JP2007204718A - Nonaqueous inkjet ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment dispersed nonaqueous inkjet ink excellent in dispersibility, fluidity and printing stability. <P>SOLUTION: The nonaqueous inkjet ink comprises a vinyl-based pigment dispersing agent, a pigment and a liquid vehicle, wherein the vinyl-based pigment dispersing agent contains in a vinyl-based polymer main chain a carboxy-containing unit (G) represented by the formula in the figure [wherein, R<SP>1</SP>is H or methyl; X<SP>1</SP>is -O- or -NH-; X<SP>2</SP>is -(-R<SP>a1</SP>-O-)<SB>m1</SB>- (wherein, R<SP>a1</SP>is a bivalent hydrocarbon; and m1 is 1-50); X<SP>3</SP>is -(-CO-R<SP>b1</SP>-O-)<SB>m2</SB>- (wherein, R<SP>b1</SP>is a bivalent hydrocarbon; and m2 is 0-20); and Y<SP>1</SP>is a carboxy-containing aromatic-based acid anhydride residue]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pigment-dispersed non-aqueous ink jet ink excellent in dispersibility, fluidity and printing stability.

  Conventionally, as ink-jet inks, water-soluble dyes such as acid dyes, direct dyes, and basic dyes dissolved in a glycol solvent and water (Patent Document 1, Patent Document 2, and Patent Document 3) are often used. . However, water-soluble dyes that are highly soluble in water are generally used in order to obtain ink stability. Therefore, the ink-jet recorded matter generally has poor water resistance, and there is a problem that when the water is spilled, the dye in the recorded portion easily bleeds.

  In order to improve such poor water resistance, attempts have been made to change the structure of the dye or to prepare a highly basic ink (Patent Document 4). In addition, water resistance is improved by making good use of the reaction between recording paper and ink (Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8). Although these methods have a remarkable effect for specific recording paper, they are not versatile in that they are restricted by the recording paper, and when other than specific recording paper is used, a water-soluble dye is used. Ink used often does not provide sufficient water resistance of recorded matter.

  In addition, inks with good water resistance include those in which an oil-soluble dye is dispersed or dissolved in a high boiling point solvent, and those in which an oil-soluble dye is dissolved in a volatile solvent, but the dye has various resistances such as light resistance. Since it is inferior to a pigment, an ink using a pigment as a colorant is desired. However, the ink using the pigment has a problem that the viscosity is high and the ink cannot be ejected or the printing stability is deteriorated.

JP-A-53-614112 JP 54-89811 A JP 55-65269 A JP 56-57862 A Japanese Patent Laid-Open No. 50-49004 JP 57-36692 A JP 59-20696 A JP 59-146889 A

  An object of the present invention is to provide a pigment-dispersed non-aqueous ink jet ink excellent in dispersibility, fluidity and printing stability.

｛一般式（１）中、Ｒ¹は水素原子又はメチル基であり、
Ｘ¹は、−Ｏ−若しくは−ＮＨ−であり、
Ｘ²は、一般式：
−（−Ｒ^a1−Ｏ−）_m1−
（式中、Ｒ^a1は炭素原子数２〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数３〜８のシクロアルキレン基であり、そしてｍ１は１〜５０の整数である）
で表される基であり、
Ｘ³は、一般式：
−（−ＣＯ−Ｒ^b1−Ｏ−）_m2−
（Ｒ^b1は炭素原子数４〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数４〜８のシクロアルキレン基であり、そしてｍ２は０〜２０の整数である）
で表される基であり、
Ｙ¹は、一般式（２）：

〔一般式（２）中、
Ａ¹〜Ａ³のうちの１つが水素原子であって、他の２つは−ＣＯＯＨである組合せであるか、Ａ¹〜Ａ³のうちの１つが−ＣＯＯＲ^c（但し、Ｒ^cは、炭素原子数１〜１８のアルキル基である）であって、他の２つは−ＣＯＯＨである組合せであるか、又はＡ¹〜Ａ³の３つが−ＣＯＯＨであり、ｋは１又は２である〕
で表される基であるか、あるいは一般式（３）：

〔一般式（３）中、
Ａ⁵〜Ａ⁷のうち１つは水素原子であって、他の２つは−ＣＯＯＨである組合せであるか、Ａ⁵〜Ａ⁷のうち１つは−ＣＯＯＲ^d（但し、Ｒ^dは、炭素原子数１〜１８のアルキル基である）であって、他の２つは−ＣＯＯＨである組合せであるか、又はＡ⁵〜Ａ⁷の３つが−ＣＯＯＨであり、
Ｒ²は、直接結合、−Ｏ−、−ＣＯ−、−ＣＯＯＣＨ₂ＣＨ₂ＯＣＯ−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、式：

で表される基、又は式：

で表される基である｝
で表されるカルボキシル基含有単位（Ｇ）を、ビニル系重合体の１分子あたり平均０．３個以上３．０個以下の量で含むことを特徴とする、ビニル系顔料分散剤と、
顔料と、
液状ビヒクルとを含むことを特徴とする非水系インクジェットインキに関する。 In the present invention, the vinyl polymer main chain has the general formula (1):

{In General Formula (1), R ¹ is a hydrogen atom or a methyl group;
X ¹ is —O— or —NH—.
X ² is a general formula:
-(-R ^a1 -O-) _m1-
(Wherein R ^a1 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m1 is an integer of 1 to 50)
A group represented by
X ³ is a general formula:
-(-CO-R ^b1 -O-) _m2-
(R ^b1 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is an integer of 0 to 20)
A group represented by
Y ¹ represents the general formula (2):

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

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

Or a group represented by the formula:

Is a group represented by
A vinyl pigment dispersant characterized in that it contains a carboxyl group-containing unit (G) in an amount of 0.3 to 3.0 on average per molecule of the vinyl polymer;
Pigments,
The present invention relates to a non-aqueous inkjet ink comprising a liquid vehicle.

  Furthermore, the present invention relates to the non-aqueous inkjet ink, wherein the liquid vehicle is an organic solvent in which a resin is dissolved.

Furthermore, the present invention relates to the non-aqueous inkjet ink, wherein Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is a group represented by the general formula (2).

The present invention relates to the non-aqueous inkjet ink described above, which is a combination in which ^one of A ^{1 to} A ^{3 in} the general formula (2) is a hydrogen atom and the other two are —COOH groups.

