JP2008266534A - Colored composition for printing and color filter substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition which is able to suppress the dry condition of a coated film and to form a precision pattern and have a long retention time of transcription properties. <P>SOLUTION: The colored composition 9 comprises a vinylic dispersing agent containing 0.3-3.0 carboxylic group-containing units (G) expressed by general formula (1) (wherein Y<SP>1</SP>expresses a carboxyl group-containing aromatic compound) per one molecule of a vinyl polymer in the main chain of the vinyl polymer, a pigment and a leveling agent. The color filter substrate carrys a printed layer by the coloring composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

 The present invention relates to a coloring composition used for forming various fine coloring patterns. In more detail, this invention relates to the coloring composition used for formation of the various fine coloring pattern by printing.

 A fine colored pattern formed by various methods using a colored composition is widely used in various fields such as electronics. For example, a coloring pattern used for a liquid crystal color display is applied with an active energy ray-curable coloring composition containing an alkali-soluble resin, a photopolymerizable compound, and a colorant by a spin coater, and then subjected to exposure and alkali development. It is formed by a photolithography method.

 However, patterning by the photolithographic method involves many steps because cleaning, coating, exposure, development, and heat treatment are repeated for each pattern such as black, red, green, and blue. There is a problem that it is difficult to perform proper patterning.

In recent years, patterning has been performed by innovative methods for low cost, large size, and high precision by various methods developed from conventional printing technology. For example, in order to form a pattern such as black, red, green, blue, etc., a method of forming a pattern on a substrate using a relief plate, or after forming a pattern on an intaglio plate, a plurality of patterns are formed on the same substrate via a blanket. The method of transferring the images in an overlapping manner is efficient. These methods are different from the photolithographic method, but the process is short. It has been a problem that the pattern shape is lowered, for example, the linearity of the film is lowered. In addition, when transferring multiple inks on the same substrate, there is a waiting time until the transfer process on the blanket. There was a case.
JP-A-6-238877 JP-A-4-45175

 Then, an object of this invention is to provide the coloring composition which can control the dry state of an ink coating film, and can form a precise pattern with long transferability duration.

The above problem can be solved by the coloring composition for printing of the present invention.

The coloring composition for printing according to the present invention is a coloring composition for printing comprising a vinyl dispersant comprising a vinyl polymer, a pigment, and a leveling agent,
The vinyl polymer main chain (A) contains 0.3 to 3.0 average carboxyl group-containing units (G) represented by the following general formula (1) per molecule of the vinyl polymer. It is a coloring composition for printing characterized by including in the following amounts.

 General formula (1)

Ｘ²は、一般式：−（−Ｒ^a1−Ｏ−）_m1− で表される基であり、
（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。）
Ｘ³は、一般式：−（−Ｃ（＝Ｏ）−Ｒ^b1−Ｏ−）_m2− で表される基であり、
（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。）
Ｙ¹は、下記一般式（２）で表される基であるか、あるいは下記一般式（３）で表される基である。

一般式（２）

X ² is a group represented by the general formula: — (— R ^a1 —O—) _m1 −,
(In the formula, 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.)
X ³ is a group represented by the general formula: — (— C (═O) —R ^b1 —O—) _m2 −,
( ^Rb1 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.)
Y ¹ is a group represented by the following general formula (2) or a group represented by the following general formula (3).

General formula (2)

〔一般式（２）中、
（ｉ）Ａ¹〜Ａ³のうちの１つが水素原子であって、他の２つは−Ｃ（＝Ｏ）ＯＨである組合せであるか、
（ii）Ａ¹〜Ａ³のうちの１つが−Ｃ（＝Ｏ）ＯＲ^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−Ｃ（＝Ｏ）ＯＨである組合せであるか、
（iii）Ａ¹〜Ａ³のうちの１つが下記一般式（２ａ）で表される基であって、他の２つは−Ｃ（＝Ｏ）ＯＨである組合せであるか、あるいは、
（iv）Ａ¹〜Ａ³の３つが−Ｃ（＝Ｏ）ＯＨであり、ｋは１又は２である。〕
一般式（２ａ）

[In general formula (2),
(I) a combination in which one of A ^{1 to} A ³ is a hydrogen atom and the other two are —C (═O) OH;
(Ii) One of A ^{1 to} A ³ is —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Iii) ^{one of} A ^{1 to} A ³ is a group represented by the following general formula (2a), and the other two are a combination of —C (═O) OH, or
(Iv) ^Three of A ^{1 to} A ³ are —C (═O) OH, and k is 1 or 2. ]
General formula (2a)

〔一般式（２ａ）中、
Ｘ²¹は、−Ｃ（＝Ｏ）Ｏ−、−Ｃ（＝Ｏ）ＮＨ−、−Ｏ−、−ＯＣ（＝Ｏ）−若しくは−ＣＨ₂Ｏ−であり、
Ｘ²²は、一般式：−（−Ｒ^a21−Ｏ−）_m21− で表される基であり、
（式中、Ｒ^a21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ｍ２１は１〜５０の整数である。）
Ｘ²³は、一般式：−（−Ｃ（＝Ｏ）−Ｒ^b21−Ｏ−）_m22− で表される基であり、
（Ｒ^b21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ｍ２２は０〜２０の整数である。）
Ｚ²¹は、下記一般式（２１）で表される基を含むビニル系重合体主鎖（Ｂ）であって、ビニル系重合体主鎖（Ａ）とビニル系重合体主鎖（Ｂ）とは同一の主鎖であるか、あるいは、それぞれ別の主鎖であることができる。〕
一般式（２１）

[In general formula (2a),
X ²¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ²² is a group represented by the general formula: — (— R ^a21 —O—) _m21 −.
(In the formula, R ^a21 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m21 is an integer of 1 to 50.)
X ²³ is a group represented by the general formula: — (— C (═O) —R ^b21 —O—) _m22 −,
(R ^b21 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m22 is an integer of 0 to 20.)
Z ²¹ is a vinyl polymer main chain (B) containing a group represented by the following general formula (21), wherein the vinyl polymer main chain (A) and the vinyl polymer main chain (B) Can be the same main chain, or each can be a different main chain. ]
Formula (21)

（一般式（２１）中、Ｒ²¹は水素原子又はメチル基である。）

一般式（３）

(In the general formula (21), R ²¹ is a hydrogen atom or a methyl group.)

General formula (3)

〔一般式（３）中、
（v）Ａ⁵〜Ａ⁷のうち１つは水素原子であって、他の２つは−Ｃ（＝Ｏ）ＯＨである組合せであるか、
（vi）Ａ⁵〜Ａ⁷のうち１つは−Ｃ（＝Ｏ）ＯＲ^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−Ｃ（＝Ｏ）ＯＨである組合せであるか、
（vii）Ａ⁵〜Ａ⁷のうちの１つが下記一般式（３ａ）で表される基であって、他の２つは−Ｃ（＝Ｏ）ＯＨである組合せであるか、あるいは、
（viii）Ａ⁵〜Ａ⁷の３つが−Ｃ（＝Ｏ）ＯＨであり、
Ｒ²は、直接結合、−ＣＨ₂−、−Ｏ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）−、−Ｃ（＝Ｏ）ＯＣＨ（ＯＣ（＝Ｏ）ＣＨ₃）ＣＨ₂ＯＣ（＝Ｏ）−、−ＳＯ₂−、−Ｃ（ＣＦ₃）₂−、
下記式（８１）で表される基、又は下記式（８２）で表される基である。〕
一般式（３ａ）

[In general formula (3),
(V) one of A ^{5 to} A ⁷ is a hydrogen atom and the other two are a combination of —C (═O) OH;
(Vi) one of A ^{5 to} A ⁷ is —C (═O) OR ^d (where R ^d is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Vii) one of A ^{5 to} A ⁷ is a group represented by the following general formula (3a) and the other two are a combination of —C (═O) OH, or
(Viii) three of A ^{5 to} A ⁷ are —C (═O) OH;
R ² is a direct bond, —CH ₂ —, —O—, —C (═O) —, —C (═O) OCH ₂ CH ₂ OC (═O) —, —C (═O) OCH (OC (═O) CH ₃ ) CH ₂ OC (═O) —, —SO ₂ —, —C (CF ₃ ) ₂ —,
The group represented by the following formula (81) or the group represented by the following formula (82). ]
General formula (3a)

〔一般式（３ａ）中、
Ｘ³¹は、−Ｃ（＝Ｏ）Ｏ−、−Ｃ（＝Ｏ）ＮＨ−、−Ｏ−、−ＯＣ（＝Ｏ）−若しくは−ＣＨ₂Ｏ−であり、
Ｘ³²は、一般式−（−Ｒ^a31−Ｏ−）_m31− で表される基であり、
（式中、Ｒ^a31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ｍ３１は１〜５０の整数である。）
Ｘ³³は、一般式−（−Ｃ（＝Ｏ）−Ｒ^b31−Ｏ−）_m32− で表される基であり、
（Ｒ^b31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ｍ３２は０〜２０の整数である。）
Ｚ³¹は、下記一般式（３１）で表される基を含むビニル系重合体主鎖（Ｃ）であって、ビニル系重合体主鎖（Ａ）とビニル系重合体主鎖（Ｃ）とは同一の主鎖であるか、あるいは、それぞれ別の主鎖であることができる。〕
一般式（３１）

[In general formula (3a),
X ³¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ³² is a group represented by the general formula — (— R ^a31 —O—) _m31 −;
(In the formula, R ^a31 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m31 is an integer of 1 to 50.)
X ³³ has the general formula - (- C (= O) -R b31 -O-) m32 - with a group represented by
(R ^b31 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m32 is an integer of 0 to 20.)
Z ³¹ is a vinyl polymer main chain (C) containing a group represented by the following general formula (31), the vinyl polymer main chain (A), the vinyl polymer main chain (C), Can be the same main chain, or each can be a different main chain. ]
General formula (31)

（一般式（３１）中、Ｒ³¹は水素原子又はメチル基である。）

式（８１）

(In the general formula (31), R ³¹ is a hydrogen atom or a methyl group.)

Formula (81)

式（８２）

Formula (82)

｝
本発明による着色組成物の好ましい態様においては、一般式（１）で示されるカルボキシル基含有単位（Ｇ）のＹ¹が、Ａ¹〜Ａ³が組合せ（ｉ）である一般式（２）で表される基であるか、あるいは、Ａ⁵〜Ａ⁷が組合せ（ｖ）である一般式（３）で表される基であるビニル系分散剤を含む。

}
In a preferred embodiment of the coloring composition according to the present invention, Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is represented by the general formula (2) in which A ^{1 to} A ³ are the combination (i). Or a vinyl dispersant which is a group represented by the general formula (3) in which A ^{5 to} A ⁷ are a combination (v).

In another preferred embodiment of the coloring composition according to the present invention, Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is represented by the general formula (2) in which A ^{1 to} A ³ are a combination (iii). Or a vinyl dispersant which is a group represented by the general formula (3) in which A ^{5 to} A ⁷ are a combination (vii).

In still another preferred embodiment of the coloring composition according to the present invention, a vinyl dispersant in which Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is a group represented by the general formula (2). including.

In still another preferred embodiment of the colored composition according to the present invention, Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is a group represented by the general formula (2).

 General formula (4):

〔一般式（４）中、
Ｇは、上記一般式（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−Ｃ（＝Ｏ）−Ｘ⁷−Ｒ⁷であり（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、Ｒ⁷は、置換基として芳香族基を有していることができる。）、
Ｘ⁴は、−Ｃ（＝Ｏ）Ｏ−、−Ｃ（＝Ｏ）ＮＨ−、−Ｏ−、−ＯＣ（＝Ｏ）−若しくは−ＣＨ₂Ｏ−であり、
Ｘ⁵は、式：−（−Ｒ^a2−Ｏ−）_m3− で表される基であり、
（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。）
Ｘ⁶は、式：−（−Ｃ（＝Ｏ）−Ｒ^b2−Ｏ−）_m4− で表される基であり、
（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。）
Ｉは、下記一般式（５１）、下記一般式（５２）、下記一般式（５３）、下記一般式（５４）、又は、下記一般式（５５）で表される基で表される架橋性官能基含有単位（Ｉ）を示し、
ｐ１、ｐ２、ｐ３、及びｐ４はビニル系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以下であり、
ｐ４は０以上１８０以下である。
一般式（４）中のカルボキシル基含有単位（Ｇ）、−Ｘ⁴−Ｘ⁵−Ｘ⁶−Ｈを含む水酸基含有単位（Ｊ）、−Ｃ（Ｒ⁵）（Ｒ⁶）−を含む主鎖構成単位（Ｋ）、及び架橋性官能基含有単位（Ｉ）の配置は、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）中に含まれているカルボキシル基含有単位（Ｇ）、水酸基含有単位（Ｊ）、主鎖構成単位（Ｋ）、及び架橋性官能基含有単位（Ｉ）は、一般式（４）で表されるビニル系重合体主鎖において、任意の順序で含まれていることを示し、更に、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る。
〕

