, the one shown in Step (c) -A of Production Method 1, polymerization initiation The polymerization conditions such as the type of agent, the type of chain transfer agent, the type and amount of solvent, and the reaction temperature are preferably those shown in Step (c) -B of Production Method 1.

  The other ethylenically unsaturated monomer used in Production Method 3 is the same as the compound used in Step (c) -C of Production Method 2. In the case of the production method 3, it is preferable to use the tricarboxylic acid anhydride (M3) among the tricarboxylic acid anhydride (M3) or the tetracarboxylic acid anhydride (M4). In particular, when tetracarboxylic dianhydride is used, gelation may occur. When tetracarboxylic dianhydride is used and an anhydrous ring remains, it can be opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in step (c) -Bb of production method 1. Yes (step (c) -Ee).

  By these production methods 1 to 3, the vinyl dispersant used in the present invention can be produced. Among these, production method 2 is preferable in that it is easy to control the number of carboxyl group-containing units (G) in one molecule of the dispersant. The number average molecular weight of the copolymer obtained in step (c) -C of production method 2 can be measured in advance, and the tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) is reacted according to the value. The amount can be determined. For example, in order to produce (c) vinyl-based dispersion resin by production method 2, the number average molecular weight of the copolymer obtained in step (c) -C is measured, and when the measured value is [X], What is necessary is just to make 0.3 mol or more and 3.0 mol or less of tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) react with resin [X] g.

  When producing the vinyl dispersion resin (c) used in the present invention by the production method 1 or 3, the number average molecular weight [Y] of the vinyl dispersant finally obtained and the tricarboxylic acid anhydride (M3) or The tricarboxylic acid anhydride (M3) having a vinyl dispersant of 0.3 mol or more and 3.0 mol or less with respect to [Y] g as a result is calculated backward from the charged mole number of the tetracarboxylic acid anhydride (M4). Or tetracarboxylic anhydride (M4) should just be made to react.

  When (c) vinyl-based dispersion resin is produced by the production method used in the present invention, an aromatic tricarboxylic acid anhydride is selected as the tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) to be used. Or aromatic tetracarboxylic acid anhydride. Of these, preferred are aromatic tricarboxylic acid anhydrides, and trimellitic acid anhydride, pyromellitic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 2,3,6,7-naphthalenetetra. Carboxylic anhydride is preferred, and most preferred is trimellitic anhydride.

  In any of production methods 1 to 3, when (c) vinyl-based dispersion resin is produced, as another ethylenically unsaturated monomer, an unsubstituted C 1-12 carbon atom which may have a branch It is preferable that an alkyl (meth) acrylate, benzyl (meth) acrylate, and an ethylenically unsaturated monomer (h) having a hydroxyl group if necessary be copolymerized. Further, 1 to 50 unsubstituted alkyl (meth) acrylates having 1 to 12 carbon atoms and 1 to 50 benzyl (meth) acrylates may be branched in one molecule of the vinyl dispersant. Polymerization is preferred.

  In addition, the (c) vinyl-based dispersion resin used in the present invention can be copolymerized with various ethylenically unsaturated monomers other than those exemplified so far as long as the dispersibility is not hindered. An ethylenically unsaturated monomer having a thermally crosslinkable group such as an isocyanato group, a block isocyanato group, an alkoxysilyl group, a 3- to 5-membered cyclic ether group, or an ethylenically unsaturated monomer having a carboxyl group Can be mentioned. However, a monomer having a carboxyl group, such as methacrylic acid or acrylic acid, is a tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) present in the vinyl dispersant in any of the production methods 1 to 3. ) Is preferably 0 to 4 times, more preferably 0 to 2 times the number of moles from the viewpoint of dispersibility (low viscosity, storage stability).

  By using a starting material appropriately selected from the listed starting materials, the (c) vinyl-based dispersion resin can be prepared by the manufacturing method used in the present invention.

The pigment composition of the present invention is obtained using the vinyl dispersant and the pigment. Here, by using (c) vinyl-based dispersion resin, a pigment composition having excellent dispersibility, fluidity, and storage stability is obtained.

(D) Branched urethane dispersion resin A (comb urethane dispersion agent)
First, (d) polyisocyanate (da) having three or more isocyanate groups as raw materials for the branched urethane-based dispersion resin A of the present invention will be described.

The polyisocyanate (da) is not particularly limited as long as it is a compound having three or more isocyanate groups in the molecule, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and araliphatics. Examples thereof include polyisocyanates and alicyclic polyisocyanates.
The polyisocyanate (da) is preferably a trimethylolpropane adduct of diisocyanate shown below, a burette reacted with water, and a trimer having an isocyanurate ring.
Examples of the diisocyanate include aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and the like.
Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane diester. Isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1 , 3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, etc. Can do.
Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 1,2-propylene diisocyanate. 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Can do.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-cyclopentane diisocyanate, and 1,3-cyclohexane. Diisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis ( (Cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and the like.

Of the above, taking into account the viscosity after pigment dispersion, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates are preferred, and alicyclic polyisocyanates, particularly isophorone diisocyanate trimers. Is preferred.
In the present invention, the proportion derived from polyisocyanate (da) in the non-volatile component of (d) branched urethane-based dispersion resin A is 25 wt% to 60 wt%. If the amount is less than 25% by weight, the pigment dispersibility is poor because there is no sufficient pigment adsorbing ability. If the amount exceeds 60% by weight, the pigment adsorbing ability is too high to obtain a sufficient steric repulsion effect, and the pigment dispersibility is lowered. To do.
Next, the monoalcohol compound (db) used as a raw material of the branched urethane type dispersion resin A of this invention is demonstrated.

The monoalcohol compound (db) is not particularly limited as long as it is a compound having one hydroxyl group in the molecule. For example, an aliphatic monoalcohol, an araliphatic monoalcohol, an alicyclic monoalcohol, etc. Is mentioned.
Examples of the aliphatic monoalcohol used in the present invention include methanol, ethanol, propanol, isopropanol, butanol, n-amyl alcohol, hexanol, heptanol, n-octanol, 2-ethylhexanol, isooctanol, nonanol, decanol and isoundecane. And straight-chain or branched aliphatic alcohols such as norl, lauryl alcohol, cetyl alcohol and stearyl alcohol. Examples of the araliphatic monoalcohol include benzyl alcohol, α-methylbenzyl alcohol, and phenethyl alcohol. Examples of the alicyclic monoalcohol include cyclopentanol, cyclohexanol, cyclohexane methanol, cycloheptanol, cyclooctanol, and tricyclodecane methanol.

Furthermore, as the monoalcohol compound (db) used in the present invention, a lactone resin (db1), an oxyalkylene resin (db2), an acrylic resin (db3) having one hydroxyl group, and A siloxane resin (d-b4) is preferred.
As the lactone resin (d-b1) having one hydroxyl group, the starting monoalcohol (d-b5), ε-caprolactone, 4-methylcaprolactone, 3,5,5-trimethylcaprolactone, 3,3,5-trimethyl A homopolymer obtained by polymerizing one monomer selected from caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and enanthlactone, or a copolymer obtained by copolymerizing two or more monomers selected from these monomers Or a mixture of two or more kinds of polymers selected from these homopolymers and copolymers.
The initiating monoalcohol (d-b5) is not particularly limited as long as it is a compound having one hydroxyl group in the molecule that acts as an initiator of the lactone resin (d-b1) and acts as an initiator for the lactone resin. For example, aliphatic monoalcohol, araliphatic monoalcohol, alicyclic monoalcohol and the like can be mentioned.
Aliphatic monoalcohols include methanol, ethanol, propanol, isopropanol, butanol, n-amyl alcohol, hexanol, heptanol, n-octanol, 2-ethylhexanol, isooctanol, nonanol, decanol, isoundecanol, lauryl alcohol, And linear or branched aliphatic alcohols such as cetyl alcohol and stearyl alcohol. Examples of the araliphatic monoalcohol include benzyl alcohol, α-methylbenzyl alcohol, and phenethyl alcohol. Examples of the alicyclic monoalcohol include cyclopentanol, cyclohexanol, cyclohexane methanol, cycloheptanol, cyclooctanol, and tricyclodecane methanol.
Furthermore, the starting monoalcohol (d-b5) may be an oxyalkylene resin (d-b2), an acrylic resin (d-b3), and a siloxane resin (d-b4) having one hydroxyl group.
The oxyalkylene resin (db2) having one hydroxyl group has one hydroxyl group in the molecule and a segment having two or more repeating units represented by the following general formula (22). There is no particular limitation.

In the formula (22), n4 represents an integer of 1 or more, and R ¹ⁿ and R ²ⁿ are n-th substituents, which are hydrogen, alkyl group, aryl group, alkenyl group, hydroxyl group, carboxyl group, epoxy group, amino group The substituent obtained by combining 1 or more types selected from the group which consists of group, an amide group, an ether group, and ester group is represented.

The acrylic resin (db3) having one hydroxyl group is not particularly limited as long as it is an acrylic resin having one hydroxyl group in the molecule. For example, a compound obtained by polymerizing an ethylenically unsaturated monomer using a compound having one or more thiol groups and one hydroxyl group in the molecule as a polymerization initiator, or a hydroxyl group in a molecule synthesized by a living polymerization method. One introduced acrylic resin is mentioned. As the ethylenically unsaturated monomer, a compound having an unsaturated double bond capable of radical polymerization is used. Examples of commercially available acrylic resins (d-b3) include UMM-1001, UME-1001, UMB-1001 (manufactured by Soken Chemical Co., Ltd.).

  Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) which are (meth) acrylic acid esters having 1 to 18 carbon atoms in the alkyl group. Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, isododecyl (meth) acrylate Rate, tridecyl (meth) acrylate, isotridecyl (meth) acrylate.

  Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, acrylic acid dimer, crotonic acid, itaconic acid, maleic acid and the like. Examples of the amide group-containing monomer include (meth) acrylamide, N-alkyl (meth) acrylamide, and N, N-dialkyl (meth) acrylamide.

  Moreover, the ethylenically unsaturated monomer which has a crosslinkable group can also be used, and an epoxy group, an alkoxysilyl group, an acetoacetyl group etc. are mentioned as a crosslinkable group.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

Examples of the alkoxysilyl group-containing monomer include γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylic. Roxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxy Propyldimethylethoxysilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyldimethylchlorosilane, γ- (meth) acryloxypropyltripropoxy Lan, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ- (meth) acryloxypentyltrimethoxy Silane, γ- (meth) acryloxyhexyltrimethoxysilane, γ- (meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- (meth) acryloxydecyltrimethoxysilane, γ- (meth) acryloxydodecyltrimethoxysilane, γ- (meth) acryloxyoctadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripyropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane And vinylmethyldipropoxysilane.
Examples of the acetoacetyl group-containing monomer include diacetone (meth) acrylamide, 2- (acetoacetoxy) ethyl (meth) acrylate, and allyl acetoacetate.

The ethylenically unsaturated monomers exemplified above can be used in combination, and there is no restriction on the type and the ratio of the combined use depending on the purpose of use.
In the present invention, the acrylic resin (d-b3) is preferably obtained by polymerizing a monomer containing 20% by weight to 70% by weight of benzyl (meth) acrylate. If the amount is less than 20% by weight, the pigment dispersibility may be deteriorated due to insufficient pigment adsorbing ability. If the amount exceeds 70% by weight, the pigment adsorptive ability is too high, and a sufficient steric repulsion effect cannot be obtained. Sexuality may decline.
The siloxane resin (db4) having one hydroxyl group is not particularly limited as long as it is a siloxane resin having one hydroxyl group in the molecule. For example, as a commercial item, FM-0411, FM-0421, FM-0425 (made by Chisso Corporation) etc. are mentioned.
Next, the compound (dc) having one or more acidic groups and two or more hydroxyl groups, which is a raw material of the branched urethane-based dispersion resin A of the present invention, will be described. By using the compound (dc), an acidic group can be introduced into the branched urethane-based dispersion resin A of the present invention.
The compound (dc) having one or more acidic groups and two or more hydroxyl groups is not particularly limited, and is specifically 2,2-bis (hydroxymethyl) butyric acid [dimethylolbutane. Acid], 2,2-bis (hydroxymethyl) propionic acid [dimethylolpropionic acid], 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, tartaric acid, dihydroxymethylacetic acid Bis (4-hydroxyphenyl) acetic acid, 4,4-bis (p-hydroxyphenyl) pentanoic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, homogentisic acid and the like. Preferably, 2,2-bis (hydroxymethyl) butyric acid [dimethylolbutanoic acid], 2,2-bis (hydroxymethyl) propionic acid [dimethylolpropionic acid], 2,2-bis (hydroxyethyl) propionic acid 2,2-bis (hydroxypropyl) propionic acid is used. Of these, dimethylolbutanoic acid and dimethylolpropionic acid are preferred.

  Moreover, you may use the acidic group containing polyol obtained by organic synthesis. For example, an acidic group-containing polyol obtained from a reaction between an acid anhydride and a polyfunctional alcohol.

  As the acid anhydride, a compound having one acid anhydride group in the molecule and a compound having two or more acid anhydride groups in the molecule can be used. These may be used alone or in combination.

  Examples of the compound having one acid anhydride group in the molecule include succinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, and aliphatic cyclic acid anhydrides such as tetrahydrophthalic anhydride, Aromatic cyclic acid anhydrides such as phthalic anhydride, isatoic anhydride, diphenic anhydride, and derivatives in which a saturated or unsaturated aliphatic hydrocarbon group, aryl group, halogen group, heterocyclic group, etc. are bonded. Can be used.

  Examples of the compound having two or more acid anhydride groups in the molecule include polycarboxylic acids such as tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, and maleic anhydride copolymer resin. Anhydrides can be used.

  More specifically, examples of the tetracarboxylic dianhydride include an aliphatic tetracarboxylic anhydride, an aromatic tetracarboxylic anhydride, or a polycyclic tetracarboxylic anhydride.

  Examples of the aliphatic tetracarboxylic acid anhydride include 1,2,3,4-butanetetracarboxylic acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5,6-tricarboxy Norbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid anhydrides and the like can be mentioned.

  Examples of the aromatic tetracarboxylic anhydride include pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride, 2,3,6 , 7-Naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-Tetraphenylsilanetetracarboxylic anhydride, 1,2,3,4-furantetracarboxylic acid Water, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, Bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4 '-Diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane anhydride, 9,9-bis (3,4-dicar Kishifeniru) fluorene anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene anhydride, and the like.

  Examples of the polycyclic tetracarboxylic acid anhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid anhydride and 3,4-dicarboxy-1,2,3. , 4-tetrahydro-6-methyl-1-naphthalene succinic anhydride and the like.

  Examples of the polyfunctional alcohol include aliphatic glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexamethylene glycol, and dodecamethylene glycol. Alicyclic glycols such as cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, etc. Aromatic diols such as glycols, bisphenols, hydroquinone and 2,2-bis (4-β-hydroxyethoxyphenyl) propane containing the above aromatic group can be used.

Furthermore, the polyfunctional alcohol may contain a unit derived from a polyfunctional alcohol having three or more hydroxy groups, such as glycerin, 1,1,1-trimethylolethane, 1,1,1- Trimethylolpropane, 1,1,1-trimethylolmethane, pentaerythritol, etc. can be used.

  Two or more of these polyfunctional alcohols can be used in combination.

In the present invention, the compound (dc) having one or more acidic groups and two or more hydroxyl groups can be used alone or in combination.
Next, an acrylic resin (dd) having two or more hydroxyl groups present with 1 to 30 atoms in between as a raw material of the branched dispersion resin A of the present invention will be described.
As an acrylic resin (dd) having two or more hydroxyl groups present with 1 to 30 atoms in between, two or more hydroxyl groups present with 1 to 30 atoms in between If it is the acrylic resin which has, it will not specifically limit. For example, it is obtained by polymerizing an ethylenically unsaturated monomer using a compound having one or more thiol groups and two or more hydroxyl groups present between 1 to 30 atoms in the molecule as a polymerization initiator. And acrylic resins having two hydroxyl groups introduced into the molecule synthesized by the living polymerization method. As the ethylenically unsaturated monomer, one having an unsaturated double bond capable of radical polymerization is used. UT-1001 (made by Soken Chemical Co., Ltd.) is mentioned as a commercial item of an acrylic resin (dd).
As an ethylenically unsaturated monomer, the monomer illustrated by the acrylic resin (d-b3) mentioned above can be used. These can be used in combination, and there is no restriction on the type and the ratio of the combination in accordance with the purpose of use.
The present invention is characterized by using an acrylic resin (dd) and / or a siloxane resin (de) having two or more hydroxyl groups present with 1 to 30 atoms in between. When the number of atoms sandwiched between hydroxyl groups is larger than 30, acrylic resin (dd) and siloxane resin (de) that contribute to dispersion stabilization are introduced into the main chain of the urethane resin. Thus, a sufficient steric repulsion effect cannot be obtained, and the pigment dispersibility is lowered. However, lactone resin (d-b1), oxyalkylene resin (d-b2), acrylic resin (d-b3), and siloxane resin (d-b4) having one hydroxyl group as monoalcohol (d-b) This is not the case when at least one resin selected from the group is used, and the acrylic resin (dd) and siloxane resin (de) may not be used.
The above-mentioned compound (dc) having one or more acidic groups and two or more hydroxyl groups, or acrylic resin (d) having two or more hydroxyl groups present with 1 to 30 atoms in between -D) and / or siloxane resin (de) is reacted with a reaction product of polyisocyanate compound (da) having three or more isocyanate groups and monoalcohol (db). In this case, it may be used in combination with the polyol compound shown below.
Examples of the polyol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, Polybutylene glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone diol, trimethylolethane, Polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbite Le, mannitol, arabitol, xylitol, galactitol, glycerol, polyglycerol, polyhydric alcohols polytetramethylene glycol;
Polyether polyols such as polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide;
Polyester polyols which are condensates of the polyhydric alcohol or polyether polyol and polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Examples include polyols such as caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyol, and polybutadiene-based polyol such as hydrogenated polybutadiene polyol.
A compound having two or more functional groups capable of reacting with an isocyanate group, for example, a polyamine having at least two primary or secondary amino groups may be used in combination.

Furthermore, the present invention is characterized in that the monoalcohol (db) contains (meth) acrylate (db-6) containing one hydroxyl group. By using (meth) acrylate (d-b6) containing one hydroxyl group, the branched urethane-based dispersion resin A into which an ethylenically unsaturated group is introduced can be obtained.
The (meth) acrylate (d-b6) containing one hydroxyl group is not particularly limited as long as it is a (meth) acrylate compound having one hydroxyl group in the molecule. For example, pentaerythritol tri (meta) ) Acrylate, dipentaerythritol penta (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 4-hydroxybutyl (Meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone modified 2-H Rokishiechiru (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate. Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable.
Furthermore, the present invention is characterized in that the monoalcohol (db) includes a monoalcohol (db7) containing a thermosetting site. By using a monoalcohol (d-b7) containing a thermosetting part, a branched urethane-based dispersion resin A into which a thermosetting part has been introduced can be obtained.
The monoalcohol (d-b7) having a thermosetting functional group is not particularly limited as long as it is a compound having one or more thermosetting functional groups and one hydroxyl group. Examples of thermosetting functional groups include Michael additions such as cyclic ether groups such as epoxy groups and oxetane groups, cyclocarbonate groups, blocked isocyanate groups, benzoxazine groups, acid anhydride groups, and α, β-unsaturated carbonyl groups. Examples include functional groups that can be used for reaction, acetylene compounds that can be cyclic trimerized, functional groups that can be used for Diels-Alder reactions such as 1,3-butadiene and ethylene, alkoxysilyl groups, amino groups and methylol groups that melamine compounds have It is done. Of these, an oxetane group and a cyclocarbonate group are preferable. Oxetane alcohol and glycerin cyclocarbonate are particularly preferred.