〔一般式（４）中、
Ｇは、請求項１に記載の一般式（１）で示されるカルボキシル基含有単位（Ｇ）を示し、
Ｒ⁴は、水素原子又はメチル基を示し、
Ｒ⁵は、水素原子又はメチル基を示し、
Ｒ⁶は、芳香族基、又は−ＣＯ−Ｘ⁷−Ｒ⁷（但し、Ｘ⁷は、−Ｏ−若しくは−ＮＨ−であり、Ｒ⁷は、水素原子又は炭素原子数１〜１８の直鎖状若しくは分岐状のアルキル基であり、前記Ｒ⁷は、置換基として芳香族基を有していることができる）であり、
Ｘ⁴は、−ＣＯＯ−、−ＣＯＮＨ−、−Ｏ−、−ＯＣＯ−若しくは−ＣＨ₂Ｏ−であり、
Ｘ⁵は、式：
−（−Ｒ^a2−Ｏ−）_m3−、
（式中、Ｒ^a2は炭素原子数２〜８の直鎖状若しくは分岐状のアルキレン基、又は炭素原子数３〜８のシクロアルキレン基であり、そしてｍ３は１〜５０の整数である）
で表される基であり、
Ｘ⁶は、式：
−（−ＣＯ−Ｒ^b4−Ｏ−）_m4−
（式中、Ｒ^b2は炭素原子数４〜８の直鎖状若しくは分岐状のアルキレン基であり、そしてｍ４は０〜２０の整数である）
で表される基であり、
一般式（４）中の前記カルボキシル基含有単位（Ｇ）、−Ｃ（＝Ｏ）−Ｘ⁴−Ｘ⁵−Ｘ⁶−Ｈを含む水酸基含有単位（Ｊ）、及び−Ｃ（Ｒ５）（Ｒ６）−を含む主鎖構成単位（Ｋ）は、ランダム型又はブロック型で含まれていることができ、
一般式（４）中に含まれている前記カルボキシル基含有単位（Ｇ）、前記水酸基含有単位（Ｊ）、及び主鎖構成単位（Ｋ）は、それらが複数個で存在する場合は、相互に同一又は異なっていることができ、そして
ｐ１、ｐ２、及びｐ３はビニル系顔料分散剤一分子あたりの各構成単位の平均個数を示し、ｐ１は０．３以上３．０以下であり、ｐ２は０以上１８０以下であり、ｐ３は６以上２５０以下である〕
で示される上記非水性インクジェットインキに関する。 Furthermore, the present invention provides
General formula (4):

[In general formula (4),
G represents a carboxyl group-containing unit (G) represented by the general formula (1) according to claim 1,
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ is an aromatic group, or —CO—X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or a straight chain having 1 to 18 carbon atoms. A branched or branched alkyl group, and R ⁷ can have an aromatic group as a substituent).
X ⁴ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—;
X ⁵ is the formula:
-(-R ^a2 -O-) _m3- ,
(Wherein R ^a2 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m3 is an integer of 1 to 50)
A group represented by
X ⁶ is the formula:
-(-CO-R ^b4 -O-) _m4-
(Wherein R ^b2 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20)
A group represented by
The carboxyl group-containing unit (G) in the general formula (4), a hydroxyl group-containing unit (J) containing —C (═O) —X ⁴ —X ⁵ —X ⁶ —H, and —C (R 5) (R 6 )-Containing main chain structural units (K) can be included in random or block form,
When the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain constituent unit (K) contained in the general formula (4) are present in a plurality, P1, p2 and p3 represent the average number of each structural unit per molecule of the vinyl pigment dispersant, p1 is 0.3 or more and 3.0 or less, and p2 is 0 to 180 and p3 is 6 to 250]
This relates to the non-aqueous ink-jet ink represented by

  Furthermore, the present invention relates to the non-aqueous inkjet ink, wherein the vinyl pigment dispersant has a number average molecular weight of 500 or more and 20000 or less.

  According to the present invention, a pigment-dispersed non-aqueous ink-jet ink excellent in dispersibility, fluidity and printing stability can be provided.

  As the pigment contained in the inkjet ink of the present invention, an achromatic pigment such as carbon black, titanium oxide, calcium carbonate, or a chromatic organic pigment can be used. Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red, soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, alizarin, indanthrone, and thioindigo. Derivatives from vat dyes such as maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, isoindolinone yellow , Isoindolinone organic pigments such as isoindolinone orange, pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioy Digo-based organic pigments, condensed azo-based organic pigments, benzimidazolone-based organic pigments, quinophthalone-based organic pigments such as quinophthalone yellow, isoindoline-based organic pigments such as isoindoline yellow, and other pigments such as flavanthrone yellow and acylamide yellow Nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet and the like.

When organic pigments are exemplified by color index (CI) numbers, C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 8893, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154 155, 166, 168, 180, 185, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, C.I. I. Pigment violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, C.I. I. Pigment green 7, 36, C.I. I. Pigment brown 23, 25, 26, and the like.

  Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline organic pigments, etc. are light-resistant. Is preferable because it is excellent. The organic pigment is preferably a fine pigment having an average particle diameter of 10 to 300 nm as measured by laser scattering. When the average particle diameter of the pigment is less than 10 nm, the light resistance is lowered due to the small particle diameter, and when it exceeds 300 nm, it is difficult to maintain stable dispersion, and the pigment is likely to precipitate.

  The organic pigment can be refined by the following method. That is, a mixture comprising at least three components of an organic pigment, a water-soluble inorganic salt that is at least 3 times the weight of the organic pigment, and a water-soluble solvent is made into a clay-like mixture, and is kneaded strongly with a kneader or the like and then refined. And stirred with a high speed mixer or the like to form a slurry. Next, filtration and washing of the slurry are repeated to remove the water-soluble inorganic salt and the water-soluble solvent. In the miniaturization step, a resin, a pigment derivative, or the like may be added. Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride. These inorganic salts are used in the range of 3 times by weight or more, preferably 20 times by weight or less of the organic pigment. When the amount of the inorganic salt is less than 3 times by weight, a treated pigment having a desired size cannot be obtained. On the other hand, if the amount is more than 20 times by weight, the washing process in the subsequent step is great, and the substantial amount of the organic pigment is reduced.

  The water-soluble solvent is an organic solvent and a water-soluble inorganic salt that is used as a crushing aid, and is used for efficient crushing efficiently, especially if it is a solvent that dissolves in water. Although not limited, a high boiling point solvent having a boiling point of 120 to 250 ° C. is preferable from the viewpoint of safety because the temperature rises during kneading and the solvent is easily evaporated. Examples of water-soluble solvents include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight Examples thereof include polypropylene glycol.

  In the present invention, the pigment is preferably contained in the ink-jet ink in the range of 0.5 to 10% by weight in order to obtain a sufficient concentration and sufficient light resistance.

As the surface charge of the pigment of the present invention, any surface charge can be used as long as it can be dispersed, but the surface is preferably basic. By having a basic surface, the carboxyl group of the dispersant represented by the formula (1) is strongly adsorbed on the pigment surface, so that an inkjet ink having low viscosity and high printing stability can be obtained. Originally, pigments having a basic surface can be used as they are, but for pigments having neutral and acidic surfaces, it is preferable to use them with the surface made basic by a known treatment method.

In addition to a method of directly treating a pigment with a basic, a basic pigment derivative may be used in combination with the pigment. As the pigment derivative, a pigment derivative represented by the following general formula (2) is preferably used.
General formula (5)
P- [XYZN (R ⁴ ) R ⁵ ] _v
(Wherein, P is an organic pigment residue or heterocyclic residue, X is _{-SO 2 -, - CO 2 -} , - CH 2 -, - CH 2 S -, - CH 2 O -, - O- , -COO -, - NH- and divalent bonding group selected from the group consisting of -CH ₂ NHCOCH-, Y is a direct bond or -N (R) - (where, R represents H or a C1-18 An alkyl group or Z—N (R ⁴ ) R ⁵ ) or —O—, Z is an alkylene group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ are each independently an optionally substituted carbon atom having 1 to 18 carbon atoms. (R ⁴ and R ⁵ may form an optionally substituted ring which may further contain N, O or S), and v represents an integer of 1 to 3.)

  Specific examples of the organic dye residue P include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyrimidine, anthanthrone, indanthrone, flavan. There are throne, perinone, perylene, and thioindigo. Specific examples of the heterocyclic residue P include thiophene, furan, xanthene, pyrrole, imidazole, isoindoline, isoindolinone, benzimidazolone, indole, quinoline, carbazole, acridine, acridone, and anthraquinone. . When P is a heterocyclic ring, the pigment derivative of the general formula (5) is advantageous in terms of versatility because it is hardly colored.

