JP2009191251A - Inkjet ink and color filter substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide inkjet ink of low viscosity, good temporal stability with finely dispersed pigment at high solid content and high pigment concentration, extremely excellent in discharge property, and providing printed matter with good resistance; and further to provide color filter substrate formed by the inkjet method using the ink. <P>SOLUTION: The inkjet ink includes a dispersed resin (A), a pigment (B), a heat reactive compound (C), and a solvent (D), wherein the dispersed resin (A) includes a resin type dispersant (A-1) having an aromatic carboxyl group and vinyl resin (A-2) with a tertiary amino group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an inkjet ink and a color filter substrate. The inkjet ink of this invention can be used suitably for manufacture of the color filter board | substrate of a liquid crystal display panel, for example.

  Ink-jet printing techniques have become so popular that they can be used not only as industrial-use on-demand printing but also as personal-use printers. In recent years, ink-jet printing is used to draw patterns rather than images. Development to applications is required. Among them, the production of color filters by an ink jet printing method has attracted attention.

  Conventionally, a color filter substrate is manufactured by applying a photoresist solution in which a pigment is dispersed on a transparent substrate, and then repeating processes such as drying, exposure, development, and curing. Therefore, productivity is low and the demand for cost reduction is high. In particular, with the increase in size of liquid crystal display panels, a technique for replacing photoresist has been demanded. In accordance with these requirements, manufacturing methods and manufacturing facilities have been reviewed, and the manufacture of color filter substrates by the inkjet method has attracted attention. The inkjet method is particularly advantageous in that the manufacturing apparatus can be easily downsized and the productivity is high. Furthermore, in recent years, pigment-based inks have begun to be used in ink jet methods due to advances in technology related to printer heads and inks. As a result, light resistance and fastness have also been improved. Also from this point, various proposals have been made, in which it is advantageous to apply the ink jet method to color filter substrate applications (for example, Patent Documents 1 to 3).

When an inkjet printing method is used for the purpose of describing a pattern such as a color filter substrate, the ink used is required to have a high solid differentiation and a high pigment concentration from the viewpoint of productivity. However, high solidification and high pigment concentration reduces the amount of solvent in the ink and makes it easy to dry. As a result, the ink viscosity increases at the nozzle part of the inkjet head, making the discharge unstable, and the vicinity of the nozzle The solid matter adheres to the surface of the nozzle and the flight direction of the droplet is bent. In some cases, the solid matter is deposited inside the nozzle and non-ejection occurs, which adversely affects the ejection.
JP-A-1-217302 Japanese Patent Laid-Open No. 7-174915 JP-A-8-75916

  An object of the present invention is to provide an inkjet ink having a high solid content and a high pigment concentration, a low viscosity, good temporal stability, a finely dispersed state of the pigment, excellent dischargeability, and good printed material resistance. There is a thing. Another object of the present invention is to provide a color filter substrate formed by the ink jet method using the above ink.

According to the present invention, the subject is an inkjet ink comprising a dispersion resin (A), a pigment (B), a heat-reactive compound (C), and a solvent (D),
Solved by inkjet ink, in which the dispersion resin (A) is a dispersion resin comprising a resin type dispersant (A-1) having an aromatic carboxyl group and a vinyl resin (A-2) having a tertiary amino group can do.

  In still another preferred embodiment of the ink-jet ink according to the present invention, the resin type dispersant (A-1) having an aromatic carboxyl group comprises a polymer (A-3) having a hydroxyl group and an aromatic tricarboxylic acid anhydride ( It is a resin-type dispersant formed by reacting A-4a) and / or aromatic tetracarboxylic dianhydride (A-4b). Preferably, the polymer (A-3) having a hydroxyl group is a polymer (A-3a) having a hydroxyl group at one end or a polymer (A-3b) having a hydroxyl group in a side chain. More preferably, the polymer (A-3a) having a hydroxyl group at one end is a polymer (A-3c) having two hydroxyl groups at one end.

  In still another preferred embodiment of the inkjet ink according to the present invention, the amine value of the vinyl resin (A-2) having a tertiary amino group is 50 to 500 mgKOH / g.

  In still another preferred embodiment of the ink-jet ink according to the present invention, it further contains a pigment derivative (E) represented by the following general formula (1), more preferably the pigment derivative (E) is a pigment derivative having an acidic substituent. is there.

General formula (1)
G ⁶ -Z ⁶ q (1)
(In general formula (1),
G ⁶ is a q-valent chromogenic compound residue,
Z ⁶ is a basic substituent, an acidic substituent, or a neutral substituent,
q is an integer of 1 to 4. )

  In a preferred embodiment of the inkjet ink according to the present invention, the thermoreactive compound (C) is a melamine compound, a benzoguanamine compound, a carbodiimide compound, an epoxy compound, an oxetane compound, a phenol compound, a benzoxazine compound, a blocked carboxylic acid compound, or a blocked form. It is 1 type, or 2 or more types of compounds chosen from the group which consists of an isocyanate compound, an acrylate-type monomer, and a silane coupling agent, and also in a more preferable aspect, a melamine compound or a benzoguanamine compound is included at least.

  In the preferable aspect of the inkjet ink by this invention, solid content is 3 to 60 weight% with respect to the inkjet ink total weight.

  In the preferable aspect of the inkjet ink by this invention, content of a pigment (B) is 1-30 weight% with respect to inkjet ink.

  In a preferred embodiment of the ink-jet ink according to the present invention, the weight ratio of the pigment (B) to the resin-type dispersant (A) is 100: 3 to 100: 150.

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

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

  The ink-jet ink of the present invention contains the resin-type dispersant excellent in pigment dispersibility, has good heat resistance and chemical resistance, and has low viscosity and stable viscosity over time despite high pigment concentration. Moreover, the ejection stability is good, and a printing layer having sufficient resistance and printing density can be provided. Further, when a color filter substrate is produced using the ink composition for inkjet recording of the present invention, a high-performance color filter can be produced much more efficiently than the conventional method.

(1) Dispersing resin (A)
(1-1) Dispersant (A-1) having an aromatic carboxyl group
The dispersant (A-1) having an aromatic carboxyl group of the present invention preferably has a number average molecular weight of 500 to 30,000. If it is less than 500 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may deteriorate, which is not preferable.

  The dispersant (A-1) having an aromatic carboxyl group of the present invention preferably has an acid value of 10 to 200 mgKOH / g.

  The dispersant (A-1) having an aromatic carboxyl group of the present invention has an aromatic carboxyl group in the molecule. The production method includes, for example, production of reacting an aromatic tricarboxylic acid anhydride (A-4a) and / or an aromatic tetracarboxylic acid dianhydride (A-4b) with a polymer (A-3) having a hydroxyl group. Method 1, production method 2 for producing a polymer using a monomer having an aromatic carboxyl group, aromatic tricarboxylic acid anhydride (A-4a) and / or aromatic tetra while polymerizing a monomer having a hydroxyl group Any one of the manufacturing method 3 with which carboxylic dianhydride (A-4b) is made to react is mentioned. Among these, from the viewpoint of pigment dispersibility, a solvent-affinity part block comprising a plurality of polymer parts and a polycarboxylic acid block having a high affinity for a vinyl resin having a tertiary amino group comprising a plurality of carboxyl groups What was made by the manufacturing method 1 which can manufacture with good balance is preferable.

<Polymer having hydroxyl group (A-3)>
As the polymer (A-3) having a hydroxyl group used as a precursor of the dispersant having an aromatic carboxyl group of the present invention, a polymer (A-3a) having a hydroxyl group at one end, and a hydroxyl group in the side chain And the polymer (A-3b). Furthermore, as a polymer (A-3a) having a hydroxyl group at one end, a polymer (A-3c) having two hydroxyl groups at one end is preferred.

[Polymer having hydroxyl group at one end (A-3a)]
First, the polymer (A-3a) having a hydroxyl group at one end will be described. As a polymer (A-3a) having a hydroxyl group at one end used in the present invention, a polyester and / or polyether polymer (A-3a-1) having a hydroxyl group at one end and a hydroxyl group at one end Vinyl polymer (A-3a-2).

[Polyester and / or polyether polymer (A-3a-1) having a hydroxyl group at one end]
As the polyester and / or polyether polymer (A-3a-1) having a hydroxyl group at one end, those represented by the following general formula (2) are preferable.