一般式（５１）：

[In general formula (4),
G represents a carboxyl group-containing unit (G) represented by the general formula (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 —C (═O) —X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or the number of carbon atoms. 1 to 18 linear or branched alkyl groups, and R ⁷ may have an aromatic group as a substituent).
X ⁴ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ⁵ is a group represented by the formula: — (— R ^a2 —O—) _m3 −;
(In the formula, 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.)
X ⁶ is a group represented by the formula: — (— C (═O) —R ^b2 —O—) _m4 −,
(In the formula, R ^b2 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20.)
I is a crosslinkability represented by a group represented by the following general formula (51), the following general formula (52), the following general formula (53), the following general formula (54), or the following general formula (55). A functional group-containing unit (I),
p1, p2, p3, and p4 represent the average number of each structural unit per molecule of the vinyl-based dispersant,
p1 is 0.3 or more and 3.0 or less,
p2 is 0 or more and 180 or less,
p3 is 6 or more and 250 or less,
p4 is 0 or more and 180 or less.
A main chain containing a carboxyl group-containing unit (G) in formula (4), a hydroxyl group-containing unit (J) containing —X ⁴ —X ⁵ —X ⁶ —H, and —C (R ⁵ ) (R ⁶ ) —. The arrangement of the structural unit (K) and the crosslinkable functional group-containing unit (I) can be included in a random type or a block type,
The carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) contained in the general formula (4) are represented by the general formula (4 In the vinyl polymer main chain represented by (1), it is indicated that they are contained in an arbitrary order, and when they are present in plural, they can be the same or different from each other.
]

General formula (51):

〔式中、Ｒ⁵¹は水素原子又はメチル基であり、
Ｔ¹は、下記式（８３）、式（８４）、又は式（８５）で表される基であり、
式（８３）

[Wherein R ⁵¹ represents a hydrogen atom or a methyl group;
T ¹ is a group represented by the following formula (83), formula (84), or formula (85);
Formula (83)

式（８４）

Formula (84)

式（８５）

Formula (85)

（Ｒ^a51及びＲ^b51は、それぞれ、炭素数１〜８の直鎖状若しくは分岐状のアルキレン基である。）
Ｔ²は、下記式（８６）、式（８７）、又は式（８８）で表される基である。
式（８６）

(R ^a51 and R ^b51 are each a linear or branched alkylene group having 1 to 8 carbon atoms.)
T ² is a group represented by the following formula (86), formula (87), or formula (88).
Formula (86)

（Ｒ^c51及びＲ^d51は、それぞれ、炭素数１〜８の直鎖状若しくは分岐状のアルキレン基であるか、又は、Ｒ^c51とＲ^d51とが一体となって炭素数３〜８の環状構造を表す。）
式（８７）

(R ^c51 and R ^d51 are each a linear or branched alkylene group having 1 to 8 carbon atoms, or R ^c51 and R ^d51 are integrated to form a cyclic structure having 3 to 8 carbon atoms. Represents.)
Formula (87)

（Ｒ^e51、Ｒ^f51、及びＲ^g51は、それぞれ、水素原子又は炭素数１〜８の直鎖状若しくは分岐状のアルキレン基である。）
式（８８）

(R ^e51 , R ^f51 , and R ^g51 are each a hydrogen atom or a linear or branched alkylene group having 1 to 8 carbon atoms.)
Formula (88)

（ｎ５１は、１〜８の整数である。）
〕
一般式（５２）：

(N51 is an integer of 1-8.)
]
Formula (52):

〔式中、Ｒ⁵²は水素原子又はメチル基であり、
Ｒ^a52は、炭素数１〜８の直鎖状若しくは分岐状のアルキレン基であり、
Ｒ^b52は、炭素数１〜８の直鎖状若しくは分岐状のアルキル基である。〕
一般式（５３）：

[Wherein R ⁵² represents a hydrogen atom or a methyl group;
R ^a52 is a linear or branched alkylene group having 1 to 8 carbon atoms,
R ^b52 is a linear or branched alkyl group having 1 to 8 carbon atoms. ]
Formula (53):

〔式中、Ｒ⁵³は水素原子又はメチル基である。〕
一般式（５４）：

[Wherein, R ⁵³ represents a hydrogen atom or a methyl group. ]
Formula (54):

〔式中、Ｒ⁵⁴及びＲ^c54は、それぞれ、水素原子又はメチル基であり、
Ｒ^a54及びＲ^b54は、それぞれ、炭素数１〜８の直鎖状若しくは分岐状のアルキレン基である。〕
一般式（５５）：

[ ^Wherein , R ⁵⁴ and R ^c54 each represent a hydrogen atom or a methyl group,
R ^a54 and R ^b54 are each a linear or branched alkylene group having 1 to 8 carbon atoms. ]
Formula (55):

〔式中、Ｒ⁵⁵及びＲ^d55は、それぞれ、水素原子又はメチル基であり、
Ｘ^a55は、−Ｃ（＝Ｏ）Ｏ−、−Ｃ（＝Ｏ）ＮＨ−、−Ｏ−、−ＯＣ（＝Ｏ）−若しくは−ＣＨ₂Ｏ−であり、
Ｘ^b55は、式：−（−Ｒ^b55−Ｏ−）_m55− で表される基であり、
（式中、Ｒ^b55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ｍ５５は１〜５０の整数である。）
Ｘ^c55は、式：−（−Ｃ（＝Ｏ）−Ｒ^c55−Ｏ−）_n55− で表される基であり、
（式中、Ｒ^c55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ｎ５５は０〜２０の整数である。）
Ｔ⁵は、下記式（８９）、式（９０）、又は式（９１）で表される基である。
式（８９）

[ ^Wherein , R ⁵⁵ and R ^d55 each represent a hydrogen atom or a methyl group,
X ^a55 is —C (═O) O—, —C (═O) ^NH— , ^—O— , —OC (═O) — or —CH ₂ O—,
X ^b55 is a group represented by the formula: — (— R ^b55 —O—) _m55 −;
(In the formula, R ^b55 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m55 is an integer of 1 to 50.)
X ^c55 is a group represented by the formula: — (— C (═O) —R ^c55 —O—) _n55 —,
( ^Wherein R ^c55 is a linear or branched alkylene group having 4 to 8 carbon atoms, and n55 is an integer of 0 to 20)
T ⁵ is a group represented by the following formula (89), formula (90), or formula (91).
Formula (89)

式（９０）

Formula (90)

式（９１）

Formula (91)

（Ｒ^e55、Ｒ^f55は、それぞれ、炭素数１〜８の直鎖状若しくは分岐状のアルキレン基である。）〕
本発明による着色組成物の更に別の好ましい態様においては、ビニル系分散剤の数平均分子量が５００以上４００００以下である。

(R ^e55 and R ^f55 are each a linear or branched alkylene group having 1 to 8 carbon atoms.)]
In still another preferred embodiment of the colored composition according to the present invention, the vinyl dispersant has a number average molecular weight of 500 or more and 40000 or less.

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(A) 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 dianhydride (M4) is produced. Process,
(B) It is manufactured by a manufacturing method including a step of copolymerizing the ethylenically unsaturated monomer obtained in step (A) with another ethylenically unsaturated monomer.

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(C) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer,
(D) It is manufactured by a manufacturing method including a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) with a hydroxyl group of the copolymer obtained in the step (C).

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(E) While the ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride ( It is produced by a production method in which M4) is reacted.

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(F) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having a carboxyl group;
(G) In the copolymer obtained in step (F), an ethylenically unsaturated compound having an epoxy group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) may be used simultaneously or It is manufactured by the manufacturing method including the process made to react in arbitrary orders.

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(H) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having an epoxy group;
(I) a step of reacting an ethylenically unsaturated compound having a carboxyl group with the epoxy group of the copolymer obtained in step (H),
(J) It is produced by a production method comprising a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) with a hydroxyl group of the copolymer obtained in the step (I). .

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(K) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group,
(L) An ethylenically unsaturated compound having an isocyanate group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) are simultaneously added to the hydroxyl group of the copolymer obtained in the step (K). Or it is manufactured by the manufacturing method including the process made to react in arbitrary orders.

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(M) 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 dianhydride (M4) is produced. Process,
(N) a step of copolymerizing the ethylenically unsaturated monomer obtained in step (M) (provided that an unreacted hydroxyl group remains);
(O) It is manufactured by the manufacturing method including the process of making the ethylenically unsaturated compound which has an isocyanate group react with the hydroxyl group of the copolymer obtained by process (N).

In still another preferred embodiment of the coloring composition according to the present invention,
Vinyl polymer
(P) 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 dianhydride (M4) is produced. Process,
(Q) A step of copolymerizing the ethylenically unsaturated monomer obtained in step (P) with an ethylenically unsaturated monomer having a carboxyl group,
(R) The copolymer obtained in step (Q) is produced by a production method including a step of reacting an ethylenically unsaturated compound having an epoxy group.

  In still another preferred embodiment of the coloring composition according to the present invention, the tricarboxylic acid anhydride (M3) or the tetracarboxylic dianhydride (M4) is trimellitic acid anhydride or pyromellitic acid anhydride.

 In still another preferred embodiment of the coloring composition according to the present invention, the composition further comprises a thermoreactive compound, in particular, the thermoreactive compound is a melamine compound, a benzoguanamine compound, a carbodiimide compound, an epoxy compound, an oxetane compound, a phenol compound, One or more compounds selected from the group consisting of benzoxazine compounds, blocked carboxylic acid compounds, blocked isocyanate compounds, acrylate monomers, and silane coupling agents.

 In still another preferred embodiment of the colored composition according to the present invention, it further comprises a binder resin, and in particular, the binder resin is a thermoplastic resin.

 In still another preferred embodiment of the coloring composition according to the present invention, the pigment composition further includes a pigment derivative, and in particular, the pigment derivative is a compound represented by the general formula (5).

General formula (5)
G ^1- (E) q (5)
(In the formula, G ¹ is a chromogenic compound residue,
E is a basic substituent, an acidic substituent, or a neutral substituent;
q is an integer of 1 to 4. )
In still another preferred embodiment of the coloring composition according to the present invention, the pigment derivative is a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine having a basic group. It is at least one basic derivative selected from the group consisting of derivatives.

 In still another preferred embodiment of the coloring composition according to the present invention, an organic solvent is further included.

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

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

 In still another preferred embodiment of the coloring composition according to the present invention, the weight ratio of the pigment to the vinyl dispersant is 100: 3 to 100: 150.

 In still another preferred embodiment of the colored composition according to the present invention, the viscosity at 25 ° C. is 2 to 40 mPa · s.

 In still another preferred embodiment of the coloring composition according to the present invention, it is for a color filter substrate.

 The present invention also relates to a color filter substrate carrying a printed layer comprising the above colored composition.

 Since the coloring composition of the present invention contains the vinyl dispersant (A) [particularly, the vinyl dispersant (a)], the fluidity of the ink during the printing process is maintained, so that it can be applied efficiently. It can be controlled to the optimum properties in each step of processing, patterning, and transfer, and the transfer property has a long duration, so that precise black, red, green, blue, etc. patterns can be formed on the substrate.

[Vinyl dispersant]
The coloring composition for printing of the present invention contains a vinyl dispersant.

 In the vinyl dispersant (a) that can be used in the present invention, the carboxyl group-containing unit (G) represented by the general formula (1) is converted into one molecule of the vinyl polymer in the vinyl polymer main chain. As long as it has a structure containing an average of 0.3 or more and 3.0 or less, its chemical structure and manufacturing method are not particularly limited.

In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance between these two functional parts. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important. In the carboxyl group-containing unit (G) represented by the general formula (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 having two or three carboxyl groups and 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.

In the vinyl dispersant (a) used in the present invention, the carboxyl group-containing unit (G) represented by the general formula (1) in one molecule [particularly, the group Y ¹ in the general formula (1)] is an average of 0. It is important to include 3 or more and 3.0 or less. 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.

In the general formula (1), from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability, the general formula (1) is a general formula (1 ′) in which X ¹ is —C (═O) O—:

であることが好ましく、更に、Ｒ^a1は炭素原子数１〜４の炭化水素基（例えば、メチレン基、エチレン基、直鎖状若しくは分岐状プロピレン基、又は直鎖状若しくは分岐状ブチレン基）であることが好ましく、ｍ１は１〜１０であることが好ましく（更に好ましくは１〜３）、Ｒ^b1は、ペンタメチレン基であることが好ましく、ｍ２は０〜５であることが好ましい（更に好ましくは０〜３）。

Further, 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). Preferably, 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). 0-3).

In particular, Y ¹ is a combination in which one of A ^{1 to} A ³ in general formula (2) is a hydrogen atom and the other two are —C (═O) OH, or It is preferable that one of A ^{5 to} A ⁷ in the formula (3) is a hydrogen atom and the other two are —C (═O) OH.

As another embodiment, ^one of A ^{1 to} A ^{3 in} the general formula (2) is a group represented by the general formula (2a), and the other two are —C (═O) OH. Or one of A ^{5 to} A ^{7 in} the general formula (3) is a group represented by the general formula (3a), and the other two are —C (═O). A combination that is OH is preferred. One embodiment of the vinyl dispersant of the present invention including such a combination can be represented by, for example, general formula (4A).