  As the catalyst used for the production of the branched dispersion resin A of the present invention, a known catalyst can be used. Examples thereof include tertiary amine compounds and organometallic compounds.

  Examples of tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo. -[4.3.0] -5-Nonene etc. are mentioned.

  Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of the tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron, such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid. These can be used alone or in combination.

  Although the branched urethane-based dispersion resin A of the present invention can be produced using only the raw materials mentioned so far, it is preferable to use a solvent because of problems such as high viscosity and non-uniform reaction. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned.

  The reaction temperature for obtaining the branched urethane resin dispersant A of the present invention is preferably 40 to 140 ° C. More preferably, it is 50-120 degreeC.

The manufacturing method of the branched urethane type dispersion resin A of this invention is shown below.
As a first method, a polyisocyanate (da) having three or more isocyanate groups and a monoalcohol (db) are mixed at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. After reacting to a terminal isocyanate compound,
A compound (dc) having one or more acidic groups and two or more hydroxyl groups, and two or more hydroxyl groups present with 1 to 30 atoms in between with respect to the terminal isocyanate compound It can be obtained by polymerizing the acrylic resin (dd) and / or the siloxane resin (de) under the condition that the hydroxyl group is excessive.
As a second method, polyisocyanate (da) having three or more isocyanate groups and monoalcohol (db) are used in a molar ratio of NCO / OH = 3/2 to 3 / 0.5. After reacting to a terminal isocyanate compound,
A compound (dc) having one or more acidic groups and two or more hydroxyl groups, and two or more hydroxyl groups present with 1 to 30 atoms in between with respect to the terminal isocyanate compound A lactone resin (dd) having one hydroxyl group as a monoalcohol (db) is polymerized with an acrylic resin (dd) and / or a siloxane resin (d-e) under the condition of excess hydroxyl group. It can be obtained by using at least one resin selected from the group consisting of b1), oxyalkylene resin (db2), acrylic resin (db3), and siloxane resin (db4).
As a third method, polyisocyanate (da) having three or more isocyanate groups is reacted with monoalcohol (b) at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. After making the terminal isocyanate compound,
It can be obtained by polymerizing a polyol compound containing a compound (dc) having one or more acidic groups and two or more hydroxyl groups with respect to the terminal isocyanate compound under conditions that cause excess hydroxyl groups. A mono-alcohol (d-b) of a lactone resin (d-b1), an oxyalkylene resin (d-b2), an acrylic resin (d-b3), and a siloxane resin (d-b4) having one hydroxyl group It must be at least one resin selected from the group.

  The first step in which (da) and (db) are reacted, and the second step in which the reactant in the first step and the polyol compound are reacted are both reactions of an isocyanate group and a hydroxyl group. Urethane technology can be used. A terminal isocyanate compound can be obtained by adjusting the molar ratio of the isocyanate (NCO) group and the hydroxyl group (OH) group (first step). The branched urethane-based dispersion resin A of the present invention is produced by a reaction (second step) between the terminal isocyanate compound and the polyol compound.

  In the first step of the above production method, polyisocyanate (da) having three or more isocyanate groups and monoalcohol (db) are reacted at a ratio lower than the molar ratio of NCO / OH = 3/2. When it is made, the isocyanate group utilized by the next reaction decreases and the target branched urethane type dispersion resin A cannot be obtained. Further, when the reaction is carried out at a ratio higher than the molar ratio of NCO / OH = 3 / 0.5, gelation occurs in the next reaction or a resin having a high molecular weight is generated.

  The acid value of the branched urethane-based dispersion resin A of the present invention is preferably 10 to 100, more preferably 20 to 90, and particularly preferably 30 to 80. When the acid value is less than 10, the pigment dispersibility may be deteriorated because there is not sufficient pigment adsorbing ability. When the acid value exceeds 100, sufficient pigment repelling effect is not obtained due to the pigment adsorbing ability being too high. On the contrary, the pigment dispersibility may decrease.

Moreover, it is preferable that the weight average molecular weights (polystyrene conversion value by GPC measurement) of the branched urethane type dispersion resin A of this invention are 1000-100000, It is more preferable that it is 1000-50000, It is 1000-30000 Is particularly preferred. When the weight average molecular weight is less than 1000, sufficient steric repulsion effect cannot be maintained, and thus the pigment dispersibility may be deteriorated. When the weight average molecular weight exceeds 100,000, the pigment dispersibility may be reduced due to the interparticle cross-linking of the pigment. There is.
The pigment composition of the present invention is obtained using the branched urethane-based dispersion resin A and the pigment. Here, by using the branched urethane-based dispersion resin A, a pigment composition having excellent dispersibility, fluidity, and storage stability is obtained.

(E) Branched urethane dispersion resin B (comb urethane dispersion agent)
First, regarding the polyisocyanate (ea) having three or more isocyanate groups as a raw material of the branched urethane-based dispersion resin B of the present invention, the polyisocyanate (da) used in the branched urethane-based dispersion resin A is described. The same can be used.
In this invention, the ratio derived from polyisocyanate (ea) in the non-volatile component of the branched urethane type dispersion resin B is 25 to 60 weight%, It is characterized by the above-mentioned. If the amount is less than 25% by weight, the pigment dispersibility is poor because there is no sufficient pigment adsorbing ability. If the amount exceeds 60% by weight, the pigment adsorbing ability is too high to obtain a sufficient steric repulsion effect, and the pigment dispersibility is lowered. To do.
Next, the monoalcohol compound (eb) used as a raw material of the branched urethane-based dispersion resin B of the present invention and an acrylic resin (e-) having two or more hydroxyl groups present with 1 to 30 atoms in between As for d), the same polyisocyanate (db) and acrylic resin (dd) used in the branched urethane-based dispersion resin A can be used.
Next, a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms in between, which is a raw material for the branched urethane-based dispersion resin B of the present invention, will be described.

As a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms in between, two or more hydroxyl groups present with 1 to 30 atoms in between It will not specifically limit if it is a siloxane resin to have. For example, FM-DA11, FM-DA21, FM-DA26 (Chisso Corporation) is mentioned as a commercial item.
The present invention is characterized by using an acrylic resin (ed) and / or a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms in between. When the number of atoms sandwiched between hydroxyl groups becomes larger than 30, acrylic resin (ed) and siloxane resin (ee) contributing to dispersion stabilization are introduced into the main chain of the urethane resin. Thus, a sufficient steric repulsion effect cannot be obtained, and the pigment dispersibility is lowered. However, lactone resin (d-b1), oxyalkylene resin (d-b2), acrylic resin (d-b3), and siloxane resin (d-b4) having one hydroxyl group as monoalcohol (eb) This is not the case when at least one resin selected from the group is used, and the acrylic resin (ed) and the siloxane resin (ee) may not be used. In this case, a polyol compound (df) is used in place of the acrylic resin (ed) and the siloxane resin (ee).

 The acrylic resin (ed) and / or siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms in between is a polysiloxane having three or more isocyanate groups. Although it reacts with the reaction product of an isocyanate compound (a) and monoalcohol (b), you may use together with a polyol compound in this reaction. As the polyol compound, the above-mentioned polyol compound (df) can be used.

Examples of the polyol compound (ef) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,3-butanediol, 1, 4-butanediol, polybutylene glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone diol , Trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol Sorbitol, mannitol, arabitol, xylitol, galactitol, glycerol, polyglycerol, polyhydric alcohols such as polytetramethylene glycol;
2,2-bis (hydroxymethyl) butyric acid [dimethylolbutanoic acid], 2,2-bis (hydroxymethyl) propionic acid [dimethylolpropionic acid], 2,2-bis (hydroxyethyl) propionic acid, 2,2 -Bis (hydroxypropyl) propionic acid, tartaric acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (p-hydroxyphenyl) pentanoic acid, 2,4-dihydroxybenzoic acid, 3,5- Acidic group-containing low molecular weight polyhydric alcohols such as dihydroxybenzoic acid and homogentisic acid;
Polyether polyols such as polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide;
Polyester polyols which are condensates of the polyhydric alcohol or polyether polyol and polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Examples include polyols such as caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyol, and polybutadiene-based polyol such as hydrogenated polybutadiene polyol.

 A compound having two or more functional groups capable of reacting with an isocyanate group, for example, a polyamine having at least two primary or secondary amino groups may be used in combination.

 Next, as the compound having an acid anhydride group (eg), a compound having one acid anhydride group in the molecule and a compound having two or more acid anhydride groups in the molecule are used. it can. These may be used alone or in combination.

  Examples of the compound having one acid anhydride group in the molecule include succinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, and aliphatic cyclic acid anhydrides such as tetrahydrophthalic anhydride, Aromatic cyclic acid anhydrides such as phthalic anhydride, isatoic anhydride, diphenic anhydride, trimellitic anhydride, saturated or unsaturated aliphatic hydrocarbon groups, aryl groups, halogen groups, heterocyclic groups, etc. Bonded derivatives or the like can be used.

  Examples of the compound having two or more acid anhydride groups in the molecule include polycarboxylic acids such as tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, and maleic anhydride copolymer resin. Anhydrides can be used.

