JP2007302884A - Colored resin composition and inkjet ink produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition having excellent surface smoothness and flatness in picture element and provide inkjet ink produced by using the colored resin composition. <P>SOLUTION: The colored resin composition contains a pigment, a pigment derivative and a resin carrier and has viscosity of 3-200 mPa s (at a shearing rate of 100 (1/s)) at a solid concentration of ≥20 wt.% and <40 wt.%, a T.I. value (defined by the ratio (ηa /ηb ) of the viscosity ηa (mPa s) at a shearing rate of 10 (1/s) to the viscosity ηb (mPa s) at a shearing rate of 1,000 (1/s)) of 1-2, viscosity of 10-200 mPa s (under a condition shown above) and a T.I. value of 1-3 (under a condition shown above) at a solid concentration of ≥40 wt.% and ≤60 wt.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a colored resin composition, an ink jet ink, and a method for producing them. Furthermore, the present invention relates to a printed matter using an inkjet ink.

  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, blue, green; 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 filter segments of different hues in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine mosaic shape. It consists of filter segments arranged in a constant array. 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 steps 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 ink jet 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.

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 ink in the region divided by the black matrix by the ink jet method. An ink composition having physical properties that can be dispersed and contained at a high concentration in order to provide a pigment concentration necessary for a color filter substrate, and at the same time, can be stably ejected to a desired position on the substrate by an inkjet method. Has been developed.
However, when the viscosity stability decreases dramatically due to drying of the ink, when discharging with an inkjet device, the ink viscosity increases due to slight drying at the nozzle, resulting in clogging of the nozzle and a decrease in discharge stability. Connected. Furthermore, in the drying process of the coating film, a film is stretched on the surface, resulting in uneven drying, surface smoothness is impaired, and in the case of a colored composition that requires light transmittance, the transmittance and contrast are lowered. In addition, there is a problem that the in-pixel flatness in the area divided by the black matrix is deteriorated.

For example, Japanese Patent Application Laid-Open No. 11-84123 discloses a method for preventing such problems from deteriorating ejection properties and in-pixel flatness with ink having a low pigment concentration and solid content concentration. However, at a low pigment concentration or a low solid content concentration, the film thickness becomes too thick when a coating film having a required color density is formed. Further, the amount of ink to be filled in the area divided by the black matrix is increased, the ink overflows beyond the black matrix, the ink is mixed into the adjacent area, and the hue of the filter segment is damaged. Japanese Patent Laid-Open No. 2003-66222 discloses a method for improving the in-pixel flatness by controlling the temperature and time during drying. However, the above problem cannot be solved only by controlling such a process.
Japanese Patent Laid-Open No. 11-84123 JP 2003-66222 A

  An object of an embodiment of the present invention is to provide a colored resin composition excellent in surface smoothness and in-pixel flatness, and an inkjet ink using the colored resin composition.

The present inventors have clarified the causal relationship between the physical properties and the performance of the color filter substrate by paying attention to the patterning characteristics of the colored resin composition, particularly the viscosity.
That is, the present invention is a colored resin composition containing a pigment, a pigment derivative, and a resin carrier, and has a viscosity (however, the shear rate is 100 (1 / s) at a solid content concentration of 20 wt% or more and less than 40 wt%. 3 to 200 (mPa · s), and T. is limited to a certain case. I. The value (however, the ratio (ηa / ηb) between the viscosity ηa (mPa · s) at a shear rate of 10 (1 / s) and the viscosity ηb (mPa · s) at a shear rate of 1000 (1 / s)). In the solid content concentration of 40 wt% or more and 60 wt% or less, and the viscosity is 10 to 200 (mPa · s). I. The present invention relates to a colored resin composition having a value of 1 to 3.

（式中、Ｒ₁は水素またはメチル基を表す。Ｒ₂はアルキレン基を表す。ｍは１〜２０の整数を表す。）
一般式（２）：
（ＨＯＯＣ―）_ｅ―Ｒ’１―（―ＣＯＯ―[―Ｒ’３―ＣＯＯ―]_ｆ―Ｒ’２）_ｇ （２）
（式中、Ｒ’１は４価のテトラカルボン酸化合物残基、Ｒ’２はモノアルコール残基、Ｒ’３はラクトン残基、ｅは２または３の整数、ｆは１〜５０の整数、ｇは（４−ｅ）を表す。）
一般式（３）：

｛一般式（３）中、Ｒ’’^３は水素原子又はメチル基であり、
Ｘ^１は、−ＣＯＯ−、−ＣＯＮＨ−、−Ｏ−、−ＯＣＯ−若しくは−ＣＨ_２Ｏ−であり、Ｘ^２は、一般式：
−（−Ｒ^ａ１−Ｏ−）_ｍ１−
（式中、Ｒ^ａ１は炭素原子数２〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数３〜８のシクロアルキレン基であり、そしてｍ１は１〜５０の整数である）
で表される基であり、
Ｘ^３は、一般式：
−（−ＣＯ−Ｒ^ｂ１−Ｏ−）_ｍ２−
（Ｒ^ｂ１は炭素原子数４〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数４〜８のシクロアルキレン基であり、そしてｍ２は０または１〜２０の整数である）
で表される基であり、
Ｙ^１は、一般式（４）：

（一般式（４）中、
Ａ^１〜Ａ^３のうちの１つが水素原子であって、他の２つは−ＣＯＯＨである組合せであるか、Ａ^１〜Ａ^３のうちの１つが−ＣＯＯＲ^ｃ（但し、Ｒ^ｃは、炭素原子数１〜１８のアルキル基である）であって、他の２つは−ＣＯＯＨである組合せであるか、又はＡ^１〜Ａ^３の３つが−ＣＯＯＨの組合せであり、ｋは１又は２である）
で表される基であるか、あるいは一般式（５）：

（一般式（５）中、
Ａ^５〜Ａ^７のうち１つは水素原子であって、他の２つは−ＣＯＯＨである組合せであるか、Ａ^５〜Ａ^７のうち１つは−ＣＯＯＲ^ｄ（但し、Ｒ^ｄは、炭素原子数１〜１８のアルキル基である）であって、他の２つは−ＣＯＯＨである組合せであるか、又はＡ^５〜Ａ^７の３つが−ＣＯＯＨの組合せであり、
Ｒ^２は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２ＯＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、式：

で表される基、又は式：

で表される基である） Furthermore, the above-mentioned colored resin composition, wherein a compound having a weight average molecular weight of 2000 to 10,000 is contained in an amount of 5% by weight or more based on the total solid content, is also preferable. Here, the compound having a weight average molecular weight of 2000 to 10000 preferably has at least one structure represented by the following general formulas (1) to (3).
General formula (1):

(In the formula, R ₁ represents hydrogen or a methyl group. R ₂ represents an alkylene group. M represents an integer of 1 to 20.)
General formula (2):
(HOOC-) _e- R'1-(-COO-[-R'3-COO-] _f- R'2) _g (2)
Wherein R′1 is a tetravalent tetracarboxylic acid compound residue, R′2 is a monoalcohol residue, R′3 is a lactone residue, e is an integer of 2 or 3, and f is an integer of 1 to 50 , G represents (4-e).)
General formula (3):

{In General Formula (3), R ″ ³ is a hydrogen atom or a methyl group,
X ¹ is —COO—, —CONH—, —O—, —OCO—, or —CH ₂ O—, and X ² is represented by the general formula:
-(-R ^a1 -O-) _m1-
(Wherein R ^a1 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)
A group represented by
X ³ is a general formula:
-(-CO-R ^b1 -O-) _m2-
(R ^b1 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 0 or an integer of 1 to 20)
A group represented by
Y ¹ represents the general formula (4):

(In general formula (4),
A one is hydrogen atom of A ¹ to A ^3, or the other two are combined is ^-COOH, one of -COOR ^c (where, ^{R c} of the A 1 to A ³ are, The other two are —COOH, or ^three of A ^{1 to} A ³ are —COOH, and k is 1 or 2)
Or a group represented by the general formula (5):

(In general formula (5),
One of A ^{5 to} A ⁷ is a hydrogen atom and the other two are combinations of —COOH, or one of A ^{5 to} A ⁷ is —COOR ^d (where R ^d is The other two are —COOH, or three of A ^{5 to} A ⁷ are —COOH combinations,
R ² is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

Or a group represented by the formula:

Is a group represented by

Furthermore, the colored resin composition containing an alkoxyalkyl group-containing melamine compound or an alkoxyalkyl group-containing benzoguanamine compound is also preferable.
In addition, the above-described colored resin composition in which a coating layer of a pigment derivative and a resin carrier is formed on the pigment surface is also preferable.

It can be set as inkjet ink using the said colored resin composition.

  According to the present invention, a colored resin composition having an effect excellent in dispersion stability and ejection stability during long-time continuous ejection is provided. In addition, there is an effect that there is no occurrence of drying unevenness. For this reason, the colored resin composition excellent in surface smoothness and in-pixel flatness can be provided.

  Further, it is possible to provide a colored resin composition having a low viscosity and a good viscosity stability with time when used as a paint or an ink even though the chemical resistance is good and the pigment concentration is high. In addition, it is possible to provide an inkjet ink having low viscosity and good ejection stability while maintaining resistance.

  In addition, by using the inkjet ink of the present invention, 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.

The colored resin composition of the present invention includes a pigment, a pigment derivative, and a resin carrier. Furthermore, it is preferable that 5% by weight or more of a compound having a weight average molecular weight of 2000 to 10,000 is contained in the solid content.
The colored resin composition of the present invention is characterized by satisfying the following viscosity physical properties I and II.
(Viscosity properties I)
When the solid content concentration is 20% by weight or more and less than 40% by weight, the viscosity (provided that the shear rate is 100 (1 / s)) is 3 to 200 (mPa · s); I. The value (provided that the ratio (ηa / ηb) of the viscosity ηa (mPa · s) at a shear rate of 10 (1 / s) to the viscosity ηb (mPa · s) at a shear rate of 1000 (1 / s)) is 1 ~ 2.
(Viscosity properties II)
When the solid content concentration is 40% by weight or more and 60% by weight or less, the viscosity (however, only when the shear rate is 100 (1 / s)) is 10 to 200 (mPa · s); I. The value (provided that the ratio (ηa / ηb) of the viscosity ηa (mPa · s) at a shear rate of 10 (1 / s) to the viscosity ηb (mPa · s) at a shear rate of 1000 (1 / s)) is 1 ~ 3.