 General formula (4A):

〔一般式（４Ａ）中、曲線部分はビニル系重合体主鎖を描写したものであり、
Ｒ¹及びＸ¹〜Ｘ³は、一般式（１）における各基と同じ意味であり、
Ｒ¹¹及びＸ¹¹〜Ｘ¹³は、それぞれ、一般式（１）におけるＲ¹及びＸ¹〜Ｘ³と同じ意味であり（但し、Ｒ¹¹とＲ¹、Ｘ¹¹とＸ¹、Ｘ¹²とＸ²、Ｘ¹³とＸ³は、それぞれ、互いに独立しているものとする）、
Ｙ²は、一般式（２’）：

[In general formula (4A), the curved portion is a depiction of the vinyl polymer main chain,
R ¹ and X ^{1 to} X ³ have the same meaning as each group in the general formula (1),
R ¹¹ and X ^{11 to} X ¹³ have the same meaning as R ¹ and X ^{1 to} X ³ in the general formula (1), respectively (provided that R ¹¹ and R ¹ , X ¹¹ and X ¹ , X ¹² and X ^{13 2} , X ¹³ and X ³ are assumed to be independent from each other),
Y ² represents the general formula (2 ′):

〔一般式（２’）中、ｋ’は１又は２である〕
又は、一般式（３’）：

[In general formula (2 ′), k ′ is 1 or 2]
Or, general formula (3 ′):

〔一般式（３’）中、Ｒ^2'は、前記一般式（３）における基Ｒ²と同じ意味である〕
で表される４価の有機残基である。
Ｅ¹〜Ｅ⁴は、ビニル系重合体主鎖の末端を示す。ここで、Ｅ¹末端若しくはＥ²末端は、Ｅ³末端又はＥ⁴末端と結合していてもよい。但し、Ｅ¹末端とＥ²末端とが同時に同じ末端に結合することはない。〕
一般式（４Ａ）において、Ｅ¹末端若しくはＥ²末端が、Ｅ³末端又はＥ⁴末端と結合している場合〔例えば、一般式（２ａ）において、ビニル系重合体主鎖（Ｂ）がビニル系重合体主鎖（Ａ）と同一主鎖であるか、あるいは、一般式（３ａ）において、ビニル系重合体主鎖（Ｃ）がビニル系重合体主鎖（Ａ）と同一主鎖である場合〕、そのビニル系重合体主鎖内に、
一般式（４Ｂ）：

[In the general formula (3 ′), R ^{2 ′} has the same meaning as the group R ² in the general formula (3)].
Is a tetravalent organic residue.
E ^{1 to} E ⁴ represent the ends of the vinyl polymer main chain. Here, the E ¹ terminal or the E ² terminal may be bonded to the E ³ terminal or the E ⁴ terminal. However, the E ¹ end and the E ² end are not simultaneously bonded to the same end. ]
In general formula (4A), when E ¹ terminal or E ² terminal is bonded to E ³ terminal or E ⁴ terminal [for example, in general formula (2a), the vinyl polymer main chain (B) is vinyl Is the same main chain as the main polymer chain (A) or, in the general formula (3a), the main vinyl polymer chain (C) is the same main chain as the main vinyl polymer chain (A). Case), in the vinyl polymer main chain,
General formula (4B):

〔式中、Ｒ¹及びＸ¹〜Ｘ³、Ｒ¹¹及びＸ¹¹〜Ｘ¹³、並びにＹ²は、一般式（４Ａ）における各基と同じ意味であり、
一般式（４ｂ）：

Wherein, R ¹ and X ¹ ~X ^3, R ¹¹ and X ¹¹ to X ^13, and Y ² has the same meaning as the group in the general formula (4A),
General formula (4b):

で表される主鎖構成単位（Ｂ）は、ビニル系重合体主鎖を構成可能な構成単位〔例えば、後述の一般式（４ｊ）で表される水酸基含有単位（Ｊ）若しくは一般式（４ｋ）で表される主鎖構成単位（Ｋ）、一般式（１）で示されるカルボキシル基含有単位（Ｇ）（但し、一般式（１）において、一般式（２）中のＡ¹〜Ａ³がいずれも一般式（２Ａ）で表される基ではなく、一般式（３）中のＡ⁵〜Ａ⁷がいずれも一般式（３Ａ）で表される基でないものとする）、又は一般式（５１）〜（５５）で表される架橋性官能基含有単位（Ｉ）〕であり、
ｍ４１は、０以上４３０以下である〕
で表される主鎖構成単位を含む。

The structural unit (B) represented by the formula is a structural unit capable of constituting a vinyl polymer main chain [for example, a hydroxyl group-containing unit (J) or a general formula (4k represented by the general formula (4j) described later) ), A carboxyl group-containing unit (G) represented by the general formula (1) (in the general formula (1), A ^{1 to} A ³ in the general formula (2)) Are not groups represented by the general formula (2A), and A ^{5 to} A ⁷ in the general formula (3) are not all groups represented by the general formula (3A)), or a general formula The crosslinkable functional group-containing units (I) represented by (51) to (55),
m41 is 0 or more and 430 or less]
The main chain structural unit represented by these is included.

In general formula (4A), when neither E ¹ terminal nor E ² terminal is bonded to E ³ terminal or E ⁴ terminal [for example, in general formula (2a), a vinyl polymer main chain (B ) Is a main chain different from the vinyl polymer main chain (A), or in the general formula (3a), the vinyl polymer main chain (C) is different from the vinyl polymer main chain (A). In the case of a chain], the description of the present specification regarding the vinyl polymer main chain (A) is Z ²¹ [that is, the vinyl polymer main chain (B) containing a group represented by the general formula (21)] Alternatively, Z ³¹ [that is, the vinyl polymer main chain (C) containing a group represented by the general formula (31)] can be applied as it is according to the common general technical knowledge of those skilled in the art.
Furthermore, in the general formula (1), Y ¹ is preferably a group represented by the general formula (2), and more preferably, k is 1. When Y ¹ is represented by the general formula (3), R ² is a direct bond, —C (═O) OCH ₂ CH ₂ OC (═O) —, or a group represented by the formula (81). It is preferable that
Formula (81)

本発明で用いるビニル系分散剤（ａ）としては、一般式（１）で表されるカルボキシル基含有単位（Ｇ）と、一般式（４ｋ）：

As a vinyl type dispersing agent (a) used by this invention, the carboxyl group containing unit (G) represented by General formula (1), and General formula (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、更に所望により含有することのできる、一般式（４ｊ）：

[In General Formula (4k), R ⁵ and R ⁶ have the same meaning as described above]
And a general formula (4j) that can be optionally contained:

〔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（５１）〜（５５）のいずれかで表される架橋性官能基含有単位（Ｉ）との各構成単位からなるブロック共重合体又はランダム共重合体を挙げることができる。

[In the general formula (4j), R ⁴ , X ⁴ , X ⁵ , and X ⁶ have the same meaning as described above.]
A block copolymer or a random copolymer consisting of structural units of a hydroxyl group-containing unit (J) represented by formula (I) and a crosslinkable functional group-containing unit (I) represented by any one of the general formulas (51) to (55) Mention may be made of copolymers.

Accordingly, preferred vinyl dispersants (a) according to the present invention are represented by the general formula (4) or the general formula (4a):
-[G] p1- [J] p2- [K] p3- [I] p4- (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 represented by the general formula (4k). Wherein I is a crosslinkable functional group-containing unit represented by any one of the general formulas (51) to (55), and p1 is 0.3 to 3.0 (preferably 0) .35 to 2.0, more preferably 0.4 to 1.5, p2 is 0 to 180 (preferably 0.05 to 50), and p3 is 6 to 250 (preferably 10 to 100). P4 is 0 or more and 180 or less (preferably 0.1 or more and 180 or less, more preferably 0.5 or more and 100 or less, and further preferably 2 or more and 50 or less).

 In the general formula (4a), the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) are each a block copolymerization type. Alternatively, it can exist in a random copolymer form. Furthermore, a plurality of carboxyl group-containing units (G), hydroxyl group-containing units (J), main chain constituent units (K), and crosslinkable functional group-containing units (I) are present in the general formula (4a). can do. 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 addition, the arrangement of the carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) in the general formula (4a) is [G] p1, It does not mean that [J] p2, [K] p3, and [I] p4 are included in this order, and each unit G, J, K, and I can be included in any order. Means.

In the hydroxyl group-containing unit (J) contained in the vinyl dispersant (a) used in the present invention represented by the general formula (4) or the general formula (4a), X ⁴ is —C (═O) O—. 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). Preferably, 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 0). 3).

In the vinyl dispersant (a) used in the present invention represented by the general formula (4) or the general formula (4a), R ⁵ is a methyl group and R ⁶ is —C as the main chain structural unit (K). It preferably contains a main chain structural unit (K1) which is (═O) —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 to 100 per molecule of the vinyl polymer, and the vinyl dispersant (a) of this embodiment is excellent in dispersion ability.

Furthermore, in the vinyl dispersant (a) used in the present invention represented by the general formula (4) or the general formula (4a), R ⁵ is a methyl group as the main chain structural unit (K), and R ⁶ is It is preferable to include a main chain structural unit (K2) which is —C (═O) —O—R ⁷ (wherein R ⁷ is a linear or branched alkyl group having 2 to 12 carbon atoms). It is more preferable that the main chain structural unit (K2) coexists with the main chain structural unit (K1) in the vinyl dispersant (a).

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

 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. it can. 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, 0.01 to 10 , Preferably 0.05-2. Furthermore, when the main chain structural unit (K4) is allowed to coexist with other main chain structural units (K), the ratio [K4 / K] is, for example, 0 to 0.2, preferably 0 to 0.1. Can be.

The vinyl dispersant (a) used in the present invention represented by the general formula (4) or the general formula (4a) is any of the general formulas (51) to (55) as the crosslinkable functional group-containing unit (I). Although the crosslinkable functional group containing unit represented by these is mentioned, Preferably, it is as follows.
T ^{1 in the} general formula (51) is a group represented by the following formula (84) or formula (85).
Formula (84)

又は式（８５）

Or formula (85)

であることが好ましく、より好ましくは、Ｒ^a51が、−ＣＨ₂−ＣＨ₂−であるか、
Ｒ^b51が、−（ＣＨ₃）Ｃ（ＣＨ₃）−である。
一般式（５１）のＴ²は、
Ｒ^c51がエチル基であって、かつ、Ｒ^d51がメチル基であるか、
Ｒ^f51が水素原子であって、かつ、Ｒ^e51およびＲ^g51がメチル基であるか、
ｎ５１が５であるものが好ましい。
一般式（５２）は、
Ｒ^a52がメチレン基であって、Ｒ^b52がエチル基であるものが好ましい。
一般式（５４）は、
Ｒ^a54およびＲ^b54が、メチレン基であるものが好ましい。
一般式（５５）のＸ^a55は、−Ｃ（＝Ｏ）Ｏ−が好ましく、
一般式（５５）のＸ^b55は、Ｒ^b55が−ＣＨ₂−ＣＨ₂−であり、ｍ５５が１であるのが好ましい。
一般式（５５）のＸ^c55が、ｎ５５が０であるものが好ましい。
一般式（５５）のＴ⁵は、Ｒ^e55が−ＣＨ₂−ＣＨ₂−であるか、Ｒ^f55が−（ＣＨ₃）Ｃ（ＣＨ₃）−であるのが好ましい。

More preferably, R ^a51 is —CH ₂ —CH ₂ —,
R ^b51 is — (CH ₃ ) C (CH ₃ ) —.
T ^{2 in the} general formula (51) is
^Whether R ^c51 is an ethyl group and R ^d51 is a methyl group,
R ^f51 is a hydrogen atom and R ^e51 and R ^g51 are methyl groups,
n51 is preferably 5.
The general formula (52) is
R ^a52 is ^{preferably a} methylene group and R ^b52 is preferably an ethyl group.
The general formula (54) is
R ^a54 and R ^b54 are preferably methylene groups.
X ^{a55 in the} general formula (55) is preferably —C (═O) O—,
In X ^b55 of the general formula (55), R ^b55 is ^preferably —CH ₂ —CH ₂ —, and m55 is preferably 1.
X ^{c55 in the} general formula (55) is preferably one in which n55 is 0.
In T ⁵ of the general formula (55), R ^e55 is ^preferably —CH ₂ —CH ₂ —, or R ^f55 is ^preferably — (CH ₃ ) C (CH ₃ ) —.

 The terminal of the main chain of the vinyl-based 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, derived from a polymerization initiator, It may have a chemical structure derived from a chain transfer agent, a solvent, or an ethylenically unsaturated monomer.

 The number average molecular weight of the vinyl dispersant (a) used in the present invention is preferably 500 or more and 40000 or less, more preferably 1000 or more and 20000 or less, and most preferably 1500 or more and 16000 or less. Even if the number average molecular weight is less than 500 or more than 40000, the dispersibility or fluidity may be lowered.

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

As a manufacturing method of the vinyl type dispersing agent (A) used by this invention, the following manufacturing methods 1-8 can be mentioned.
Manufacturing method 1:
(A) 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 dianhydride (M4) is produced. Process,
(B) The ethylenically unsaturated monomer and another ethylenically unsaturated monomer [any crosslinkable functional group represented by the general formulas (51) to (53) (that is, the general formula (51) To an ethylenically unsaturated monomer having a portion excluding the main chain component from the crosslinkable functional group-containing unit represented by (53)].
Manufacturing method 2:
(C) An ethylenically unsaturated monomer (h) having a hydroxyl group is replaced with another ethylenically unsaturated monomer [ethylene having any crosslinkable functional group represented by the general formulas (51) to (53). A copolymer with a unsaturated unsaturated monomer),
(D) It consists of a step of reacting a hydroxyl group of the copolymer with a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4).
Manufacturing method 3:
(E) Ethylenically unsaturated monomer (h) having a hydroxyl group is replaced with another ethylenically unsaturated monomer [ethylene having any crosslinkable functional group represented by the general formulas (51) to (53) A tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) is simultaneously reacted with the hydroxyl group.

Further, when the vinyl dispersant (A) of the present invention contains any of the crosslinkable functional groups having an unsaturated bond represented by the general formula (54) or (55) as the crosslinkable functional group, Production methods 4 to 8 can be exemplified.
Manufacturing method 4:
(F) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having a carboxyl group (preferably together with another ethylenically unsaturated monomer);
(G) In the copolymer obtained in step (F), an ethylenically unsaturated compound having an epoxy group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) may be used simultaneously or It includes the step of reacting in any order.

 In the step (G), the ethylenically unsaturated compound having an epoxy group reacts with the carboxyl group of the copolymer obtained in the step (F), and the crosslinkability having an unsaturated bond represented by the general formula (54). Generate a functional group. On the other hand, tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) reacts with the hydroxyl group of the copolymer.