  More specifically, examples of the tetracarboxylic dianhydride include an aliphatic tetracarboxylic anhydride, an aromatic tetracarboxylic anhydride, or a polycyclic tetracarboxylic anhydride.

  Examples of the aliphatic tetracarboxylic acid anhydride include 1,2,3,4-butanetetracarboxylic acid anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid anhydride, 1,3-dimethyl-1, 2,3,4-cyclobutanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, 2,3,5-tricarboxycyclopentylacetic anhydride, 3,5,6-tricarboxy Norbornane-2-acetic anhydride, 2,3,4,5-tetrahydrofurantetracarboxylic anhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Anhydrides, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic acid anhydrides and the like can be mentioned.

  Examples of the aromatic tetracarboxylic anhydride include pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride, 2,3,6 , 7-Naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-Tetraphenylsilanetetracarboxylic anhydride, 1,2,3,4-furantetracarboxylic acid Water, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, Bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4 '-Diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane anhydride, 9,9-bis (3,4-dicar Kishifeniru) fluorene anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene anhydride, and the like.

 Examples of the polycyclic tetracarboxylic acid anhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid anhydride and 3,4-dicarboxy-1,2,3. , 4-tetrahydro-6-methyl-1-naphthalene succinic anhydride and the like.

 These can be used in combination, and there is no restriction on the type and the ratio of the combination in accordance with the purpose of use. In the present invention, an aromatic acid anhydride is preferable, and trimellitic anhydride and pyromellitic anhydride are more preferable.

  Furthermore, the present invention is characterized in that the monoalcohol (eb) contains (meth) acrylate (eb6) containing one hydroxyl group. By using (meth) acrylate (e-b6) containing one hydroxyl group, branched urethane-based dispersion resin B into which an ethylenically unsaturated group has been introduced can be obtained.

 Specific examples of (meth) acrylate (e-b6) containing one hydroxyl group include those similar to (meth) acrylate (d-b6) that can be used in branched urethane-based dispersion resin A. It is not limited to these.

 Furthermore, the present invention is characterized in that the monoalcohol (eb) contains a monoalcohol (eb7) containing a thermosetting site. By using a monoalcohol (e-b7) containing a thermosetting site, a branched urethane-based dispersion resin B into which a thermosetting site has been introduced can be obtained.

 As the monoalcohol (e-b7) having a thermosetting functional group, the same monoalcohol (e-b7) having a thermosetting functional group used in the branched urethane-based dispersion resin A can be used.

  As the catalyst used in the production of the branched urethane-based dispersion resin B of the present invention, a known catalyst can be used as in the production of the branched urethane-based dispersion resin A.

  Although the branched urethane-based dispersion resin B of the present invention can be produced using only the raw materials listed so far, it is preferable to use a solvent because of problems such as high viscosity and non-uniform reaction. As the solvent used, known ones can be used as in the production of the branched urethane-based dispersion resin A.

 The reaction temperature for obtaining the branched urethane-based dispersion resin B of the present invention is preferably 40 to 140 ° C. More preferably, it is 50-120 degreeC.

  The manufacturing method of the branched urethane type dispersion resin B of this invention is shown below.

As the first method, first, a polyisocyanate (ea) having three or more isocyanate groups and a monoalcohol (eb) are mixed at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. After reacting at a ratio to make a terminal isocyanate compound,
An acrylic resin (ed) and / or a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms in between with respect to the terminal isocyanate compound, To obtain a terminal hydroxyl group compound.

 Next, branched urethane type dispersion resin B can be obtained by making the acid anhydride group in the compound (eg) which has an acid anhydride group react with the hydroxyl group in the said terminal hydroxyl group compound.

As the second method, first, a polyisocyanate (ea) having three or more isocyanate groups and a monoalcohol (eb) are mixed at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. After reacting at a ratio to make a terminal isocyanate compound,
An acrylic resin (ed) and / or a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms in between with respect to the terminal isocyanate compound, A lactone resin (d-b1), an oxyalkylene resin (d-b2), an acrylic resin (d-b3), and a siloxane resin that are polymerized under the following conditions and further have one hydroxyl group as monoalcohol (eb) The terminal hydroxyl compound is obtained by using at least one resin selected from the group (d-b4).

 Next, branched urethane type dispersion resin B can be obtained by making the acid anhydride group in the compound (eg) which has an acid anhydride group react with the hydroxyl group in the said terminal hydroxyl group compound.

As a third method, first, a polyisocyanate (ea) having three or more isocyanate groups and a monoalcohol (eb) are mixed at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. After reacting at a ratio to make a terminal isocyanate compound,
The terminal hydroxyl compound is obtained by polymerizing the polyol compound (ef) to the terminal isocyanate compound under the condition that the hydroxyl group becomes excessive.

 Next, the branched urethane-based dispersion resin B can be obtained by reacting the acid anhydride group in the compound having an acid anhydride group (eg) with the hydroxyl group in the terminal hydroxyl compound, Group of lactone resin (d-b1), oxyalkylene resin (d-b2), acrylic resin (d-b3), and siloxane resin (d-b4) having one hydroxyl group as monoalcohol (eb) It is necessary to be at least one resin selected from.

  The first step of reacting (ea) and (eb) and the second step of reacting the reaction product of the first step and the polyol compound are both reactions of isocyanate groups and hydroxyl groups, and are well-known. Urethane technology can be used. A terminal isocyanate compound can be obtained by adjusting the molar ratio of the isocyanate (NCO) group and the hydroxyl group (OH) group (first step). A terminal hydroxyl compound can be obtained by the reaction of the terminal isocyanate compound and the polyol compound (second step). Furthermore, the third step is a reaction between a hydroxyl group and an acid anhydride group, and a known esterification technique can be used. By adjusting the molar ratio of the hydroxyl group to the acid anhydride group, the branched urethane-based dispersion resin B of the present invention is produced.

  In the first step of the production method, polyisocyanate (ea) having three or more isocyanate groups and monoalcohol (b) were reacted at a ratio lower than the molar ratio of NCO / OH = 3/2. In this case, the isocyanate group used in the next reaction decreases, and the target branched urethane-based dispersion resin B cannot be obtained. Further, when the reaction is carried out at a ratio higher than the molar ratio of NCO / OH = 3 / 0.5, gelation occurs in the next reaction or a resin having a high molecular weight is generated.

  The acid value of the branched urethane-based dispersion resin B of the present invention is preferably 10 to 100, more preferably 20 to 90, and particularly preferably 30 to 80. When the acid value is less than 10, the pigment dispersibility may be deteriorated because there is not sufficient pigment adsorbing ability. When the acid value exceeds 100, sufficient pigment repelling effect is not obtained due to the pigment adsorbing ability being too high. On the contrary, the pigment dispersibility may decrease.

Moreover, it is preferable that the weight average molecular weights (polystyrene conversion value by GPC measurement) of the branched urethane type dispersion resin B of this invention are 1000-100000, It is more preferable that it is 1000-50000, It is 1000-50000 Is particularly preferred. When the weight average molecular weight is less than 1000, sufficient steric repulsion effect cannot be maintained, and thus the pigment dispersibility may be deteriorated. When the weight average molecular weight exceeds 100,000, the pigment dispersibility may be reduced due to the interparticle cross-linking of the pigment. There is.
The pigment composition of the present invention is obtained using the branched urethane-based dispersion resin B and the pigment. Here, by using the branched urethane-based dispersion resin B, a pigment composition having excellent dispersibility, fluidity, and storage stability is obtained.

When a color filter is manufactured using the inkjet ink of the present invention, since the color filter is required to be transparent, the dispersion that constitutes the inkjet ink of the present invention in the entire wavelength region of 400 to 700 nm in the visible light region. The resin transmittance is preferably 80% or more, and more preferably 95% or more.

[D] Thermally reactive compound The inkjet ink of the present invention contains a thermally reactive compound. The thermoreactive compound that can be used in the ink-jet ink of the present invention is non-reactive at room temperature. For example, at a temperature of 100 ° C. or higher (preferably 150 ° C. or higher), a crosslinking reaction, polymerization reaction, It is a compound showing a condensation reaction or a polyaddition reaction. The molecular weight of the thermally reactive compound that can be used in the ink composition of the present invention is not particularly limited, but is preferably 50 to 2000, more preferably 100 to 1000.

  As the heat-reactive compound, for example, a melamine compound, a benzoguanamine compound, an epoxy compound, a phenol compound, a blocked isocyanate compound, an acrylate monomer, or a silane coupling agent can be used.

  Examples of the melamine compound include those having an imino group, a methylol group, and / or an alkoxymethyl group, and a melamine compound containing only an alkoxymethyl group is particularly preferable. Specific examples of the alkoxymethyl group-containing melamine compound include hexamethoxymethylol melamine and hexabutoxymethylol melamine, but are not necessarily limited thereto.

  The following can be mentioned as a specific example of the commercial item of a melamine compound. However, it is not necessarily limited to these. Nikarak MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-43, MX-302 manufactured by Sanwa Chemical Co., Ltd., Cymel 300 manufactured by Nihon Cytex Industries 301, 303, 350, 285, 232, 235, 236, 238, My Coat 506, 508.

  Examples of the benzoguanamine compound include those having an imino group, a methylol group, and an alkoxymethyl group, and an alkoxymethyl group-containing benzoguanamine compound is particularly preferable. Specific examples of commercially available benzoguanamine compounds include Nicalak BX-4000 and SB-401 manufactured by Sanwa Chemical Co., and Cymel 1123 manufactured by Nihon Cytex Industries.

  Examples of the epoxy compound include bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, Methylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, diglycidyl terephthalate, diglycidyl o-phthalate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and Polypropy Glycol polyol glycidyl ethers such as diglycidyl ether, may be mentioned polyglycidyl isocyanurate, not necessarily limited thereto.