  When the colored resin composition of the present invention is used as an ink, the solid content of the ink composition (hereinafter sometimes referred to as solid content concentration) is preferably 3 to 60 weights with respect to the total weight of the ink composition. %, More preferably 4 to 40% by weight. When the solid content is 3% by weight or more, the concentration of the ink film becomes appropriate and the resistance is excellent. When it is 60% by weight or less, the viscosity of the ink becomes appropriate and the stability over time is excellent.

  When the solvent is adjusted so that the solid content is 20% by weight or more and less than 40% by weight or 40% by weight or more and 60% by weight, the composition satisfying the above viscosity physical property I or II is the colored resin of the present invention. It is a composition.

T.A. I. The value indicates thixotropic properties and is represented by the following relationship (A).
Relationship (I)
T.A. I. Value = viscosity measured at a rotor speed of 10 (1 / S) in the rheometer / viscosity measured at a rotor speed of 1000 (1 / S) in the rheometer

  The solid content concentration, viscosity, and T.I. I. Regarding the relationship of the values, more preferably, the viscosity is 10 to 150 (mPa · s) and T.I. at a solid content concentration of 40% by weight to 60% by weight. I. The viscosity is 10 to 100 (mPa · s) and T.p. is preferably 1 to 3 at a solid content concentration of 40% by weight to 60% by weight. I. The value is 1-3.

The colored resin composition of the present invention contains a pigment.
As the pigment, an organic pigment, an inorganic pigment, or carbon black can be used, and two or more kinds of pigments may be mixed and used.

  Examples of carbon black include acetylene black, channel black, and furnace black.

  Organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthra Anthraquinone pigments such as pyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment Examples thereof include pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, brown rice, 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, bitumen, cobalt blue, cerulean blue, Examples thereof include cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

  Moreover, the pigment which can be used for the colored resin composition of this invention is shown by a color index (CI) number below.

  Examples of the red coloring composition 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 and / or an orange pigment can be used in combination with the red coloring composition.

  Examples of the yellow coloring composition 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, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199 can be used.

  Examples of the orange coloring composition include C.I. I. Orange pigments such as Pigment orange 36, 43, 51, 55, 59, 61 can be used.

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

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

  The colored resin composition of the present invention may contain a pigment alone or 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 0.01 μm or more and 0.3 μm or less, particularly 0.01 μm or more and 0.1 μm or less. 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 apparatus such as a sand mill, a kneader, or a two-roll.

  In the colored resin composition of the present invention, the pigment is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 25% by weight, based on the weight of the entire composition. When the content of the pigment is 1% by weight or more, the concentration of the ink film of the ink composition when the ink is used is sufficient, and when it is 30% by weight or less, the viscosity does not increase and the stability over time is excellent.

  The compound having a weight average molecular weight of 2000 to 10000 is preferably used in an amount of 3 to 150 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the pigment. When the compound having a weight average molecular weight of 2000 to 10000 is 3 parts by weight or more, the viscosity of the ink composition is sufficiently low, and when it is 150 parts by weight or less, the ink composition is excellent in film forming properties.

  The colored resin composition of the present invention contains a pigment derivative.

  Here, the pigment derivative refers to a compound in which a specific substituent is introduced into the organic pigment residue described in the color index.

Examples of the pigment derivative include, for example, the general formula (6):
G ^1- (E) q (6)
(Wherein, G ¹ is a chromogenic compound residue, E is a basic substituent, an acidic substituent, or a neutral substituent, and q is an integer of 1 to 4). Can be used.

  Examples of the basic substituent of the group E include substituents represented by the following general formula (7), general formula (8), general formula (9), and general formula (10).

Ｘ^３１：−ＳＯ_２−、−ＣＯ−、−ＣＨ_２ＮＨＣＯＣＨ_２−、−ＣＨ_２−又は直接結合
を表す。
ｐ：１〜１０の整数を表す。
Ｒ^３３、Ｒ^３４：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、又はＲ^３３とＲ^３４とで一緒になって更なる窒素原子、酸素原子又は硫黄原子を含む置換されていてもよい複素環を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。 General formula (7):

X ^{31 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
p: represents an integer of 1 to 10.
R ³³ and R ³⁴ : each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a combination of R ³³ and R ³⁴ And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

Ｒ^３５、Ｒ^３６：それぞれ独立に、置換されていてもよいアルキル基、置換されていて
もよいアルケニル基、置換されていてもよいフェニル基、又はＲ^３５とＲ^３６とで一緒になって更なる窒素原子、酸素原子又は硫黄原子を含む置換されていてもよい複素環を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。 General formula (8):

R ³⁵ , R ³⁶ : each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a combination of R ³⁵ and R ³⁶ And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

Ｘ^３２：−ＳＯ_２−、−ＣＯ−、−ＣＨ_２ＮＨＣＯＣＨ_２−、−ＣＨ_２−又は直接結合を表す。
Ｒ^３７：置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
Ｒ^３８、Ｒ^３９、Ｒ^１０、Ｒ^１１：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜５が好ましい。 General formula (9):

X ^{32 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
R ³⁷ : 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 ³⁸ , R ³⁹ , 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.

Ｘ^３３：−ＳＯ_２−、−ＣＯ−、−ＣＨ_２ＮＨＣＯＣＨ_２−、−ＣＨ_２−又は直接結合を表す。
Ｙ：−ＮＲ^１２−Ｚ−ＮＲ^１３−又は直接結合を表す。
Ｒ^１２、Ｒ^１３：それぞれ独立に水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜５が好ましい。
Ｚ：置換されていてもよいアルキレン基、置換されていてもよいアルケニレン基、又は置換されていてもよいフェニレン基を表す。アルキレン基及びアルケニレン基の炭素数は１〜８が好ましい。
Ｐ：下記一般式（１１）で示される置換基又は下記一般式（１２）で示される置換基を表す。
Ｑ：水酸基、アルコキシル基、前記一般式（８）で示される置換基又は前記一般式（９）で示される置換基を表す。 General formula (10):

X ^{33 represents} —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 alkylene group and an alkenylene group, 1-8 are preferable.
P: A substituent represented by the following general formula (11) or a substituent represented by the following general formula (12).
Q: represents a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (8) or a substituent represented by the general formula (9).

ｒ：１〜１０の整数を表す。
Ｒ^１４、Ｒ^１５：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、又はＲ^１４とＲ^１５とで一緒になって更なる窒素原子、酸素原子又は硫黄原子を含む置換されていてもよい複素環を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。 General formula (11):

r represents an integer of 1 to 10.
R ¹⁴ and R ¹⁵ : each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a combination of R ¹⁴ and R ¹⁵ And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

Ｒ^１６：置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜５が好ましい。 Formula (12):

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.

Examples of the acidic substituent or neutral substituent of the group E include substituents represented by the following general formula (13), general formula (14), and general formula (15).
General formula (13):
-SO ₃ M / l (13)
M: represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom.
l: Valency of M

Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４：水素原子又は炭素数１〜３０のアルキル基を表す（但し全てが水素原子である場合は除く）。 General formula (14):

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).

Ａ^３２：水素原子、ハロゲン原子、−ＮＯ_２、−ＮＨ_２又はＳＯ_３Ｈを表す。
ｙ：１〜４の整数を表す。 Formula (15):

A ^{32 represents a} hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ or SO ₃ H.
y: represents an integer of 1 to 4.

Examples of the chromophoric compound residue G ¹ include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, and indanthrone. Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, or Residues such as metal complex dyes, anthraquinone residues, or triazine residues can be exemplified.

  In particular, when the pigment derivative is an anthraquinone derivative, anthraquinone having the above basic substituent, acidic substituent or neutral substituent can be used. In the case of a triazine derivative, an alkyl group such as a methyl group or an ethyl group; an amino group; an alkylamino group such as a dimethylamino group, a diethylamino group or a dibutylamino group; a nitro group; a hydroxyl group; a methoxy group, an ethoxy group or a butoxy group An alkoxy group such as a group; a halogen such as chlorine; a phenyl group optionally substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group or a hydroxyl group; or a methyl group, an ethyl group, a methoxy group, an ethoxy group, an amino group; 1,3,5-triazine which may have a substituent such as a group, a dimethylamino group, a diethylamino group, a nitro group, or a phenylamino group which may be substituted with a hydroxyl group, etc. A derivative into which a group, an acidic substituent or a neutral substituent is introduced can be used.

  Of these, pigment derivatives containing a triazine ring and an anthraquinone group are more preferred. A pigment derivative with a triazine ring and an anthraquinone group structure exhibits a higher adsorptivity to the pigment and provides high dispersibility, while at the same time causing a curing reaction of the thermoreactive compound more effectively and further improving the resistance. Can be expected.

The colored resin composition of the present invention contains a resin carrier.
The resin carrier is a non-reactive resin even at the reaction temperature of the thermoreactive compound described later, and is preferably a thermoplastic resin.

  Examples of the resin carrier include petroleum resin, maleic acid resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, alkyd resin, acrylic resin, polyester resin, amino resin, vinyl resin, or butyral resin. Can be used.

A resin carrier having a crosslinkable functional group can also be used. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an alkoxyl group.
As the resin having a crosslinkable functional group, an acrylic resin having a hydroxyl group or a carboxyl group is preferable because the resin is slowly crosslinked by an esterification reaction.
The acrylic resin having a hydroxyl group or a carboxyl group is a resin obtained by copolymerizing a monomer having a hydroxyl group or a monomer having a carboxyl group and an acrylic monomer having no hydroxyl group or carboxyl group.