Moreover, when the vinyl type dispersing agent (A) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these are used in the step (F). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.
Manufacturing method 5:
(H) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having an epoxy group (preferably together with another ethylenically unsaturated monomer);
(I) a step of reacting an ethylenically unsaturated compound having a carboxyl group with the epoxy group of the copolymer obtained in step (H),
(J) The process of making tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) react with the hydroxyl group of the copolymer obtained by process (I) is included.

 In the step (I), the ethylenically unsaturated compound having a carboxyl group reacts with the epoxy group of the copolymer obtained in the step (H) to form a crosslinkable compound having an unsaturated bond represented by the general formula (54). Generate a functional group.

Moreover, when the vinyl type dispersing agent (A) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these are used in the step (H). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.
Production method 6:
(K) a step of copolymerizing the ethylenically unsaturated monomer (h) having a hydroxyl group (preferably together with another ethylenically unsaturated monomer);
(L) An ethylenically unsaturated compound having an isocyanate group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) are simultaneously added to the hydroxyl group of the copolymer obtained in the step (K). Or the process made to react in arbitrary orders is included.

 In the step (L), the ethylenically unsaturated compound having an isocyanate group reacts with the hydroxyl group of the copolymer obtained in the step (K), and the crosslinkable functional group having an unsaturated bond represented by the general formula (55). Create a group. On the other hand, tricarboxylic anhydride (M3) or tetracarboxylic dianhydride (M4) also reacts with the hydroxyl group of the copolymer.

Moreover, when the vinyl type dispersing agent (A) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these are used in the step (K). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.
Manufacturing method 7:
(M) 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 dianhydride (M4) is produced. Process,
(N) The ethylenically unsaturated monomer obtained in step (M) (provided that an unreacted hydroxyl group remains) is copolymerized (preferably together with another ethylenically unsaturated monomer). Process,
(O) The process which makes the ethylenic unsaturated compound which has an isocyanate group react with the hydroxyl group of the copolymer obtained by process (N) is included.

In the manufacturing method 7, the crosslinkable functional group which has an unsaturated bond shown by General formula (55) is formed in a process (O). Moreover, when the vinyl type dispersing agent (A) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional groups, these are used in the step (N). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.
Production method 8:
(P) 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 dianhydride (M4) is produced. Process,
(Q) A step of copolymerizing the ethylenically unsaturated monomer obtained in step (P) and the ethylenically unsaturated monomer having a carboxyl group (preferably together with another ethylenically unsaturated monomer). ,
(R) A step of reacting the copolymer obtained in step (Q) with an ethylenically unsaturated compound having an epoxy group is included.

 In the manufacturing method 8, the crosslinkable functional group which has an unsaturated bond shown by General formula (54) is formed in a process (R). Moreover, when the vinyl type dispersing agent (A) of the present invention includes any of the crosslinkable functional groups represented by the general formulas (51) to (53) as the crosslinkable functional group, these are used in the step (Q). An ethylenically unsaturated monomer having a crosslinkable functional group is copolymerized.

 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. Although not specifically, a (meth) acrylate monomer 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-hydride) N- (hydroxyalkyl) (meth) acrylamide such as xylbutyl) (meth) acrylamide, or vinyl ether monomers having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2 -Hydroxyalkyl vinyl ethers such as-(or 3- or 4-) hydroxybutyl vinyl ether, or allyl ether monomers having a hydroxyl group, such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, And hydroxyalkyl allyl ethers such as 2- (or 3- or 4-) hydroxybutyl allyl ether.

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

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

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

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

 In addition, in the production method used in the present invention, in one of the tetracarboxylic dianhydrides (M4) described later, one acid anhydride of one molecule is converted to water, an alcohol having 1 to 18 carbon atoms, or 5 to 5 carbon atoms. 18 cycloalcohols (eg 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, straight chain Is branched dodecanol or cyclododecanol, linear or branched myristyl alcohol or cyclomyristyl alcohol, linear or branched cetyl alcohol or cyclocetyl alcohol, linear or branched stearyl alcohol or cyclostearyl Tetracarboxylic acid monoanhydrides and tetracarboxylic acid monoester monoanhydrides that have been ring-opened with an alcohol etc. can also be used as the tricarboxylic acid anhydride (M3) in the production method used in the present invention. In the present specification, an aliphatic tetracarboxylic acid monoester monoanhydride is an aliphatic tricarboxylic acid anhydride, an aromatic tetracarboxylic acid monoester monoanhydride is an aromatic tricarboxylic acid anhydride, a polycyclic tetracarboxylic acid anhydride. The monoester monoanhydride is described as a polycyclic tricarboxylic acid anhydride. Specific examples of these tetracarboxylic anhydride monoester monoanhydrides are obvious to those skilled in the art from the tetracarboxylic dianhydrides described below.

 Examples of the tetracarboxylic dianhydride (M4) include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and polycyclic tetracarboxylic dianhydrides.

 Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl. -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3, 5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3- Examples include cyclohexene-1,2-dicarboxylic dianhydride and bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride.

 Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic Acid dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-fura Tetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 , 4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride Bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmeta Dianhydrides, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluoric dianhydride and the like. Can be mentioned.

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

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

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

 When the ethylenically unsaturated monomer (h) having a hydroxyl group and the tricarboxylic acid anhydride (M3) are reacted in the step (A), the reaction ratio is “the ethylenically unsaturated monomer having a hydroxyl group (h)”. It is preferable that "number of moles / number of moles of tricarboxylic acid anhydride (M3)" is 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 dianhydride (M4) are reacted in the step (A), the reaction ratio is "ethylenically unsaturated monomer having a hydroxyl group (h ) / Mol of tetracarboxylic dianhydride (M4) ”is preferably 0.5 or more and 10.0 or less. More preferably, it is 1.0 or more and 5.0 or less. If it is less than 0.5, a large amount of tetracarboxylic dianhydride (M4) 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.

 In the 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.

 Further, the ethylenically unsaturated monomer (h) having a hydroxyl group and the tetracarboxylic dianhydride (M4) are expressed as "number of moles of ethylenically unsaturated monomer (h) having a hydroxyl group / tetracarboxylic dianhydride". When the reaction is performed at a "mol number of (M4)" less than 2.0, the acid anhydride group remaining at this point is opened with water or an alcohol having 1 to 18 carbon atoms [step (Aa)], unnecessary. Removal of the acid anhydride group can be facilitated.

 Subsequently, in the production method 1, the ethylenically unsaturated monomer synthesized in the step (A) and another ethylenically unsaturated monomer [crosslinkable functional group of any one of the general formulas (51) to (53)] (The ethylenically unsaturated monomer having a group may be included)].

 As another ethylenically unsaturated monomer used in the step (A), an alkyl (meth) acrylate having 1 to 18 carbon atoms which may be substituted with an aromatic group, or N- having 1 to 18 carbon atoms. Alkyl (meth) acrylamide, styrene, ethylenically unsaturated monomer (h) having a hydroxyl group (including those remaining in step (A)), and crosslinkability represented by general formulas (51) to (53) Preferably, an ethylenically unsaturated monomer selected from ethylenically unsaturated monomers having a functional group is 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.

 Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, crotonic acid, acrylic acid dimer, caprolactone adduct of acrylic acid ( Examples of the addition mole number are 1 to 5), and caprolactone adduct of methacrylic acid (addition mole number is 1 to 5).

 Examples of the ethylenically unsaturated monomer having a crosslinkable functional group represented by the general formula (51) include Karenz MOI-BM and Karenz MOI-BP (manufactured by Showa Denko).

 Examples of the ethylenically unsaturated monomer having a crosslinkable functional group represented by the general formula (52) include ETERNACOLL OXMA (manufactured by Ube Industries).

 Examples of the ethylenically unsaturated monomer having a crosslinkable functional group represented by the general formula (53) include t-butyl methacrylate and t-butyl acrylate.

 In the 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 the 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 the step (B), it is preferable to use a solvent. Solvents include acetates such as ethyl acetate, propyl acetate, butyl acetate, ethyl cellosolve acetate and propylene glycol monomethyl ether acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, and 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 the step (Aa) or the step (Bb), the number of moles of water to be reacted or the alcohol having 1 to 18 carbon atoms is 0.9 to 5 times (preferably with respect to the number of moles of the remaining acid anhydride. Is preferably 1 to 2 times. If it is less than 0.9 times, a lot of highly reactive acid anhydride groups remain, and if it exceeds 5 times, water or alcohol having 1 to 18 carbon atoms remains, anyway, it has been developed for use in inks and paints. If this is a problem. However, in the case where the water to be reacted or the alcohol having 1 to 18 carbon atoms is reacted more than 1 time with respect to the number of moles of the remaining acid anhydride, the water remaining after the reaction or having 1 to 18 carbon atoms is reacted. The alcohol can be removed by heating or under reduced pressure. The reaction step (Aa) or the step (Bb) is preferably performed at 80 to 150 ° C.

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

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

 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 tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) react with the hydroxyl group of the copolymer obtained at the process (C) is performed. In the step (D), it is preferably performed at 80 ° C. to 150 ° C. while flowing nitrogen or dry air into the reaction vessel. Here, the catalyst illustrated at the process (A) of the manufacturing method 1 can also be used.

 When tetracarboxylic dianhydride (M4) is used in step (D) of production method 2, and an acid anhydride group remains, water or carbon atoms are obtained by the same method as in step (Bb) of production method 1. The ring can be opened with an alcohol having a number of 1 to 18 [step (Dd)].

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

 In the production method 3 used in the present invention, an ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, and a tricarboxylic acid anhydride (M3) or tetra Carboxylic dianhydride (M4) is reacted simultaneously. The reaction is preferably performed at 80 ° C. to 150 ° C. while flowing nitrogen into the reaction vessel. As a catalyst for the reaction between the hydroxyl group and the acid anhydride, the polymerization initiator shown in Step (A) of Production Method 1 can be used. The polymerization conditions such as the type, the type of chain transfer agent, the type of solvent, the amount, 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. Even in the production method 3, when an acid anhydride group remains, the ring can be opened with water or an alcohol having 1 to 18 carbon atoms by the same method as in the production method 1 (Bb) [step (Ee)]. .

 By these production methods 1 to 3, the vinyl dispersant (A) used in the present invention can be produced. Among these, production method 2 is preferable in that it is easy to control the number of carboxyl group-containing units (G) in one molecule of the dispersant. The number average molecular weight of the copolymer obtained in the step (C) of the production method 2 can be measured in advance, and the amount by which the tricarboxylic acid anhydride (M3) or tetracarboxylic dianhydride (M4) is reacted according to the value This is because it can be determined. For example, in order to produce the vinyl dispersant (A) by the production method 2, the number average molecular weight of the copolymer obtained in the step (C) is measured, and when the measured value is [X], tricarboxylic acid When the anhydride (M3) is used, 0.3 to 3.0 mol of tricarboxylic acid anhydride (M3) may be reacted with the resin [X] g. On the other hand, when tetracarboxylic dianhydride (M4) is used, 0.15 mol or more and 1.5 mol or less of tetracarboxylic dianhydride (M4) may be reacted with resin [X] g. . This is because the tetracarboxylic dianhydride (M4) has two acid anhydride groups, so the tricarboxylic acid anhydride (M3) is used to bridge the copolymer bimolecules obtained in step (C). This is because half the amount is sufficient.

  Further, in the case of using tetracarboxylic dianhydride (M4) in the step (D), when the number of hydroxyl groups contained in one molecule of the copolymer obtained in the step (C) is 1.1 or more, Ratio of the total amount <OH> of hydroxyl groups contained in the copolymer and the total amount <AH> of acid anhydride groups contained in the tetracarboxylic dianhydride (M4): The value of <OH> / <AH> is 0 It is preferably less than .9 or 1.1 or more. When the value of <OH> / <AH> is in the range of 0.9 or more and less than 1.1, the vinyl dispersant (A) may exceed the upper limit of the preferred number average molecular weight of the present invention of 40000.

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

 When the vinyl dispersant (A) is produced by the production method of the present invention, when the tricarboxylic acid anhydride (M3) is used, an aromatic tricarboxylic acid anhydride is preferable, and a trimellitic acid anhydride is more preferable. Of the above, when tetracarboxylic dianhydride (M4) is used, aromatic tetracarboxylic dianhydride is preferably used, more preferably pyromellitic dianhydride, ethylene glycol dianhydride trimellit. Acid ester, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.

 When producing the vinyl-based dispersant (A) in any of the production methods 1 to 3, an unsubstituted ethylenically unsaturated monomer having 1 to 12 carbon atoms which may have a branch is used as another ethylenically unsaturated monomer. Alkyl (meth) acrylate, benzyl (meth) acrylate, ethylenically unsaturated monomer (h) having a hydroxyl group if necessary, styrene if necessary, ethylenically unsaturated monomer having a carboxyl group if necessary The body is preferably copolymerized. Further, 1 to 50 unsubstituted alkyl (meth) acrylates having 1 to 12 carbon atoms, which may have a branch in one molecule of the vinyl dispersant (A), and 1 to 1 benzyl (meth) acrylate. Preferably 50 are copolymerized.

 The vinyl-based dispersant (A) used in the present invention can be copolymerized with various ethylenically unsaturated monomers other than those exemplified so far as long as the dispersibility is not hindered. For example, an isocyanato group , An ethylenically unsaturated monomer having a thermally crosslinkable group such as a block isocyanato group, an alkoxysilyl group, or a 3- to 5-membered cyclic ether group can be copolymerized.

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

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

 In the coloring composition for printing of the present invention, a known dispersion resin can be used in combination with a vinyl dispersant. By using the dispersion resin in combination, the dispersibility of the pigment is further improved, leading to a reduction in the viscosity of the ink and an improvement in the viscosity stability of the ink over time.