  As the phenol compound, for example, both a novolac type phenol compound obtained by reacting phenols and aldehydes under an acidic catalyst and a resol type phenol compound obtained by reacting under a basic catalyst can be used. Examples of phenols include orthocresol, paracresol, paraphenylphenol, paranonylphenol, 2,3-xylenol, phenol, metacresol, 3,5-xylenol, resorcinol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol. B, bisphenol E, bisphenol H, bisphenol S and the like. Examples of aldehydes include formaldehyde and acetaldehyde. Phenols and aldehydes may be used singly or in combination of two or more.

  Examples of the blocked isocyanate compound include hexamethylenediisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, bis (4-isocyanatocyclohexyl) methane, and tetramethylxylylene diene. Examples include diisocyanates such as isocyanate, isocyanurates of these diisocyanates, trimethylolpropane adducts, biurets, prepolymers having isocyanate residues (low polymers obtained from diisocyanates and polyols), and uretdiones having isocyanate residues. However, it is not necessarily limited to this.

  Examples of the blocking agent include phenol (dissociation temperature of 180 ° C. or higher), ε-caprolactam (dissociation temperature of 160 to 180 ° C.), oxime (dissociation temperature of 130 to 160 ° C.), or active methylene (100 to 120 ° C.). However, the present invention is not necessarily limited to this. Moreover, it is used individually by 1 type or in combination of 2 or more types.

  Examples of the acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-carboxyethyl (meth). Acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycy Ruether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, Various acrylic esters and methacrylic esters such as epoxy (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N -Hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc. It is not specified.

  When an acrylate monomer is used, a polymerization initiator can be used for the purpose of further improving curability. As the polymerization initiator, a thermal polymerization initiator may be used for the purpose of improving curability during heating. Examples of the thermal polymerization initiator include organic peroxide initiators and azo initiators.

Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-a Nopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane And aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.
Of these heat-reactive compounds, the melamine compound or benzoguanamine compound and the ink composition of the present invention are preferably contained in an amount of 1 to 40% by weight. The epoxy compound, phenol compound, blocked isocyanate compound, or acrylate monomers are preferably contained in the ink composition of the present invention in an amount of 1 to 40% by weight. The silane coupling agent is preferably contained in the ink composition of the present invention in an amount of 0.1 wt% to 40 wt%. If the content is insufficient, heat resistance or chemical resistance may be inferior. Moreover, when content exceeds 40%, the increase in a viscosity or the fall of storage stability may arise.

[F] Pigment Coating Treatment The pigment coating treatment is performed so that the pigment, the resin-type dispersant represented by the general formula (1), the organic solvent, the pigment derivative, the binder resin, and the like are uniform. It can be performed by mixing in advance and then kneading using a disperser. The blending amount of the solvent is preferably adjusted according to the mechanical properties of the mixture. Examples of the disperser used for the coating treatment of the pigment include a kneader, a roll mill, a ball mill, a Banbury mixer, a roller mill, a stone mill, and the like. A two-roll mill is preferable because it can be mixed and kneaded with one apparatus.

  The compounding amount of the raw material when coating the pigment is 1 to 30 parts by weight of the pigment derivative, 20 to 200 parts by weight of the resin-type dispersant and the binder resin (hereinafter, resin component) with respect to 100 parts by weight of the pigment, And the solvent is preferably in the range of 4 to 200 parts by weight. When the blending amount of the pigment derivative is less than 1 part by weight, the effect of lowering the viscosity of the ink is small because the anchor effect is small. When the blending amount exceeds 30 parts by weight, the pigment derivative becomes excessive and the unadsorbed pigment derivatives aggregate together. As a result, the ink thickens. In addition, when the blending amount of the resin component is less than 20 parts by weight, the pigment surface cannot be sufficiently covered, and the dispersion stability of the pigment becomes low. When the blending amount exceeds 200 parts by weight, the free resin component that does not adsorb to the pigment As a result, the viscosity of the ink increases. In addition, when the amount of the solvent is less than 4 parts by weight, the initial coating of the pigment derivative and the resin component with respect to the pigment is insufficient and the pigment is not sufficiently covered. When it exceeds the part, it is difficult to coat the pigment.

  Specifically, the coating treatment of the pigment is performed by the following two-stage process.

  The first step is a chip forming step in which wetting and adsorption of the resin component to the pigment proceed by passing the composition containing the pigment, resin component, solvent and the like through a two-roll about 20 times. In this step, about 80% by weight of the blended solvent is volatilized.

  The second step is a coating treatment step of forming a coating layer on the surface of the pigment particles by continuously heating and kneading the kneaded product in which the resin component is adsorbed to the pigment by chip formation. If the kneaded product has a high viscosity and cannot be kneaded on the machine, an appropriate amount of solvent is added to assist kneading.

  When the resin component has a crosslinkable functional group, crosslinking of the resin component occurs in the coating treatment step, and resin cutting is partially observed. This reaction is a mechanochemical reaction resulting from excessive mechanical pressurization and grinding, and further heating, and the cross-linking reaction of the resin component hardly occurs with only the pigment and the resin component. It is estimated that by using a pigment derivative when kneading the pigment and the resin component, the pigment derivative and the resin component are strongly adsorbed on the pigment surface, and further, the resin component is crosslinked by heating and pressure kneading. Is done. The heating temperature is preferably in the range of 80 ° C to 120 ° C. If the temperature is less than 80 ° C., the resin component may not be sufficiently crosslinked, and if the temperature exceeds 120 ° C., the resin component may be deteriorated.

The excess resin component that has not been adsorbed on the pigment surface is preferably removed by washing, filtration, or the like when it affects physical properties such as the viscosity of the ink. The coated pigment may be dried after washing if it does not agglomerate after drying, but it must be dried if the solvent used during the coating treatment is a solvent that can be used as a liquid medium for inkjet ink. There is no.
(8) Physical Properties, etc. In the inkjet ink of the present invention, the solid content is preferably 3 to 60% by weight, more preferably 4 to 40% by weight, based on the total weight of the ink composition. When the solid content is less than 3% by weight, the concentration and resistance of the ink film are insufficient, and when it exceeds 60% by weight, the viscosity of the ink increases and the stability over time may decrease.

  The viscosity of the inkjet ink of the present invention is preferably 2 mPa · s or more and 40 mPa · s or less, more preferably 3 mPa · s or more and 30 mPa · s or less, and further preferably 4 mPa · s or more and 20 mPa · s or less. If the viscosity is too large, stable discharge cannot be performed when continuously discharging.

  The average dispersed particle size of the inkjet ink of the present invention is preferably 5 nm to 200 nm, and more preferably 10 nm to 150 nm. If the average dispersed particle size is too large, the head is likely to be clogged, and stable ejection cannot be performed. On the other hand, when the average dispersed particle size is too small, reaggregation is likely to occur, and the temporal stability is deteriorated.

  The surface tension of the inkjet ink of the present invention is preferably 20 mN / m or more and 40 mN / m or less, and more preferably 24 mN / m or more and 35 mN / m or less. If the surface tension is too high, the ink cannot be stably ejected from the head. Conversely, if the surface tension is too low, the ink after ejection from the head cannot form droplets.

  The inkjet ink of the present invention is produced by the resin-type dispersant represented by the general formula (1), the pigment, the heat-reactive compound, the organic solvent, and, if necessary, the binder resin and / or pigment. It can be carried out by putting the derivative into a normal disperser and dispersing it until a desired average particle size / particle size distribution is obtained. The ink-jet ink raw materials may be mixed and dispersed all at once, or may be separately mixed and dispersed in consideration of the characteristics and economics of each raw material. When the viscosity of the inkjet ink is too high and dilution is necessary, the inkjet ink can be prepared by adding a liquid medium for dilution to the ink stock solution and stirring uniformly.

  As the disperser, a sand mill, a bead mill, an agitator mill, a dyno mill, a cobol mill, or the like is suitable. In each disperser, when there is a viscosity region suitable for pigment dispersion, the viscosity can be adjusted by changing the ratio of various resin components to the pigment. The ink-jet ink is preferably filtered by a filter or a centrifugal method for the purpose of removing coarse particles and foreign matters after being dispersed by a disperser.

  In producing an ink composition for inkjet recording, a surfactant-type dispersant, an anthraquinone derivative, and / or a triazine derivative can be further used. Examples of the surfactant type pigment dispersant include naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, or stearylamine acetate. be able to.

  The ink-jet ink can contain various additives in the range where the viscosity of the ink composition is 3 to 50 mPa · s at 25 ° C. For example, a surfactant can be included to control the wettability of the ink to the substrate. When selecting a surfactant, it is necessary to consider compatibility with other ink components. There are anionic, cationic, amphoteric, and nonionic surfactants, and a suitable surfactant may be selected.

  Since the inkjet ink of the present invention has a high pigment concentration and a low viscosity, it has excellent ejection stability, and since the pigment content is larger than that of a normal inkjet ink, the ejection amount can be reduced. In addition, it is possible to improve the productivity and quality of printed matter for which high print density is desired. In particular, the ink composition for inkjet recording of the present invention is suitable for the production of a color filter substrate that requires high productivity and quality.

In addition, since the inkjet ink of the present invention has a pigment dispersed at a high concentration, even if the ink composition is paper that penetrates in the depth direction or plastic that spreads in the lateral direction, glass, and metal, the print density Can be high. Furthermore, since the discharge amount can be suppressed, it is possible to avoid the ink from flowing out and being mixed because it exceeds the ink receiving amount of the receiving layer, and it is also possible to avoid the dot shape from becoming a perfect circle. It can also be used for limited applications in printing.
(9) Color filter substrate A color filter substrate can be produced by the inkjet method using the inkjet ink of the present invention. The color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television or the like.