As _{X, -SO 2 -, - CO} 2 -, - CH 2 -, - CH 2 S -, - CH 2 O -, - O -, - COO -, - NH- and -CH ₂ NHCOCH-, or they Among them, —SO ₂ —, —CO ₂ —, and —CH ₂ — are preferable. When R ⁴ and R ⁵ are alkyl groups, lower alkyl groups such as methyl group, ethyl group, propyl group, and butyl group are preferred. These alkyl groups may be branched within a range of up to 18 carbon atoms and may be substituted. Further, in some cases, R ⁴ and R ⁵ may be linked to form a 5-membered or 6-membered heterocyclic ring containing N, O or S.

The molecular skeleton of the organic pigment and the molecular skeleton of P in the pigment derivative do not necessarily match, but usually the same system is combined from the relationship of hue, and particularly for blue pigments, the phthalocyanine residue It is preferable to combine a quinacridone residue for the red pigment and a benzimidazole residue for the yellow pigment.
Specific examples of the pigment derivative include the following ag.

  The pigment derivative of the present invention is preferably contained in the ink in the range of 0.1 to 10% by weight. Further, these pigment derivatives may be added during the above-described pigment refining step.

  The pigment derivative of the present invention may be used when the pigment is dispersed in the form of a dry powder, or may be used by mixing with the pigment in advance. When using a solution dissolved or dispersed in a solvent or mineral acid aqueous solution, it is added to the pigment water or solvent slurry and adsorbed on the surface of the pigment, or in the case of an azo pigment during coupling, a phthalocyanine pigment, a quinacridone pigment and In the case of dioxazine pigments, etc., a pigment obtained by adding a powder, solution or dispersion of a pigment derivative during the pigmentation process such as the salt milling method and the sulfuric acid dissolution method, adsorbing it on the surface of the pigment, and drying after filtration if necessary It may be used as a composition.

  The greatest feature of the ink-jet ink of the present invention is that it contains the following vinyl pigment dispersant.

  The vinyl pigment dispersant (a) of the present invention is a carboxyl group-containing unit (G) represented by the general formula (1) in the vinyl polymer main chain (for example, in the acrylic polymer main chain). Is contained in an average of 0.3 or more and 3.0 or less per molecule of the vinyl polymer.

In general, pigment dispersants have a structure that has a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and that the performance of the dispersant is determined by the balance of these two functional sites. explained. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important. In the carboxyl group-containing unit (G) represented by the general formula (1), Y ¹ represented by the general formula (2) or the general formula (3) is directly bonded to the ring-constituting carbon atom of the aromatic ring. A plurality of carboxyl groups that are directly bonded to the ring-constituting carbon atoms of the aromatic ring serve as adsorption sites for the pigment. However, when Y ¹ has only one carboxyl group (outside the scope of the present invention), high dispersibility, fluidity, and storage stability are not exhibited, which is not preferable.

  The vinyl pigment dispersant (a) according to the present invention has an average of 0.3 to 3.0 carboxyl group-containing units (G) represented by the general formula (1) per molecule of the vinyl polymer. It is important to include: More preferably, it is 0.35 or more and 2.0 or less, and most preferably 0.4 or more and 1.5 or less. When the number is less than 0.3, the number of sites adsorbed on the pigment is small, and as a result, the dispersion ability is lowered. On the other hand, when the number is more than 3.0, there are too many sites to be adsorbed to the pigment, and conversely, the dispersibility may be lowered.

で表される基であることが好ましく、Ａ⁵〜Ａ⁷のうち１つは−ＣＯＯＲ^d（但し、Ｒ^dは、炭素原子数６〜１０の直鎖又は分岐アルキル基である）であって、他の２つは−ＣＯＯＨである組合せであることが好ましい。 In general formula (1), X ¹ is preferably —COO— from the viewpoint of reducing the viscosity of the pigment dispersion and storage stability, and R ^a1 is a hydrocarbon group having 1 to 4 carbon atoms ( For example, a methylene group, an ethylene group, a linear or branched propylene group, or a linear or branched butylene group is preferable, and m1 is preferably 1 to 10 (more preferably 1 to 3). ), R ^b1 is preferably a pentamethylene group, and m2 is preferably 0 to 5 (more preferably 0 to 3). In particular, Y ¹ is preferably a group represented by General Formula (2), and more preferably, in General Formula (2), all of A ^{1 to} A ³ are —COOH, and k is 1. Or a combination in which one of A ^{1 to} A ³ is a hydrogen atom, the other two are —COOH, and k is 1. Y ¹ can also be a group represented by the general formula (3). In this case, R ² is —COOCH ₂ CH ₂ OCO—, or a group represented by the formula:

And one of A ^{5 to} A ⁷ is —COOR ^d (where R ^d is a straight-chain or branched alkyl group having 6 to 10 carbon atoms), The other two are preferably a combination of —COOH.

〔一般式（４ｊ）中、Ｒ⁴、Ｘ⁴、Ｘ⁵、及びＸ⁶は、前記と同じ意味である〕
で表される水酸基含有単位（Ｊ）と、一般式（４ｋ）：

〔一般式（４ｋ）中、Ｒ⁵及びＲ⁶は、前記と同じ意味である〕
で表される主鎖構成単位（Ｋ）との各構成単位からなるブロック共重合体又はランダム共重合体を挙げることができる。 Examples of the vinyl pigment dispersant (a) according to the present invention include a carboxyl group-containing unit (G) represented by the general formula (1) and a general formula (4j):

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

[In General Formula (4k), R ⁵ and R ⁶ have the same meaning as described above]
The block copolymer or random copolymer which consists of each structural unit with the main chain structural unit (K) represented by these can be mentioned.

Accordingly, the preferred vinyl dispersant (a) according to the present invention is the general formula (4) or the general formula (4a):
-[G] p1- [J] p2- [K] p3- (4a)
It is a copolymer represented by these. Here, G is a carboxyl group-containing unit represented by the general formula (1), J is a hydroxyl group-containing unit represented by the general formula (4j), and K is the general formula (4k). ), P1 is 0.3 or more and 3.0 or less (preferably 0.35 or more and 2.0 or less, more preferably 0.4 or more and 1.5 or less), and p2 is 0. 180 or less (preferably 0.05 or more and 50 or less), and p3 is 6 or more and 250 or less (preferably 10 or more and 100 or less). In the general formula (4a), the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain constituent unit (K) each exist in a block copolymerization format or a random copolymerization format. Can do. Furthermore, the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain structural unit (K) can each be present in plural in the general formula (4a). In this case, each unit can be the same or different from each other. For example, the main chain structural unit (K) can include structural units having two or more structures.

In the hydroxyl group-containing unit (J) contained in the vinyl dispersant (a) according to the present invention represented by the general formula (4) or the general formula (4a), X ⁴ is preferably —COO—. R ^a2 is preferably a hydrocarbon group having 1 to 4 carbon atoms (for example, a methylene group, an ethylene group, a linear or branched propylene group or a linear or branched butylene group), m3 Is preferably 1 to 10 (more preferably 1 to 3), R ^b4 is preferably a pentamethylene group, and m4 is preferably 0 to 5 (more preferably 0 to 3).

In the vinyl pigment dispersant (a) according to the present invention represented by the general formula (4) or the general formula (4a), R ⁵ is a methyl group as the main chain constituent unit (K), and R ⁶ Preferably contains a main chain structural unit (K1) which is —CO—O—CH ₂ —Ar (wherein Ar is an aromatic group, particularly a phenyl group). The main chain constituent unit (K1) preferably has an average amount of 1 or more and 100 or less per molecule of the vinyl polymer, and the vinyl pigment dispersant (a) of this embodiment has a dispersibility. Excellent.