  General formula (2):

〔一般式（２）中、
Ｙ¹は、炭素原子数１〜２０、酸素原子数０〜１２、及び窒素原子数０〜３の１価の末端基であり、
Ｘ²は、−Ｏ−、−Ｓ−、又は−Ｎ（Ｒ^b）−（但し、Ｒ^b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、
Ｚ¹は、−ＯＨであり、
Ｇ¹は、−Ｒ¹¹Ｏ−で示される繰り返し単位であり、
Ｇ²は、−Ｃ（＝Ｏ）Ｒ¹²Ｏ−で示される繰り返し単位であり、
Ｇ³は、−Ｃ（＝Ｏ）Ｒ¹³Ｃ（＝Ｏ）−ＯＲ¹⁴Ｏ−で示される繰り返し単位であり、
Ｒ¹¹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、
Ｒ¹²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４〜８のシクロアルキレン基であり、
Ｒ¹³は、炭素原子数２〜６の直鎖状若しくは分岐状のアルキレン基、炭素原子数２〜６の直鎖状若しくは分岐状のアルケニレン基、炭素原子数３〜２０のシクロアルキレン基、又は炭素原子数６〜２０アリーレン基であり、
Ｒ¹⁴は、−ＣＨ（Ｒ¹⁵）−ＣＨ（Ｒ¹⁶）−であり、
Ｒ¹⁵、及びＲ¹⁶は、どちらか一方が水素原子であり、もう一方が炭素原子数１〜２０のアルキル基、炭素原子数２〜２０のアルケニル基、炭素原子数６〜２０のアリール基、アルキル部分の炭素原子数１〜２０のアルキルオキシメチレン基、アルケニル部分の炭素原子数２〜２０のアルケニルオキシメチレン基、アリール部分の炭素原子数６〜２０でアリール部分が場合によりハロゲン原子で置換されていることのあるアリールオキシメチレン基、又はＮ−メチレン−フタルイミド基であって、
Ｒ¹⁷は、前記Ｒ¹¹、−Ｃ（＝Ｏ）Ｒ¹²−、又は−Ｃ（＝Ｏ）Ｒ¹³Ｃ（＝Ｏ）−ＯＲ¹⁴−であり、
ｍ１は、０〜１００の整数であり、ｍ２は、０〜６０の整数であり、ｍ３は、０〜３０の整数であり、但しｍ１＋ｍ２＋ｍ３は、１以上１００以下の整数であり、
一般式（２）における前記繰り返し単位Ｇ¹〜Ｇ³の配置は、その順序を限定するものではなく、一般式（２）で表される重合体において、基Ｘ²と基Ｒ¹⁷との間に繰り返し単位Ｇ¹〜Ｇ³が任意の順序で含まれていることを示し、更に、それらの繰り返し単位Ｇ¹〜Ｇ³は、それぞれランダム型又はブロック型のどちらでもよい。〕

[In general formula (2),
Y ¹ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
X ² is —O—, —S—, or —N (R ^b ) — (where R ^b is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
Z ¹ is —OH;
G ¹ is a repeating unit represented by —R ¹¹ O—,
G ² is a repeating unit represented by —C (═O) R ¹² O—,
G ³ is a repeating unit represented by —C (═O) R ¹³ C (═O) —OR ¹⁴ O—,
R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ¹² is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ¹³ is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or An arylene group having 6 to 20 carbon atoms,
R ¹⁴ is —CH (R ¹⁵ ) —CH (R ¹⁶ ) —,
One of R ¹⁵ and R ¹⁶ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, an alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, an aryl moiety optionally having 6 to 20 carbon atoms in the aryl moiety, and optionally substituted with a halogen atom An aryloxymethylene group, or an N-methylene-phthalimide group,
R ¹⁷ is R ¹¹ , —C (═O) R ¹² —, or —C (═O) R ¹³ C (═O) —OR ¹⁴ —,
m1 is an integer of 0-100, m2 is an integer of 0-60, m3 is an integer of 0-30, provided that m1 + m2 + m3 is an integer of 1-100.
The arrangement of the repeating units G ^{1 to} G ^{3 in} the general formula (2) does not limit the order thereof, and in the polymer represented by the general formula (2), between the group X ² and the group R ^17. Indicates that the repeating units G ^{1 to} G ³ are included in an arbitrary order, and these repeating units G ^{1 to} G ³ may be either random type or block type, respectively. ]

In the general formula (2), Y ¹ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability.

As another embodiment, the Y ¹ in the general formula (2) preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the dispersant having an aromatic carboxyl group.

  In the general formula (2), m2 is preferably an integer of 3 to 15 from the viewpoints of lowering the viscosity of the pigment dispersion and storage stability.

In the general formula (2), when m2 = 0 and m3 = 0, Y ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms, or an ethylenically unsaturated dialkyl group. It preferably has a double bond.

  The polyester and / or polyether polymer (A-3a-1) having a hydroxyl group at one end represented by the general formula (2) can be produced by a known method, such as monoalcohol, primary monoamine, Easily obtained by ring-opening polymerization of a cyclic compound selected from the group of alkylene oxide, lactone, lactide, dicarboxylic anhydride, and epoxide using a compound selected from the group of secondary monoamines and monothiols as an initiator. It is done.

  The monoalcohol 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, benzyl alcohol, phenoxyethyl alcohol, paracumyl Aromatic ring-containing monoalcohol such as enoxyethyl 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 monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl Pyrether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol mono Hexyl 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- Ethyl hexyl ether, tripropylene glycol monomethyl ether, tripropylene 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, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoether Ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, alkylene glycol monoalkyl ethers such as tetramethyl diethylene glycol monomethyl ether, and the like.

  A monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol. In this case, active energy ray-curing performance can be imparted to the produced dispersant having an aromatic carboxyl group.

  Examples of the group having an ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group (hereinafter referred to as “(meth) acryloyl” or “(meth) acrylate”). Each represents “acryloyl and / or methacryloyl” or “methacrylate and / or acrylate”, with a (meth) acryloyl group being preferred. The type of the group having a double bond may be one type or a plurality of types.

  As the monoalcohol having an ethylenically unsaturated double bond, a compound containing one, two, and three or more ethylenically unsaturated double bonds can be used. Examples of the monoalcohol having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate (in the case of “(meth) acrylate”, acrylate and / or methacrylate). The same shall apply hereinafter.), 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ester Ether, 4-hydroxybutyl vinyl ether. 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. Is mentioned.

Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained as a mixture of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively. Therefore, in order to control the molecular weight of the produced dispersant, HPLC (high speed It is necessary to determine the ratio of monoalcohols by liquid chromatography) method or hydroxyl value measurement. This is because the molecular weight of the dispersant is determined by the number of monoalcohols and the ratio of raw materials forming G ^{1 to} G ³ .

  Among the above-mentioned monoalcohols, those having two or more ethylenically unsaturated double bonds are preferable in the case of use in an active energy ray-curable pigment composition in terms of curability.

  Examples of the primary monoamine include methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine, and 1-hexylamine. , Cyclohexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1-decylamine, 1-dodecylamine, 1 Aliphatic primary monoamines such as myristylamine, cetylamine, 1-stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldecylamine, 2-hexyldecylamine, behenylamine, oleylamine, etc. , 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, 3-isobutyoxypropylamine, 3-decyloxypropylamine, 3- Examples include alkoxyalkyl primary monoamines such as myristyloxypropylamine and aromatic primary monoamines such as benzylamine. Examples of secondary monoamines include dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1-pentylamine, diisopentylamine, and di-1-hexylamine. , Dicyclohexylamine, di- (4-methyl-2-pentyl) amine, di-1-heptylamine, di-1-octylamine, isooctylamine, di- (2-ethylhexyl) amine, di-1-nonylamine, Diisononylamine, di-1-decylamine, di-1-dodecylamine, di-1-myristylamine, dicetylamine, di-1-stearylamine, diisostearylamine, di- (2-octyldecyl) amine, di- (2 -Octyldodecyl) amine, di- (2-hexyldecyl) a Emissions, N- methylethylamine, N- methylbutylamine, N- methyl isobutyl amine, N- methyl-propylamine, N- methyl hexylamine, piperazine, aliphatic secondary monoamine such as an alkyl-substituted piperazines.

  Examples of the monothiol include methylthiol, ethylthiol, 1-propylthiol, isopropylthiol, 1-butylthiol, isobutylthiol, tert-butylthiol, 1-pentylthiol, isopentylthiol, 3-pentylthiol, 1- Hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol, 1-octylthiol, isooctylthiol, 2-ethylhexylthiol, 1-nonylthiol, isononylthiol, 1-decylthiol, 1- Dodecylthiol, 1-myristylthiol, cetylthiol, 1-stearylthiol, isostearylthiol, 2-octyldecylthiol, 2-octyldodecylthiol, 2-hexyldecylthiol Aliphatic monothiols such as behenylthiol and oleylthiol, methyl thioglycolate, octyl thioglycolate, thioglycolic acid alkyl esters such as methoxybutyl thioglycolate, methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate And mercaptopropionic acid alkyl esters such as mercaptopropionic acid tridecyl.

  The compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol referred to in the present invention is not limited to the above examples, but is a hydroxyl group, primary amino group, secondary amino group, or thiol. Any compound can be used as long as it is a compound having one group, and it may be used alone or in combination of two or more.

Here, the portion other than the hydroxyl group, primary amino group, secondary amino group, or thiol group of the monoalcohol, primary monoamine, secondary monoamine, or monothiol is the Y ¹ in the general formula (2). Constitute.

From the group consisting of alkylene oxides, lactones, lactides, and combinations of dicarboxylic acid anhydrides and epoxides, with the compound selected from the group of the exemplified monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. The selected cyclic compound can be subjected to ring-opening polymerization to produce a polymer represented by the general formula (2) in which Z ¹ is —OH. However, the dicarboxylic acid anhydride and the epoxide are always used at the same time and are alternately polymerized.