 The dispersion resin that can be used in combination with the vinyl dispersant is not particularly limited. Specific examples of commercially available dispersion resins include the following.

 BYK Chemie Anti-Terra-U, U100, 203, 204, 205, Disperbyk-101, 102, 106, 107, 110, 111, 130, 140, 142, 170, 171, 174, 180, 2001, BYK- P104, P105, 9076.

Solspers 3000, 13940, 17000, 21000, 24000, 26000, 366000, 41000, 41090, 53095, manufactured by Abyssia
EFKA CHEMICALS EFKA 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766, EFKA Polymer 100, 150, 400, 401, 402, 403, 450, 451, 452, 453.

 Manufactured by Kyoeisha Chemical Co., Ltd., Floren TG-710, Flownon SH-290, SP-1000, Polyflow No. 50E, no. 300, Disparon KS-860, 873SN, 874, # 2150, # 7004, Nikko Chemical Co., Ltd. Nikkor T106, MYS-IEX, Hexagline 4-0.

A known dispersion resin includes a polyester-based dispersion resin. As long as the polyester-based dispersion resin has a structure represented by the general formula (70), its chemical structure and manufacturing method are not particularly limited. The production method includes, for example, a first step of producing a polyester having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, a polyester having a hydroxyl group at one end, and a tetracarboxylic acid. And a method comprising a second step of reacting dianhydride.
Formula (70):
( _HOOC- ) _e70 -R ^a71 -(-COO-[-R ^a73 -COO-] _f70 -R ^a72 ) _g70
(In the general formula (10), R ^a71 is a tetravalent tetracarboxylic acid compound residue,
R ^a72 is a monoalcohol residue,
R ^a73 is a lactone residue,
e70 represents an integer of 2 or 3, f70 represents an integer of 1 to 50, and g70 represents (4-e). )
[About pigments]
The coloring composition for printing of the present invention contains a pigment.

 As the pigment, an organic pigment, an inorganic pigment, or carbon black such as acetylene black, channel black, or furnace black can be used.

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

 Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, brown rice, molybdenum red, Molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, bitumen, cobalt blue, cerulean blue, Examples thereof include cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

 In the following, pigments that can be used in the colored composition according to the present invention are indicated by color index (CI) numbers.

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

 Examples of the yellow coloring composition include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199 can be used.

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

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

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

 The coloring composition for printing of this invention can contain the said pigment individually by 1 type or in mixture of 2 or more types.

 The particle diameter of the pigment is preferably sufficiently small with respect to the wavelength of visible light from the viewpoint of the absorption coefficient of visible light (appropriate spectrum) and transparency. That is, the pigment preferably has an average primary particle size of 0.01 μm or more and 0.3 μm or less, particularly 0.01 μm or more and 0.1 μm or less. The primary particle diameter refers to the diameter of the smallest unit pigment particle, and is measured with an electron microscope. The primary particle diameter of the pigment can be controlled within an appropriate range using a known dispersing apparatus such as a sand mill, a kneader, or a two-roll.

In the coloring composition for printing of the present invention, the pigment is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 25% by weight, based on the weight of the entire composition. When the pigment content is less than 1% by weight, the concentration of the ink film is insufficient, and when it exceeds 30% by weight, the viscosity may increase or the stability over time may decrease. The weight ratio of the pigment to the vinyl dispersant is preferably 100: 3 to 100: 150, more preferably 100: 5 to 100: 100. When the weight ratio is less than 100: 3, the viscosity of the coloring composition may not be sufficiently lowered, and when it exceeds 100: 150, the film forming property of the coloring composition may be deteriorated.
[About leveling agents]
The coloring composition for printing of the present invention contains a leveling agent.

 As the leveling agent, an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant can be used.

 Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monolauryl sulfate, Examples include ethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, or polyoxyethylene alkyl ether phosphate. be able to.

 Nonionic surfactants include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, Or a dimethyl polysiloxane polyalkylene oxide copolymer etc. can be mentioned.

 Examples of the chaotic surfactant include alkyl quaternary ammonium salts and ethylene oxide adducts thereof.

 Examples of amphoteric surfactants include alkylbetaines such as alkyldimethylaminoacetic acid betaines, or alkylimidazolines.

 The coloring composition for printing of this invention can contain the said leveling agent individually by 1 type or in mixture of 2 or more types.

In the coloring composition for printing of the present invention, the leveling agent is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.02 to 5.0% by weight, based on the weight of the entire composition. It is preferable. When the content of the leveling agent is less than 0.01% by weight, repelling occurs on the blanket during ink coating, and a uniform ink film cannot be formed. When the content exceeds 10% by weight, the physical properties of the ink film deteriorate. Sometimes.
[About thermally reactive compounds]
The colored composition of the present invention can contain a heat-reactive compound in order to ensure the coating strength after curing. The heat-reactive compound that can be used in the colored composition of the present invention is non-reactive at room temperature, but for example, at a temperature of 100 ° C. or higher (preferably 150 ° C. or higher), a crosslinking reaction, a polymerization reaction, It is a compound showing a condensation reaction or a polyaddition reaction. Although the molecular weight of the heat-reactive compound which can be used for the coloring composition of this invention is not specifically limited, Preferably it is 50-2000, More preferably, it is 100-1000.

 Examples of thermally reactive compounds include melamine compounds, benzoguanamine compounds, epoxy compounds, oxetane compounds, phenolic compounds, benzoxazine compounds, blocked carboxylic acid compounds, blocked isocyanate compounds, carbodiimide compounds, acrylate monomers, or silane couplings. An agent can be used.

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

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

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

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

 Among them, preferred are alkamine-containing melamine compounds, Nicalac MW-30M, MW-30, MW-22, MS-21, MX-45, MX-500, MX-520, MX-, manufactured by Nippon Carbide Corporation. 43, MX-302, Cymel 300, 301, 303, 350, 285, 232, 235, 236, 238, My Coat 506, 508 manufactured by Nippon Cytex Industries.

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

  Among these, Nicalac BX-4000 and SB-401 manufactured by Nihon Cytex Industries and Cymel 1123 manufactured by Nihon Cytex Industry, which are benzoguanamine compounds containing an alkoxyalkyl group, are preferable.

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

 Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] benzene, and bis [1-ethyl (3-oxetanyl). ] Methyl ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxy) methyloxetane, oxetanylsilsesquioxane , Oxetanyl silicate, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,4-bis [[(3-ethyloxetane-3-yl) methoxy] methyl] biphenyl 1-ethyl-3-oxetanylmethyl methacrylate, benzene It can be mentioned 1,4-dicarboxylic acid bis [1-ethyl (3-oxetanyl) methyl] ester and the like, not necessarily limited thereto.

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

  Specific examples of commercially available benzoxazine compounds include, but are not necessarily limited to, benzoxazine Pd type and benzoxazine Fa type manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the blocked carboxylic acid compounds include 1,2-phthalic acid, 1,3-phthalic acid, 1,4-phthalic acid, 1,2,4-trimellitic acid, pyromellitic acid, cyclohexane. Dicarboxylic acid, succinic acid, adipic acid, butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid, C1-CIC acid, CIC acid, C3-CIC acid, Bis-CIC acid, etc. It is not limited to.

Examples of the blocking agent include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, but are not necessarily limited thereto. is not. Moreover, it is used individually by 1 type or in combination of 2 or more types.
As the blocked isocyanate compound, for example, hexamethylene diisocyanate, isophorone diisocyanate, toluidine isocyanate, diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, bis (4-isocyanatocyclohexyl) methane, tetra Diisocyanates such as methylxylylene diisocyanate, isocyanurates of these diisocyanates, trimethylolpropane adduct type, biuret type, prepolymers having isocyanate residues (low polymers obtained from diisocyanates and polyols), uretdiones having isocyanate residues, etc. However, the present invention is not necessarily limited to this.

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

 Specific examples of commercially available carbodiimide compounds include Carbodilite V-01, V-03, V-05 manufactured by Nisshinbo Co., Ltd., but are not necessarily limited thereto.

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

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

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

Among these heat-reactive compounds, melamine compounds or benzoguanamine compounds, epoxy compounds, phenolic compounds, blocked isocyanate compounds, or acrylate monomers are contained in an amount of 1% to 40% by weight in the colored composition of the present invention. It is preferable that it is contained. Moreover, it is preferable that the silane coupling agent is contained in the coloring composition of the present invention in an amount of 0.1 wt% to 40 wt%. If the content is insufficient, heat resistance or chemical resistance may be inferior. Moreover, when content exceeds 40 weight%, the increase in a viscosity or the fall of storage stability may arise.
[Binder resin]
The coloring composition for printing of the present invention can further contain a binder resin. The binder resin is a non-reactive resin even at the reaction temperature of the thermoreactive compound, and is preferably a thermoplastic resin.

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

 A binder resin having a crosslinkable functional group can also be used. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an alkoxyl group.

 As the resin having a crosslinkable functional group, an acrylic resin having a hydroxyl group or a carboxyl group is preferable because the resin is slowly crosslinked by an esterification reaction.

 The acrylic resin having a hydroxyl group or a carboxyl group is a resin obtained by copolymerizing a monomer having a hydroxyl group or a monomer having a carboxyl group and an acrylic monomer having no hydroxyl group or carboxyl group.

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

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

As the acrylic monomer having no hydroxyl group and no carboxyl group, a monomer represented by the general formula (20) may be used.
Formula (20):

Ｒ⁴³：炭素数１〜３０のアルキル基、−ＣＨ₂−ＣＨ＝ＣＨ₂、置換されていてもよいフェニル基又はＣ＝０−Ｃ（Ｒ⁵¹）＝ＣＨ₂を表す。
Ｒ⁴¹及びＲ⁵¹：水素原子又はメチル基を表す。
Ｒ⁴²：炭素数１〜４アルキレン基を表す。
ｓ：１〜１００の整数を表す。

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

 Examples of the monomer represented by the general formula (20) include methoxypolyethylene glycol monomethacrylate, methoxypolyethyleneglycol monoacrylate, octoxypolyethyleneglycol monoacrylate, octoxypolyethyleneglycolpolypropyleneglycolmonomethacrylate, octoxypolyethyleneglycolpolypropyleneglycolmonoacrylate. , Lauroxy polyethylene glycol monoacrylate, lauroxy polyethylene glycol monoacrylate, stearoxy polyethylene glycol monomethacrylate, stearoxy polyethylene glycol-polypropylene glycol monoacrylate, allyloxy polyethylene glycol-polypropylene glycol monomethacrylate, allyloxy Polyethylene glycol-polypropylene glycol monoacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol dimethacrylate, polytetramethylene glycol diacrylate , Poly (ethylene glycol-tetramethylene glycol) dimethacrylate, poly (ethylene glycol-tetramethylene glycol) diacrylate, poly (propylene glycol-tetramethylene glycol) dimethacrylate, poly (propylene glycol-tetramethylene glycol) diacrylate Polyethylene glycol-polypropylene glycol-polyethylene glycol diacrylate, nonylphenoxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol-polypropylene glycol monomethacrylate, nonylphenoxypolypropylene glycol-polyethylene glycol monomethacrylate, nonylphenoxypoly (ethylene glycol-propylene glycol) Examples thereof include monoacrylate, phenol ethylene oxide modified acrylate, nonylphenol ethylene oxide modified acrylate, bisphenol F ethylene oxide modified diacrylate, and the like. These are commercially available as, for example, the Blemmer series from Nippon Oil & Fat Co., Ltd. and the Aronix series from Toa Gosei Co., Ltd.

 Examples of the acrylic monomer having no hydroxyl group or carboxyl group other than the monomer represented by the general formula (20) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth). (Meth) acrylic acid alkyl esters such as acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styrene, α-methyl Styrene, vinyl toluene, vinyl acetate and the like can be mentioned. In addition, monomers generally used for the synthesis of acrylic resins, such as alkyl (meth) acrylates in which some or all of the hydrogen atoms of the alkyl group are substituted with aromatic rings, heterocyclic rings, halogen atoms, or the like, can be used.

 The resin having a crosslinkable functional group is preferably a resin having a phosphoric acid group or a sulfonic acid group because the dispersibility of the pigment and the stability over time are improved and the colored composition has a low viscosity. .

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

The phosphate group contained in the resin having a phosphate group may be a monovalent phosphate group represented by the formula (22) or a divalent phosphate group represented by the formula (23).
Formula (22):

式（２３）：

Formula (23):

リン酸基を有する樹脂としては、例えば、エチレングリコールメタクリレートフォスフェート、プロピレングリコールメタクリレートフォスフェート、エチレングリコールアクリレートフォスフェート、プロピレングリコールアクリレートフォスフェートに代表されるような一般式（２４）で示されるモノマーを重合成分として含有するビニル系重合体を挙げることができる。
一般式（２４）：

As the resin having a phosphoric acid group, for example, a monomer represented by the general formula (24) represented by ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate is used. Examples thereof include a vinyl polymer contained as a polymerization component.
General formula (24):

Ｒ⁴⁴：水素又はメチル基を表す。
Ｒ⁴⁵：アルキレン基を表す。
ｕ：１〜２０の整数を表す。

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

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

これらのリン酸基を有するモノマーは、特公昭５０−２２５３６、特開昭５８−１２８３９３に記載の方法で製造することができる。市販品としては、ホスマーＭ、ホスマーＣＬ、ホスマーＰＥ、ホスマーＭＨ（以上ユニケミカル社製）、ライトエステルＰ−１Ｍ（以上共栄社化学社製）、ＪＡＭＰ−５１４（以上城北化学工業社製）、ＫＡＹＡＭＥＲ ＰＭ−２、ＫＡＹＡＭＥＲ ＰＭ−２１（以上日本化薬社製）等がある。

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

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

 Examples of the resin having a sulfonic acid group include a vinyl polymer containing a monomer having a sulfonic acid group as a polymerization component.