Furthermore, in the vinyl pigment dispersant (a) according to the present invention represented by the general formula (4) or the general formula (4a), R ⁵ is a methyl group as the main chain constituent unit (K), R ⁶ preferably includes a main chain structural unit (K2) in which —CO—O—R ⁷ (wherein R ⁷ is a linear or branched alkyl group having 2 to 10 carbon atoms). More preferably, the main chain structural unit (K2) coexists with the main chain structural unit (K1) in the vinyl pigment dispersant (a).

Furthermore, in the vinyl pigment dispersant (a) according to the present invention represented by the general formula (4) or the general formula (4a), R ⁵ is a methyl group as the main chain constituent unit (K). , R ⁶ is an aromatic group (particularly a phenyl group), the main chain structural unit (K3) alone or in combination with the main chain structural unit (K1) and / or the main chain structural unit (K2). It is preferable to include. Furthermore, as the main chain structural unit (K), a main chain structural unit (K4) in which R ⁵ is a hydrogen atom and R ⁶ is a carboxyl group is converted into the main chain structural unit (K1), main chain structural unit ( K2) and / or the main chain structural unit (K3) can be included together.

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

  The terminal of the main chain of the vinyl pigment dispersant (a) represented by the general formula (4) is a known polymerization method of an ethylenically unsaturated monomer or a structure considered in the polymerization process, for example, a polymerization initiator. It may have a chemical structure derived from an origin, a chain transfer agent, a solvent, or an ethylenically unsaturated monomer.

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

  The number average molecular weight of the vinyl pigment dispersant (a) according to the present invention is preferably 500 or more and 20000 or less, more preferably 1000 or more and 10,000 or less, and most preferably 1500 or more and 8000 or less. Even if the number average molecular weight is less than 500 or more than 20000, the dispersibility or fluidity may be lowered.

  The vinyl pigment dispersant (a) according to the present invention can be prepared by the production method according to the present invention. According to the production method of the present invention to be described later, not only the vinyl pigment dispersant (a) but also the vinyl pigment dispersant (A) having a wide structure including the vinyl pigment dispersant (a). Can be manufactured. That is, the vinyl pigment dispersant (a) according to the present invention can be prepared by selecting a specific starting material in the production method of the present invention described later.

Examples of the method for producing the vinyl pigment dispersant (A) of the present invention include the following production methods 1 to 3.
Manufacturing method 1:
(A) A step of producing an ethylenically unsaturated monomer obtained by previously reacting an ethylenically unsaturated monomer (h) having a hydroxyl group with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4). ,
(B) It comprises a step of copolymerizing the ethylenically unsaturated monomer with another ethylenically unsaturated monomer.

Manufacturing method 2:
(C) a step of copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer,
The process comprises a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) with the hydroxyl group of the copolymer.

Manufacturing method 3:
While copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer, a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) is simultaneously added to the hydroxyl group. Let it react.

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

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

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

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

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

  Further, in the method of the present invention, one acid anhydride of one molecule with respect to a tetracarboxylic acid dianhydride having two acid anhydrides per molecule in a tetracarboxylic acid anhydride (M4) described later. C1-C18 alcohol or C5-C18 cycloalcohol (for example, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched Pentanol or cyclopentanol, linear or branched hexanol or cyclohexanol, linear or branched heptanol or cycloheptanol, linear or branched octanol or cyclooctanol, linear or branched Nonanol or cyclononanol, linear or branched Decanol or cyclodecanol, linear or branched dodecanol or cyclododecanol, linear or branched myristyl alcohol or cyclomyristyl alcohol, linear or branched cetyl alcohol or cyclocetyl alcohol, linear Tetracarboxylic anhydride monoester monoanhydride that has been ring-opened in the form of a branched or branched stearyl alcohol or cyclostearyl alcohol can also be used as the tricarboxylic anhydride (M3) in the method of the present invention. In the present specification, an aliphatic tetracarboxylic acid monoester monoanhydride is an aliphatic tricarboxylic acid anhydride, an aromatic tetracarboxylic acid monoester monoanhydride is an aromatic tricarboxylic acid anhydride, a polycyclic tetracarboxylic acid anhydride. The monoester monoanhydride is described as a polycyclic tricarboxylic acid anhydride. Specific examples of these tetracarboxylic acid anhydride monoester monoanhydrides are obvious to those skilled in the art from the tetracarboxylic acid anhydrides described below.

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

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

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

Examples of the polycyclic tetracarboxylic acid anhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid anhydride and 3,4-dicarboxy-1,2,3. , 4-tetrahydro-6-methyl-1-naphthalene succinic anhydride and the like.
The tetracarboxylic acid anhydride may be either monoanhydride or dianhydride.
Among the above, it is preferable to use an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride, more preferably trimellitic acid anhydride, pyromellitic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride. 2,3,6,7-naphthalenetetracarboxylic acid anhydride is preferable, and trimellitic acid anhydride is more preferable.

The production method 1 according to the present invention will be described in more detail.
In the production method 1 of the present invention, first, Step A in which an ethylenically unsaturated monomer (h) having a hydroxyl group is reacted with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid anhydride (M4) is performed. This step A is preferably carried out at 80 ° C. to 150 ° C. by adding a polymerization inhibitor while flowing dry air into the reactor so that the monomer does not thermally polymerize. More preferably, it is 90 to 130 ° C. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

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

  When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic acid anhydride (M4) are reacted in the step A, the reaction ratio is “mole of the ethylenically unsaturated monomer (h) having a hydroxyl group”. The number / number of moles of tetracarboxylic acid anhydride (M4) ”is preferably 0.9 or more and 1.1 or less. More preferably 1. If it is less than 0.9, a large amount of tetracarboxylic acid anhydride (M4) remains, which is not preferable. If it exceeds 1.1, a compound in which an ethylenically unsaturated monomer (h) having two hydroxyl groups is added to one tetracarboxylic acid anhydride (M4) can be formed, which may cause gelation in Step B. Absent.

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

Furthermore, after reacting the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic acid anhydride (M4) at the above ratio, the acid anhydride remaining at this time is converted to water or carbon atoms of 1 to 18 carbon atoms. Ring opening with alcohol (step Aa) to facilitate removal of unnecessary tetracarboxylic anhydride (M4).
Then, in the manufacturing method 1, the process B which copolymerizes the ethylenically unsaturated monomer synthesize | combined at the process A and another ethylenically unsaturated monomer is performed.
As another ethylenically unsaturated monomer used in Step A, an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with an aromatic group, N-alkyl having 1 to 18 carbon atoms ( It is preferred that an ethylenically unsaturated monomer selected from (meth) acrylamide, styrene and an ethylenically unsaturated monomer having a hydroxyl group (h) (including those remaining in Step A) be copolymerized.

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

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

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

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

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

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

Next, the manufacturing method 2 according to the present invention will be described in detail.
In the production method 2 according to the present invention, first, the step C of copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer is performed. As another ethylenically unsaturated monomer, an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with the aromatic ring exemplified in Step B of Production Method 1 or an aromatic ring. It is preferable that an ethylenically unsaturated monomer selected from N-alkyl (meth) acrylamide having 1 to 18 carbon atoms and styrene which may be copolymerized is copolymerized.