  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, and 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 to 6) ), Epoxy (meth) acrylate, hydroxyl-terminated urethane (meth) acrylate, N-methylolacrylamide, allyl alcohol, polyethylene glycol monomethacrylate, polyethylene glycol Acrylate, 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 Mono methacrylate, propylene glycol polybutylene glycol mono acrylate.

  As monomers having a carboxyl group, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 2-carboxyethyl acrylate, ω-carboxy-polycaprolactone monoacrylate, monohydroxyethyl phthalate , Glutaconic acid, tetrahydrophthalic acid and the like.

As the acrylic monomer having no hydroxyl group or carboxyl group, a monomer represented by the following general formula (16) may be used.
Formula (16):

Ｒ^４３：炭素数１〜３０のアルキル基、−ＣＨ_２−ＣＨ＝ＣＨ_２、置換基されていてもよいフェニル基又はＣ＝０−Ｃ（Ｒ^５１）＝ＣＨ_２を表す。
Ｒ^４１及びＲ^５１：水素原子又はメチル基を表す。
Ｒ^４２：炭素数１〜４アルキレン基を表す。
ｓ：１〜１００の整数を表す。

R ^43: an alkyl _group, -CH ₂ -CH = CH _2, optionally substituted phenyl group or a ^{C = 0-C (R 51} ) = CH 2 having from 1 to 30 carbon atoms.
R ⁴¹ and R ⁵¹ represent a hydrogen atom or a methyl group.
R ⁴² represents a C 1-4 alkylene group.
s: represents an integer of 1 to 100.

  Examples of the monomer represented by the general formula (16) include methoxypolyethylene glycol monomethacrylate, methoxypolyethyleneglycol monoacrylate, octoxypolyethyleneglycol monoacrylate, octoxypolyethyleneglycolpolypropyleneglycolmonomethacrylate, octoxypolyethyleneglycolpolypropyleneglycolmonoacrylate. , Lauroxy polyethylene glycol monoacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate, stearoxy polyethylene glycol-polypropylene glycol monoacrylate, 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, polytetramethylene 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, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol-polypropylene glycol monomethacrylate, nonylphenoxypolypropylene glycol-polyethylene glycol monomethacrylate, nonylphenoxypoly (ethylene glycol-propylene glycol) Examples thereof include monoacrylate, phenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, bisphenol F ethylene oxide modified diacrylate, and the like. These are commercially available as, for example, the Blemmer series from Nippon Oil & Fat Co., Ltd. and the Aronix series from Toa Gosei Co., Ltd.

  Examples of the acrylic monomer having no hydroxyl group and carboxyl group other than the monomer represented by the general formula (16) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). (Meth) acrylic acid alkyl esters such as acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styrene, α-methyl Styrene, vinyl toluene, vinyl acetate and the like can be mentioned. In addition, monomers generally used for the synthesis of acrylic resins, such as alkyl (meth) acrylates in which some or all of the hydrogen atoms of the alkyl group are substituted with aromatic rings, heterocyclic rings, halogen atoms, or the like, can be used.

  The colored resin composition of the present invention preferably contains a compound having a weight average molecular weight (Mw) of 2000 to 10,000 in a part of the resin carrier. The viscosity of the colored resin composition of the present invention and T.I. I. This is because the value relationship can be maintained.

  A colored resin composition dispersed with a compound having Mw = 2000 to 10,000 has less intermolecular interaction and physical entanglement between compounds than a pigment dispersion dispersed with a compound having the same structure and Mw> 10000. Has a low viscosity and a low thixotropy. In addition, compounds with Mw = 2000 to 10000 often have moderate dispersibility, but compounds with Mw <2000 have low dispersion performance and dispersion stability cannot be obtained, or the viscosity increases with time, or dispersion progresses. Absent.

  As above-mentioned, the compound of Mw = 2000-10000 functions as a dispersing agent. For the above reasons, it is desirable to use a compound having a weight average molecular weight of Mw = 2000 to 10,000 in order to obtain a colored resin composition having low viscosity and low thixotropy.

  In order to obtain a colored resin composition having low viscosity and low thixotropy, it is preferable to use a compound having a weight average molecular weight of Mw = 2000 to 10,000 in an amount of 5 wt% or more based on the total solid content in the colored resin composition.

  In the present invention, for the reasons described above, the viscosity of the colored resin composition and the T.I. I. Any compound having a weight average molecular weight of 2000 to 10000 may be used as long as the relationship of values can be adjusted.

  The compound having a weight average molecular weight of 2000 to 10000 may be a known compound, or the resin carrier or the heat-reactive compound. Furthermore, an oligomer or a resin having a function of pigment dispersion or dispersion stabilization is preferable, and a compound having a structure represented by the following general formulas (1) to (3) is particularly preferable.

（式中、Ｒ₁は水素またはメチル基を表す。Ｒ₂はアルキレン基を表す。ｍは１〜２０の整数を表す。）
一般式（１）で表される構造を有する化合物は、リン酸基を有するオリゴマーまたは樹脂である。該化合物を用いると顔料の分散性及び経時での安定性が向上し、更にインクジェットインキが低粘度となる。 General formula (1):

(In the formula, R ₁ represents hydrogen or a methyl group. R ₂ represents an alkylene group. M represents an integer of 1 to 20.)
The compound having the structure represented by the general formula (1) is an oligomer or resin having a phosphate group. When the compound is used, the dispersibility of the pigment and the stability over time are improved, and the inkjet ink has a low viscosity.

  Phosphoric acid groups are alkali metals such as sodium, potassium and lithium, polyvalent metals such as calcium, magnesium, aluminum and zinc, ammonia, or ethylamine, dibutylamine, triethanolamine, ethylamine, propylamine, butylamine, pentylamine, A salt may be formed with an organic amine such as hexylamine, octylamine, dodecylamine, stearylamine, oleylamine, distearylamine and the like.

The phosphate group may be a monovalent phosphate group represented by the formula (17) or a divalent phosphate group represented by the formula (18).
Formula (17):

式（１８）：

Formula (18):

一般式（１）で表される構造を有する化合物としては、下記一般式（１９）で示されるリン酸基を有するモノマーを重合成分として含有する樹脂を含んでいてもよい。一般式（１９）で示されるリン酸基を有するモノマーとしては、例えば、エチレングリコールメタクリレートフォスフェート、プロピレングリコールメタクリレートフォスフェート、エチレングリコールアクリレートフォスフェート、プロピレングリコールアクリレートフォスフェートが挙げられる。
一般式（１９）：

The compound having a structure represented by the general formula (1) may include a resin containing a monomer having a phosphate group represented by the following general formula (19) as a polymerization component. Examples of the monomer having a phosphate group represented by the general formula (19) include ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, and propylene glycol acrylate phosphate.
General formula (19):

Ｒ^４４：水素又はメチル基を表す。
Ｒ^４５：アルキレン基を表す。
ｕ：１〜２０の整数を表す。

R ⁴⁴ represents hydrogen or a methyl group.
R ⁴⁵ represents an alkylene group.
u: represents an integer of 1-20.

  Although the specific example of the monomer which has a phosphoric acid group is shown below, it is not restricted to this.

 The above-mentioned monomers having a phosphate group can be used alone or in combination of two or more. Moreover, it is good also considering the monomer which has a phosphate group as a copolymer with another monomer. 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 preferably 0.1 to 5 parts by weight or less with respect to 100 parts by weight of all monomers. Further preferred.

  These monomers having a phosphoric acid group can be produced by the methods described in JP-B-50-22536 and JP-A-58-128393. These documents are incorporated herein in their entirety. Commercially available products include Phosmer M, Phosmer CL, Phosmer PE, Phosmer MH (manufactured by Unichemical Co., Ltd.), light ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.), JAMP-514 (manufactured by Johoku Chemical Industry Co., Ltd.), KAYAMERPM -2, KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.).

  For example, an oligomer or resin having a phosphate group can be obtained by radical polymerization of a monomer having a phosphate group and a monomer having no phosphate group. As a monomer which does not have a phosphoric acid group, the monomer which has the hydroxyl group illustrated previously, the monomer which has a carboxyl group, the monomer which does not have a hydroxyl group and a carboxyl group can be used.

  The synthesis of the oligomer or resin having a phosphoric acid group is carried out in the presence of an initiator in an inert gas stream at 50 to 150 ° C. for 2 to 10 hours. If necessary, it may be performed in the presence of a solvent. Initiators include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate, 2,2 ′ -Azo compounds such as azobisisobutyronitrile can be mentioned. The initiator is preferably used in an amount of 1 to 20 parts by weight with respect to 100 parts by weight of the monomer.

  In addition, as solvents used in the synthesis of resins having functional groups, acetate solvents such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate, ketone solvents such as cyclohexanone and methyl isobutyl ketone, xylene, ethylbenzene and the like Can be mentioned.

  Moreover, it is preferable that the compound which has a structure represented by General formula (1) contains resin which contains the monomer shown by the following general formula (20) or general formula (21) as a polymerization component. By using these resins, the dispersibility of the pigment and the stability over time are improved, and the inkjet ink has a low viscosity.

Formula (20):

Formula (21):

In the general formula (20) and the general formula ^{(21), R 46} and ^{R 48} represent a hydrogen atom or a methyl ^{group, R 47} and ^{R 49} represent a C1-4 alkylene group having a carbon atom, v and w are 1 Represents an integer of ~ 100.

  Examples of the monomer represented by the general formula (20) and the general formula (21) 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 tetramethylene oxide Modified bisphenol A dimethacryl Over bets, and propylene oxide tetramethylene oxide-modified bisphenol A diacrylate. These are commercially available as, for example, the Blemmer series from Nippon Oil & Fat Co., Ltd. and the Aronix series from Toa Gosei Co., Ltd.