 Examples of the monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid, p-styrenesulfonic acid, methallylsulfonic acid, allylsulfonic acid, Examples include methallyloxybenzenesulfonic acid, allyloxybenzenesulfonic acid, 2-sulfoethyl methacrylate, 4-sulfobutyl methacrylate, and the like.

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

 The weight average molecular weight (Mw) of the resin having a phosphoric acid group or a sulfonic acid group is preferably 1000 to 50000, and more preferably 2000 to 30000.

 A resin having a phosphoric acid group can be obtained by radical polymerization of a monomer having a phosphoric acid group and a monomer having no phosphoric acid group. A resin having a sulfonic acid group can be obtained by radical polymerization of a monomer having a sulfonic acid group and a monomer having no sulfonic acid group. As the monomer not having a phosphoric acid group and the monomer not having a sulfonic acid group, the monomer having a hydroxyl group, the monomer having a carboxyl group, and the monomer having no hydroxyl group and a carboxyl group exemplified above can be used.

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

 As the solvent used in the synthesis of the resin having a sulfonic acid group, it is preferable to use water and / or a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohol solvents such as ethyl alcohol, isopropyl alcohol, and n-propyl alcohol, and mono- or dialkyl ethers of ethylene glycol or diethylene glycol.

 In addition, as a solvent used when synthesizing a resin having a functional group other than a sulfonic acid group, an acetic acid ester solvent such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate, a ketone solvent such as cyclohexanone or methyl isobutyl ketone, Examples include xylene and ethylbenzene.

Moreover, it is preferable to use resin which contains the monomer shown by General formula (25) or General formula (26) as a polymerization component as resin. By using these resins, the dispersibility of the pigment and the stability over time are improved, and the colored composition has a low viscosity.
Formula (25)

式（２６）

Formula (26)

一般式（２５）及び一般式（２６）中、Ｒ⁴⁶及びＲ⁴⁸は水素原子又はメチル基を表し、Ｒ⁴⁷及びＲ⁴⁹は炭素原子数１〜４アルキレン基を表し、ｖ及びｗは１〜１００の整数を表す。

In the general formula (25) and the general formula (26), R ⁴⁶ and R ⁴⁸ represent a hydrogen atom or a methyl group, R ⁴⁷ and R ⁴⁹ represent a C1-4 alkylene group having a carbon atom, v and w are 1 An integer of 100 is represented.

 As monomers represented by the general formula (25) and the general formula (26), paracumylphenol ethylene oxide modified acrylate, ethylene oxide modified bisphenol A dimethacrylate, ethylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A dimethacrylate, Propylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, ethylene oxide-propylene oxide modified bisphenol A diacrylate, propylene oxide ethylene oxide (block type) modified bisphenol A dimethacrylate, propylene oxide tetramethylene oxide modified Bisphenol A dimethacrylate , And propylene oxide tetramethylene oxide-modified bisphenol A diacrylate. These are commercially available as, for example, the Blemmer series from Nippon Oil & Fat Co., Ltd. and the Aronix series from Toa Gosei Co., Ltd.

 The monomers represented by the general formula (25) and the general formula (26) can be used alone or in combination of two or more. Moreover, it is preferable that the copolymerization ratio of the monomer monomer shown by General formula (25) and General formula (26) in a copolymer is 0.1-50 weight part with respect to 100 weight part of all the monomers.

 The weight average molecular weight (Mw) of the resin containing the monomer represented by general formula (25) or general formula (26) as a polymerization component is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

The resin containing the monomer represented by the general formula (25) and the general formula (26) as a polymerization component includes a monomer represented by the general formula (25) and the general formula (26) and another monomer, a hydroxyl group or a carboxyl group. It can be obtained by radical polymerization in the same manner as the acrylic resin having As the other monomer, a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having no hydroxyl group and a carboxyl group, a monomer having a phosphoric acid group, and a monomer having a sulfonic acid group can be used.
[About pigment derivatives]
The coloring composition for printing of the present invention can further contain a pigment derivative.

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

Examples of the basic substituent of the group E include substituents represented by general formula (61), general formula (62), general formula (63), and general formula (64).
Formula (61):

式中、Ｘ⁶¹：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−又は直接結合を表す。
ｐ₆₁：１〜１０の整数を表す。
Ｒ^a61、Ｒ^b61：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、又はＲ^a61とＲ^b61とで一緒になって更なる窒素原子、酸素原子又は硫黄原子を含む置換されていてもよい複素環を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
一般式（６２）：

In the formula, X ^{61 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
p ₆₁ : represents an integer of 1 to 10.
R ^a61 , R ^b61 : each independently an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or a combination of R ^a61 and R ^b61 And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
General formula (62):

Ｒ^a62、Ｒ^b62：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、又はＲ^a62とＲ^b62とで一緒になって更なる窒素原子、酸素原子又は硫黄原子を含む置換されていてもよい複素環を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
一般式（６３）：

R ^a62 , R ^b62 : each independently an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or a combination of R ^a62 and R ^b62 And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
General formula (63):

Ｘ⁶³：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−又は直接結合を表す。
Ｒ^a63：置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
Ｒ^b63、Ｒ^c63、Ｒ^d63、Ｒ^e63：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜５が好ましい。
一般式（６４）：

X ^{63 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
R ^{a63 represents an optionally} substituted alkyl group, an ^optionally substituted alkenyl group, or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ^b63 , R ^c63 , R ^d63 , R ^e63 : each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
Formula (64):

Ｘ⁶⁴：−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−ＣＨ₂−又は直接結合を表す。
Ｙ⁶⁴：−ＮＲ^a64−Ｚ⁶⁴−ＮＲ^b64−又は直接結合を表す。
Ｒ^a64、Ｒ^b64：それぞれ独立に水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜５が好ましい。
Ｚ⁶⁴：置換されていてもよいアルキレン基、置換されていてもよいアルケニレン基、又は置換されていてもよいフェニレン基を表す。アルキレン基及びアルケニレン基の炭素数は１〜８が好ましい。
Ｐ⁶⁴：一般式（６５）で示される置換基又は一般式（６６）で示される置換基を表す。
Ｑ⁶⁴：水酸基、アルコキシル基、一般式（６２）で示される置換基又は一般式（６３）で示される置換基を表す。
一般式（６５）：

X ^{64 represents} —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
Y ⁶⁴ represents —NR ^a64 —Z ⁶⁴ —NR ^b64 — or a direct bond.
R ^a64 and R ^b64 each independently represent a hydrogen atom, an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.
Z ^{64 represents an} alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted. As for carbon number of an alkylene group and an alkenylene group, 1-8 are preferable.
P ⁶⁴ represents a substituent represented by the general formula (65) or a substituent represented by the general formula (66).
Q ^{64 represents a} hydroxyl group, an alkoxyl group, a substituent represented by the general formula (62) or a substituent represented by the general formula (63).
Formula (65):

ｒ₆₅：１〜１０の整数を表す。
Ｒ^a65、Ｒ^b65：それぞれ独立に、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、置換されていてもよいフェニル基、又はＲ^a65とＲ^b65とで一緒になって更なる窒素原子、酸素原子又は硫黄原子を含む置換されていてもよい複素環を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
一般式（６６）：

r ₆₅ : represents an integer of 1 to 10.
R ^a65 , R ^b65 : each independently an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group, an ^optionally substituted phenyl group, or a combination of R ^a65 and R ^b65 And an optionally substituted heterocyclic ring containing a nitrogen atom, an oxygen atom or a sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
General formula (66):

Ｒ^a66：置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜１０が好ましい。
Ｒ^b66、Ｒ^c66、Ｒ^d66、Ｒ^e66：それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基又は置換されていてもよいフェニル基を表す。アルキル基及びアルケニル基の炭素数は１〜５が好ましい。

R ^{a66 represents an optionally} substituted alkyl group, an ^optionally substituted alkenyl group, or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ^b66 , R ^c66 , R ^d66 , R ^e66 : each independently represents a hydrogen atom, an ^optionally substituted alkyl group, an ^optionally substituted alkenyl group or an ^optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferred.

Examples of the acidic substituent or neutral substituent of the group E include substituents represented by the general formula (67), the general formula (68), and the general formula (69).
Formula (67):
-SO ₃ M ⁶⁷ / l ⁶⁷ (67)
M ^{67 represents a} hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom.
l ⁶⁷ : General valence of M ⁶⁷ (68):

Ｒ^a68、Ｒ^b68、Ｒ^c68、Ｒ^d68：水素原子又は炭素数１〜３０のアルキル基を表す（但し全てが水素原子である場合は除く）。
一般式（６９）：

R ^a68 , R ^b68 , R ^c68 , R ^d68 : each represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (except when all are hydrogen atoms).
Formula (69):

Ａ⁶⁹：水素原子、ハロゲン原子、−ＮＯ₂、−ＮＨ₂又はＳＯ₃Ｈを表す。
ｋ₆₉：１〜４の整数を表す。

A ^{69 represents a} hydrogen atom, a halogen atom, —NO ₂ , —NH ₂ or SO ₃ H.
k ₆₉ : represents an integer of 1 to 4.

Examples of the chromogenic compound residue G ⁶ include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrone, and indanthrone. Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, or Examples thereof include metal complex dyes, anthraquinone residues, and triazine residues.

 Moreover, as an anthraquinone derivative, the anthraquinone which has a basic substituent, an acidic substituent, or a neutral substituent can be used. The triazine derivative includes an alkyl group such as a methyl group or an ethyl group, or an alkylamino group such as an amino group or a dimethylamino group, a diethylamino group, or a dibutylamino group, or a nitro group, a hydroxyl group, a methoxy group, or an ethoxy group. Or an alkoxy group such as a butoxy group, or a halogen such as chlorine, or a phenyl group which may be substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group, or the like, or a methyl group, an ethyl group, a methoxy group or an ethoxy group A 1,3,5-triazine which may have a substituent such as a phenylamino group which may be substituted with a group, an amino group, a dimethylamino group, a diethylamino group, a nitro group or a hydroxyl group; A derivative into which a substituent, an acidic substituent, or a neutral substituent is introduced can be used.

Of these, pigment derivatives containing a triazine ring and an anthraquinone group are more preferred. A pigment derivative with a triazine ring and an anthraquinone group structure has a higher adsorptivity to the pigment and a high dispersibility, while at the same time causing a curing reaction of the thermally reactive compound more effectively and further improving the resistance. Can be expected.
[About organic solvents]
The coloring composition of the present invention can further contain an organic solvent. As organic solvents, 2-heptanone, 4-heptanone, cyclohexanone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-amyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl isobutyl Ketone, n-butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Pyrene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate N, N-dimethylformamide, 1,2,3-trichloropropane, o-chlorotoluene, o-xylene, m- Xylene, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol, diisobutyl ketone, ethylene glycol monobutyl ether , Ethylene glycol monohexyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, tri Propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, γ-butyrolactone, N, N-dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, o -Diethylbenzene, m-diethylbenzene, p-diethylben Emissions, o- dichlorobenzene, m- dichlorobenzene, n- butylbenzene, sec- butylbenzene, tert- butylbenzene, cyclohexanol, methyl cyclohexanol. These may be used alone or in combination of two or more. The organic solvent is preferably contained in the colored composition of the present invention in an amount of 60% by weight to 95% by weight.
[About pigment coating]
In the pigment coating treatment, the pigment, the vinyl-based dispersant represented by the general formula (1), the organic solvent, the pigment derivative, and the binder resin are mixed in advance so as to be uniform and then kneaded using a disperser. This can be done. The blending amount of the solvent is preferably adjusted according to the mechanical properties of the mixture. Examples of the disperser used for the coating treatment of the pigment include a kneader, a roll mill, a ball mill, a Banbury mixer, a roller mill, a stone mill, and the like. A two-roll mill is preferable because it can be mixed and kneaded with one apparatus.

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

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

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

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

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

The excess resin component that has not been adsorbed on the pigment surface is preferably removed by washing, filtration, or the like when it affects physical properties such as viscosity of the colored composition. In addition, the coating pigment may be dried after washing if it does not aggregate even if dried, but if the solvent used in the coating treatment is a solvent that can be used as the liquid medium of the coloring composition, it is intentionally dried. There is no need.
[Production of colored composition]
In the production of the colored composition of the present invention, the vinyl dispersant represented by the general formula (1), the pigment, and the leveling agent, and if necessary, the heat-reactive compound, the binder resin, the pigment derivative, and the organic solvent are usually used. It is possible to carry out by dispersing in a disperser and dispersing until a desired average particle size / particle size distribution is obtained. The raw materials for the coloring composition may be mixed and dispersed all at once, or may be mixed and dispersed separately in consideration of the characteristics and economics of each raw material. When the viscosity of the coloring composition is too high and dilution is required, the coloring composition can be prepared by adding a liquid medium for dilution to the coloring composition stock solution and stirring uniformly.

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

In producing the coloring composition, a surfactant-type dispersant, an anthraquinone derivative, and / or a triazine derivative can be further used. Examples of the surfactant type pigment dispersant include naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl phenyl ether, or stearylamine acetate. be able to.
[About printing]
The coloring composition of the present invention is suitably used for printing. Examples of printing methods to which the colored composition of the present invention can be applied include gravure offset printing, waterless offset printing, silk screen printing, and the like.
[Color filter substrate]
A color filter substrate can be produced by a printing method using the colored composition of the present invention. The color filter substrate can be used for, for example, a liquid crystal display panel used for a thin television or the like.