Here, the reaction order of the cyclic compound selected from the group consisting of alkylene oxide, lactone, lactide, and a combination of dicarboxylic anhydride and epoxide may be any, for example, the initiator as the first step After the alkylene oxide is polymerized, the lactone can be polymerized in the second stage, and the dicarboxylic acid anhydride and the epoxide can be alternately polymerized in the third stage. In this example, the initiator for polymerizing the lactone in the second stage is an alkylene oxide polymer having a hydroxyl group at one end polymerized in the first stage. The initiator for alternately polymerizing dicarboxylic acid anhydrides and epoxides in the third stage is a block copolymer of an alkylene oxide polymer having a hydroxyl group at one end and a lactone polymer polymerized by the second stage. It becomes a polymer. In the production method of the present invention, Z ^{1 in the} polymer represented by the general formula (2) is used as an initiator for producing the polymer represented by the general formula (2) described below. An —OH compound and a polymer represented by the general formula (4) described later can also serve as an initiator.

The reaction sequence of the cyclic compound is not limited to the combination of the first-stage alkylene oxide, the second-stage lactone, and the third-stage dicarboxylic anhydride and epoxide, but the alkylene oxide, lactone (and / or lactide). , And a combination of a dicarboxylic acid anhydride and an epoxide can be carried out in any order one to several times. Alternatively, for any combination of alkylene oxide, lactone (and / or lactide), and dicarboxylic anhydride and epoxide, without performing any ring-opening polymerization, any cyclic compound is selected from them, Ring-opening polymerization can also be carried out.

  As the alkylene oxide, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As for the polymerization mole number of the alkylene oxide with respect to 1 mol of initiators, 0-100 are preferable.

The polymerization of the alkylene oxide can be carried out in a known manner, for example, in the presence of an alkali catalyst at a temperature of 100 to 200 ° C. under a pressurized state. An alkylene oxide polymer having a hydroxyl group at one end obtained by polymerizing an alkylene oxide to a hydroxyl group of a monoalcohol is commercially available, for example, a NOOX series manufactured by NOF Corporation, a BLEMMER series manufactured by NOF Corporation, In the raw material for the dispersant having an aromatic carboxyl group of the present invention, Z ¹ is —OH and only G ¹ is included among the repeating units of G ^{1 to} G ^{3 in} the polymer represented by the general formula (2). It can also be used as it is. Specific examples of commercially available products include 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.

Here, the alkylene group of the alkylene oxide constitutes R ¹¹ in the repeating unit G ¹ in the general formula (2).

  Specific examples of lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone, of which δ- Use of valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone is preferable from the viewpoint of ring-opening polymerization.

  In the production method of the present invention, the lactone can be used without being limited to the above examples, and may be used alone or in combination of two or more. Use of two or more types in combination is preferable in terms of workability and compatibility with other resins, since the crystallinity may decrease and become liquid at room temperature.

  As a lactide, what is shown by following General formula (3) is preferable (a glycolide is included).

  General formula (3):

〔一般式（３）中、
Ｒ³¹及びＲ³²は、それぞれ独立して、水素原子、飽和若しくは不飽和の直鎖若しくは分枝の炭素原子数１〜２０のアルキル基であり、
Ｒ³³及びＲ³⁴は、それぞれ独立して、水素原子、ハロゲン原子、又は飽和若しくは不飽和の直鎖若しくは分枝の炭素原子数１〜９の低級アルキル基である。〕

[In general formula (3),
R ³¹ and R ³² are each independently a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. ]

  As a raw material for the dispersant having an aromatic carboxyl group of the present invention, particularly preferred lactides are lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane-2). , 5-dione). Of the lactones or lactides, lactones are preferably used as raw materials for the dispersant having an aromatic carboxyl group of the present invention.

  The ring-opening polymerization of lactone and / or lactide can be carried out in a known manner, for example, by charging an initiator, lactone and / or lactide, and a polymerization catalyst into a reactor connected to a dehydrating tube or 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 in monoalcohol, it is preferable to add a polymerization inhibitor and to react under a dry air flow.

  The number of moles of lactone and / or lactide polymerized per mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.

  As the polymerization catalyst, a known catalyst can be used without limitation. For example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, Quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium bromide, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide , Benzyltrimethylphosphonium chloride, benzyltrimethyl In addition to quaternary phosphonium salts such as phosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, potassium acetate, sodium acetate, potassium benzoate, Examples include organic carboxylates such as sodium benzoate, alkali metal alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride. It is done. 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 exceeds 3000 ppm, the resin may be intensely colored. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of lactone and / or lactide is extremely slow, which is not preferable.

  The polymerization temperature of the lactone and / or lactide is 100 ° C. to 220 ° C., preferably 110 ° C. to 210 ° C. When the reaction temperature is less than 100 ° C., the reaction rate is very slow, and when it exceeds 220 ° C., side reactions other than the addition reaction of lactone and / or lactide, for example, depolymerization of lactone adducts to lactone monomers, cyclic lactone dimers and trimers Generation is likely to occur.

Here, the portion other than the ester group of lactone or lactide constitutes R ¹² in the repeating unit G ² in the general formula (2).

  Examples of the dicarboxylic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, glutaric anhydride, dodecenyl succinic anhydride, and chlorendec acid anhydride.

  Examples of the epoxide include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, 2,4-dibromophenyl glycidyl ether, Examples include 3-methyl-dibromophenyl glycidyl ether (where the bromo substitution position is arbitrary), allyl glycidyl ether, ethoxyphenyl glycidyl ether, glycidyl (meth) acrylate, glycidyl phthalimide, and styrene oxide.

Dicarboxylic anhydride and epoxide are used simultaneously for the initiator and react alternately. At this time, the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator first reacts with the acid anhydride group of the dicarboxylic acid anhydride to form a carboxyl group, and then the epoxide is added to the carboxyl group. The epoxy group reacts to form a hydroxyl group. Further, the reaction similar to the above can be sequentially proceeded so that the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group. The number of moles of polymerization of dicarboxylic anhydride and epoxide with respect to 1 mole of initiator is preferably 0 to 30 moles. Moreover, the reaction ratio ([Ad] / [Ae]) of dicarboxylic acid anhydride and epoxide is:
0.8 ≦ [Ad] / [Ae] ≦ 1.0
([Ad] is the number of moles of dicarboxylic anhydride and [Ae] is the number of moles of epoxide)
It is preferable that If it is less than 0.8, the epoxide remains undesirably, and if it exceeds 1.0, a polymer having a hydroxyl group at one end cannot be obtained, and a polymer having a carboxyl group at one end is formed, which is not preferable.

  The alternating polymerization of the dicarboxylic acid anhydride and the epoxide is preferably performed in the range of 50 ° C to 180 ° C, more preferably 60 ° C to 150 ° C. When the reaction temperature is less than 50 ° C or exceeds 180 ° C, the reaction rate is extremely slow.

Here, the portion other than the dicarboxylic anhydride group of the dicarboxylic anhydride constitutes R ¹³ in the repeating unit G ³ in the general formula (2), and the portion other than the oxygen atom forming the cyclic ether of the epoxide is the above-mentioned R ¹⁴ in the repeating unit G ³ in the general formula (2) is constituted.

  When the monoalcohol, dicarboxylic acid anhydride, or epoxide having an ethylenically unsaturated double bond is used when producing the polymer represented by the general formula (2), a polymerization inhibitor may be used. preferable. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, phenothiazine and the like are preferable, and these may be used alone or in combination from 0.01% to 6%. %, Preferably in the range of 0.05% to 1.0%.

[Vinyl polymer having a hydroxyl group at one end (A-3a-2)]
As the vinyl polymer (A-3a-2) having a hydroxyl group at one end, a polymer represented by the following general formula (4) is preferable.

  General formula (4):

〔一般式（４）中、
Ｙ²は、ビニル重合体の重合停止基であり、
Ｚ²は、−ＯＨ、又は−Ｒ²⁸（ＯＨ）₂であり、Ｒ²⁸は、炭素原子数１〜１８の３価の炭化水素基であり、
Ｒ²¹及びＲ²²は、それぞれ独立に水素原子又はメチル基であり、
Ｒ²³及びＲ²⁴は、いずれか一方が水素原子、他の一方が芳香族基、又は−Ｃ（＝Ｏ）−Ｘ⁶−Ｒ²⁵（但し、Ｘ⁶は、−Ｏ−若しくは−Ｎ（Ｒ²⁶）−であり、
Ｒ²⁵及びＲ²⁶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置換基として芳香族基を有していることができるものであり、
Ｘ⁴は、直接結合、−Ｏ−Ｒ²⁷−又は−Ｓ−Ｒ²⁷−であり、
Ｒ²⁷は、炭素数１〜１８の直鎖状若しくは分岐状のアルキレン基であり、
ｎは、２〜５０である。〕

[In general formula (4),
Y ² is a polymerization stopping group of the vinyl polymer,
Z ² is —OH or —R ²⁸ (OH) ₂ , R ²⁸ is a trivalent hydrocarbon group having 1 to 18 carbon atoms,
R ²¹ and R ²² are each independently a hydrogen atom or a methyl group,
One of R ²³ and R ²⁴ is a hydrogen atom, the other is an aromatic group, or —C (═O) —X ⁶ —R ²⁵ (where X ⁶ is —O— or —N (R ²⁶ )-
R ²⁵ and R ²⁶ are each a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, which can have an aromatic group as a substituent,
X ⁴ is a direct bond, —O—R ²⁷ — or —S—R ²⁷ —,
R ²⁷ is a linear or branched alkylene group having 1 to 18 carbon atoms,
n is 2-50. ]

  The polymer represented by the general formula (4) is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer.