  As a monomer contained as a polymerization component in a compound having a structure represented by the general formula (1), the monomers represented by the general formula (20) and the general formula (21) may be used alone or in combination of the phosphorous. It can be used in combination with a monomer having an acid group. As the monomer having a phosphate group that is copolymerized with the monomer represented by the general formula (20) and the general formula (21), a monomer represented by the general formula (19) is preferable. The copolymerization ratio of the monomers represented by the general formula (20) and the general formula (21) in the copolymer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the total monomers.

General formula (2):
(HOOC-) _e- R'1-(-COO-[-R'3-COO-] _f- R'2) _g (2)
Wherein R′1 is a tetravalent tetracarboxylic acid compound residue, R′2 is a monoalcohol residue, R′3 is a lactone residue, e is an integer of 2 or 3, and f is an integer of 1 to 50 , G represents (4-e).)

  The dispersant represented by the general formula (2) may be synthesized using any production method as long as it has the structure represented by the general formula (2). It is preferable to produce from a first step of producing a polyester having a hydroxyl group at one end by ring-opening polymerization and a second step of reacting a hydroxyl group at one end of the polyester with a tetracarboxylic dianhydride.

  The monoalcohol of the present invention may be any compound as long as it is a compound having one hydroxyl group. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 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-octyldeca Nord, 2-octyldodecanol, 2-hexyldecanol, aliphatic monoalcohols such as behenyl alcohol, oleyl alcohol, aromatic monoalcohols such as benzyl alcohol, 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 mono Propyl 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 Dimonohexyl 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, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether, tripropylene Glycol monomethyl ether, Propylene glycol monoethyl ether, tripropylene 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, tetra Ethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapro Examples include alkylene glycol monoalkyl ethers such as pyrene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

  Further, a monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol of the present invention. In this case, it is suitable for use in an active energy ray-curable resin composition.

Examples of the ethylenically unsaturated double bond referred to in the present invention include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferred. These may be used alone or in combination, and different types of ethylenically unsaturated double bonds may be used in combination.
Monoalcohols having an ethylenically unsaturated double bond are divided by the number of ethylenically unsaturated double bonds. Examples of monoalcohols having one ethylenically unsaturated double bond include 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 ( And (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, and the like. Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate and glycerin di (meth) acrylate. Examples of the monoalcohol having 3 ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having 5 ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate.

  Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained as a mixture with pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively. It is necessary to determine the body ratio.

  Of these, the use of those having two or more ethylenically unsaturated double bonds is preferable because it becomes a dispersant having excellent curability when an active energy ray-curable resin composition is obtained.

  A hydroxyl group at one end obtained by addition polymerization of an alkylene oxide starting from a hydroxyl group of the aliphatic monoalcohol, aromatic monoalcohol, alkylene glycol monoalkyl ether, and monoalcohol having an ethylenically unsaturated double bond exemplified above. Polyalkylene glycols having the formula also fall within the scope of the monoalcohols of the present invention. In addition, polyalkylene glycols having a hydroxyl group at one end obtained by addition polymerization of an alkylene oxide to a compound having a phenolic hydroxyl group, such as phenol or cumylphenol, also fall within the scope of the monoalcohol of the present invention. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and combinations of two or more thereof. 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. As commercial products, there are UNIOX series manufactured by NOF Corporation and BLEMMER series manufactured by NOF Corporation. 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, 10APB-500B, etc.

  Among the above monoalcohols, for example, 4-methyl-2-pentanol, isopentanol, isooctanol, 2-ethylhexanol, isononanol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol If a branched aliphatic monoalcohol such as polyalkylene glycol having a hydroxyl group at one end is used, the crystallinity may be lowered and the liquid state may be obtained at room temperature. This is preferable.

  A polyester having a hydroxyl group at one end can be obtained by ring-opening polymerization of a lactone using a monoalcohol as an initiator. Specific examples of the lactone used in the present invention include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. . Of these, δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone are preferably used in terms of ring-opening polymerizability.

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

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

  The number of moles of lactone added per mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles, and most preferably 4 to 16 moles. When the added mole number is 1 mol or more, the effect as a dispersant can be sufficiently obtained, and when it is 50 mol or less, the molecular weight of the dispersant does not become too large, and the dispersibility and fluidity are excellent.

Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium. Quaternary ammonium salts such as iodo, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethyl In addition to quaternary phosphonium salts such as suphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, organic compounds such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate In addition to alkali metal alcoholates such as carboxylates, sodium alcoholates and potassium alcoholates, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride, and the like. 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 resin becomes intensely colored, which adversely affects the stability of the product. Conversely, the amount of catalyst used is 0.1 p.
If it is less than pm, the ring-opening polymerization rate of the cyclic ester is extremely slow, which is not preferable.

  In the reaction, no solvent or a suitable dehydrated organic solvent can 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 100 ° C to 220 ° C, preferably 110 ° C to 210 ° C. When the reaction temperature is 100 ° C. or lower, the reaction rate is extremely slow, and when the reaction temperature is 210 ° C. or higher, side reactions other than the lactone addition reaction, for example, decomposition of lactone adducts into lactone monomers, formation of cyclic lactone dimers and trimers, etc. tend 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, Phenothiazine and the like are preferable. These may be used alone or in combination in the range of 0.01% to 6%, preferably 0.05% to 1.0%.

Examples of the tetracarboxylic dianhydride used in the second step include 1,2,3,4-butanetetracarboxylic dianhydride, 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, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3- Aliphatic tetracarbonates such as methyl-3-cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Bonn acid dianhydride,
Pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4 '-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3 -Dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Anhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide Dianhydride, 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-dicarboxyl) Nyl) fluorenedioic anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenedioic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro- Aromatic tetracarboxylic dianhydrides such as 1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride Can be mentioned.

  The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydrides. These may be used alone or in combination. Further, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of lowering the viscosity of the pigment dispersion, more preferably a tetracarboxylic dianhydride having two or more aromatic rings. is there.

  The reaction ratio in the second step is as follows: <H> for the number of hydroxyl groups in the polyester having a hydroxyl group at one end, and <N> for the number of anhydrous rings of the tetracarboxylic anhydride. <H> / <N> <1.2 is preferable, 0.7 << H> / <N> <1.1, and most preferably <H> / <N> = 1. When the reaction is carried out 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 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.
General formula (3):

｛一般式（３）中、Ｒ’’３は水素原子又はメチル基であり、
Ｘ^１は、−ＣＯＯ−、−ＣＯＮＨ−、−Ｏ−、−ＯＣＯ−若しくは−ＣＨ_２Ｏ−であり、Ｘ^２は、一般式：
−（−Ｒ^ａ１−Ｏ−）_ｍ１−
（式中、Ｒ^ａ１は炭素原子数２〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数３〜８のシクロアルキレン基であり、そしてｍ１は１〜５０の整数である）
で表される基であり、
Ｘ^３は、一般式：
−（−ＣＯ−Ｒ^ｂ１−Ｏ−）_ｍ２−
（Ｒ^ｂ１は炭素原子数４〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数４〜８のシクロアルキレン基であり、そしてｍ２は０または１〜２０の整数である）
で表される基であり、
Ｙ^１は、一般式（４）：

{In General Formula (3), R ″ 3 is a hydrogen atom or a methyl group,
X ¹ is —COO—, —CONH—, —O—, —OCO—, or —CH ₂ O—, and X ² is represented by the general formula:
-(-R ^a1 -O-) _m1-
(Wherein R ^a1 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)
A group represented by
X ³ is a general formula:
-(-CO-R ^b1 -O-) _m2-
(R ^b1 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 0 or an integer of 1 to 20)
A group represented by
Y ¹ represents the general formula (4):

（一般式（４）中、
Ａ^１〜Ａ^３のうちの１つが水素原子であって、他の２つは−ＣＯＯＨである組合せであるか、Ａ^１〜Ａ^３のうちの１つが−ＣＯＯＲ^ｃ（但し、Ｒ^ｃは、炭素原子数１〜１８のアルキル基である）であって、他の２つは−ＣＯＯＨである組合せであるか、又はＡ^１〜Ａ^３の３つが−ＣＯＯＨの組み合せであり、ｋは１又は２である）
で表される基であるか、あるいは一般式（５）：

(In general formula (4),
A one is hydrogen atom of A ¹ to A ^3, or the other two are combined is ^-COOH, one of -COOR ^c (where, ^{R c} of the A 1 to A ³ are, The other two are —COOH, or ^three of A ^{1 to} A ³ are a combination of —COOH, and k is 1 or 2)
Or a group represented by the general formula (5):

（一般式（５）中、
Ａ^５〜Ａ^７のうち１つは水素原子であって、他の２つは−ＣＯＯＨである組合せであるか、Ａ^５〜Ａ^７のうち１つは−ＣＯＯＲ^ｄ（但し、Ｒ^ｄは、炭素原子数１〜１８のアルキル基である）であって、他の２つは−ＣＯＯＨである組合せであるか、又はＡ^５〜Ａ^７の３つが−ＣＯＯＨの組合せであり、
Ｒ^２は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ_２ＣＨ_２ＯＣＯ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、式：

(In general formula (5),
One of A ^{5 to} A ⁷ is a hydrogen atom and the other two are combinations of —COOH, or one of A ^{5 to} A ⁷ is —COOR ^d (where R ^d is The other two are —COOH, or three of A ^{5 to} A ⁷ are —COOH combinations,
R ² is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

で表される基、又は式：

Or a group represented by the formula:

で表される基である）

Is a group represented by

  In the compound containing the structure represented by the general formula (3), the carboxyl group-containing unit (G) represented by the general formula (3) is added to one molecule of the vinyl polymer in the vinyl polymer main chain. As long as the average amount is 0.3 or more and 3.0 or less, the chemical structure and the production method are not particularly limited.