  The color filter substrate is provided with a filter segment having a desired hue, and the filter segment ejects inkjet ink for a color filter by an inkjet method in a region divided by the black matrix of the substrate on which the black matrix is formed. Is formed.

  As the substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used. The black matrix is formed on the substrate by, for example, a photolithography method in which a radical polymerization type black resist is applied, exposed, developed, and patterned, a printing method in which black ink is printed, or a vapor deposition method in which metal is evaporated and then etched. Can be formed.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. In the following examples and comparative examples, parts and% represent parts by weight and% by weight. Moreover, the weight average molecular weight of resin was measured using GPC and calculated | required in polystyrene conversion. The pigments, pigment derivatives, solvents and resin solutions used in Examples and Comparative Examples are shown below. Table 1 shows final ink compositions in Examples and Comparative Examples.

[A] Solvent (1) CBAc: Diethylene glycol monoethyl ether acetate (2) BuCBAc: Diethylene glycol monobutyl ether acetate (3) TA: Triacetin (4) EDG: Diethylene glycol monoethyl ether (5) PNB: Propylene glycol monobutyl ether (6) PGMAc: Propylene glycol monomethyl ether acetate (7) 1,3-BDGA: 1,3-butylene glycol diacetate (8) Gly: Glycerin

[B] Pigment (1) Red pigment A: C.I. I. Pigment Red 254
(2) Red pigment B: C.I. I. Pigment Red 57: 1
(3) Magenta pigment: C.I. I. Pigment Red 122
(4) Green pigment: C.I. I. Pigment Green 36
(5) Yellow pigment: C.I. I. Pigment Yellow 138
(6) Blue pigment: C.I. I. Pigment Blue 15: 6
(7) Cyan pigment: C.I. I. Pigment Blue 15: 3
(8) Violet pigment: C.I. I. Pigment Violet 23

[C] Pigment derivative:
Pigment derivative [RD-1]

顔料誘導体〔ＲＤ−２〕

Pigment derivative [RD-2]

顔料誘導体〔ＭＤ−１〕

Pigment derivative [MD-1]

顔料誘導体〔ＹＤ−１〕

Pigment derivative [YD-1]

顔料誘導体〔ＢＤ−１〕

Pigment derivative [BD-1]

顔料誘導体〔ＶＤ−１〕

Pigment derivative [VD-1]

[D] Dispersion resin << Production Example 1 (phosphate group-containing dispersion resin P-1) >>
A temperature control regulator, a cooling tube, and a stirrer are attached to a separable four-necked flask, and 100 parts of a solvent (CBAc) is charged, the temperature is raised to 100 ° C., the inside of the reaction vessel is replaced with nitrogen, The raw materials were added and the reaction was continued for 5 hours to obtain an acrylic resin solution (solid content 50%) having a weight average molecular weight (Mw) of 20,000. In addition, the weight average molecular weight of the acrylic resin was measured using GPC and determined in terms of polystyrene. The resin solution thus obtained was used as a phosphate group-containing dispersion resin (P-1).

Methacrylic acid 20 parts 2-hydroxyethyl methacrylate 20 parts n-butyl methacrylate 27 parts benzyl methacrylate 30 parts Phosmer M 3 parts 2,2'-azobisisobutyronitrile 4 parts

<< Production Example 2 (Polyester Dispersant S-1) >>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added, and it was made to react at 120 degreeC for 2 hours, and the resin type dispersing agent (S-1) was obtained. The obtained resinous dispersant (S-1) was a white wax-like solid at room temperature.

<< Production Example 3 (Polyester Dispersant S-2) >>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 169.0 parts of methoxy PEG400 (one-end methoxylated polyethylene glycol), 96.4 parts of ε-caprolactone, 84.6 parts of δ-valerolactone, In addition, 0.1 part of monobutyltin (IV) oxide was charged as a catalyst and replaced with nitrogen gas, and then heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 62.2 parts of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added, and the mixture was reacted at 120 ° C. for 2 hours. (S-2) was obtained. The obtained resinous dispersant (S-2) was a pale yellow transparent liquid at room temperature.

<< Production Example 4 (Vinyl Dispersant B-1) >>
(1) Step ((c) -C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the reaction vessel was purged with nitrogen. Isobutyl methacrylate 37.6, lauryl methacrylate 30 parts, benzyl methacrylate 10 parts, N-hydroxyethyl acrylamide (manufactured by Kojin Co., Ltd.) 2.4 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2′-azobis (2- A mixed solution in which 6 parts of methyl propionate) were uniformly mixed in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Step (c) -C of Production Example 4). Thus, a vinyl resin intermediate (C1) having a number average molecular weight of 4900 and an average number of hydroxyl groups in one molecule of 1.0 was obtained.

(2) Step ((c) -D)
In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (C1) in solid content, 3.9 parts of trimellitic anhydride, 0.1% of dimethylbenzylamine The parts were charged and reacted at 100 ° C. for 6 hours (Step (c) -D of Production Example 4). Thus, a resin type dispersant (B-1) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained. The solid content ratio in the resin-type dispersant (B-1) was 50%.

<< Production Example 5 (Vinyl Dispersant B-2) >>
(1) Step ((c) -C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. Then, 2-ethylhexyl methacrylate 30. 0 parts, 68.3 parts of benzyl methacrylate, 1.7 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2'-azobisdiisobutyrate were previously mixed uniformly. The solution was added dropwise over 2 hours, and then stirred at the same temperature for 3 hours to complete the reaction (Step (c) -C in Production Example 5). In this way, a vinyl resin intermediate (C2) having a number average molecular weight of 4800 and an average number of hydroxyl groups in one molecule of 0.5 was obtained.

(2) Step ((c) -D)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 100 parts of methoxypropyl acetate, 4.3 parts of ethylene glycol ditrimellitic anhydride ester, and 0.1 part of dimethylbenzylamine. The temperature was raised to ° C. The vinyl resin intermediate (C2) was dropped from the dropping tank into the reaction tank over 100 parts for 2 hours as a solid content, and reacted at 100 ° C. for 4 hours after completion of the appropriate condition (Step (c) of Production Example 5). D). Thereafter, 10 parts of 2-ethylhexyl alcohol was added and reacted at 90 ° C. for 5 hours to decompose the remaining anhydrous ring with alcohol (Step (c) -Dd in Production Example 5), and the average number of copolymerized ethylene glycol ditrimellitic acid skeletons That is, a vinyl dispersant (B-2) having 0.5 (average number of carboxyl group-containing units (G)) was obtained. The solid content ratio in the vinyl dispersant (B-2) was 50%.

<< Production Example 6 (Branched Urethane Dispersion Resin A (U-1)) >>
(1) Step (d-A)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 67 parts of 1-decanol and 433 parts of ε-caprolactone, and the reaction vessel was purged with nitrogen, followed by reaction at 120 ° C. for 2 hours. After completion of the reaction, it was diluted with 214 parts of methoxypropyl acetate to obtain a polycaprolactone solution (MC1).

(2) Step (d-B)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 250 parts of butyl methacrylate and 250 parts of benzyl methacrylate, the inside of the reaction vessel was purged with nitrogen, the temperature was raised to 80 ° C., and thioglycerol (Asahi) Chemical Industry Co., Ltd.) 38 parts was added dropwise over 10 minutes and reacted for 7 hours. After completion of the reaction, an acrylic resin solution (DA1) was obtained by dilution with 214 parts of methoxypropyl acetate.

(3) Step (dD)
In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 53 parts of polycaprolactone solution (MC1), 67 parts of VESTANAT T 1890/100 (Degussa Japan Co., Ltd.), 55 parts of acrylic resin solution (DA1) Then, 103 parts of methoxypropyl acetate was charged and the inside of the reaction vessel was purged with nitrogen, and then heated to 80 ° C. and reacted for 1 hour. Then, 27 parts of dimethylol butanoic acid (DMBA, Nippon Kasei Co., Ltd.) and 27 parts of methoxypropyl acetate were added and reacted at 90 ° C., and the disappearance of the 2270 cm ⁻¹ peak based on the isocyanate group was confirmed by IR. The solution was cooled to 40 ° C. to obtain a branched urethane-based dispersion resin A solution (U1).

<< Production Example 7 (Branched Urethane Dispersion Resin B (U-2)) >>
(1) Step (e-A)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 67 parts of 1-decanol and 433 parts of ε-caprolactone, and the reaction vessel was purged with nitrogen, followed by reaction at 120 ° C. for 2 hours. After completion of the reaction, it was diluted with 214 parts of methoxypropyl acetate to obtain a polycaprolactone solution (MC2).
(2) Step (e-D)
A reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 84 parts of a polycaprolactone solution (MC2), 66 parts of VESTANAT T 1890/100 (Degussa Japan Co., Ltd.), and 100 parts of methoxypropyl acetate. After the inside of the reaction vessel was purged with nitrogen, the temperature was raised to 80 ° C. and reacted for 1 hour. Then, 40 parts of dimethylol butanoic acid (DMBA, manufactured by Nippon Kasei Chemical Co., Ltd.) and 40 parts of methoxypropyl acetate were added and reacted at 90 ° C., and the disappearance of the 2270 cm ⁻¹ peak based on the isocyanate group was confirmed by IR. Furthermore, after adding 6 parts of pyromellitic dianhydride and 6 parts of methoxypropyl acetate, and making it react at 100 degreeC, after confirming the loss | disappearance of the peak of 1855cm < ^-1 > and 1785cm < ^-1 > based on an acid anhydride group by IR. The solution was cooled to 40 ° C. to obtain a branched urethane-based dispersion resin B [U-2] solution.