 The color filter substrate is provided with a filter segment of a desired hue, and the filter segment is formed on the same substrate through a blanket after forming a pattern on the substrate using a relief plate or forming a pattern on the intaglio plate. It is formed by printing a colored composition on a substrate by a method of transferring a plurality of patterns in an overlapping manner.

 As the substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate can be used.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. In the following examples and comparative examples, parts and% represent parts by weight and% by weight. Moreover, the weight average molecular weight of resin was measured using GPC and calculated | required in polystyrene conversion.
[Pigment]
1) Red pigment (A): C.I. I. Pigment Red 254
2) Red pigment (B): C.I. I. Pigment Red 57: 1
3) Magenta pigment: C.I. I. Pigment Red 122
4) Green pigment: C.I. I. Pigment Green 36
5) Yellow pigment: C.I. I. Pigment Yellow 138
6) Blue pigment: C.I. I. Pigment Blue 15: 6
7) Cyan pigment: C.I. I. Pigment Blue 15: 3
8) Violet pigment: C.I. I. Pigment Violet 23
9) Black pigment: C.I. I. Pigment Black 7
[Pigment derivatives]
Pigment derivative [RD-1]

顔料誘導体〔ＲＤ−２〕

Pigment derivative [RD-2]

顔料誘導体〔ＭＤ−１〕

Pigment derivative [MD-1]

顔料誘導体〔ＹＤ−１〕

Pigment derivative [YD-1]

顔料誘導体〔ＢＤ−１〕

Pigment derivative [BD-1]

顔料誘導体〔ＶＤ−１〕

Pigment derivative [VD-1]

顔料誘導体〔BLＤ−１〕

Pigment derivative [BLD-1]

[ビニル系分散剤]
ビニル系分散剤の製造例を以下に示す。
《製造例１（ビニル系分散剤Ａ１）》
（１）工程（Ｃ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽にメトキシプロピルアセテートを６０部仕込み、１１０℃に昇温し反応容器内を窒素置換した後、滴下槽から、ｎ−ブチルメタクリレート４０部、ベンジルメタクリレート４８部、２−ヒドロキシエチルメタクリレート１２部、メトキシプロピルアセテート４０部、及びジメチル−２，２’−アゾビスジイソブチレート６部を予め均一に混合した混合液を２時間かけて滴下し、その後３時間、同じ温度で攪拌を続け反応を終了した（製造例１の工程（Ｃ））。このようにして、数平均分子量が３８００であり、一分子中の水酸基の平均個数が３．５個であるビニル系樹脂中間体（Ｃ１）を得た。
（２）工程（Ｄ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応装置にビニル系樹脂中間体（Ｃ１）を固形分で１００部、無水トリメリット酸５．１部、及びジメチルベンジルアミン０．１部を仕込み、１００℃で６時間反応させた（製造例１の工程（Ｄ））。このようにして、一分子あたりのトリメリット酸の平均個数（すなわち、カルボキシル基含有単位（Ｇ）の平均個数）が１．０個であるビニル系分散剤（Ａ１）を得た。ビニル系分散剤（Ａ１）中の固形分比率は５０％であった。
《製造例２（ビニル系分散剤Ａ２）》
（１）工程（Ｃ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽にメトキシプロピルアセテートを６０部仕込み、１１０℃に昇温し反応容器内を窒素置換した後、滴下槽から、２−エチルヘキシルメタクリレート３０．０部、ベンジルメタクリレート６８．３部、２−ヒドロキシエチルメタクリレート１．７部、メトキシプロピルアセテート４０部、及びジメチル−２，２’−アゾビスジイソブチレート６部を予め均一に混合した混合液を２時間かけて滴下し、その後３時間、同じ温度で攪拌を続け反応を終了した（製造例２の工程（Ｃ））。このようにして、数平均分子量が４８００であり、一分子中の水酸基の平均個数が０．５個であるビニル系樹脂中間体（Ｃ２）を得た。
（２）工程（Ｄ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽にメトキシプロピルアセテートを１００部、エチレングリコールジ無水トリメリット酸エステル４．３部、及びジメチルベンジルアミン０．１部を仕込み、１００℃に昇温した。滴下槽からビニル系樹脂中間体（Ｃ２）を固形分で１００部２時間かけて反応槽に滴下し、適下終了後、１００℃で４時間反応させた（製造例２の工程（Ｄ））。その後、２−エチルヘキシルアルコール１０部を加え９０℃で５時間反応させ、残存する無水環をアルコール分解し（製造例（分散剤Ａ２）の工程（Ｄｄ））、エチレングリコールジトリメリット酸骨格の平均共重合個数（すなわち、カルボキシル基含有単位（Ｇ）の平均個数）が０．５個であるビニル系分散剤（Ａ２）を得た。ビニル系分散剤（Ａ２）中の固形分比率は５０％であった。
《製造例３（ビニル系分散剤Ａ３）》
（１）工程（Ｃ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽にメトキシプロピルアセテートを６０部仕込み、１１０℃に昇温し反応容器内を窒素置換した後、滴下槽から、メチルメタクリレート２２部、ラウリルメタクリレート３０部、ベンジルメタクリレート３０部、スチレン１０部、ブレンマーＡＥ−２００（２−ヒドロキシエチルアクリレート１モルに、エチレンオキサイドを平均３．５モル付加させた水酸基を有するエチレン性不飽和単量体、日本油脂社製）８部、メトキシプロピルアセテート４０部、及びジメチル−２，２’−アゾビスジイソブチレート６部を予め均一に混合した混合液を２時間かけて滴下し、その後３時間、同じ温度で攪拌を続け反応を終了した（製造例３の工程（Ｃ））。このようにして、数平均分子量が４４００であり、一分子中の水酸基の平均個数が１．３個であるビニル系樹脂中間体（Ｃ３）を得た。
（２）工程（Ｄ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応装置にビニル系樹脂中間体（Ｃ３）を固形分で１００部、無水トリメリット酸４．４部、ジメチルベンジルアミン０．１部を仕込み、１００℃で６時間反応させた（製造例３の工程（Ｄ））。このようにして、一分子あたりのトリメリット酸の平均個数（すなわち、カルボキシル基含有単位（Ｇ）の平均個数）が１．０個であるビニル系分散剤（Ａ３）を得た。ビニル系分散剤（Ａ３）中の固形分比率は５０％であった。
《製造例４（ビニル系分散剤Ａ４）》
（１）工程（Ｃ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽にメトキシプロピルアセテートを６０部仕込み、１１０℃に昇温し反応容器内を窒素置換した後、滴下槽から、メチルメタクリレート２０部、イソブチルメタクリレート３７．６、ラウリルメタクリレート３０部、ベンジルメタクリレート１０部、Ｎ−ヒドロキシエチルアクリルアミド（興人社製）２．４部、メトキシプロピルアセテート４０部、及びジメチル−２，２’−アゾビス（２−メチルプロピオネート）６部を予め均一に混合した混合液を２時間かけて滴下し、その後３時間、同じ温度で攪拌を続け反応を終了した（製造例４の工程（Ｃ））。このようにして、数平均分子量が４９００であり、一分子中の水酸基の平均個数が１．０個であるビニル系樹脂中間体（Ｃ４）を得た。
（２）工程（Ｄ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応装置にビニル系樹脂中間体（Ｃ４）を固形分で１００部、無水トリメリット酸３．９部、及びジメチルベンジルアミン０．１部を仕込み、１００℃で６時間反応させた（製造例４の工程（Ｄ））。このようにして、一分子あたりのトリメリット酸の平均個数（すなわち、カルボキシル基含有単位（Ｇ）の平均個数）が１．０個であるビニル系分散剤（Ａ４）を得た。ビニル系分散剤（Ａ４）中の固形分比率は５０％であった。
《製造例５（ビニル系分散剤Ａ５）》
（１）工程（Ｃ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽にメトキシプロピルアセテート６０部を仕込み、１１０℃に昇温し反応容器内を窒素置換した後、滴下槽から、ｎ−ブチルメタクリレート３０部、メチルメタクリレート３０部、ベンジルメタクリレート３５部、２−ヒドロキシエチルメタクリレート５部、メトキシプロピルアセテート４０部、及びジメチル−２，２’−アゾビスジイソブチレート６部を予め均一に混合した混合液を２時間かけて滴下し、その後３時間、同じ温度で攪拌を続け反応を終了した（製造例５の工程（Ｃ））。このようにして、数平均分子量が３８００であり、一分子中の水酸基の平均個数が１．５個であるビニル系樹脂中間体（Ｃ５）を得た。
（２）工程（Ｄ）
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応装置にビニル系樹脂中間体（Ｃ５）を固形分で１００部、ピロメリット酸二無水物２．９部、及びジメチルベンジルアミン０．１部を仕込み、１００℃で６時間反応させた（製造例５の工程（Ｄ））。

[Vinyl dispersant]
Production examples of vinyl dispersants are shown below.
<< Production Example 1 (Vinyl Dispersant A1) >>
(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. Part mixture, 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 added dropwise over 2 hours. Thereafter, stirring was continued at the same temperature for 3 hours to complete the reaction (Step (C) of Production Example 1). Thus, a vinyl 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)
100 parts of vinyl resin intermediate (C1) in solid content, 5.1 parts of trimellitic anhydride, and 0.1 parts of dimethylbenzylamine in a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer Was reacted at 100 ° C. for 6 hours (Step (D) of Production Example 1). In this manner, a vinyl dispersant (A1) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained. The solid content ratio in the vinyl dispersant (A1) was 50%.
<< Production Example 2 (Vinyl Dispersant A2) >>
(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. 0.0 part, 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 uniformly mixed. Was added dropwise over 2 hours, followed by stirring at the same temperature for 3 hours to complete the reaction (Step (C) of Production Example 2). Thus, a vinyl resin intermediate (C2) having a number average molecular weight of 4800 and an average number of hydroxyl groups in one molecule of 0.5 was obtained.
(2) Process (D)
A reaction vessel equipped with a gas introduction 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. The temperature was raised to ° C. The vinyl resin intermediate (C2) was added dropwise from the dropping tank to the reaction tank over 100 parts for 2 hours as a solid content, and was reacted at 100 ° C. for 4 hours after completion of the appropriate condition (Process (D) of Production Example 2). . 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 (Dispersant A2)), and the average copolymer of ethylene glycol ditrimellitic acid skeleton was obtained. A vinyl dispersant (A2) having a polymerization number (that is, an average number of carboxyl group-containing units (G)) of 0.5 was obtained. The solid content ratio in the vinyl dispersant (A2) was 50%.
<< Production Example 3 (Vinyl Dispersant A3) >>
(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 (an ethylenically unsaturated monomer having a hydroxyl group obtained by adding an average of 3.5 moles of ethylene oxide to 1 mole of 2-hydroxyethyl acrylate, (Manufactured by NOF Corporation) 8 parts, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2'-azobisdiisobutyrate were mixed in advance dropwise over 2 hours, and then the same for 3 hours. Stirring was continued at temperature to complete the reaction (Step (C) of Production Example 3). Thus, a vinyl resin intermediate (C3) 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 of a vinyl resin intermediate (C3) in solids, 4.4 parts of trimellitic anhydride, and 0.1 parts of dimethylbenzylamine are added. The mixture was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 3). Thus, a vinyl dispersant (A3) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained. The solid content ratio in the vinyl dispersant (A3) was 50%.
<< Production Example 4 (Vinyl Dispersant A4) >>
(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. Isobutyl methacrylate 37.6, lauryl methacrylate 30 parts, benzyl methacrylate 10 parts, N-hydroxyethyl acrylamide (manufactured by Kojin Co., Ltd.) 2.4 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2′-azobis (2- A mixed solution in which 6 parts of methyl propionate) were uniformly mixed in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction (Step (C) of Production Example 4). Thus, a vinyl resin intermediate (C4) 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)
100 parts of vinyl resin intermediate (C4) in solid content, 3.9 parts of trimellitic anhydride, and 0.1 part of dimethylbenzylamine in a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer And reacted at 100 ° C. for 6 hours (Step (D) of Production Example 4). In this manner, a vinyl dispersant (A4) having an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained. The solid content ratio in the vinyl dispersant (A4) was 50%.
<< Production Example 5 (Vinyl Dispersant A5) >>
(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. A mixture of 30 parts of methyl methacrylate, 35 parts of benzyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate in advance. The mixture was added dropwise over 2 hours, and then the reaction was continued for 3 hours at the same temperature to complete the reaction (Step (C) of Production Example 5). In this manner, a vinyl resin intermediate (C5) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 1.5 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 vinyl resin intermediate (C5) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine in an amount of 0. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 5).

In this manner, a vinyl dispersant (A5) having an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8 was obtained.
<< Production Example 6 (Vinyl Dispersant A6) >>
(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. 5 parts, 48 parts of benzyl methacrylate, 23.5 parts of 2-hydroxyethyl methacrylate, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were mixed uniformly in advance. The solution was added dropwise over a period of time, and the reaction was then continued for 3 hours at the same temperature to complete the reaction.

In this manner, a vinyl resin intermediate (C6) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 1.0 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 vinyl resin intermediate (C6) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine in an amount of 0. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 6).

Thus, a vinyl dispersant (A6) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 7 (Vinyl Dispersant A7) >>
(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. .5 parts, 48 parts of benzyl methacrylate, 13.5 parts of 2-hydroxyethyl methacrylate, 10 parts of methacrylic acid, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate are previously mixed uniformly. The mixed solution was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction.

Thus, a vinyl resin intermediate (C7) having a number average molecular weight of 3800 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 of vinyl resin intermediate (C7) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine were added in an amount of 0.1%. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 7).