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 (3), Y ¹ represented by the general formula (4) or the general formula (5) is directly bonded to the ring-constituting carbon atom of the aromatic ring. A plurality of carboxyl groups that are directly bonded to the ring-constituting carbon atoms of the aromatic ring serve as adsorption sites for the pigment. Therefore, the compound including the structure represented by the general formula (3) exhibits high dispersibility, fluidity, and storage stability.

  The compound having the structure represented by the general formula (3) (hereinafter referred to as the vinyl dispersant (a)) contains a carboxyl group represented by the general formula (3) with respect to one molecule of the vinyl polymer. It is preferable that an average of 0.3 to 3.0 units (G) is included. 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. In the case of 0.3 or more, there are many sites adsorbed on the pigment, and the dispersion ability is excellent. Moreover, when it is 3.0 or less, the site | part which adsorb | sucks to a pigment is moderate, and it is excellent in the dispersibility.

In General Formula (3), X ¹ is preferably —COO— from the viewpoint of reducing the viscosity of the pigment dispersion and storage stability. R ^a1 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). m1 is preferably 1 to 10, more preferably 1 to 3. R ^b1 is preferably a pentamethylene group. m2 is preferably 0 to 5, more preferably 0 to 3. Y ¹ is preferably a group represented by General Formula (4), and more preferably, in General Formula (4), all of A ^{1 to} A ³ are —COOH and k is 1. , A ^{1 to} A ³ are combinations in which one 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 (5). In this case, R ² is —COOCH ₂ CH ₂ OCO—, or a group represented by the formula:

で表される基であることが好ましい。Ａ^５〜Ａ^７のうち１つは−ＣＯＯＲ^ｄ（但し、Ｒ^ｄは、炭素原子数６〜１０の直鎖又は分岐アルキル基である）であって、他の２つは−ＣＯＯＨである組合せであることが好ましい。

It is preferable that it is group represented by these. One of A ^{5 to} A ⁷ is —COOR ^d (where R ^d is a straight-chain or branched alkyl group having 6 to 10 carbon atoms), and the other two are —COOH. It is preferable that

  The vinyl dispersant (a) used in the present invention includes a carboxyl group-containing unit (G) represented by the general formula (3) and a general formula (4j):

〔一般式（４ｊ）中、
Ｒ^４は、水素原子又はメチル基を示し、
Ｘ^４は、−ＣＯＯ−、−ＣＯＮＨ−、−Ｏ−、−ＯＣＯ−若しくは−ＣＨ_２Ｏ−であり、Ｘ^５は、式：
−（−Ｒ^ａ２−Ｏ−）_ｍ３−、
（式中、Ｒ^ａ２は炭素原子数１〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数３〜８のシクロアルキレン基であり、そしてｍ３は１〜５０の整数である）
で表される基であり、
Ｘ^６は、式：
−（−ＣＯ−Ｒ^ｂ４−Ｏ−）_ｍ４−
（式中、Ｒ^ｂ４は炭素原子数４〜８の直鎖状若しくは分岐状のアルキレン基であり、そしてｍ４は０〜２０の整数である）〕で表され、末端が水素と結合すると水酸基を有する水酸基含有単位（Ｊ）と、一般式（４ｋ）：

[In general formula (4j),
R ⁴ represents a hydrogen atom or a methyl group,
X ⁴ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—, and X ⁵ is a group represented by the formula:
-(-R ^a2 -O-) _m3- ,
(Wherein R ^a2 is a linear or branched alkylene group having 1 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 represents the formula:
-(-CO-R ^b4 -O-) _m4-
(Wherein R ^b4 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20)], and when the terminal is bonded to hydrogen, a hydroxyl group is formed. Hydroxyl group-containing unit (J) having the general formula (4k):

〔一般式（４ｋ）中、
Ｒ^５は、水素原子又はメチル基を示し、
Ｒ^６は、芳香族基、又は−ＣＯ−Ｘ^７−Ｒ^７（但し、Ｘ^７は、−Ｏ−若しくは−ＮＨ−であり、Ｒ^７は、水素原子又は炭素原子数１〜１８の直鎖状若しくは分岐状のアルキル基であり、前記Ｒ^７は、置換基として芳香族基を有していることができる）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 general formula (4k),
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ is an aromatic group, or —CO—X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or a straight chain having 1 to 18 carbon atoms. Or a branched alkyl group, and R ⁷ can have an aromatic group as a substituent. ]
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 vinyl dispersant (a) used in the present invention includes a copolymer represented by the general formula (4a), that is, the general formula (4b).
General formula (4a):
-[G] p1- [J] p2- [K] p3- (4a)
General formula (4b):

ここで、Ｇは、前記一般式（３）で表されるカルボキシル基含有単位であり、Ｊは、前記一般式（４ｊ）で表される水酸基含有単位であり、Ｋは、前記一般式（４ｋ）で表される主鎖構成単位である。ｐ１は０．３以上３．０以下、好ましくは０．３５以上２．０以下、更に好ましくは０．４以上１．５以下である。ｐ２は０以上１８０以下、好ましくは０．０５以上５０以下である。ｐ３は６以上２５０以下、好ましくは１０個以上１００個以下である。また、前記一般式（４ａ）において、カルボキシル基含有単位（Ｇ）と水酸基含有単位（Ｊ）と主鎖構成単位（Ｋ）とは、それぞれ、ブロック共重合形式又はランダム共重合形式で存在することができる。更に、前記カルボキシル基含有単位（Ｇ）、前記水酸基含有単位（Ｊ）、及び主鎖構成単位（Ｋ）は、前記一般式（４ａ）中に、それぞれ複数個で存在することができる。この場合は、それぞれの単位が相互に同一又は異なっていることができる。例えば、主鎖構成単位（Ｋ）が２種又はそれ以上の構造の構成単位を含んでいることができる。

Here, G is a carboxyl group-containing unit represented by the general formula (3), J is a hydroxyl group-containing unit represented by the general formula (4j), and K is the general formula (4k). ) Is a main chain constituent unit. p1 is 0.3 to 3.0, preferably 0.35 to 2.0, and more preferably 0.4 to 1.5. p2 is 0 or more and 180 or less, preferably 0.05 or more and 50 or less. p3 is 6 or more and 250 or less, preferably 10 or more and 100 or less. In the general formula (4a), 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 dispersant (a) used in the present invention represented by the general formula (4b) or the general formula (4a), X ⁴ may be —COO—. preferable. R ^a2 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, and more preferably 1 to 3. R ^b4 is preferably a pentamethylene group. m4 is preferably 0 to 5, and more preferably 0 to 3.

In the vinyl dispersant (a) used in the present invention represented by the general formula (4b) or the general formula (4a), R ⁵ is a methyl group as the main chain structural unit (K), and R ⁶ Preferably includes 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 constituent unit (K1) preferably has an average amount of 1 or more and 100 or less per molecule of the vinyl polymer, and the vinyl dispersant (a) of this embodiment is excellent in dispersion ability. .

Further, in the vinyl-based dispersant (a) used in the present invention represented by the general formula (4b) or the general formula (4a), in the main chain structural unit (K), R ⁵ is a methyl group, R ⁶ preferably includes a main chain structural unit (K2) in which —CO—O—R ⁷ (wherein R ⁷ is a linear or branched alkyl group having 2 to 10 carbon atoms). It is more preferable that the main chain structural unit (K2) coexists with the main chain structural unit (K1) in the vinyl dispersant (a).

Furthermore, in the vinyl dispersant (a) used in the present invention represented by the general formula (4b) or the general formula (4a), R ⁵ is a methyl group as the main chain constituent unit (K), The main chain structural unit (K3) in which R ⁶ is an aromatic group (particularly a phenyl group) is used alone or together 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 dispersant (a) represented by the general formula (4b) 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 dispersant (a) used in the present invention, the main chain structural unit (K) in which R ⁶ is a carboxyl group (—COOH) in the general formula (4b) is replaced with 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 vinyl dispersant (a) 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 to be described later, not only the vinyl dispersant (a) but also all vinyl dispersants (A) having a wide structure including the vinyl dispersant (a). Can be manufactured. That is, the vinyl-based dispersant (a) 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.

As a manufacturing method of the vinyl type dispersing agent (A) used by this invention, the following manufacturing methods 1-3 can be mentioned.
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,
(D) It comprises a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) with a 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. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and combinations of two or more thereof. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and combinations of two or more of these. 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. A tetracarboxylic acid monoester monoanhydride obtained by ring opening of an acid anhydride with an alcohol having 1 to 18 carbon atoms or a cycloalcohol having 5 to 18 carbon atoms is also used in the production method used in the present invention. It can be used as (M3). 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 alcohol having 1 to 18 carbon atoms or the cycloalcohol having 5 to 18 carbon atoms include 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 -Like nonanol or cyclononanol, linear or branched decanol or cyclodecanol, linear or branched dodecanol or cyclododecanol, linear or branched myristyl alcohol or cyclo Li myristyl alcohol, linear or branched cetyl alcohol or cycloalkyl cetyl alcohol, such as linear or branched stearyl alcohol or cycloalkyl stearyl alcohol.

  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, Step A in which an ethylenically unsaturated monomer (h) having a hydroxyl group is reacted with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) is performed. This step A is preferably carried out at 80 ° C. to 150 ° C. by adding a polymerization inhibitor while flowing dry air into the reactor so that the monomer does 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.

  When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tricarboxylic acid anhydride (M3) are reacted in Step A, the reaction ratio is “the number of moles of the ethylenically unsaturated monomer (h) having a hydroxyl group”. / Mole number of tricarboxylic acid 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 B decreases, which is not preferable.

  When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic acid anhydride (M4) are reacted in the step A, the reaction ratio is “mole of the ethylenically unsaturated monomer (h) having a hydroxyl group”. The number / number of moles of tetracarboxylic acid 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. If it exceeds 1.1, a compound in which an ethylenically unsaturated monomer (h) having two hydroxyl groups is added to one tetracarboxylic acid anhydride (M4) can be formed, which may cause gelation in Step B. Absent.