 << Phosphate group-containing dispersion resin (P-2) >>: Dysper BYK-111 manufactured by Big Chemie

[E] Thermally Reactive Compound (1) Alkoxyalkyl group-containing melamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalak MX-43
(2) Imino group / methylol group-containing melamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalak MX-417
(3) Alkoxyalkyl group-containing benzoguanamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalac SB-401
(4) Imino group / methylol group-containing benzoguanamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalak BL-60
(5) Acrylic monomer Aronix M-400 manufactured by Toagosei Co., Ltd.
(6) Isocyanate compound Death module BL-4265 manufactured by Bayer
(7) Epoxy compound EPPN-201 manufactured by Nippon Kayaku Co., Ltd.

Example 1
90 parts of a red pigment (1), 10 parts of a pigment derivative (RD-1), 104 parts of a phosphate group-containing dispersion resin (P-1) solution, and 15 parts of a polyester dispersant (S-2) are uniformly stirred. A mixture was obtained. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating pigment and 450 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 20 parts of a melamine compound (MX-417), 20 parts of an acrylic monomer (M400), a solvent ( TA) 122 parts were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

Example 2
90 parts of red pigment (1), 10 parts of pigment derivative (RD-1), 15 parts of polyester dispersant (S-1), 104 parts of vinyl dispersant (B-1) solution are uniformly stirred, and the mixture is stirred. Obtained. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 450 parts of solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of melamine compound (MX-43), 18 parts of solvent (CBAc), solvent (TA ) 84 parts were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

Example 3
90 parts of the red pigment (2), 10 parts of the pigment derivative (RD-2), 15 parts of the polyester dispersant (S-1), and 104 parts of the vinyl dispersant (B-1) solution are uniformly stirred to obtain a mixture. Obtained. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 450 parts of solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of melamine compound (MX-43), 18 parts of solvent (CBAc), solvent (TA ) 84 parts were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

Example 4
90 parts of a red pigment (2), 10 parts of a pigment derivative (RD-2), 15 parts of a polyester dispersant (S-2), and 104 parts of a branched urethane-based dispersion resin A (U-1) solution are uniformly stirred. A mixture was obtained. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 450 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 20 parts of a melamine compound (MX-417), acrylic monomer (M-400) 20 Part, 42 parts of solvent (BuCBAC) and 60 parts of solvent (TA) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

Example 5
90 parts of magenta pigment, 10 parts of pigment derivative (MD-1), 15 parts of polyester dispersant (S-2), and 104 parts of branched urethane dispersion resin B (U-2) solution are uniformly stirred to obtain a mixture. It was. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 20 parts of a melamine compound (MX-417) and an isocyanate compound (BL-4265) 20 Part, 81 parts of solvent (CBAc) and 69 parts of solvent (TA) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 15% was obtained.

Example 6
90 parts of a green pigment, 10 parts of a pigment derivative (BD-1), 60 parts of a phosphate group-containing dispersion resin (P-1) solution, and 20 parts of a polyester dispersant (S-1) are uniformly stirred to obtain a mixture. It was. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  150 parts of the coating pigment and 225 parts of solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of melamine compound (MX-417), 86 parts of solvent (CBAc), solvent 55 parts of (TA) was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 18% was obtained.

Example 7
90 parts of a green pigment, 10 parts of a pigment derivative (BD-1), 20 parts of a polyester dispersant (S-1) and 60 parts of a vinyl dispersant (B-2) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  150 parts of the coating pigment and 225 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of the melamine compound (MX-43), 86 parts of the solvent (CBAc), and the solvent. 55 parts of (TA) was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 18% was obtained.

Example 8
90 parts of yellow pigment, 10 parts of pigment derivative (YD-1), 20 parts of polyester dispersant (S-1) and 94 parts of vinyl dispersant (B-2) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating pigment and 251 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of the melamine compound (MX-417), 117 parts of the solvent (CBAc), and the solvent 92 parts of (TA) was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 18% was obtained.

Example 9
90 parts of yellow pigment, 10 parts of pigment derivative (YD-1), 20 parts of polyester dispersant (S-2), and 94 parts of vinyl dispersant (U-1) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating pigment and 251 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a benzoguanamine compound (BL-60), 140 parts of a solvent (CBAc), a solvent. 69 parts of (TA) was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 18% was obtained.

Example 10
90 parts of a blue pigment, 10 parts of a pigment derivative (BD-1), 110 parts of a phosphate group-containing dispersion resin (P-1) solution, and 12 parts of a phosphate group-containing dispersion resin (P-2) are uniformly stirred and mixed. Got. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill, and further 20 parts of a benzoguanamine compound (SB-401) and 20 parts of an acrylic monomer (M-400). Part, 287 parts of solvent (CBAc) and 105 parts of solvent (TA) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 11% was obtained.

Example 11
90 parts of a blue pigment, 10 parts of a pigment derivative (BD-1), 12 parts of a polyester dispersant (S-1), and 110 parts of a vinyl dispersant (B-1) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill, and further 20 parts of a benzoguanamine compound (SB-401) and 20 parts of an acrylic monomer (M-400). Part, 287 parts of solvent (CBAc) and 105 parts of solvent (TA) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 11% was obtained.

Example 12
90 parts of a cyan pigment, 10 parts of a pigment derivative (BD-1), and 134 parts of a branched urethane-based dispersion resin B (U-2) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 20 parts of a benzoguanamine compound (BL-60), 20 parts of an epoxy compound (EPPN-201), 222 parts of solvent (CBAc), 47 parts of solvent (BuCBAC) and 47 parts of solvent (TA) were added and mixed. Dust and coarse matter were filtered and an inkjet ink having a pigment concentration of 12% was obtained.

Example 13
90 parts of violet pigment, 10 parts of pigment derivative (VD-1), 104 parts of vinyl dispersant (B-1) solution and 15 parts of polyester dispersant (S-2) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating pigment and 390 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill, and further 20 parts of the melamine compound (MX-43), 41 parts of the solvent (CBAc), and the solvent (TA ) 76 parts were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 14% was obtained.

<< Comparative Example 1 >>
100 parts of the red pigment (1), 104 parts of the phosphate group-containing dispersion resin (P-1) solution, and 15 parts of the polyester dispersant (S-2) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, it did not become a clean sheet after the solvent was evaporated. Further, 52 parts of a solvent (PGMAc) was added and the two rolls were heated to 80 ° C. and kneaded, but a clean sheet could not be formed. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 450 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 20 parts of a melamine compound (MX-417), 20 parts of an acrylic monomer (M-400), 122 parts of solvent (TA) was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

<< Comparative Example 2 >>
90 parts of red pigment (1), 10 parts of pigment derivative (RD-1), 15 parts of polyester dispersant (S-1), 104 parts of vinyl dispersant (B-1) solution are uniformly stirred, and the mixture is stirred. Obtained. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 450 parts of the solvent (CBAC) were mixed in a mixer, and further dispersed in a sand mill. Further, 52 parts of the solvent (CBAc) and 90 parts of the solvent (TA) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

<< Comparative Example 3 >>
90 parts of red pigment (2) and 10 parts of pigment derivative (RD-2) were uniformly stirred, and 52 parts of solvent (PGMAc) was further added and the two rolls were heated to 80 ° C. and kneaded. The rear sheet was not formed and remained in powder form.

  100 parts of the obtained powdery solid and 478 parts of solvent (CBAc) are placed in a mixer and mixed, further placed in a sand mill for dispersion, and further 40 parts of melamine compound (MX-43) and 57 parts of solvent (CBAc). Then, 94 parts of solvent (TA) was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 13% was obtained.

<< Comparative Example 4 >>
90 parts of magenta pigment, 10 parts of pigment derivative (MD-1), 15 parts of polyester dispersant (S-2), and 104 parts of branched urethane dispersion resin B (U-2) solution are uniformly stirred to obtain a mixture. It was. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 20 parts of a melamine compound (MX-417) and an isocyanate compound (BL-4265) 20 And 150 parts of solvent (CBAc) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 15% was obtained.

<< Comparative Example 5 >>
90 parts of a green pigment, 10 parts of a pigment derivative (BD-1), 20 parts of a polyester dispersant (S-1) and 60 parts of a vinyl dispersant (B-2) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  150 parts of the coating pigment and 225 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of the melamine compound (MX-43), 86 parts of the solvent (CBAc), and the solvent. (EDG) 55 parts was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 18% was obtained.

<< Comparative Example 6 >>
90 parts of yellow pigment, 10 parts of pigment derivative (YD-1), 20 parts of polyester dispersant (S-1) and 94 parts of vinyl dispersant (B-2) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 251 parts of solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of melamine compound (MX-417), 140 parts of solvent (CBAc), solvent (PNB) 69 was added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 18% was obtained.

<< Comparative Example 7 >>
90 parts of a blue pigment, 10 parts of a pigment derivative (BD-1), 110 parts of a phosphate group-containing dispersion resin (P-1) solution, and 12 parts of a phosphate group-containing dispersion resin (P-2) are uniformly stirred and mixed. Got. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill, and further 20 parts of a benzoguanamine compound (SB-401) and 20 parts of an acrylic monomer (M-400). Part, 287 parts of solvent (CBAc) and 105 parts of solvent (PGMAc) were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 11% was obtained.

<< Comparative Example 8 >>
90 parts of a cyan pigment, 10 parts of a pigment derivative (BD-1), and 134 parts of a branched urethane-based dispersion resin B (U-2) solution were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 310 parts of the solvent (CBAc) are mixed in a mixer, further dispersed in a sand mill, and further 20 parts of a benzoguanamine compound (BL-60), 20 parts of an epoxy compound (EPPN-201), 222 parts of solvent (CBAc) and 94 parts of solvent (1,3-BDGA) were added and mixed. Dust and coarse matter were filtered and an inkjet ink having a pigment concentration of 12% was obtained.