The copolymerization ratio between the ethylenically unsaturated monomer (h) having a hydroxyl group and another ethylenically unsaturated monomer is such that one molecule after polymerization has an average of at least 0.3 to 177 hydroxyl groups. Decided to enter.
The polymerization conditions such as the type of polymerization initiator, the type of chain transfer agent, the type of solvent, the amount, and the reaction temperature in step C are preferably the same as in step B of production method 1.

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

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

Next, the manufacturing method 3 according to the present invention will be described in detail.
In the production method 3 according to the present invention, an ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, and a tricarboxylic acid anhydride (M3) or tetracarboxylic acid is added to the hydroxyl group. The acid anhydride (M4) is reacted at the same time. The reaction is preferably performed at 80 ° C. to 150 ° C. while flowing nitrogen into the reaction vessel. As a catalyst for the reaction between the hydroxyl group and the acid anhydride, the one shown in Step A of Production Method 1, the type of polymerization initiator, The polymerization conditions such as the type of chain transfer agent, the type and amount of solvent, and the reaction temperature are preferably those shown in Step B of Production Method 1.

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

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

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

  When the vinyl pigment dispersant (A) is produced by the production method of the present invention, the tricarboxylic acid anhydride (M3) or the tetracarboxylic acid anhydride (M4) to be used is selected from aromatic tricarboxylic acid anhydrides. Or aromatic tetracarboxylic acid anhydride. Of these, preferred are aromatic tricarboxylic acid anhydrides, and trimellitic acid anhydride, pyromellitic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 2,3,6,7-naphthalenetetra. Carboxylic anhydride is preferred, and most preferred is trimellitic anhydride.

  When producing the vinyl pigment dispersant (A) in any of production methods 1 to 3, the other ethylenically unsaturated monomer may have a branched chain having 1 to 12 unsubstituted carbon atoms. It is preferable that the alkyl (meth) acrylate, benzyl (meth) acrylate, and an ethylenically unsaturated monomer (h) having a hydroxyl group if necessary are copolymerized. Furthermore, 1 to 50 unsubstituted alkyl (meth) acrylates having 1 to 12 carbon atoms and 1 benzyl (meth) acrylate may be branched in one molecule of the vinyl pigment dispersant (A). It is preferred that ~ 50 are copolymerized.

  In addition, the vinyl pigment dispersant (A) of the present invention can be copolymerized with various ethylenically unsaturated monomers other than those exemplified so far as long as the pigment dispersibility is not hindered. , Ethylenically unsaturated monomers having thermally crosslinkable groups such as isocyanato groups, block isocyanate groups, alkoxysilyl groups, 3-5 membered cyclic ether groups, and ethylenically unsaturated monomers having a carboxyl group Is mentioned. However, a monomer having a carboxyl group, such as methacrylic acid or acrylic acid, is a tricarboxylic acid anhydride (M3) or tetracarboxylic acid present in the vinyl pigment dispersant (A) in any of production methods 1 to 3. From the viewpoint of pigment dispersibility (lowering viscosity and storage stability), the use range is preferably 0 to 4 times, more preferably 0 to 2 times the number of moles of the anhydride (M4).

  The vinyl pigment dispersant (a) can be prepared by the production method according to the present invention by using a starting material appropriately selected from the listed starting materials.

As the organic solvent used in the present invention, organic solvents generally used for inkjet inks can be widely used. If it supplements, if the dispersing agent shown by Formula (1) is an organic solvent which melt | dissolves or suspends uniformly, there will be no restriction | limiting in particular. Specific examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl- n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl Ketones such as ketone, cyclohexanone, methylcyclohexanone, isophorone, methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, isobutyl acetate, acetic acid Esters such as xylyl, octyl acetate, methyl lactate, propyl lactate, butyl lactate, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether , Glycols and glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene Glycol acetates such as polyglycol monomethyl ether acetate, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane, unsaturated hydrocarbons such as 1-hexene, 1-heptene and 1-octene , Cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, cyclic esters such as γ-butyrolactone, δ-valerolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, etc. Nitrogen-containing heterocycles, cyclohexene, cycloheptene, cyclooctene, cyclic unsaturated hydrocarbons such as 1,1,3,5,7-cyclooctatetraene and cyclododecene, and aromatic hydrocarbons such as benzene, toluene and xylene Etc. These organic solvents may be used alone or in combination of two or more.

  In the ink-jet ink of the present invention, a resin can be added in order to impart fixability during color development. Usable resins include petroleum resin, casein, shellac, rosin modified maleic acid resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenolic resin, alkyd resin , Polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, ethylene vinyl acetate resin, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene-maleic acid resin, styrene-acrylic resin, polyamide resin, butyral resin and the like.

  The inkjet ink of the present invention includes a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, an antioxidant, an antistatic agent, an antiblocking agent, an antifoaming agent, a viscosity modifier, a wax, a surfactant, and a leveling agent. Various additives such as can be used.

  The ink-jet ink of the present invention can also be used as a radiation curable ink containing a polymerizable monomer or oligomer and cured by ultraviolet rays or electron beams. As the monomer polymerizable by radiation of the present invention, there are two types, radical polymerization and cationic polymerization.

Specific examples of the monofunctional monomer that is cured by radical polymerization include butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, and 2-methoxyethyl. Acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, glycidyl acrylate, isobornyl acrylate, isodecyl acrylate, phenoxy methacrylate, stearyl acrylate, Tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate, 2-hydroxypro Acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, benzyl Examples include, but are not limited to, acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, and dipropylene glycol acrylate. Of these, isooctyl acrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, methylphenoxyethyl acrylate, and butoxyethyl acrylate are preferable. Furthermore, isobornyl acrylate and 2-phenoxyethyl acrylate are particularly preferable from the viewpoint of curability and compatibility as an inkjet ink. Specific examples of monofunctional monomers that cure by cationic polymerization include ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, Monomers such as octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether Vinyl ether compounds, monofunctional alicyclic epoxy, 1 although monofunctional oxetane, and the like is not limited to these. These compounds may be used alone or in combination of two or more as required.

  Specific examples of bifunctional monomers that cure by radical polymerization include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Ethoxylated 1,6-hexanediol diacrylate, propoxylated 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol diacrylate , Tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalate neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate Examples include (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, and the like. is not. Specific examples of bifunctional monomers that cure by cationic polymerization include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, butanediol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and hexane. Examples include, but are not limited to, diol divinyl ether, cyclohexane dimethanol divinyl ether, bifunctional alicyclic epoxy, bifunctional oxetane, and the like. These compounds may be used alone or in combination of two or more as required.

  Specific examples of trifunctional monomers that are cured by radical polymerization include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetra Examples thereof include, but are not limited to, methylol methane triacrylate, caprolactone-modified trimethylol propane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, and the like. Specific examples of the trifunctional monomer that cures by cationic polymerization include, but are not limited to, trimethylolpropane trivinyl ether, trifunctional alicyclic epoxy, and trifunctional oxetane. These compounds may be used alone or in combination of two or more as required.