  In step 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 Aa) to facilitate removal of unnecessary tetracarboxylic anhydride (M4).
Then, in the manufacturing method 1, the process B which copolymerizes the ethylenically unsaturated monomer synthesize | combined at the process 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 ( It is preferred that an ethylenically unsaturated monomer selected from (meth) acrylamide, styrene and an ethylenically unsaturated monomer having a hydroxyl group (h) (including those remaining in Step A) be copolymerized.

  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 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 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 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.

  If step Aa is not performed after step A, the acid anhydride remaining after step B can be ring-opened with water or an alcohol having 1 to 18 carbon atoms (step Bb). In step Aa or step Bb, the number of moles of water to be reacted or alcohol having 1 to 18 carbon atoms is 0.9 times or more and 5 times or less (preferably 1 or more times) with respect to the number of moles of the remaining acid anhydride. 2 times or less). If it is less than 0.9 times, many highly reactive anhydrous rings remain, and if it exceeds 5 times, water or alcohol having 1 to 18 carbon atoms remains, anyway, if 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. It is preferable to perform reaction process Aa or process Bb at 80-150 degreeC.

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 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 B of Production Method 1 or an aromatic ring. It is preferable that an ethylenically unsaturated monomer selected from N-alkyl (meth) acrylamide having 1 to 18 carbon atoms and styrene which may be copolymerized is 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 are preferably the same as in step B of production method 1.

  Then, in the manufacturing method 2, the process D which makes a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) react with the hydroxyl group of the copolymer obtained at the process C is performed. In the process D, it is preferable to carry out at 80 to 150 ° C. while flowing nitrogen or dry air to the reaction vessel. Here, the catalyst exemplified in Step A of Production Method 1 can also be used.

  In step 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 acid anhydride (M4) is used and an anhydrous ring remains, it can be ring-opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in Step Bb of Production Method 1 ( Step Dd).

Next, manufacturing 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 performed 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 A of Production Method 1, the type of polymerization initiator, The polymerization conditions such as the type of chain transfer agent, the type and amount of solvent, and the reaction temperature are preferably those shown in Step 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 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, the ring can be opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in Step Bb of Production Method 1 (Step Ee). ).

  By these production methods 1 to 3, the vinyl dispersant (A) 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 of Production Method 2 can be measured in advance, and the amount of the tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) to be reacted can be determined according to the value. . For example, to produce the vinyl dispersant (A) by production method 2, the number average molecular weight of the copolymer obtained in step C is measured, and when the measured value is [X], the resin [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 g.

  When the vinyl dispersant (A) used in the present invention is produced by the production method 1 or 3, the number average molecular weight [Y] of the finally obtained vinyl dispersant (A) and the tricarboxylic acid anhydride ( M3) or the tetracarboxylic acid anhydride (M4) charged from the number of moles charged, as a result, the vinyl dispersant (A) has a tricarboxylic acid of 0.3 mol or more and 3.0 mol or less with respect to [Y] g. It is sufficient that the acid anhydride (M3) or the tetracarboxylic acid anhydride (M4) is reacted.

  When the vinyl dispersant (A) is produced by the production method used in the present invention, the tricarboxylic anhydride (M3) or the tetracarboxylic anhydride (M4) is selected as an aromatic tricarboxylic anhydride or aromatic. Group tetracarboxylic anhydrides are preferred. Of these, aromatic tricarboxylic acid anhydrides are more preferable, and trimellitic acid anhydride, pyromellitic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 2,3,6,7-naphthalene. Tetracarboxylic acid anhydride is preferred, and most preferred is trimellitic anhydride.

  When producing the vinyl-based dispersant (A) in any of the production methods 1 to 3, an unsubstituted ethylenically unsaturated monomer having 1 to 12 carbon atoms which may have a branch as another ethylenically unsaturated monomer 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, which may have a branch in one molecule of the vinyl dispersant (A), and 1 to 1 benzyl (meth) acrylate. Preferably 50 are copolymerized.

  In addition, the vinyl dispersant (A) 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 present in the vinyl dispersant (A) in any of the production methods 1 to 3. It is preferable from the viewpoint of dispersibility (low viscosity, storage stability) that the use range is 0 to 4 times, more preferably 0 to 2 times the number of moles of the product (M4).

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

  The colored resin composition of the present invention is obtained using the vinyl dispersant (A) [or particularly the vinyl dispersant (a)] and the pigment (P). Here, by using the vinyl dispersant (A) [or particularly the vinyl dispersant (a)], a colored resin composition having excellent dispersibility, fluidity, and storage stability is obtained.

  The colored resin composition of the present invention preferably further contains a thermally reactive compound. The heat-reactive compound that can be used in the ink composition 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 that exhibits a polycondensation 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 alkoxyalkyl group-containing melamine compound include hexamethoxymethylol melamine or hexabutoxymethylol melamine.

  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 alkoxyalkyl 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. Can do.

  Examples of the blocking agent used in the blocked isocyanate compound 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 ˜120 ° C.). 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 and the like can be mentioned.

  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.
In the present invention, alkoxyalkylated melamine and alkoxyalkyl group-containing benzoguanamine compounds are particularly preferred.
These thermally reactive compounds are preferably contained in the colored resin composition in an amount of 1% by weight to 40% by weight. When the content of these heat-reactive compounds is 1% by weight or more, the heat resistance and chemical resistance are excellent. Moreover, when content is 40% or less, there is no increase in a viscosity and it is excellent in storage stability.

  The colored resin composition can contain an organic solvent for the purpose of promoting adsorption with the pigment, pigment derivative, and resin, and for reducing the viscosity of the composition. As the organic solvent, for example, aromatic hydrocarbons, alcohols, esters, ethers, ketones, glycol ethers, alicyclic hydrocarbons, aliphatic hydrocarbons and the like can be used.

  In the colored resin composition of the present invention, it is preferable that a coating layer of a pigment derivative and a resin carrier is formed on the surface of the pigment.

  The coating treatment of the pigment can be performed by mixing the pigment, the organic solvent, the pigment derivative, the resin carrier, and the like in advance so as to be uniform, 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.

  In the production of the colored resin composition of the present invention, the pigment, the heat-reactive compound, the organic solvent, and, if necessary, the binder resin and / or pigment derivative are charged into a normal disperser, and the desired average is obtained. It can be carried out by dispersing until the particle size / size distribution is obtained. The raw materials for the colored resin composition 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 ink composition is too high and dilution is necessary, a liquid medium for dilution can be added to the ink stock solution and stirred uniformly to prepare the ink composition.

  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 composition for inkjet recording 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 a colored resin composition, 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.

  An ink jet ink using the above colored resin composition is also an embodiment of the present invention. In the inkjet ink of the present invention, an organic solvent known as technical common sense in the inkjet field can be used. In general, an organic solvent used in an ink composition for ink jet recording has a high solubility in a resin, and when ejecting ink from an ink jet printer, the organic solvent has a small swelling action on a printer member in contact with the ink. Those having a viscosity of as low as possible are preferred. The organic solvent is selected from the viewpoints of solubility in the resin, swelling action on the printer member, viscosity, and drying property of the ink in the nozzle, such as an alcohol solvent, a glycol solvent, an ester solvent, and / or a ketone solvent. These can be used alone or in admixture of two or more.

  Examples of the alcohol solvent include hexanol, heptanol, octanol, nonanol, decanol, undecanol, cyclohexanol, benzyl alcohol, and amyl alcohol.

  Examples of glycol solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene group Monoethyl ether, propylene glycol isopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, may be mentioned 1-butoxyethoxy propanol, or 1-methoxy-2-propyl acetate and the like.

  Examples of the ester solvent include ethyl lactate, lactic acid propane, and butyl lactate.

  Examples of the ketone solvent include cyclohexanone, ethyl amyl ketone, diacetone alcohol, diisobutyl ketone, isophorone, methylcyclohexanone, and acetophenone.

  The ink-jet ink of the present invention can contain various additives as long as the above viscosity conditions are satisfied. For example, a surfactant can be included in order 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.

  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. When the viscosity is 40 mPa · s or less, stable and continuous discharge is possible.

  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. When the average dispersed particle size is 200 nm or less, the head is less likely to be clogged, and stable ejection is possible. When the average dispersed particle size is 5 nm or more, reaggregation hardly occurs and the temporal stability is excellent.

  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. When the surface tension is 40 mN / m or less, the colored resin composition can be stably discharged from the head, and when the surface tension is 20 mN / m or more, the ink reliably forms droplets.

  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 colored resin composition of the present invention and the inkjet ink using the colored resin composition of the present invention are suitable for producing a color filter substrate that requires high productivity and quality.

  In addition, since the inkjet ink of the present invention has a high concentration of pigment, the printing density can be increased even for paper that penetrates the ink in the depth direction, plastic, glass, and metal that spreads in the lateral direction. it can. 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.

  The ink-jet ink of the present invention is preferably used for color filter applications. In particular, the voids in the black matrix are preferably used for forming a color filter by an ink jet method.

  The ink jet method refers to a method in which ink jet ink is ejected by an ink jet ejecting apparatus in a region divided by a black matrix of a substrate on which a black matrix is formed.

  The black matrix is formed 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. It can be formed on a substrate.

[Example]
EXAMPLES Hereinafter, although a 1st embodiment is concretely demonstrated by an Example, 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.