The part of the repeating unit of the polymer represented by the general formula (4), that is, {-[C (R ²¹ ) (R ²³ ) -C (R ²² ) (R ²⁴ )] _n —} is mutually identical. (Homopolymer) made of a different material or (copolymer) made of a different material. In a preferred embodiment of the polymer represented by the general formula (4), R ²¹ and R ²² are either a hydrogen atom, the other is a hydrogen atom or a methyl group, and R ²³ and R ²⁴ are either One is a hydrogen atom and the other is —C (═O) —O—R ²⁹ (R ²⁹ is a linear or branched alkyl group having 1 to 8 carbon atoms and has an aromatic group as a substituent. And —X ⁴ —Z ² is —S—CH ₂ CH ₂ —OH or S—CH ₂ CH (OH) CH ₂ —OH.

Y ² in the general formula (4), that is, the polymerization termination group of the vinyl polymer is any known polymerization termination introduced when the polymerization of a normal ethylenically unsaturated monomer is carried out in the usual manner. And is obvious to those skilled in the art. Specifically, it can be, for example, a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even if Y ² has any of these chemical structures, the dispersant of the present invention can exert its effect without being affected by the polymerization termination group Y ² .

Among the polymers represented by the general formula (4), those in which Z ² is —OH can be produced by a known method, for example, a compound having a hydroxyl group and a thiol group and an ethylenically unsaturated monomer. Can be obtained by mixing and heating.

  Examples of the compound having a hydroxyl group and a thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, 2-mercapto-3-butanol and the like. It is done.

Among the polymers represented by the general formula (4), those in which Z ² is —R ²⁸ (OH) ₂ can be produced by a known method, for example, a compound having two hydroxyl groups and one thiol group; It can be obtained by mixing and heating an ethylenically unsaturated monomer. In this case, among the polymers (A-3) having a hydroxyl group at one end, the polymer (A-3c) having two hydroxyl groups at one end, which is the most preferable mode, is obtained.

  Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2-propanediol. (Thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto- Examples include 2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

  Preferably, bulk polymerization or solution polymerization is performed using a compound having 1 to 30 parts by weight of a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours. If the compound having a hydroxyl group and a thiol group is less than 1 part by weight, the molecular weight may increase, and the year of the dispersion may increase, which may be undesirable. If it exceeds 30 parts by weight, the molecular weight is decreased, and the steric repulsion effect due to the solvent affinity block is decreased, which may be undesirable.

  Since the thiol group becomes a radical generating group for polymerizing the ethylenically unsaturated monomer, another polymerization initiator is not necessarily required for the polymerization, but it can also be used. When using this polymerization initiator, 0.001-5 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer include acrylic monomers and monomers other than acrylic monomers. Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate (Meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide (note that “(meth) acrylamide” represents acrylamide and / or methacrylamide. The same), N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acrylamides such as acryloylmorpholine. Can be mentioned.

  Examples of the monomer other than the acrylic monomer include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether. And fatty acid vinyls such as vinyl acetate and vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.

  In addition, the carboxyl group-containing ethylenically unsaturated monomer can be used alone or in combination with the monomer. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-couplerlactone-added acrylic acid, ε-couplerlactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. 1 type (s) or 2 or more types can be selected from these.

  In the step of producing the polymer represented by the general formula (4), no solvent or a solvent may be used depending on the case. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used, but are not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used.

  The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The solvent used can be removed by an operation such as distillation after completion of the reaction, or can be used as it is as a part of the product of the dispersant.

[Polymer having hydroxyl group in side chain (A-3b)]
The polymer (A-3b) having a hydroxyl group in the side chain of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a hydroxyl group and, if necessary, another ethylenically unsaturated monomer. Examples of the ethylenically unsaturated monomer having a hydroxyl group include a (meth) acrylate monomer having a hydroxyl group, such as 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, and alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, or (Meth) acrylamide monomers having a hydroxyl group, such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meta N- () such as acrylamide (Droxyalkyl) (meth) acrylamide or vinyl ether monomer having a hydroxyl group, such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxy Hydroxyalkyl vinyl ethers such as butyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, 2- (or 3- or 4-) And hydroxyalkyl allyl ethers such as hydroxybutyl allyl ether. Moreover, the monomer which has two hydroxyl groups, such as glycerol mono (meth) acrylate, is also mentioned. Further, a product obtained by reacting an ethylenically unsaturated monomer having a cyclic ether group such as an epoxy group with a carboxyl group-containing ethylenically unsaturated monomer such as (meth) acrylic acid, or (meth) acrylic acid Examples include those obtained by reacting a carboxyl group-containing ethylenically unsaturated monomer such as a monofunctional cyclic ether compound such as a monofunctional epoxy compound.

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

  The copolymerization ratio between the ethylenically unsaturated monomer having a hydroxyl group and another ethylenically unsaturated monomer is determined so that an average of at least 0.3 to 177 hydroxyl groups per molecule after polymerization. Is preferred.

  Examples of other ethylenically unsaturated monomers include the acrylic monomers described in the process for producing the polymer represented by the general formula (4) and monomers other than the acrylic monomers. Can be used arbitrarily.

As the polymerization initiator, for example, the azo compound and the organic peroxide described in the process for producing the polymer represented by the general formula (4) can be used. When using this polymerization initiator, 0.01-20 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers.
As the polymerization solvent, the solvent described in the process for producing the polymer represented by the general formula (4) can be used in the same manner.

<< Reaction of OH resin and acid anhydride >>
Next, a polymer (A-3a) having a hydroxyl group at one end or a polymer (A-3b) having a hydroxyl group in a side chain and a tricarboxylic acid anhydride (A-4a) "and / or tetracarboxylic dianhydride" The step of reacting (A-4b) will be described.

  The hydroxyl group of the polymer having a hydroxyl group at one end (A-3a) or the polymer having a hydroxyl group in the side chain (A-3b), an aromatic tricarboxylic acid anhydride (A-4a) and / or an aromatic tetra The dispersant having an aromatic carboxyl group of the present invention can be obtained by reacting with the anhydride group of carboxylic dianhydride (A-4b).

  Examples of the aromatic tricarboxylic acid anhydride (A-4a) include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride). ), Naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2 , 8-naphthalene tricarboxylic acid anhydride, etc.), 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, '- biphenyl sulfonic tricarboxylic acid anhydride and the like.

Examples of the aromatic tetracarboxylic dianhydride (A-4b) include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride. Ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl sulfone Tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldipheny Silane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) ) Diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic 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 (triphenyl) Ruphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride and the like.

  The aromatic tricarboxylic acid anhydride (A-4a) and aromatic tetracarboxylic acid dianhydride (A-4b) used in the present invention are not limited to the compounds exemplified above, and have any structure. It doesn't matter. These may be used alone or in combination. Those used in the present invention are preferably trimellitic anhydride and pyromellitic dianhydride.

  The number of moles of the hydroxyl group of the polymer (A-3) is <H>, and the mole of the carboxylic acid anhydride group of the aromatic tricarboxylic acid anhydride (A-4a) or the aromatic tetracarboxylic dianhydride (A-4b). When the number is <N>, the reaction ratio is preferably 0.3 ≦ <H> / <N> ≦ 3, more preferably 0.5 ≦ <H> / <N> ≦ 2. In particular, when the polymer (A-3c) is used for the polymer (A-3a), it is preferable that 1 <H> / <N> ≦ 2. If the reaction is carried out with <H> / <N> <1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water or alcoholicized with a monofunctional alcohol.

  When the polymer (A-3b) is used, it is preferable to introduce 0.3 to 3 aromatic tricarboxylic acids and / or aromatic tetracarboxylic acids into one molecule. Specifically, the number average molecular weight of the polymer (A-3b) is measured, and when the measured value is [X], when the aromatic tricarboxylic acid anhydride (A-4a) is used, the resin [X ] 0.3 to 3 mol of aromatic tricarboxylic acid anhydride may be reacted with respect to g. On the other hand, when using aromatic tetracarboxylic dianhydride (A-4b), 0.15 mol or more and 1.5 mol or less of aromatic tetracarboxylic dianhydride is reacted with resin [X] g. Just do it. This is because the aromatic tetracarboxylic dianhydride has two acid anhydride groups, and therefore the aromatic tricarboxylic acid anhydride (A-4a) is used to bridge the polymer (A-3b) molecule. This is because half the amount is sufficient.

  A catalyst may be used for the reaction of the polymer (A-3) with the tricarboxylic acid anhydride (A-4a) or the tetracarboxylic acid dianhydride (A-4b). As the catalyst, for example, a tertiary amine compound can be used, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-. Examples include undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene.

The reaction of the polymer (A-3) with the tricarboxylic acid anhydride (A-4a) and / or the tetracarboxylic acid dianhydride (A-4b) may be carried out without a solvent, or a suitable dehydrated organic solvent. May be used. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product of the dispersant. The solvent to be used is not particularly limited, but the solvent described in the process for producing the polymer represented by the general formula (4) can be used in the same manner.

  The reaction temperature between the polymer (A-3) and the tricarboxylic acid anhydride (A-4a) and / or tetracarboxylic dianhydride (A-4b) is preferably 50 ° C to 180 ° C, more preferably 60 ° C. C. to 160.degree. C. When the reaction temperature is less than 50 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C., the acid anhydride that has reacted and opened the ring forms a cyclic anhydride again, which may make it difficult to complete the reaction.