  In the case of the radiation curable type, it is desirable to mix a photopolymerization initiator in the ink. As radical photopolymerization initiators, benzophenone, 4,4-diethylaminobenzophenone, diethylthioxanthone, 2-methyl-1- (4-methylthio) phenyl-2-morpholinopropan-1-one, 4-benzoyl-4′- Methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, bis-2,6-dimethoxybenzoyl -2,4,4-trimethylpentylphosphine oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethyl- 2-hydroxyacetophenone, 2,2-di Examples include methoxy-2-phenylacetophenone, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (morpholinophenyl) -butan-1-one. These radical photopolymerization initiators can be used alone or in combination. Examples of the photopolymerization accelerator used in combination with the radical photopolymerization initiator include p-dimethylaminobenzoic acid ethyl ester and benzyl 4-dimethylaminobenzoate. These radical photopolymerization accelerators can be used alone or in combination. In the case of a radical polymerization system, a photopolymerization initiator is not necessarily required when an electron beam is used for radiation. In the case of cationic polymerization, a cationic photopolymerization initiator is an essential component regardless of the type of radiation. Specific examples of the cationic photopolymerization initiator include arylsulfonium salt derivatives (for example, Cyracure UVI-6990, Union Carbide, Silacure). UVI-6974, Adeka optomer SP-150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172 manufactured by Asahi Denka Kogyo Co., Ltd., allyl iodonium salt derivatives (for example, RP manufactured by Rhodia) -2074), allene-ion complex derivatives (for example, Irgacure 261 manufactured by Ciba Geigy), diazonium salt derivatives, triazine initiators and other acid generators such as other halides. Examples of the photopolymerization accelerator used in combination with the cationic photopolymerization initiator include anthracene and anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd., 9,10-dibutoxyanthracene produced by Kawasaki Kasei, 10-ethoxyanthracene, 9,10-dipropoxyanthracene). These cationic photopolymerization initiators and cationic photopolymerization accelerators can be used alone or in combination.

  The inkjet ink of the present invention is obtained by dissolving or suspending the dispersant represented by the formula (1) in an organic solvent, and then adding a pigment to the organic solvent and stirring and mixing until uniform using a high speed mixer or the like. After that, it can be produced by dispersing using various dispersers such as a bead mill such as a horizontal sand mill, a vertical sand mill and an annular sand mill, a roll mill, and a medialess disperser. In addition, the pigment derivative may be used by treating it in advance by adding it during the production of the pigment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. The number average molecular weight is a polystyrene equivalent molecular weight when using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector and using THF as a developing solvent.

<< Production Example 1 >>
(1) Step (A)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 192.1 parts trimellitic anhydride, 130.4 parts 2-hydroxyethyl methacrylate, and 0.3 parts hydroquinone monomethyl ether, and dried air The ethylenically unsaturated monomer (a1) in which trimellitic acid was added to 2-hydroxyethyl methacrylate was obtained (Step A of Production Example 1).

(2) Process (B)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. 38.5 parts, benzyl methacrylate 46.1 parts, 2-hydroxyethyl methacrylate 2.2 parts, ethylenically unsaturated monomer (a1) 13.2 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2 ' -A mixed liquid in which 8 parts of azobisdiisobutyrate was uniformly mixed in advance was added dropwise over 2 hours, and then the stirring was continued at the same temperature for 3 hours to complete the reaction (Step B of Production Example 1).
Thus, the number average molecular weight is 2450, and the average number of copolymerized ethylenically unsaturated monomers (a1) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. An acrylic pigment-dispersed resin (A1) was obtained.

<< Production Example 2 >>
(1) Process (C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 40 parts, 48 parts of benzyl methacrylate, 12 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were previously mixed uniformly over 2 hours. Then, the mixture was stirred for 3 hours at the same temperature to complete the reaction (Step C of Production Example 2).
Thus, an acrylic resin intermediate (C1) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 3.5 was obtained.

(2) Process (D)
In a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of acrylic resin intermediate (C1) in solids, 2.5 parts of trimellitic anhydride, and dimethylbenzylamine 0.1 Parts were charged and reacted at 100 ° C. for 6 hours (Step D of Production Example 2).
In this way, an acrylic pigment dispersant (A2) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.5 was obtained.

<< Production Example 3 >>
Except that the amount of trimellitic anhydride charged in Step D of Production Example 2 is 3.5 parts, the average number of trimellitic acids per molecule (ie, carboxyl group) is exactly the same as in Production Example 2. An acrylic pigment dispersant (A3) having an average number of content units (G) of 0.7 was obtained.

<< Production Example 4 >>
Except that the amount of trimellitic anhydride charged in Step D of Production Example 2 is 5.1 parts, the average number of trimellitic acids per molecule (ie, carboxyl group) is exactly the same as in Production Example 2. An acrylic pigment dispersant (A4) having an average content unit (G) of 1.0 was obtained.

<< Production Example 5 >>
Except that the amount of trimellitic anhydride charged in Step D of Production Example 2 is 7.1 parts, the average number of trimellitic acids per molecule (that is, carboxyl group) is exactly the same as Production Example 2. An acrylic pigment dispersant (A5) having an average number of content units (G) of 1.4 was obtained.

<< Production Example 6 >>
Except that the amount of trimellitic anhydride charged in Step D of Production Example 2 is 10.1 parts, the average number of trimellitic acids per molecule (ie, carboxyl group) is exactly the same as in Production Example 2. An acrylic pigment dispersant (A6) having an average number of content units (G) of 2.0 was obtained.

<< Production Example 7 >>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 41.9 parts, benzyl methacrylate 50.0 parts, 2-hydroxyethyl methacrylate 6.8 parts, trimellitic anhydride 1.2 parts, methoxypropyl acetate 40 parts, and 2,2'-azobisisobutyronitrile 2 A mixed solution in which 0.0 part was uniformly mixed in advance was dropped over 2 hours, and then the stirring was continued at the same temperature for 3 hours to complete the reaction. Thus, an acrylic pigment dispersant (A7) having a number average molecular weight of 15400 and an average number of hydroxyl groups in one molecule of 1.0 was obtained.

<< Production Example 8 >>
(1) Step (A)
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 218.1 parts of pyromellitic anhydride, 130.1 parts of 2-hydroxyethyl methacrylate, and 0.3 parts of hydroquinone monomethyl ether, and dried air Was allowed to react at 100 ° C. for 5 hours to obtain ethylenically unsaturated monomer (a8 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate (Step A of Production Example 8).

(2) Process (Aa)
Adhering to the ethylenically unsaturated monomer (a8 ′) by adding 36 parts of water to the ethylenically unsaturated monomer (a8 ′) obtained in (1) above and reacting at 90 ° C. for 5 hours. The remaining acid anhydride was hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (a8) (Step Aa of Production Example 8).

(3) Process (B)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. 84.6 parts, benzyl methacrylate 46.1 parts, 2-hydroxyethyl methacrylate 0.7 parts, ethylenically unsaturated monomer (a8) 14.7 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2 ' -A mixed solution in which 6 parts of azobisdiisobutyrate was uniformly mixed in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Step B of Production Example 8).
Thus, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (a8) per molecule (that is, the average number of carboxyl group-containing units (G)) is 0.5. An acrylic pigment-dispersed resin (A8) was obtained.

<< Production Example 9 >>
(1) Process (C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., the inside of the reaction vessel was purged with nitrogen, and then 2-ethylhexyl methacrylate was added from the dropping vessel. 30.0 parts, 68.3 parts of benzyl methacrylate, 1.7 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were previously mixed uniformly. The liquid was added dropwise over 2 hours, and then the reaction was continued at the same temperature for 3 hours to complete the reaction (Step C of Production Example 9). Thus, an acrylic resin intermediate (C2) having a number average molecular weight of 4800 and an average number of hydroxyl groups in one molecule of 0.5 was obtained.

(2) Process (D)
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade and a thermometer was charged with 100 parts of methoxypropyl acetate, 4.3 parts of ethylene glycol ditrimellitic anhydride ester and 0.1 part of dimethylbenzylamine, and 100 ° C. The temperature was raised to. 100 parts (solid content) of acrylic resin intermediate (C2) was dropped from the dropping tank into the reaction tank over 2 hours, and after completion of the appropriate condition, the mixture was reacted at 100 ° C. for 4 hours (Step D of Production Example 9).