The pigments, pigment derivatives, solvents, and resin type dispersants used in Examples and Comparative Examples are shown below. In addition, the final ink compositions in Examples and Comparative Examples are shown in Table 2 (Examples) and Table 3 (Comparative Examples).
(1) Pigment red pigment: C.I. I. Pigment Red 254 ("Irga Four RED B-CF" manufactured by Ciba Specialty Chemicals)
Green pigment: C.I. I. Pigment Green 36 (“Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.)
Blue pigment: C.I. I. Pigment Blue 15: 6 (Toyo Ink Manufacture “Rionol Blue E”)
Yellow pigment: C.I. I. Pigment Yellow 138 (“Rionogen Yellow 1010” manufactured by Toyo Ink Manufacturing Co., Ltd.)
Magenta pigment: C.I. I. Pigment Red 122 (“Rionogen Magenta 5750” manufactured by Toyo Ink Co., Ltd.)
Cyan pigment: C.I. I. Pigment Blue 15: 3 (“Rionol Blue FG-7351” manufactured by Toyo Ink Manufacturing Co., Ltd.)
(2) Pigment derivative:

Pigment derivative [1]
(For red)

Pigment derivative [2]
(For green, blue, cyan)

Pigment derivative [3]
(For yellow)

Pigment derivative [4]
(For magenta)

(3) Solvent CBAc: Diethylene glycol monoethyl ether acetate BuCBAc: Diethylene glycol monobutyl ether acetate PGMAc: Propylene glycol monomethyl ether acetate

(4) Resin Examples of resin production are shown below. The weight average molecular weight and number average molecular weight of various resins shown in the production examples were measured using GPC and determined in terms of polystyrene.

<< Production Example 1 (Resin R1) >>
A temperature control regulator, a cooling tube, and a stirrer were attached to a separable four-necked flask, charged with 100 parts of a solvent (CBAc), heated to 100 ° C. and purged with nitrogen in the reaction vessel. 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) shown in Table 1. The resin solution thus obtained was used as a binder resin [R1].
(Raw material of resin R1)
Methacrylic acid 20 parts 2-Hydroxyethyl methacrylate 20 parts n-Butyl methacrylate 27 parts Benzyl methacrylate 30 parts Phosmer M (manufactured by Unichemical Co., Ltd.) 3 parts 2,2'-azobisisobutyronitrile 10 parts

<< Production Example 2 (Resin R2) >>
It was produced by the same method except that the raw material was changed to the following in R1.
(Raw material of resin R2)
Methacrylic acid 20 parts 2-Hydroxyethyl methacrylate 20 parts n-Butyl methacrylate 27 parts Benzyl methacrylate 30 parts "Phosmer M (Unichemical Co., Ltd.)" 3 parts 2,2'-azobisisobutyronitrile 4 parts

<< Production Example 3 (Resin R3) >>
A temperature control regulator, a cooling tube, and a stirrer were attached to a separable four-necked flask, charged with 150 parts of a solvent (CBAc), heated to 110 ° C., and purged with nitrogen in the reaction vessel. The raw materials were added and the reaction was continued for 5 hours to obtain a solution (solid content 40%) of an acrylic resin having a weight average molecular weight (Mw) shown in Table 1. The resin solution thus obtained was used as a binder resin [R3].
(Raw material of resin R3)
Methacrylic acid 20 parts 2-Hydroxyethyl methacrylate 20 parts n-Butyl methacrylate 27 parts Benzyl methacrylate 30 parts Phosmer M (manufactured by Unichemical Co., Ltd.) 3 parts 2,2'-azobisisobutyronitrile 20 parts

<< Production Example 4 (Resin S1) >>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is 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 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 reacted at 120 ° C. for 2 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant (S1). The obtained dispersant was a pale yellow waxy solid at room temperature, the weight average molecular weight (Mw) was 4000, and the acid value was 49 mgKOH / g.

<< Production Example 5 (Resin S2) >>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 13.7 parts of 1-dodecanol, 336.3 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst. After replacing with gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, pyromellitic anhydride 8.0 parts was added, and it was made to react at 120 degreeC for 2 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant (S1). The obtained dispersant was a light yellow waxy solid at room temperature, the weight average molecular weight (Mw) was 14400, and the acid value was 12 mgKOH / g.

<< Production Example 6 (Resin S3) >>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 123.4 parts of 1-dodecanol, 226.6 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst, and nitrogen. After replacing with gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 72.2 parts of pyromellitic anhydride was added and reacted at 120 ° C. for 2 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant (S1). The obtained dispersant was a pale yellow waxy solid at room temperature, the weight average molecular weight (Mw) was 1850, and the acid value was 90 mgKOH / g.

<< Production Example 7 (Resin A1) >>
Process (C)
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 60 parts of solvent (PGMAc) was charged, the temperature was raised to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. The mixed solution was added from the dropping tube over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Step C of Production Example 1). Thus, a vinyl resin intermediate (C1) having a number average molecular weight (Mn) of 3800, a weight average molecular weight (Mw) of 6900, and an average number of hydroxyl groups in one molecule of 3.5 was obtained.
(Raw material for vinyl resin intermediate C1)
n-butyl methacrylate 40 parts benzyl methacrylate 48 parts 2-hydroxyethyl methacrylate 12 parts methoxypropyl acetate 40 parts dimethyl-2,2'-azobisdiisobutyrate 6 parts Step (D)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 100 parts of vinyl resin intermediate (C1) in solids, 5.1 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine The mixture was charged and reacted at 100 ° C. for 6 hours (Step D of Production Example 1). Thus, a resin type dispersant (A1) 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 (A1) was 50%.

<< Production Example 8 (Resin Dispersant A2) >>
Process (C)
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 60 parts of solvent (PGMAc) was charged, the temperature was raised to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. The mixed solution was added from the dropping tube over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Step C of Production Example 1). Thus, a vinyl resin intermediate (C2) having a number average molecular weight (Mn) of 7000, a weight average molecular weight (Mw) of 13800, and an average number of hydroxyl groups in one molecule of 3.5 was obtained.
(Raw material for vinyl resin intermediate C2)
n-butyl methacrylate 40 parts benzyl methacrylate 48 parts 2-hydroxyethyl methacrylate 12 parts PGMac 40 parts dimethyl-2,2'-azobisdiisobutyrate 3 parts Step (D)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 100 parts of vinyl resin intermediate (C1) in solid content, 2.8 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine The mixture was charged and reacted at 100 ° C. for 6 hours (Step D of Production Example 1). In this way, a resin type dispersant (A2) 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 (A2) was 50%.
(5) Melamine resin Alkoxyalkyl group-containing melamine resin manufactured by Sanwa Chemical Co., Ltd. NIKALAC MX-43
(6) Benzoguanamine resin Alkoxyalkyl group-containing benzoguanamine resin manufactured by Sanwa Chemical Co., Ltd. Nicalak SB-401

Example 1
90 parts of red pigment, 10 parts of pigment derivative [1], and 133 parts of resin (R1) were added and stirred uniformly to obtain a mixture. The mixture was placed in a two-roll roll heated to 60 ° C. and kneaded until the solvent volatilized, and then the kneaded product was taken out. The kneaded product was cooled to room temperature and then coarsely pulverized, 50 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. for further kneading. The solvent was volatilized and the heated kneaded product became rubbery. The kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain 167 parts of a coated pigment. 167 parts of the coating treatment pigment and 476 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours. Further, 40 parts of melamine resin (MX-43) and 66 parts of solvent (CBAc) are added. Mix in a mixer. Finally, pressure filtration was performed with a membrane filter to obtain an ink composition for inkjet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%.

Example 2
90 parts of red pigment, 10 parts of pigment derivative [1], 100 parts of resin (R2) and 33 parts of resin (S1) were added and stirred uniformly to obtain a mixture. The mixture was placed in a two-roll roll heated to 60 ° C. and kneaded until the solvent volatilized, and then the kneaded product was taken out. The kneaded product was cooled to room temperature and then coarsely pulverized, 50 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. to further knead. The solvent was volatilized and the heated kneaded product became rubbery. The kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain 167 parts of a coated pigment. 167 parts of the coating treatment pigment and 476 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours. Further, 40 parts of melamine resin (MX-43) and 66 parts of solvent (CBAc) are added. Mix in a mixer. Finally, pressure filtration was performed with a membrane filter to obtain an ink composition for inkjet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%.

Example 3
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 100 parts of resin (R1) was used instead of 100 parts of resin (R2).
Example 4
90 parts of red pigment, 10 parts of pigment derivative [1], 100 parts of resin (A1), 33 parts of resin (S1) and 410 parts of solvent (CBAc) are placed in a sand mill and dispersed for 4 hours. Further, melamine resin (MX- 43) 40 parts of solvent and 86 parts of solvent (CBAc) are mixed in a mixer and pressure filtered through a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%. It was.
Example 5
In Example 2, 100 parts of resin (A1) is used instead of 100 parts of resin (R2), and 40 parts of benzoguanamine resin (Nicarac SB-401) is used instead of 40 parts of melamine resin (MX-43). Thus, an ink-jet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained.

<< Comparative Example 1 >>
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (R2) was used instead of 133 parts of the resin (R1).
<< Comparative Example 2 >>
90 parts of red pigment, 10 parts of pigment derivative [1], 120 parts of resin (R2) and 13 parts of resin (S1) were added and stirred uniformly to obtain a mixture. The mixture was placed in a two-roll roll heated to 60 ° C. and kneaded until the solvent volatilized, and then the kneaded product was taken out. The kneaded product was cooled to room temperature and then coarsely pulverized, 50 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. for further kneading. The solvent was volatilized and the heated kneaded product became rubbery. The kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain 167 parts of a coated pigment. 167 parts of the coating treatment pigment and 476 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours. Further, 40 parts of melamine resin (MX-43) and 66 parts of solvent (CBAc) are added. Mix in a mixer. Finally, pressure filtration was performed with a membrane filter to obtain an ink composition for inkjet recording having a pigment concentration (PC) of 13% and a solid content concentration of 28%.
<< Comparative Example 3 >>
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (R3) was used instead of 133 parts of the resin (R1).
<< Comparative Example 4 >>
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 33 parts of resin (S2) was used instead of 33 parts of resin (S1).
<< Comparative Example 5 >>
In Example 2, an ink-jet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner except that 33 parts of the resin (S3) was used instead of 33 parts of the resin (S1).
Example 6
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (A1) was used instead of 133 parts of the resin (R1).
Example 7
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 2, except that 100 parts of the resin (A1) was used instead of 100 parts of the resin (R2).
<< Comparative Example 6 >>
An inkjet ink having a pigment concentration of 13% and a solid content concentration of 28% was obtained in the same manner as in Example 1, except that 133 parts of the resin (A2) was used instead of 133 parts of the resin (R1).