(1-2) Vinyl resin having a tertiary amino group (A-2)
The vinyl resin (A-2) having a tertiary amino group of the present invention preferably has an amine value of 50 to 500 mgKOH / g, more preferably 100 to 400 mgKOH / g, and 200 to 350 mgKOH / g. Most preferred. Even if the amine value is less than 50 mgKOH / g or more than 400 mgKOH / g, the viscosity and viscosity stability of the pigment dispersion may be deteriorated.

  The number average molecular weight of the vinyl resin (A-2) having a tertiary amino group of the present invention is preferably 500 to 30,000. If it is less than 500 or more than 30,000, the viscosity and viscosity stability of the pigment dispersion may deteriorate, which is not preferable.

  The vinyl resin (A-2) having a tertiary amino group of the present invention can be obtained by polymerizing an ethylenically unsaturated monomer having a tertiary amino group and other ethylenically unsaturated monomers as necessary. be able to. Examples of the ethylenically unsaturated monomer having a tertiary amino group include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meta) N, N-dialkylamino group-containing (meth) acrylates such as acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) Examples include N, N-dialkylamino group-containing (meth) acrylamides such as acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. Of these, N, N-dialkylamino group-containing (meth) acrylates are preferable, and N, N-dimethylaminoethyl (meth) acrylate is more preferable.

  Examples of other ethylenically unsaturated monomers include the acrylic monomers described in the process for producing the polymer represented by the general formula (4) and monomers other than the acrylic monomers. Can be used arbitrarily.

  As the polymerization initiator, for example, the azo compound and the organic peroxide described in the process for producing the polymer represented by the general formula (4) can be used. When using this polymerization initiator, 0.01-20 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers.

  Similarly to the step of producing the polymer represented by the general formula (4), a solvent-free or a solvent can be used depending on the case. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, hexane, toluene, xylene, acetone, methyl ethyl ketone, methoxypropyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl. Ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used, but are not particularly limited, and can be arbitrarily selected from applications, costs, and the like. Two or more kinds of polymerization solvents may be mixed and used.

  The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The solvent used can be removed by an operation such as distillation after completion of the reaction, or can be used as it is as a part of the product of the dispersant.

(1-3) Blending ratio In the pigment composition of the present invention, blending of a pigment, a dispersant (A-1) having an aromatic carboxyl group, and a vinyl resin (A-2) having a tertiary amino group The ratio is 5 to 100 parts by weight of the dispersant (A-1) having an aromatic carboxyl group and 1 to 50 parts by weight of the vinyl resin (A-2) having a tertiary amino group with respect to 100 parts by weight of the pigment. Part.

(1-4) Combined use of dispersion resin In the inkjet ink of the present invention, a known dispersion is used together with a dispersant (A-1) having an aromatic carboxyl group and a vinyl resin (A-2) having a tertiary amino group. A resin can be used in combination. By using the dispersion resin in combination, the dispersibility of the pigment is further improved, leading to a reduction in the viscosity of the ink, an improvement in the viscosity stability over time of the ink, and an improvement in the ejection properties as an inkjet ink.

  The dispersion resin that can be used in combination with the dispersant (A-1) having an aromatic carboxyl group and the vinyl resin (A-2) having a tertiary amino group is not particularly limited. Specific examples of commercially available dispersion resins include the following.

  BYK Chemie's dispersion resins include Anti-Terra-U, U100, 203, 204, 205, Disperbyk-101, 102, 106, 107, 110, 111, 130, 140, 142, 170, 171, 174, 180. 2001, BYK-P104, P105, 9076, and the like.

  Examples of the dispersion resin manufactured by Avicia include Solspers 3000, 13940, 17000, 21000, 24000, 26000, 366000, 41000, 41090, and 53095.

  Examples of the dispersion resin manufactured by Efka CHEMICALS include Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766, Efka Polymer 100, 150, 400, 401, 402, 403. , 450, 451, 452, 453, and the like.

  Examples of the dispersion resin manufactured by Kyoeisha Chemical Co., Ltd. include Floren TG-710, Flownon SH-290, SP-1000, Polyflow No. 50E, No. 300, etc. are Disparon KS-860, 873SN, 874, # 2150, # 7004, etc. as dispersion resins manufactured by Enomoto Kasei Co., and Nikkor T106, MYS-IEX, Hexagline 4-0 are dispersion resins manufactured by Nikko Chemical Co., Ltd. As the dispersion resin manufactured by Ajinomoto Fine Techno Co., Ajisper PB711, 811, 821 and the like can be mentioned.

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

(2) Pigment (B)
The ink-jet ink of the present invention contains a pigment.

  As the pigment, an organic pigment, an inorganic pigment, or carbon black such as acetylene black, channel black, or furnace black can be used, and two or more kinds of pigments may be mixed and used.

  Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, or metal-free phthalocyanine, Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, iso Examples thereof include indoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, 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, bituminous, cobalt blue, cerulean blue, Examples thereof include cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

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

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

  Examples of yellow ink-jet inks 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 orange inkjet ink include C.I. I. Orange pigments such as Pigment orange 36, 43, 51, 55, 59, 61 can be used.
Examples of green inkjet ink include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, and 58 can be used. A yellow pigment can be used in combination with the green inkjet ink.

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

  The ink-jet ink of the present invention may contain the 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.

  As the surface state of the pigment used in the present invention, those having an acidic surface are preferable. When a pigment having an acidic surface is used, it becomes easy to interact with the dispersion resin, leading to low viscosity of the ink-jet ink, improvement of stability over time, and stabilization of ejection.

  The amine adsorption amount can be used as an index of the acidity of the pigment surface. The amine adsorption amount referred to in the present invention is defined as a case where n-hexylamine is measured as an adsorbed amine substance in accordance with the method described in Coloring Materials, 67 [9], 547-554 (1994). A preferable range of the amine adsorption amount of the pigment used in the present invention is 50 to 700 μmol / g, and more preferably 100 to 600 μmol / g. Specifically, C.I. I. Pigment Green 58 (actual value 550 μmol / g), C.I. I. Pigment Yellow 150 (actual measurement value: 215 μmol / g) can be exemplified, but the invention is not limited thereto.

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

  Examples of the thermally reactive compound (C) include melamine compounds, benzoguanamine compounds, carbodiimide compounds, epoxy compounds, oxetane compounds, phenol compounds, benzoxazine compounds, blocked carboxylic acid compounds, blocked isocyanate compounds, acrylate monomers, and One or more compounds selected from the group consisting of silane coupling agents can be used. Particularly preferred is a thermoreactive compound (C) containing at least a melamine compound or a benzoguanamine compound.

  Examples of the melamine compound or benzoguanamine compound include those having an imino group, a methylol group, or an alkoxymethyl group. Among these, a melamine compound or a benzoguanamine compound containing an alkoxyalkyl group is preferable. When a melamine compound or benzoguanamine compound containing an alkoxyalkyl group is used, the storage stability of the paint or ink containing the colored resin composition of the present invention is remarkably improved.

  Examples of the melamine compound or benzoguanamine compound containing an alkoxyalkyl group include hexamethoxymethylol melamine, hexabutoxymethylol melamine, tetramethoxymethylol benzoguanamine, tetrabutoxymethylol benzoguanamine and the like, but are not necessarily limited thereto. .

  Specific examples of commercially available melamine compounds include the following. However, it is not necessarily limited to these.

  Nikarak MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX750, MX-708, MX- manufactured by Sanwa Chemical Co., Ltd. 706, MX-042, MX-035, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410, MX-302, Cymel 300, 301, 303 manufactured by Nihon Cytex Industry 350, 370, 325, 327, 703, 712, 01, 285, 232, 235, 236, 238, 211, 254, 204, 202, 207, My Coat 506, 508, 212, 715, and the like.

  Among them, an alkoxyalkyl group-containing melamine compound is preferable. Nikalac MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX manufactured by Sanwa Chemical Co., Ltd. -43, MX-302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, My Coat 506, 508 manufactured by Nippon Cytex Industries.

  Specific examples of commercially available benzoguanamine compounds include, for example, Nikalac BX-4000, SB-401, BX-37, SB-355, SB-303, SB301, BL-60, SB-255, SB manufactured by Sanwa Chemical Co., Ltd. -203, SB-201, Nippon Cytex Industry's Cymel 1123, My Coat 105, 106, 1128 and the like.

  Among these, Sanka Chemical's Nikalac BX-4000 and SB-401 and Nippon Cytex Industries' Cymel 1123, which are alkoxyalkyl group-containing benzoguanamine compounds, are preferable.

  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 isocyanate compound of the blocked isocyanate compound include hexamethylenediisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, bis (4-isocyanatocyclohexyl) methane, tetra Diisocyanates such as methylxylylene diisocyanate, isocyanurates of these diisocyanates, trimethylolpropane adduct type, biuret type, prepolymers having isocyanate residues (low polymers obtained from diisocyanates and polyols), uretdiones having isocyanate residues, etc. However, the present invention is not necessarily limited to this.

  Examples of the blocking agent for 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 to 120 ° C.). ° C) and the like, but is not necessarily limited thereto. Moreover, it is used individually by 1 type or in combination of 2 or more types.