(3) Process (Dd)
Thereafter, 10 parts of 2-ethylhexyl alcohol was added and reacted at 90 ° C. for 5 hours to decompose the remaining anhydrous ring with alcohol (Step Dd of Production Example 9), and the average number of copolymerized ethylene glycol ditrimellitic acid skeletons (ie, An acrylic pigment dispersion resin (A9) having an average number of carboxyl group-containing units (G) of 0.5 was obtained.

<< Production Example 10 >>
In Step D of Production Example 9, except that 6.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluoric acid anhydride was used instead of 4.8 parts of ethylene glycol ditrimellitic anhydride ester Is the same method as in Production Example 9, and the average number of 9,9-bis (3,4-dicarboxyphenyl) fluorene per molecule (that is, the average number of carboxyl group-containing units (G)) is 0. Five acrylic pigment dispersion resins (A10) were obtained.

<< Production Example 11 >>
(1) Process (C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. 21.2 parts, 30.0 parts of 2-ethylhexyl methacrylate, 30 parts of benzyl methacrylate, 10 parts of styrene, ethyl ester having a hydroxyl group obtained by adding 2 mol of ε-caprolactone to 1 mol of 2-hydroxyethyl methacrylate Unsaturated monomer; Daicel Chemical Industries, Ltd.) 8 parts, acrylic acid 0.8 part, methoxypropyl acetate 40 parts, and dimethyl-2,2′-azobisdiisobutyrate 5 parts mixed in advance The solution was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Production Example 1). Step C). Thus, an acrylic resin intermediate (C3) having a number average molecular weight of 5500 and an average number of hydroxyl groups in one molecule of 1.2 was obtained.

(2) Process (D)
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 100 parts of an acrylic resin intermediate (C3) (solid content), 3.5 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine And reacted at 100 ° C. for 6 hours (Step D of Production Example 11). In this way, an acrylic pigment dispersant (A11) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained.

<< Production Example 12 >>
(1) Process (C)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. , 30 parts of lauryl methacrylate, 30 parts of benzyl methacrylate, 10 parts of styrene, BLEMMER AE-200 (ethylenically unsaturated monomer having an average of 3.5 moles of ethylene oxide added to 1 mole of 2-hydroxyethyl acrylate) Manufactured by Nippon Oil & Fats Co., Ltd.) 8 parts, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were mixed in advance over 2 hours, and then dropped for 3 hours. Stirring was continued at the same temperature to complete the reaction (Step C of Production Example 12). Thus, an acrylic resin intermediate (C4) having a number average molecular weight of 4400 and an average number of hydroxyl groups in one molecule of 1.3 was obtained.

(2) Process (D)
In a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts (solid content) of an acrylic resin intermediate (C4), 4.4 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine And reacted at 100 ° C. for 6 hours (Step D of Production Example 12). In this way, an acrylic pigment dispersant (A12) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained.

<< Production Example 13 >>
(1) Process (C)
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. , Isobutyl methacrylate 37.6, lauryl methacrylate 30 parts, benzyl methacrylate 10 parts, N-hydroxyethylacrylamide (manufactured by Kojin Co., Ltd.) 2.4 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2′-azobis (2 -Methylpropionate) A mixed solution in which 6 parts was previously mixed uniformly was dropped over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Step C of Production Example 13). Thus, an acrylic resin intermediate (C5) having a number average molecular weight of 4900 and an average number of hydroxyl groups in one molecule of 1.0 was obtained.
(2) Process (D)
In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts (solid content) of an acrylic resin intermediate (C5), 3.9 parts of trimellitic anhydride, and dimethylbenzylamine 0.1 Parts were charged and reacted at 100 ° C. for 6 hours (Step D of Production Example 13). In this way, an acrylic pigment dispersant (A13) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained.

  As described above, the acrylic pigment dispersant (a) of the present invention is a tricarboxylic acid anhydride (M3) or tetracarboxylic acid anhydride (M4) and ethylene having a hydroxyl group in the same manner as in Production Examples 1 to 13. It can manufacture by making a reactive unsaturated monomer (h) and another ethylenically unsaturated monomer react by the method in any one of the manufacturing methods 1-3.

<< Comparative Example 1 >>
Except that the amount of trimellitic anhydride charged in Step D of Production Example 2 is 0.5 parts, the average number of trimellitic acids per molecule (ie, carboxyl group) is exactly the same as in Production Example 2. An acrylic resin (B1) having an average content unit (G) of 0.1 was obtained.

<< Comparative Example 2 >>
Except that the amount of trimellitic anhydride charged in Step D of Production Example 2 is 17.7 parts, the average number of trimellitic acids per molecule (that is, carboxyl group) is exactly the same as Production Example 2. An acrylic resin (B2) having an average number of content units (G) of 3.5 was obtained.

<< Comparative Example 3 >>
100 parts of the acrylic resin intermediate (C1) obtained in Production Example 2 in solid content, 2.7 parts of succinic anhydride, and a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and 0.1 part of dimethylbenzylamine was charged and reacted at 100 ° C. for 6 hours. In this way, an acrylic resin (B3) having an average number of succinic acids per molecule of 1.0 was obtained.

<< Comparative Example 4 >>
100 parts of the acrylic resin intermediate (C1) obtained in Production Example 2 in solid content, 3.9 parts of phthalic anhydride, and a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and 0.1 part of dimethylbenzylamine was charged and reacted at 100 ° C. for 6 hours. Thus, an acrylic resin (B4) having an average number of phthalic acids per molecule of 1.0 was obtained.

<< Comparative Example 5 >>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 40 parts, 50 parts of benzyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate are mixed uniformly in advance. Was added dropwise over 2 hours, followed by stirring at the same temperature for 3 hours to complete the reaction. Thus, an acrylic resin (B5) having a number average molecular weight of 4000 was obtained.

<< Comparative Example 6 >>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 60 parts of methoxypropyl acetate, heated to 110 ° C., and the inside of the reaction vessel was purged with nitrogen. 10 parts of isobutyl methacrylate, 18 parts of dodecyl methacrylate, 3 parts of 2-hydroxyethyl methacrylate, 1 part of methacrylic acid, 4 parts of methacrylsulfoethyl, 40 parts of methoxypropyl acetate, and dimethyl-2,2′-azobisdiisobutyrate A mixed solution in which 6 parts were uniformly mixed in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction. In this manner, an acrylic resin (B6) having a number average molecular weight of 4400 was obtained. Only the acrylic resin (B6) solution was turbid.

Further, the pigment derivatives represented by the general formula (5) were obtained by synthesizing those having properties as shown in Table 2 below by known methods.

Next, pigment dispersions A to S were prepared by blending as shown in Table 3 below. These dispersions were charged with a pigment, a pigment derivative, and a dispersion resin in an organic solvent, stirred until uniform using a high speed mixer or the like, and then the obtained mill base was dispersed in a horizontal sand mill for about 1 hour.