<< Comparative Example 9 >>
90 parts of violet pigment, 10 parts of pigment derivative (VD-1), 104 parts of vinyl dispersant (B-1) solution and 15 parts of polyester dispersant (S-2) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 52 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

  167 parts of the coating treatment pigment and 390 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 20 parts of the melamine compound (MX-43), 41 parts of the solvent (CBAc), and solvent (Gly) ) 76 parts were added and mixed. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 14% was obtained.

  The viscosity and fluidity of the inks obtained in Examples 1 to 13 and Comparative Examples 1 to 9 were evaluated by the following methods. Further, the inks obtained in Examples 1 to 13 and Comparative Examples 1 to 9 were ejected by an ink jet printer having a piezo head capable of changing the frequency of 4 to 10 KHz, and the ejection stability was evaluated by the following method.

  The ink obtained in Examples 1 to 13 and Comparative Examples 1 to 9 was ejected and dried at a predetermined position of the glass substrate using the ink jet printer, followed by heat curing at 230 ° C. for 20 minutes. The coating film reliability was evaluated by the following method. The results are shown in Tables 1 to 3. In addition, the ink obtained in Examples 1 to 13 and Comparative Examples 1 to 9 was discharged onto a cardboard using the inkjet printer and dried, followed by drying at room temperature to form a coating film. It was evaluated with. The results are shown in Tables 1 to 3.

[viscosity]
The viscosity (η: mPa · s) at a shear rate of 100 (1 / s) was measured with a dynamic viscoelasticity measuring device.
[Liquidity]
Using a dynamic viscoelasticity measuring device, the viscosity (ηa: mPa · s) at a shear rate of 10 (1 / s) was measured, and the viscosity (η: mPa · s) at a shear rate of 100 (1 / s) measured previously. The ratio ηa / η was determined, and the fluidity was evaluated according to the following criteria.
○: 0.9 ≦ ηa / η <1.5
×: 1.5 ≦ ηa / η

[Storage stability]
The viscosity was measured after heating in an oven at 45 ° C. for 7 days.
○: Thickening rate within 10% compared to viscosity before heating ×: 30% or more thickening rate compared to viscosity before heating [chemical resistance]
The glass substrate on which the coating film was formed was immersed in N-methylpyrrolidone, and the color change ΔE of the coating film before and after immersion was measured.
○: ΔE ≦ 2
Δ: 2 <ΔE ≦ 4
×: ΔE> 4

[Discharge stability]
The printing state was visually observed, and the ejection stability was evaluated according to the following criteria.
○: Nozzle missing after intermittent 15 minutes is 5% or less.
Δ: Nozzle missing after 15 minutes of intermittent operation is 10% or less.
X: Nozzle omission is 50% or more after intermittent 15 minutes.
[Print density]
The solid printing was performed on the cardboard, and the OD value was measured after drying.
○: OD value 1.2 or more ×: OD value less than 1.2

  The ink-jet ink of the present invention has good chemical resistance, and even when the pigment concentration is high, when used as a paint or ink, it has low viscosity and good viscosity stability over time. In addition, when used as an inkjet ink, an ink having low viscosity and good ejection stability can be obtained while maintaining durability. Further, by using the ink composition of the present invention as an inkjet ink, it is possible to produce a color filter, a package, an outdoor signboard, or the like that is much more efficient than a conventional method.

  As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (16)

 An ink-jet ink comprising a solvent containing an ester derivative of a trihydric or higher polyhydric alcohol, a pigment, a pigment derivative, a dispersion resin, and a thermally reactive compound.  The inkjet ink according to claim 1, wherein the ester derivative of a trihydric or higher polyhydric alcohol is triacetin.  The inkjet ink according to claim 1 or 2, wherein the solvent further contains a dialkylene glycol monoalkyl ether compound or a trialkylene glycol monoalkyl ether compound having a boiling point of 200 ° C or higher.  The inkjet ink according to any one of claims 1 to 3, wherein the ester derivative of a trihydric or higher polyhydric alcohol is 3 to 50% by weight based on the total amount of the solvent. The inkjet ink according to any one of claims 1 to 4, wherein the pigment derivative is a compound represented by the following general formula (1).
General formula (1)
G ¹ -eq
(In General Formula (1), G ¹ is a q-valent chromogenic compound residue,
e is a basic substituent, an acidic substituent, or a neutral substituent;
q is an integer of 1 to 4. )
  The pigment derivative includes at least one basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group, The inkjet ink of any one of Claims 1-5. The inkjet ink according to any one of claims 1 to 6, wherein the dispersion resin is one or more selected from the group consisting of the following (a) to (e).
[
(A) a dispersion resin containing one or more phosphoric acid groups or a dispersion resin containing a monomer represented by the following general formula (2) as a polymerization component;
(B) a polyester-based dispersion resin represented by the following general formula (3),
(C) a vinyl-based dispersion resin containing a carboxyl group-containing unit (G) represented by the following general formula (4) in an amount of 0.3 to 3.0 in average per molecule of the vinyl polymer;
(D) Terminal obtained by reacting polyisocyanate (da) having three or more isocyanate groups with monoalcohol (db) at a molar ratio of NCO / OH = 3/2 to 3 / 0.5. For isocyanate compounds,
A compound (dc) having one or more acidic groups and two or more hydroxyl groups;
A condition in which a polyol compound containing an acrylic resin (dd) and / or a siloxane resin (de) having two or more hydroxyl groups present with 1 to 30 atoms sandwiched therebetween is excessive in hydroxyl groups A dispersion resin obtained by polymerization with
A branched urethane-based dispersion resin in which the proportion derived from polyisocyanate (da) in the nonvolatile component is 25% to 60% by weight of the total dispersion resin,
(E) Terminal obtained by reacting polyisocyanate (ea) having three or more isocyanate groups with monoalcohol (eb) at a molar ratio of NCO / OH = 3/2 to 3 / 0.5 For isocyanate compounds,
A polyol compound containing an acrylic resin (ed) and / or a siloxane resin (ee) having two or more hydroxyl groups present with 1 to 30 atoms sandwiched between them under the condition that the hydroxyl group is excessive. A hydroxyl group in a terminal hydroxyl group compound obtained by polymerization;
A dispersion resin obtained by reacting an acid anhydride group in a compound having an acid anhydride group (eg),
A branched urethane-based dispersion resin in which the proportion derived from polyisocyanate (ea) in the nonvolatile component is 25% to 60% by weight of the entire dispersion resin.
General formula (2):

(In General Formula (2), R ¹ represents hydrogen or a methyl group.
R ² represents an alkylene group.
m represents an integer of 1 to 20. )
General formula (3):
(HOOC-) _e -R ^a1 -(-COO-[-R ^a3 -COO-] _f -R ^a2 ) _g
(In the general formula (3), R ^a1 is a tetravalent tetracarboxylic acid compound residue,
R ^a2 is a monoalcohol residue,
R ^a3 is a lactone residue,
e represents an integer of 2 or 3, f represents an integer of 1 to 50, and g represents (4-e). )
General formula (4):

(In general formula (4),
R ^b1 is a hydrogen atom or a methyl group,
X ¹ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—;
X ² is a group represented by the following general formula (23),
X ³ is a group represented by the following general formula (24),
Y ¹ is a group represented by the general formula (5) or a group represented by the general formula (6). )

Formula (23)
-(-R ^b2 -O-) _m1-
(In General Formula (23), R ^b2 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m1 is an integer of 1 to 50. is there.)
General formula (24)
-(-CO-R ^b3 -O-) _m2-
(In the general formula (24), R ^b3 is a linear or branched alkylene group having 4 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is an integer of 0 to 20. is there.)
General formula (5)

(In general formula (5),
A combination in which ^{one of} A ^{1 to} A ³ is a hydrogen atom and the other two are —COOH;
A one is -COOR ^c1 of the A ¹ to A ^3, a or the other two are combined is -COOH, or three of A ¹ to A ³ is -COOH, k is 1 or 2 It is.
R ^c1 is an alkyl group having 1 to 18 carbon atoms. )
General formula (6)

(In general formula (6),
A combination in which one of A ^{5 to} A ⁷ is a hydrogen atom and the other two are —COOH;
One of A ^{5 to} A ⁷ is —COOR ^d2 and the other two are combinations that are —COOH, or three of A ^{5 to} A ⁷ are —COOH.
However, ^Rd2 is a C1-C18 alkyl group.
R ^d1 is a group represented by a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, formula (25), or a formula It is group represented by (26). )

Formula (25)


Formula (26)

]   The thermally reactive compound is one or more compounds selected from the group consisting of melamine compounds, benzoguanamine compounds, epoxy compounds, phenolic compounds, blocked isocyanate compounds, acrylate monomers, and silane coupling agents. The inkjet ink as described in any one of 1-7.   The inkjet ink according to claim 1, further comprising a binder resin.   The inkjet ink according to claim 9, wherein the binder resin is a thermoplastic resin.   The inkjet ink according to any one of claims 1 to 10, wherein the solid content is 3 to 60% by weight based on the total weight of the ink composition.   The inkjet ink according to any one of claims 1 to 11, wherein the pigment content is 1 to 30% by weight based on the total weight of the ink composition.   The inkjet ink according to any one of claims 1 to 12, wherein a weight ratio of the pigment to the dispersion resin is 100: 3 to 100: 150.   The inkjet ink as described in any one of Claims 1-13 whose viscosity in 25 degreeC is 2-40 mPa * s.   The inkjet ink according to claim 1, which is for a color filter substrate. A color filter substrate carrying a printing layer made of the ink composition for ink jet recording according to claim 1.