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

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

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-a Nopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane And aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  Among these heat-reactive compounds, melamine compounds or benzoguanamine compounds, epoxy compounds, phenolic compounds, blocked isocyanate compounds, or acrylate monomers are contained in an amount of 1% to 40% by weight in the inkjet ink of the present invention. It is preferably contained. The silane coupling agent is preferably contained in the ink-jet ink of the present invention in an amount of 0.1% to 40% by weight. If the content is insufficient, heat resistance or chemical resistance may be inferior. On the other hand, if the content exceeds 40%, the viscosity may increase or the storage stability may decrease.

(4) Organic solvent (D)
The ink-jet ink of the present invention contains an organic solvent.

  In this invention, the organic solvent normally used in inkjet ink can be used. In general, the organic solvent used in the ink jet ink has high solubility in the resin, and when the ink is ejected from the ink jet printer, there is little swelling action on the printer member in contact with the ink, and the viscosity of the solvent should be as small as possible. A low one is 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 Cole monoethyl ether, propylene glycol isopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, triacetin, 1-butoxyethoxypropanol, or 1 -Methoxy-2-propyl acetate and the like can be mentioned.

  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.

(5) Pigment derivative (E)
The inkjet ink of the present invention can be used in combination with a pigment derivative for the purpose of controlling the surface state of the pigment surface.

Examples of the pigment derivative include, for example, the general formula (1):
G ^6- (Z ⁶ ) q (1)
(In the formula, G ⁶ is a chromogenic compound residue, Z ⁶ is a basic substituent, an acidic substituent, or a neutral substituent, and q is an integer of 1 to 4)
The compound represented by these can be used.

In the general formula (1), examples of the basic substituent of Z ⁶ include a substituent represented by the following general formula (5), general formula (6), general formula (7), or general formula (8). Can be mentioned.

  General formula (5):

（一般式（５）中、
Ｘ⁶¹は、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−、又は直接結合であり、
ｐは、１〜１０の整数であり、
Ｒ⁶¹、及びＲ⁶²は、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Ｒ⁶¹とＲ⁶²とで一緒になって更なる窒素原子、酸素原子若しくは硫黄原子を含む置換されていてもよい複素環であり、前記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。）

(In general formula (5),
X ⁶¹ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond,
p is an integer of 1 to 10,
R ⁶¹ and R ⁶² are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ⁶¹ and R ⁶² together. In addition, the alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms, which may be a substituted heterocyclic ring containing a further nitrogen atom, oxygen atom or sulfur atom. )

  General formula (6):

（一般式（６）中、
Ｒ⁶³、Ｒ⁶⁴は、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Ｒ⁶³とＲ⁶⁴とで一緒になって更なる窒素原子、酸素原子若しくは硫黄原子を含む置換されていてもよい複素環であり、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。）

(In general formula (6),
R ⁶³ and R ⁶⁴ each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ⁶³ and R ^{64 taken} together. It is an optionally substituted heterocyclic ring containing a further nitrogen atom, oxygen atom or sulfur atom, and the alkyl group and alkenyl group preferably have 1 to 10 carbon atoms. )

  General formula (7):

（一般式（７）中、
Ｘ⁶²は、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−、又は直接結合であり、
Ｒ⁶⁵は、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であり、前記アルキル基及びアルケニル基の炭素数は１〜１０が好ましく、
Ｒ⁶⁶、Ｒ⁶⁷、Ｒ⁶⁸、及びＲ⁶⁹は、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であり、前記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。）

(In general formula (7),
X ⁶² is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond,
R ⁶⁵ is an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group, and the alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms,
R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , and R ⁶⁹ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. The alkyl group and alkenyl group preferably have 1 to 5 carbon atoms. )

  General formula (8):

（一般式（８）中、
Ｘ⁶³は、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−、又は直接結合であり、
Ｙ⁶³は、−ＮＲ⁷⁰−Ｚ−ＮＲ⁷¹−、又は直接結合えあり、
Ｒ⁷⁰及びＲ⁷¹は、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であり、前記アルキル基及びアルケニル基の炭素数は１〜５が好ましく、
Ｚは、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であり、前記アルキレン基及びアルケニレン基の炭素数は１〜８が好ましく、
Ｐは、下記一般式（９）で示される置換基、又は下記一般式（１０）で示される置換基であり、
Ｑは、水酸基、アルコキシル基、前記一般式（６）で示される置換基又は前記一般式（７）で示される置換基である。

(In general formula (8),
X ⁶³ is —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond,
Y ⁶³ may be —NR ⁷⁰ —Z—NR ⁷¹ — or a direct bond;
R ⁷⁰ and R ⁷¹ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group, As for carbon number, 1-5 are preferred,
Z is an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted, and the alkylene group and the alkenylene group preferably have 1 to 8 carbon atoms,
P is a substituent represented by the following general formula (9) or a substituent represented by the following general formula (10),
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (6) or a substituent represented by the general formula (7).

  General formula (9):

〔一般式（９）中、
ｒは、１〜１０の整数であり、
Ｒ⁷²、及びＲ⁷³は、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Ｒ⁷²とＲ⁷³とで一緒になって更なる窒素原子、酸素原子若しくは硫黄原子を含む置換されていてもよい複素環であり、前記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。〕

[In general formula (9),
r is an integer of 1 to 10,
R ⁷² and R ⁷³ are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ⁷² and R ^{73 taken} together. In addition, the alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms, which may be a substituted heterocyclic ring containing a further nitrogen atom, oxygen atom or sulfur atom. ]

  General formula (10):

〔一般式（１０）中、
Ｒ⁷⁴は、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であり、前記アルキル基及びアルケニル基の炭素数は１〜１０が好まく、
Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、及びＲ⁷⁸は、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であり、前記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。〕）

[In general formula (10),
R ⁷⁴ is an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group, and the alkyl group and the alkenyl group preferably have 1 to 10 carbon atoms. ,
R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , and R ⁷⁸ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. The alkyl group and alkenyl group preferably have 1 to 5 carbon atoms. ])

In the general formula (1), examples of the acidic substituent of Z ⁶ or the neutral substituent include substituents represented by the following general formula (11), general formula (12), or general formula (13). be able to.
General formula (11):
-SO ₃ M / l (11)
(In general formula (11),
M is a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom, or aluminum atom, and l is the valence of M. )

  Formula (12):

（一般式（１２）中、
Ｒ⁷⁹、Ｒ⁸⁰、Ｒ⁸¹、及びＲ⁸²は、水素原子、又は炭素数１〜３０のアルキル基である。〔但し全てが水素原子である場合は除く〕）

(In general formula (12),
R ⁷⁹ , R ⁸⁰ , R ⁸¹ , and R ⁸² are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. [Except when all are hydrogen atoms])

  General formula (13):

（一般式（１３）中、
Ａ²は、水素原子、ハロゲン原子、−ＮＯ₂、−ＮＨ₂、又はＳＯ₃Ｈであり、
ｋ₁は、１〜４の整数である。）

(In general formula (13),
A ² is a hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ , or SO ₃ H;
k ₁ is an integer of 1 to 4. )

  The chromogenic compound refers to a compound having a generally known dye skeleton and a compound having a skeleton similar to the dye skeleton, which hardly absorbs in the visible light region.

  Examples of the chromogenic compound residue G include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, or polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, 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 metals A complex dye, an anthraquinone residue, a triazine residue, or the like can be given.

  Moreover, as an anthraquinone derivative, the anthraquinone which has the said basic substituent, an acidic substituent, or a neutral substituent can be used. The triazine derivative includes 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, or a methoxy group. , An alkoxy group such as an ethoxy group or a butoxy group, a halogen such as chlorine, a phenyl group which may be 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 Group, methoxy group, ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, or optionally substituted with a phenylamino group which may be substituted with a hydroxyl group, etc. 1, 3, 5 -Use a derivative in which the above basic substituent, acidic substituent or neutral substituent is introduced into triazine. Door can be.

  In particular, when a pigment having a low surface acidity (for example, CI Pigment Blue 15: 6 measured value 26 μmol / g, etc.) having an amine adsorption amount of less than 50 μmol / g on the surface of the pigment (B) is used, a pigment having an acidic functional group It is preferable to use a derivative. When a pigment derivative having an acidic functional group is used, it becomes easy to interact with the dispersion resin, leading to low viscosity of the inkjet ink, improvement of stability over time, and stabilization of ejection.

(6) Binder resin The dispersant (A-1) having an aromatic carboxyl group and / or the vinyl resin (A-2) having a tertiary amino group of the present invention can also be used as a binder resin.

  In addition to the dispersant having an aromatic carboxyl group and the vinyl resin having a tertiary amino group, examples of resins that can be used in the inkjet ink of the present invention include thermoplastic resins and thermosetting resins. And active energy ray-curable resin. The binder resin is a non-reactive resin even at the reaction temperature of the thermoreactive compound, and is preferably a thermoplastic resin.

  Examples of the binder resin 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 binder resin 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.

  The weight average molecular weight (Mw) of the binder resin is preferably 1,000 to 50,000, and more preferably 2,000 to 30,000.