Abbreviations in Table 3 E5B02 ... Clariant quinacridone pigment, Hostaperm Red E5B02
FG7351 ・ ・ ・ Phthalocyanine pigment manufactured by Toyo Ink, Lionol Blue FG-7351
R960 ・ ・ ・ Titanium oxide pigment made by Dupont, Taipure R960
BGAc ... ethylene glycol monobutyl ether acetate

The pigment dispersion A was converted into an ink with the following formulation to obtain an inkjet ink.
Pigment dispersion A 35.0 parts Vinyl resin VYHD (vinyl chloride resin made by Dow Chemicals) 3.0 parts Cyclohexanone 20.0 parts Diethylene glycol monobutyl ether acetate 10.0 parts Ethylene glycol monobutyl ether acetate 32. 0 copies

Ink jet ink was obtained with the same formulation except that pigment dispersion A was changed to pigment dispersion B in Example 1.

Inkjet ink was obtained with the same formulation except that Pigment Dispersion A was changed to Pigment Dispersion C in Example 1.

Pigment dispersion D 20.0 parts Vinyl resin VYHD (vinyl chloride resin made by Dow Chemicals) 4.5 parts Cyclohexanone 20.0 parts Diethylene glycol monobutyl ether acetate 10.0 parts Ethylene glycol monobutyl ether acetate 45. 5 copies

Inkjet ink was obtained in the same formulation except that the pigment dispersion D was changed to the pigment dispersion E in Example 4.

In Example 4, except that the pigment dispersion D was changed to the pigment dispersion F, an inkjet ink was obtained with the same formulation.

Inkjet ink was obtained with the same formulation except that the pigment dispersion D was changed to the pigment dispersion G in Example 4.

-Pigment dispersion H 50.0 parts-Vinyl resin VYHD (Chloroacetate resin made by Dow Chemicals) 2.0 parts-Cyclohexanone 20.0 parts-Diethylene glycol monobutyl ether acetate 10.0 parts-Ethylene glycol monobutyl ether acetate 18.0 parts

Inkjet ink was obtained with the same formulation as in Example 8, except that Pigment Dispersion H was changed to Pigment Dispersion I.

In Example 8, except that the pigment dispersion H was changed to the pigment dispersion J, an inkjet ink was obtained with the same formulation.

  In Example 8, an ink-jet ink was obtained with the same formulation except that the pigment dispersion H was changed to the pigment dispersion K.

・ Pigment dispersion L 35.0 parts ・ Vinyl resin VMCA (vinyl chloride resin made by Dow Chemicals) 3.0 parts ・ Gamma butyrolactone 10.0 parts ・ Diethylene glycol diethyl ether 52.0 parts

・ Pigment dispersion M 20.0 parts ・ Vinyl resin VYHD (Chloro-acetate resin made by Dow Chemicals) 5.0 parts ・ Gamma butyrolactone 10.0%
・ Diethylene glycol diethyl ether 65.0 parts
[Comparative Example 1]

Inkjet ink was obtained with the same formulation except that pigment dispersion A was changed to pigment dispersion N in Example 1.
[Comparative Example 2]

Ink jet ink was obtained in the same formulation as in Example 4, except that Pigment Dispersion D was changed to Pigment Dispersion O.
[Comparative Example 3]

Inkjet ink was obtained with the same formulation except that Pigment Dispersion A was changed to Pigment Dispersion P in Example 1.
[Comparative Example 4]

Inkjet ink was obtained in the same formulation except that the pigment dispersion D was changed to the pigment dispersion Q in Example 4.
[Comparative Example 5]

Inkjet ink was obtained with the same formulation except that pigment dispersion A was changed to pigment dispersion R in Example 1.
[Comparative Example 6]

In Example 4, except that the pigment dispersion D was changed to the pigment dispersion S, an inkjet ink was obtained with the same formulation.

As a measure of dispersibility for the inkjet inks of Examples 1 to 13 and Comparative Examples 1 to 6, (1)
(2) Viscosity was measured as a measure of dispersed particle size and fluidity, and (3) discharge state was evaluated as a measure of printing stability.

(1) Dispersed particle size: The ink-jet ink was diluted 200 to 1000 times with ethyl acetate and measured with a particle size distribution meter Microtrac UPA (Nikkiso Co., Ltd.).
(2) Viscosity: The inkjet ink was adjusted to 25 ° C. and measured with an E-type viscometer RE80 (manufactured by Toki Sangyo Co., Ltd.).
(3) Printing stability: The inkjet ink was printed with a large-format inkjet printer IP6600 (manufactured by Seiko I Infotech), and the printing state of the nozzle check pattern was observed. A print defect such as nozzle missing or bending is 1% or less, and 1 to 10% is Δ, and a print defect more than that is ×.
The evaluation results are shown in Table 4 below.

The ink-jet inks of Examples 1 to 13 showed values suitable for the ink-jet ink in terms of viscosity and dispersed particle diameter, and as a result showed excellent printing stability. On the other hand, Comparative Examples 1, 5, and 6 were high in viscosity and sometimes had a large dispersed particle size, and thus could hardly be ejected from the printer head. Comparative Examples 2 to 4 were able to be ejected, but due to their high viscosity, there were very many ejection defects.

Claims (6)

In the vinyl polymer main chain, the general formula (1):

{In General Formula (1), R ¹ is a hydrogen atom or a methyl group;
X ¹ is —O— or —NH—.
X ² is a general formula:
-(-R ^a1 -O-) _m1-
(Wherein R ^a1 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m1 is an integer of 1 to 50)
A group represented by
X ³ is a general formula:
-(-CO-R ^b1 -O-) _m2-
(R ^b1 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m2 is an integer of 0 to 20)
A group represented by
Y ¹ represents the general formula (2):

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

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

Or a group represented by the formula:

Is a group represented by
A vinyl pigment dispersant containing a carboxyl group-containing unit (G) represented by an average amount of 0.3 to 3.0 per molecule of the vinyl polymer;
Pigments,
A non-aqueous ink-jet ink comprising a liquid vehicle. The non-aqueous inkjet ink according to claim 1, wherein the liquid vehicle is an organic solvent in which a resin is dissolved. The non-aqueous inkjet ink according to claim 1 or 2, wherein Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is a group represented by the general formula (2). 4. The combination according to claim 1, wherein one of A ^{1 to} A ^{3 in} the general formula (2) is a hydrogen atom and the other two are —COOH groups. 5. Water-based inkjet ink. General formula (4):

[In general formula (4),
G represents a carboxyl group-containing unit (G) represented by the general formula (1) according to claim 1,
R ⁴ represents a hydrogen atom or a methyl group,
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ is an aromatic group, or —CO—X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or a straight chain having 1 to 18 carbon atoms. A branched or branched alkyl group, and R ⁷ can have an aromatic group as a substituent).
X ⁴ is —COO—, —CONH—, —O—, —OCO— or —CH ₂ O—;
X ⁵ is the formula:
-(-R ^a2 -O-) _m3- ,
(Wherein R ^a2 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m3 is an integer of 1 to 50)
A group represented by
X ⁶ is the formula:
-(-CO-R ^b4 -O-) _m4-
(Wherein R ^b2 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20)
A group represented by
The carboxyl group-containing unit (G) in the general formula (4), a hydroxyl group-containing unit (J) containing —C (═O) —X ⁴ —X ⁵ —X ⁶ —H, and —C (R 5) (R 6 )-Containing main chain structural units (K) can be included in random or block form,
When the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), and the main chain constituent unit (K) contained in the general formula (4) are present in a plurality, P1, p2 and p3 represent the average number of each structural unit per molecule of the vinyl pigment dispersant, p1 is 0.3 or more and 3.0 or less, and p2 is 0 to 180 and p3 is 6 to 250]
The non-aqueous inkjet ink of any one of Claims 1 thru | or 4 shown by these. The non-aqueous inkjet ink according to any one of claims 1 to 5, wherein the number average molecular weight is 500 or more and 20000 or less.