Example 8
90 parts of green pigment, pigment derivative [2]
10 parts, 75 parts of resin (A1) and 25 parts of resin (S1) were added and stirred uniformly to obtain a mixture. The mixture was placed in a two-roll roll heated to 60 ° C. and kneaded until the solvent volatilized, and then the kneaded product was taken out. The kneaded product was cooled to room temperature and then coarsely pulverized, 50 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. for further kneading. The solvent was volatilized and the heated kneaded product became rubbery. The kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain a coated pigment. 150 parts of the coating pigment and 250 parts of solvent (CBAc) are mixed in a mixer, and further mixed in a sand mill for 4 hours. Further, 40 parts of melamine resin (MX-43) and 66 parts of solvent (CBAc) are added. Mix in a mixer. Finally, pressure filtration was performed with a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 16.7% and a solid content concentration of 32%.

<< Comparative Example 7 >>
In Example 8, 75 parts of the resin (A1) is replaced with 75 parts of the resin (A2), and 25 parts of the resin (S1) is replaced with 25 parts of the resin (S2). An ink-jet ink having 7% and a solid content concentration of 32% was obtained.
Example 9
90 parts of yellow pigment, 10 parts of pigment derivative [3], 100 parts of resin (A1) and 33 parts of resin (S1) were added and stirred uniformly to obtain a mixture. The mixture was placed in a two-roll roll heated to 60 ° C. and kneaded until the solvent volatilized, and then the kneaded product was taken out. The kneaded product was cooled to room temperature and then coarsely pulverized, 50 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. for further kneading. The solvent was volatilized and the heated kneaded product became rubbery. The kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain 167 parts of a coated pigment. 167 parts of the coated pigment and 267 parts of solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours. Further, 40 parts of melamine resin (MX-43) and 53 parts of solvent (CBAc) are added. Mix in a mixer. Finally, pressure filtration was performed with a membrane filter to obtain an ink composition for ink jet recording having a pigment concentration (PC) of 15.4% and a solid content concentration of 32%.
<< Comparative Example 8 >>
The pigment concentration was changed to 15. in the same manner as in Example 9 except that 100 parts of the resin (A1) was replaced with 100 parts of the resin (A2) and 33 parts of the resin (S1) was replaced with 33 parts of the resin (S2). An ink-jet ink having 4% and a solid content concentration of 32% was obtained.

Example 10
90 parts of a blue pigment, 10 parts of pigment derivative [4], 100 parts of resin (A1) and 33 parts of resin (S1) were added and stirred uniformly to obtain a mixture. The mixture was placed in a two-roll roll heated to 60 ° C. and kneaded until the solvent volatilized, and then the kneaded product was taken out. The kneaded product was cooled to room temperature and then coarsely pulverized, 50 parts of a solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. for further kneading. The solvent was volatilized and the heated kneaded product became rubbery. The kneaded product was formed into a sheet and cooled to room temperature, and then coarsely pulverized to obtain 167 parts of a coated pigment. 167 parts of the coating treatment pigment and 552 parts of the solvent (CBAc) are mixed in a mixer, and further dispersed in a sand mill for 4 hours. Further, 40 parts of melamine resin (MX-43) and 60 parts of solvent (CBAc) are added. Mix in a mixer. Finally, pressure filtration was performed with a membrane filter to obtain an ink composition for inkjet recording having a pigment concentration (PC) of 12% and a solid content concentration of 25%.
<< Comparative Example 9 >>
In Example 10, except that 100 parts of the resin (A1) is replaced with 100 parts of the resin (A2), and 33 parts of the resin (S1) is further replaced with 33 parts of the resin (S2), and the pigment concentration is 12%. An ink-jet ink having a solid content concentration of 25% was obtained.

<Creation of high solid content ink>
10 g of the ink prepared in Examples 1 to 10 and Comparative Examples 1 to 9 was taken in a plastic cup, and the cup containing the ink was placed in a 50 ° C. oven for about 12 hours and dried. By drying in this manner, a high solid content ink having a solid content concentration adjusted to about 43% was prepared.
"Evaluation of the physical properties"
The viscosity and fluidity of the inks obtained in Examples 1 to 10 and Comparative Examples 1 to 9 were evaluated by the following methods. Moreover, the following method evaluated the surface smoothness at the time of ink drying obtained in Examples 1-10 and Comparative Examples 1-9. The results are shown in Tables 4 and 5.

[viscosity]
The viscosity (η: mPa · s) at 25 ° C. and a shear rate of 100 (1 / s) was measured with a dynamic viscoelasticity measuring apparatus.
[Liquidity]
The viscosity was measured in a range of 25 ° C. and a shear rate of 1 (1 / s) to 2000 (1 / s) with a dynamic viscoelasticity measuring device. I. Value (ratio of viscosity (ηa: mPa · s) at a shear rate of 10 (1 / s) and viscosity (ηb: mPa · s) at a shear rate of 1000 (1 / s). TI value = ηa / Ηb).
[Surface smoothness during ink drying]
The ink was dropped on the glass plate, and after 1 minute from dropping, the glass plate was placed on a hot plate warmed to 90 ° C. After 5 minutes, the roughness (Ra) of the dried ink surface was observed using a non-contact three-dimensional surface shape measuring machine.
○: Ra <200 nm
Δ: 200 nm ≦ Ra <300 nm
×: 300 nm ≦ Ra

注１：表２中の数値は、固形分を示す。
注２：表２中の数値は、生成されたインク組成物中での含有量を示す。

Note 1: Numerical values in Table 2 indicate solid content.
Note 2: Numerical values in Table 2 indicate the content in the produced ink composition.

注１：表３中の数値は、固形分を示す。
注２：表３中の数値は、生成されたインク組成物中での含有量を示す。

Note 1: Numerical values in Table 3 indicate solid content.
Note 2: The numerical values in Table 3 indicate the content in the produced ink composition.

According to the inks of Examples 1 to 10, the surface smoothness when the ink of the present invention was dried was remarkably excellent. On the other hand, the inks of Comparative Examples 1 to 9, which are outside the scope of the present invention, that is, Comparative Examples 1 to 9, have an ink viscosity outside the scope of the present invention. I. The value did not satisfy the value of the present invention, and the surface smoothness when the ink was dried was inferior in surface smoothness.

Claims (8)

  A colored resin composition comprising a pigment, a pigment derivative, and a resin carrier, and only when the solid content concentration is 20% by weight or more and less than 40% by weight and the viscosity (however, the shear rate is 100 (1 / s)). The same shall apply hereinafter) is 3 to 200 (mPa · s), and T.W. I. The value (however, the ratio (ηa / ηb) between the viscosity ηa (mPa · s) at a shear rate of 10 (1 / s) and the viscosity ηb (mPa · s) at a shear rate of 1000 (1 / s)). In the solid content concentration of 40 wt% or more and 60 wt% or less, and the viscosity is 10 to 200 (mPa · s). I. A colored resin composition having a value of 1 to 3.   The colored resin composition according to claim 1, further comprising a compound having a weight average molecular weight of 2,000 to 10,000 in an amount of 5% by weight or more based on the total solid content. The colored resin composition according to claim 1 or 2, wherein the compound having a weight average molecular weight of 2,000 to 10,000 has at least one structure represented by the following general formulas (1) to (3). General formula (1):

(In the formula, R1 represents hydrogen or a methyl group. R2 represents an alkylene group. M represents an integer of 1 to 20.)
General formula (2):
(HOOC-) _e- R'1-(-COO-[-R'3-COO-] _f- R'2) _g (2) (wherein R'1 is a tetravalent tetracarboxylic acid compound residue R′2 is a monoalcohol residue, R′3 is a lactone residue, e is an integer of 2 or 3, f is an integer of 1 to 50, and g is (4-e).)
General formula (3):

{In General Formula (3), R ″ 3 is a hydrogen atom or a methyl group, X ¹ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—, ² is a general formula:
-(-R ^a1 -O-) _m1-
(Wherein R ^a1 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)
A group represented by
X ³ is a general formula:
-(-CO-R ^b1 -O-) _m2-
(R ^b1 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 0 or an integer of 1 to 20)
A group represented by
Y ¹ represents the general formula (4):

(In general formula (4),
A one is hydrogen atom of A ¹ to A ^3, or the other two are combined is ^-COOH, one of -COOR ^c (where, ^{R c} of the A 1 to A ³ are, The other two are —COOH, or ^three of A ^{1 to} A ³ are —COOH, and k is 1 or 2)
Or a group represented by the general formula (5):

(In general formula (5),
One of A ^{5 to} A ⁷ is a hydrogen atom and the other two are combinations of —COOH, or one of A ^{5 to} A ⁷ is —COOR ^d (where R ^d is The other two are —COOH, or three of A ^{5 to} A ⁷ are —COOH combinations,
R ² is a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, a formula:

Or a group represented by the formula:

Is a group represented by   Furthermore, the colored resin composition as described in any one of Claims 1-3 containing an alkoxyalkyl group containing melamine compound or an alkoxyalkyl group containing benzoguanamine compound.   The colored resin composition according to any one of claims 1 to 4, wherein a coating layer of a pigment derivative and a resin carrier is formed on the pigment surface.   An inkjet ink using the colored resin composition according to any one of claims 1 to 5.   The inkjet ink according to claim 6, which is used for a color filter substrate. A color filter substrate carrying a printed layer made of the inkjet ink according to claim 6.