(7) Pigment coating treatment The pigment coating treatment includes pigment (B), dispersion resin (A), the dispersion resin, organic solvent (D), pigment derivative (E), if necessary, known dispersion resins and The binder resin can be mixed in advance so as to be uniform, and then kneaded 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 blending amount of the raw material for coating the pigment (B) is 1 to 30 parts by weight of the pigment derivative (E), the dispersion resin (A), a known dispersion resin and binder resin (hereinafter referred to as 100 parts by weight of the pigment). And abbreviated as resin component.) It is preferably in the range of 20 to 200 parts by weight and solvent (D) 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. Further, when the blending amount of the resin component is less than 20 parts by weight, the pigment surface cannot be sufficiently coated, 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. 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 coated, so that the viscosity of the ink may not be stable, and 200 weight 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. However, if the solvent used during the coating process is a solvent that can be used as a liquid medium for inkjet ink, it must be dried. There is no.

(8) Physical Properties etc. In the inkjet ink of the present invention, the solid content is preferably 3 to 60% by weight, more preferably 4 to 40% by weight, based on the total weight of the ink composition. When the solid content is less than 3% by weight, the concentration and resistance of the ink film are insufficient, and when it exceeds 60% by weight, the viscosity of the ink increases and the stability over time may decrease.

  The viscosity at 25 ° C. of the inkjet ink of the present invention is preferably 2 mPa · s or more and 40 mPa · s or less, more preferably 3 mPa · s or more and 30 mPa · s or less, and further preferably 4 mPa · s or more and 20 mPa · s or less. If the viscosity is too large, stable discharge cannot be performed when continuously discharging.

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

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

  The inkjet ink of the present invention can be produced by dispersing resin (A), pigment (B), heat-reactive compound (C), solvent (D), and, if necessary, pigment derivative (E), known dispersion resin. , And a binder resin are charged into a normal disperser and dispersed until a desired average particle size and particle size distribution are obtained. The ink-jet ink raw materials may be mixed and dispersed all at once, or may be separately mixed and dispersed in consideration of the characteristics and economics of each raw material. When the viscosity of the inkjet ink is too high and dilution is necessary, the inkjet ink can be prepared by adding a liquid medium for dilution to the ink stock solution and stirring uniformly.

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

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

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

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

  In addition, since the inkjet ink of the present invention has a pigment dispersed at a high concentration, the printing density can be reduced even with paper, plastic, glass, and metal in which the inkjet ink penetrates in the depth direction and spreads in the lateral direction. Can be high. Furthermore, since the discharge amount can be suppressed, it is possible to avoid the ink from flowing out and being mixed because it exceeds the ink receiving amount of the receiving layer, and it is also possible to avoid the dot shape from becoming a perfect circle. It can also be used for limited applications in printing.

(9) Color filter substrate A color filter substrate can be produced by the inkjet method using the inkjet ink of the present invention. The color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television or the like.

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

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

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

[1] Dispersing resin (A)
(1) Production Example 1 of Resin Type Dispersant Having Aromatic Carboxyl Group (Dispersant A-1-a)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of dipropylene glycol monomethyl ether acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 40 parts of methacrylate, 28 parts of benzyl methacrylate, 20 parts of butyl acrylate, 12 parts of 2-hydroxyethyl methacrylate, 40 parts of dipropylene glycol monomethyl ether acetate and 6 parts of dimethyl-2,2'-azobisdiisobutyrate The mixed liquid mixture was added dropwise over 2 hours, and then stirring was continued at the same temperature for 3 hours to complete the reaction. In this way, an intermediate having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 3.5 was obtained. The intermediate was charged with 100 parts of solid, 5.1 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine, and reacted at 100 ° C. for 6 hours. In this way, a dispersant having an aromatic carboxyl group having an average number of trimellitic acids per molecule of 1, an acid value of 30 mg KOH / g per solid content, and a number average molecular weight of 4,000 (A-1- a) was obtained. A dispersant (A-1-a) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(2) Production Example 2 of Resin Type Dispersant Having Aromatic Carboxyl Group (Dispersant A-1-b)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of dipropylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of azobisisobutyronitrile was added in 20 portions every 30 minutes, The reaction was continued for 12 hours at 80 ° C., and it was confirmed that 95% had reacted by solid content measurement. Next, 30 parts of pyromellitic anhydride, 190 parts of dipropylene glycol monomethyl ether acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added, and at 120 ° C. The reaction was performed for 7 hours. Dispersant having an aromatic carboxyl group having an acid value of 42 mgKOH / g and a number average molecular weight of 4,100 per solid content after confirming by titration that 98% or more of the acid anhydride is half-esterified (A-1-b) was obtained. A dispersant (A-1-b) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(3) Production Example 3 of Resin Type Dispersant Having Aromatic Carboxyl Group (Dispersant A-1-c)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of dipropylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 4.4 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 times. Every 30 minutes, the reaction was continued for 12 hours at 80 ° C., and it was confirmed that 95% had reacted by solid content measurement. Next, 12 parts of trimellitic anhydride, 190 parts of dipropylene glycol monomethyl ether acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added at 120 ° C. The reaction was carried out for 2 hours at 80 ° C. for 5 hours. It is confirmed by titration that 90% or more of the acid anhydride is half-esterified, and a dispersant having an aromatic carboxyl group having an acid value of 44 mgKOH / g and a number average molecular weight of 5,200 per solid content (A-1- c) was obtained. A dispersant (A-1-c) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(4) Production Example 4 (Dispersant A-2-a) of Vinyl Resin (A-2) Having Tertiary Amino Group
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of dipropylene glycol monomethyl ether acetate and heated to 100 ° C. while purging with nitrogen. In a dropping tank, 200 parts of N, N-dimethylaminoethyl methacrylate, 61 parts of dipropylene glycol monomethyl ether acetate and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were charged and stirred until uniform. Then, it was dripped at reaction tank over 2 hours, and reaction was continued at the same temperature for 3 hours after that. Thus, a vinyl resin (A-2-a) having a tertiary amino group having an amine value per solid content of 345 mg KOH / g and a number average molecular weight of 2,500 was obtained. A dispersant (A-2-a) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(5) Production Example 5 (Dispersant A-2-b) of Vinyl Resin (A-2) Having Tertiary Amino Group
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of dipropylene glycol monomethyl ether acetate and heated to 100 ° C. while purging with nitrogen. In a dropping tank, 180 parts of N, N-dimethylaminoethyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of dipropylene glycol monomethyl ether acetate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) After charging and stirring until uniform, it was added dropwise to the reaction vessel over 2 hours, and then the reaction was continued for 3 hours at the same temperature. Thus, a vinyl resin (A-2-b) having a tertiary amino group having an amine value per solid content of 315 mgKOH / g and a number average molecular weight of 3,000 was obtained. A dispersant (A-2-b) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(6) Production Example 6 of vinyl-based resin (A-2) having tertiary amino group (dispersant A-2-c)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of dipropylene glycol monomethyl ether acetate and heated to 100 ° C. while purging with nitrogen. In a dropping tank, 170 parts of N, N-dimethylaminoethyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 20 parts of methacrylic acid, 61 parts of dipropylene glycol monomethyl ether acetate, and 2,2′-azobis (2,4-dimethylvalero) 6 parts of nitrile) was added and stirred until uniform, and then dropped into the reaction vessel over 2 hours, and then the reaction was continued at the same temperature for 3 hours. In this manner, a vinyl resin (A-2-c) having a tertiary amino group having an amine value per solid content of 303 mg KOH / g, an acid value of 65 mg KOH / g, and a number average molecular weight of 4,000 was obtained. A dispersant (A-2-c) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(7) Production Example 7 of vinyl resin (A-2) having tertiary amino group (dispersant A-2-d)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of dipropylene glycol monomethyl ether acetate and heated to 100 ° C. while purging with nitrogen. In a dropping tank, 20 parts of N, N-dimethylaminoethyl methacrylate, 90 parts of methyl methacrylate, 90 parts of n-butyl acrylate, 61 parts of dipropylene glycol monomethyl ether acetate, and 2,2′-azobis (2,4-dimethylvaleronitrile) ) Was stirred until it became uniform, and then dropped into the reaction vessel over 2 hours, and then the reaction was continued for 3 hours at the same temperature. In this way, a vinyl resin (A-2-d) having a tertiary amino group having an amine value per solid content of 31 mg KOH / g and a number average molecular weight of 3,500 was obtained. A dispersant (A-2-d) solution having a solid concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(8) Comparative production example 1 of urea resin (U-1) having an amino group
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of dehydrated dipropylene glycol monomethyl ether acetate, 45 parts of tetraethylenepentamine was charged, and the temperature was raised to 40 ° C. After adding 155 parts of hexamethylene diisocyanate biuret body ("Takenate D-165N-90CX" manufactured by Takeda Pharmaceutical Co., Ltd.) and 67 parts of dehydrated dipropylene glycol monomethyl ether acetate to the dropping tank and stirring until uniform, It was added dropwise to the reaction vessel over 4 hours, and then the reaction was continued for 3 hours at the same temperature. Thus, a urea resin (U-1) having an amino group with an amine value of 45 mg KOH / g per solid content was obtained. A dispersant (U-1) solution having a solid content concentration of 50% by weight was prepared with dipropylene glycol monomethyl ether acetate.

(9) Dispersion resin manufactured by Ajinomoto Fine Techno Co., Ltd. Ajisper PB821 50% solution (U-2)
(Acid value 17 mg KOH / g, amine value 8-11 mg KOH / g, solvent dipropylene glycol methyl ether acetate)
(10) Dispersing resin EFKA-4300 50% solution (U-3) manufactured by Ciba Specialty Chemicals
(Amine value 52-60 mg KOH / g, solvent dipropylene glycol methyl ether acetate / methoxypropyl acetate)

[2] Pigment (B)
(B-1) Red pigment A: C.I. I. Pigment Red 254
(B-2) Red pigment B: C.I. I. Pigment Red 177
(B-3) Magenta pigment: C.I. I. Pigment Red 122
(B-4) Green pigment A: C.I. I. Pigment Green 36
(B-5) Green pigment B: C.I. I. Pigment Green 58
(B-6) Yellow pigment A: C.I. I. Pigment Yellow 138
(B-7) Yellow pigment B: C.I. I. Pigment Yellow 150
(B-8) Blue pigment: C.I. I. Pigment Blue 15: 6
(B-9) Cyan pigment: C.I. I. Pigment Blue 15: 3
(B-10) Violet pigment: C.I. I. Pigment Violet 23

[3] Thermally reactive compound (C)
(MX-43): Alkoxyalkyl group-containing melamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalak MX-43
(MX-417): Imino group / methylol group-containing melamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalak MX-417
(SB-401): Alkoxyalkyl group-containing benzoguanamine compound manufactured by Sanwa Chemical Co., Ltd. Nicalak SB-401
(BL-60): Imino group / methylol group-containing benzoguanamine compound manufactured by Sanwa Chemical Co., Ltd. Nicarac BL-60
(M-400): Toray Gosei Co., Ltd. acrylic monomer Aronix M-400
(BL-4265): Bayer Isocyanate Compound Desmodur BL-4265
(EPPN-201): Epoxy compound EPPN-201 manufactured by Nippon Kayaku Co., Ltd.

[4] Solvent (D)
(CBAc): Diethylene glycol monoethyl ether acetate (BuCBAc): Diethylene glycol monobutyl ether acetate (PGMAc): Propylene glycol monomethyl ether acetate (DPMA): Dipropylene glycol monomethyl ether acetate (13BGDA): 1,3-butylene glycol diacetate (TPM) ): Tripropylene glycol monomethyl ether (TPNB): Tripropylene glycol monobutyl ether

[5] Pigment derivative (E)
(E-1)

  General formula (14):

  (E-2)

  Formula (15):

  (E-3)

Formula (16):

  (E-4)

  Formula (17):

  (E-5)

  General formula (18):

  (E-6)

  General formula (19):

Example 1
90 parts of red pigment A, 10 parts of pigment derivative (E-1), 106 parts of resin type dispersant (A-1-a) solution having an aromatic carboxyl group, 26 parts of vinyl resin (A-2-a) solution Then, 242 parts of solvent (CBAc) was placed in a mixer and mixed, and further dispersed in a sand mill to obtain a dispersion. Further, 20 parts of a benzoguanamine compound (BL-60), 165 parts of a solvent (CBAc) and 55 parts of a solvent (BuCBAC) were added and mixed in a homodispa. Dust and coarse substances were filtered and an inkjet ink having a pigment concentration of 14% was obtained.

  In the same manner as in Example 1, the inks were dispersed and prepared so as to have the compositions of Examples 2 to 30 and Comparative Examples 1 to 18 in the composition tables of Tables 1 to 7, and ink jet inks were obtained.

  The viscosity and fluidity, storage stability, and haze of the inkjet inks obtained in Examples 1-30 and Comparative Examples 1-18 were evaluated by the following methods. Moreover, it discharged with the inkjet printer which has a piezo head which can change the frequency of 4-10KHz, and evaluated the ejection stability, printing density, heat resistance, and chemical resistance with the following method. The results are shown in Tables 8-14.

[viscosity]
The viscosity (η: mPa · s) at a shear rate of 100 (1 / s) was measured with a dynamic viscoelasticity measuring device.
○: η <20
Δ: 20 ≦ ηa / η <30
×: η ≦ 30

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

[Storage stability]
After heating in a 45 ° C. oven for 7 days, the viscosity was measured.
○: Thickening rate ≦ ± 10% compared to the viscosity before heating
×: Thickening rate> ± 10% compared to the viscosity before heating

[Haze]
Using a spin coater, the substrate coated on glass at 1500 rpm was dried on a hot plate at 100 ° C. for 3 minutes, and the haze of the coated surface was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).
○: T <5
×: T ≧ 5

[Discharge stability A]
The ink was ejected onto the cardboard using the inkjet printer and dried, followed by drying at room temperature to form a coating film. The printed state was visually observed, and the ejection stability was evaluated according to the following criteria.
◯: Nozzle missing after 15 minutes is 5% or less.
(Triangle | delta): Nozzle omission is 10% or less after continuous 15 minutes.
X: Nozzle missing after 15 minutes continuously is 50% or more.

[Discharge stability B]
The ink was ejected onto the cardboard using the inkjet printer and dried, followed by drying at room temperature to form a coating film. The printed state was visually observed, and the ejection stability was evaluated according to the following criteria.
○: Nozzle missing after intermittent 15 minutes is 10% or less.
(Triangle | delta): Nozzle omission is 20% or less after intermittent 15 minutes.
X: Nozzle omission is 50% or more after intermittent 15 minutes.

[Print density]
A solid ink was printed on the cardboard using the inkjet printer, and the OD value was measured after drying.
○: OD value 1.2 or more ×: OD value less than 1.2

[chemical resistance]
Ink is ejected onto the glass substrate at a predetermined position using the inkjet printer, dried, and thermally cured at 230 ° C. for 20 minutes to form a coating film. The glass substrate is immersed in N-methylpyrrolidone, before and after the immersion. The color change ΔE of the coating film was measured.
○: ΔE ≦ 2.5
Δ: 2.5 <ΔE ≦ 5
×: ΔE> 5

[Heat-resistant]
The glass substrate on which the coating film is formed is placed in an oven at 240 ° C. for 90 minutes, and the change rate of the film thickness before and after the film Δt = {(film thickness before heat test−film thickness after heat test) / film before heat test Thickness} was measured.
○: Δt ≦ 10%
×: Δt> 10%

  The ink-jet ink of the present invention has good heat resistance and chemical resistance, and also has low viscosity, stable viscosity over time, low viscosity, and good ejection stability despite the high pigment concentration. In addition, it is possible to produce a high-performance color filter, package, outdoor signboard, or the like much more efficiently than the conventional method.

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

Claims (15)

An inkjet ink comprising a dispersion resin (A), a pigment (B), a heat-reactive compound (C), and a solvent (D),
An ink-jet ink in which the dispersion resin (A) is a dispersion resin comprising a resin-type dispersant (A-1) having an aromatic carboxyl group and a vinyl resin (A-2) having a tertiary amino group.   The resin type dispersant (A-1) having an aromatic carboxyl group is a polymer (A-3) having a hydroxyl group, an aromatic tricarboxylic acid anhydride (A-4a) and / or an aromatic tetracarboxylic acid dianhydride. The inkjet ink according to claim 1, which is a resin-type dispersant obtained by reacting a product (A-4b).   The inkjet ink according to claim 2, wherein the polymer (A-3) having a hydroxyl group is a polymer (A-3a) having a hydroxyl group at one end or a polymer (A-3b) having a hydroxyl group in a side chain.   The ink-jet ink according to claim 3, wherein the polymer (A-3a) having a hydroxyl group at one end is a polymer (A-3c) having two hydroxyl groups at one end.   The inkjet ink according to any one of claims 1 to 4, wherein an amine value of the vinyl resin (A-2) having a tertiary amino group is 50 to 500 mgKOH / g. The inkjet ink according to any one of claims 1 to 5, further comprising a pigment derivative (E) represented by the following general formula (1).
General formula (1):
G ⁶ -Z ⁶ q
(In general formula (1),
G ⁶ is a q-valent chromogenic compound residue,
Z ⁶ is a basic substituent, an acidic substituent, or a neutral substituent,
q is an integer of 1 to 4. )   The inkjet ink according to claim 6, wherein the pigment derivative (E) is a pigment derivative (E) having an acidic substituent.   Thermally reactive compound (C) is melamine compound, benzoguanamine compound, carbodiimide compound, epoxy compound, oxetane compound, phenol compound, benzoxazine compound, blocked carboxylic acid compound, blocked isocyanate compound, acrylate monomer, and silane coupling The inkjet ink according to any one of claims 1 to 7, which is one or more compounds selected from the group consisting of agents.   The inkjet ink in any one of Claims 1-8 in which a thermoreactive compound (C) contains a melamine compound and / or a benzoguanamine compound at least.   The inkjet ink in any one of Claims 1-9 whose solid content is 3 to 60 weight% with respect to the total weight of inkjet ink.   The inkjet ink according to any one of claims 1 to 10, wherein the content of the pigment (B) is 1 to 30% by weight based on the total weight of the inkjet ink. The inkjet ink according to any one of claims 1 to 11, wherein a weight ratio of the pigment (B) to the dispersion resin (A) is 100: 3 to 100: 150.   The inkjet ink in any one of Claims 1-12 whose viscosity in 25 degreeC is 2-40 mPa * s.   The inkjet ink according to any one of claims 1 to 13, which is used for a color filter substrate.   A color filter substrate comprising a printed layer formed of the inkjet ink according to claim 1.