Thus, a vinyl dispersant (A7) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 8 (Vinyl Dispersant A8) >>
(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. 5 parts, 48 parts benzyl methacrylate, 13.5 parts 2-hydroxyethyl methacrylate, 10 parts t-butyl methacrylate, 40 parts methoxypropyl acetate, and 6 parts dimethyl-2,2'-azobisdiisobutyrate in advance The mixed solution was added dropwise over 2 hours and then stirred at the same temperature for 3 hours to complete the reaction.

In this manner, a vinyl resin intermediate (C8) having a number average molecular weight of 3800 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 of vinyl resin intermediate (C8) in solid content, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine in an amount of 0.1%. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 8).

In this way, a vinyl dispersant (A8) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 9 (Vinyl Dispersant A9) >>
(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. 0.5 part, 48 parts benzyl methacrylate, 3.5 parts 2-hydroxyethyl methacrylate, 20 parts 3-ethyl-3-oxetanylmethyl methacrylate (ETERRNACOLL OXMA, Ube Industries, Ltd.), 40 parts methoxypropyl acetate, and dimethyl-2 , 2′-Azobisdiisobutyrate 6 parts of a mixture mixed in advance was added dropwise over 2 hours, followed by stirring at the same temperature for 3 hours to complete the reaction.

Thus, a vinyl resin intermediate (C9) having a number average molecular weight of 3800 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 of vinyl resin intermediate (C9) in solid content, 5.1 parts of trimellitic anhydride, and dimethylbenzylamine 0.1 Parts were charged and reacted at 100 ° C. for 6 hours.

Thus, a vinyl dispersant (A9) having a number average molecular weight of 4000 and an average number of trimellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )
<< Production Example 10 (Vinyl Dispersant A10) >>
(2) Process (D)
In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (C9) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine in an amount of 0. 1 part was charged and reacted at 100 ° C. for 6 hours.

Thus, a vinyl dispersant (A10) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 11 (Vinyl Dispersant A11) >>
(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. .5 parts, benzyl methacrylate 48 parts, 2-hydroxyethyl methacrylate 3.5 parts, 3-ethyl-3-oxetanylmethyl methacrylate (ETERRNACOLL OXMA, Ube Industries, Ltd.) 10 parts, methacrylic acid 10 parts, methoxypropyl acetate 40 parts , And 6 parts of dimethyl-2,2′-azobisdiisobutyrate were mixed in advance over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction.

Thus, a vinyl resin intermediate (C10) having a number average molecular weight of 3800 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 of vinyl resin intermediate (C10) in solid content, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine, 0.1%. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 11).

Thus, a vinyl dispersant (A11) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 12 (Vinyl Dispersant A12) >>
(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. .5 parts, 48 parts of benzyl methacrylate, 3.5 parts of 2-hydroxyethyl methacrylate, 10 parts of 3-ethyl-3-oxetanylmethyl methacrylate (ETERRNACOLL OXMA, Ube Industries, Ltd.), 10 parts of t-butyl methacrylate, methoxypropyl acetate A mixed solution in which 40 parts and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were uniformly mixed in advance was added dropwise over 2 hours, and then stirred at the same temperature for 3 hours to complete the reaction.

Thus, a vinyl resin intermediate (C11) having a number average molecular weight of 3800 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 of vinyl resin intermediate (C11) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine in an amount of 0.1%. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 12).

Thus, a vinyl dispersant (A12) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 13 (Vinyl Dispersant A13) >>
(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. .5 parts, 48 parts of benzyl methacrylate, 13.5 parts of 2-hydroxyethyl methacrylate, 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, Showa Denko) 10 parts, 40 parts of methoxypropyl acetate, and 6 parts of dimethyl-2,2′-azobisdiisobutyrate were mixed in advance in a dropwise manner over 2 hours, followed by stirring at the same temperature for 3 hours. The reaction was terminated.

Thus, a vinyl resin intermediate (C12) having a number average molecular weight of 3800 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 of vinyl resin intermediate (C12) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine were added in an amount of 0.1%. 1 part was charged and reacted at 100 ° C. for 6 hours (Step (D) of Production Example 13).

Thus, a vinyl dispersant (A13) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 14 (Vinyl Dispersant A14) >>
(1) Step (A)
A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer is charged with 218 parts of pyromellitic dianhydride, 130 parts of 2-hydroxyethyl methacrylate, and 0.3 part of hydroquinone monomethyl ether, and dry air is allowed to flow. The mixture was reacted at 100 ° C. for 5 hours to obtain an ethylenically unsaturated monomer (a14 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate.
(2) Process (Aa)
36 parts of water is added to the ethylenically unsaturated monomer (a14 ′) obtained in the preceding item (1) and reacted at 90 ° C. for 5 hours to remain in the ethylenically unsaturated monomer (a14 ′). The acid anhydride group was hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (a14).
(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, and the temperature was raised to 110 ° C., and the inside of the reaction vessel was replaced with nitrogen. .3 parts, benzyl methacrylate 48 parts, ethylenically unsaturated monomer (a14) 8.7 parts, 3-ethyl-3-oxetanylmethyl methacrylate (ETERRNACOLL OXMA, Ube Industries, Ltd.) 20 parts, methoxypropyl acetate 40 parts , And 6 parts of dimethyl-2,2′-azobisdiisobutyrate were mixed in advance over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction.

Thus, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (a14) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. A vinyl dispersion resin (A14) was obtained.
<< Production Example 15 (Vinyl Dispersant A15) >>
(1) Process (F)
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. 6 parts, benzyl methacrylate 54.8 parts, 2-hydroxyethyl methacrylate 4.0 parts, methacrylic acid 8.6 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts. A mixed solution that had been mixed uniformly in advance was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction.

Thus, a vinyl resin intermediate (F1) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 1.0 was obtained.
(2) Process (G)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of a vinyl resin intermediate (F1) in solids, 14.2 parts of glycidyl methacrylate, and 0.3 part of dimethylbenzylamine. The mixture was reacted at 100 ° C. for 8 hours while flowing dry air.

 After confirming that the acid value was 5 or less, a vinyl resin intermediate (G1) was obtained. At this time, the site where glycidyl methacrylate was reacted with methacrylic acid was 20 parts in total, 28.5 parts of n-butyl methacrylate, 48 parts of benzyl methacrylate, and 3.5 parts of 2-hydroxyethyl methacrylate. Yes.

 A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer is charged with 100 parts of a vinyl resin intermediate (G1) in solid content and 2.9 parts of pyromellitic dianhydride, and dry air is allowed to flow. The reaction was carried out at 100 ° C. for 6 hours.

Thus, a vinyl dispersant (A15) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 16 (Vinyl Dispersant A16) >>
(1) Step (H)
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. 8 parts, benzyl methacrylate 51.9 parts, 2-hydroxyethyl methacrylate 3.8 parts, glycidyl methacrylate 13.5 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts. A mixed solution that had been mixed uniformly 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, a vinyl resin intermediate (H1) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 1.0 was obtained.
(2) Step (I)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of a vinyl resin intermediate (H1) in solids, 8.2 parts of methacrylic acid, and 0.3 part of dimethylbenzylamine. The mixture was reacted at 100 ° C. for 8 hours while flowing dry air.

After confirming that the acid value was 5 or less, a vinyl resin intermediate (I1) was obtained. At this time, the site | part which made methacrylic acid react with glycidyl methacrylate is 20 parts of the whole, n-butyl methacrylate 28.5 parts, benzyl methacrylate 48 parts, and 2-hydroxyethyl methacrylate 3.5 parts. Yes.
(3) Process (J)
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer is charged with 100 parts of the vinyl resin intermediate (I1) in solids and 2.9 parts of pyromellitic dianhydride, and dry air is allowed to flow. The reaction was conducted at 100 ° C. for 6 hours.

Thus, a vinyl dispersant (A16) having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. )
<< Production Example 17 (Vinyl Dispersant A17) >>
(1) Process (K)
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. 0.0 part, benzyl methacrylate 53.9 parts, 2-hydroxyethyl methacrylate 14.2 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts uniformly mixed in advance Was added dropwise over 2 hours, followed by stirring at the same temperature for 3 hours to complete the reaction.

In this manner, a vinyl resin intermediate (K1) having a number average molecular weight of 3800 and an average number of hydroxyl groups in one molecule of 1.0 was obtained.
(2) Step (L)
A reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (K1) in solid content, 2-isocyanatoethyl methacrylate (Karenz MOI, Showa Denko) 12.2. The reaction was carried out at 100 ° C. for 8 hours while flowing dry air.

 After confirming that the acid value was 5 or less, a vinyl resin intermediate (L1) was obtained. At this time, the site where 2-isocyanatoethyl methacrylate (Karenz MOI, Showa Denko) was reacted with 2-hydroxyethyl methacrylate was 20 parts in total, 28.5 parts of n-butyl methacrylate, 48 of benzyl methacrylate 48 Parts, 2-hydroxyethyl methacrylate 3.5 parts.

 In a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (L1) in solids, 2.9 parts of pyromellitic dianhydride, and dimethylbenzylamine in an amount of 0. One part was charged and reacted at 100 ° C. for 6 hours while flowing dry air.

Thus, the vinyl dispersant having a number average molecular weight of 6000 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 0.8. (A17) was obtained.
<< Production Example 18 (Vinyl Dispersant A18) >>
(1) Process (M)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 218 parts of pyromellitic dianhydride, 130 parts of 2-hydroxyethyl methacrylate, and 0.3 part of hydroquinone monomethyl ether, and dry air is allowed to flow. The reaction was carried out at 100 ° C. for 5 hours to obtain an ethylenically unsaturated monomer (M1 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate.
(2) Process (Ma)
36 parts of water is added to the ethylenically unsaturated monomer (M1 ′) obtained in the preceding item (1) and reacted at 90 ° C. for 5 hours to remain in the ethylenically unsaturated monomer (M1 ′). The acid anhydride group was hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (M1).
(3) Process (N)
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. .3 parts, benzyl methacrylate 48 parts, ethylenically unsaturated monomer (M1) 8.7 parts, 2-hydroxyethyl methacrylate 10 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2′-azobisdiisobuty A mixed solution in which 6 parts of the rate 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, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (M1) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. Individual vinyl dispersion resin (N1) was obtained.
(3) Step (O)
A reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, 100 parts of vinyl resin intermediate (N1) in solid content, 2-isocyanatoethyl methacrylate (Karenz MOI, Showa Denko) 11.9 The reaction was carried out at 100 ° C. for 8 hours while flowing dry air.

After confirming that the acid value was 5 or less, the reaction was terminated. Thus, a vinyl dispersant (A18) having a number average molecular weight of 4500 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )
<< Production Example 19 (Vinyl Dispersant A19) >>
(1) Process (P)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is charged with 218 parts of pyromellitic dianhydride, 130 parts of 2-hydroxyethyl methacrylate, and 0.3 part of hydroquinone monomethyl ether, and dry air is allowed to flow. The mixture was reacted at 100 ° C. for 5 hours to obtain an ethylenically unsaturated monomer (P1 ′) in which pyromellitic acid was added to 2-hydroxyethyl methacrylate.
(2) Process (Pa)
36 parts of water is added to the ethylenically unsaturated monomer (P1 ′) obtained in the preceding item (1) and reacted at 90 ° C. for 5 hours to remain in the ethylenically unsaturated monomer (P1 ′). The acid anhydride group was hydrolyzed. Subsequently, the remaining water was removed under reduced pressure to obtain an ethylenically unsaturated monomer (P1).
(3) Process (Q)
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. .3 parts, benzyl methacrylate 48 parts, ethylenically unsaturated monomer (P1) 8.7 parts, methacrylic acid 8 parts, methoxypropyl acetate 40 parts, and dimethyl-2,2'-azobisdiisobutyrate 6 parts Was mixed dropwise in advance over 2 hours, followed by stirring at the same temperature for 3 hours to complete the reaction.

Thus, the number average molecular weight is 4000, and the average number of copolymerized ethylenically unsaturated monomers (P1) per molecule (that is, the average number of carboxyl group-containing units (G)) is 1.0. Individual vinyl dispersion resin (Q1) was obtained.
(3) Process (R)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of vinyl resin intermediate (Q1) in solids and 13.2 parts of glycidyl methacrylate at 100 ° C. while flowing dry air. The reaction was allowed for 8 hours.

After confirming that the acid value was 5 or less, the reaction was terminated. Thus, a vinyl dispersant (A19) having a number average molecular weight of 4500 and an average number of pyromellitic acids per molecule (that is, an average number of carboxyl group-containing units (G)) of 1.0. )
<< Comparative Production Example 1 (Vinyl Dispersant B1) >>
Except that the amount of trimellitic anhydride charged in the step (D) of Production Example 1 is 0.5 parts, the average number of trimellitic acids per molecule (ie, carboxyl) is the same as in Production Example 1. A vinyl dispersant (B1) having an average number of group-containing units (G) of 0.1 was obtained. The solid content ratio in the vinyl dispersant (B1) was 50%.
<< Comparative Production Example 2 (Vinyl Dispersant B2) >>
The average number of trimellitic acids per molecule (ie, carboxyl) is the same as in Production Example 1 except that the amount of trimellitic anhydride charged in Step (D) of Production Example 1 is 17.7 parts. A vinyl dispersant (B2) having an average number of group-containing units (G) of 3.5 was obtained. The solid content ratio in the vinyl dispersant (B2) was 50%.
<< Comparative Production Example 3 (Vinyl Dispersant B3) >>
A reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is obtained by adding 100 parts of the vinyl resin intermediate (C1) obtained in Production Example 1 in solids, 2.7 parts of succinic anhydride, and dimethyl 0.1 part of benzylamine was added and reacted at 100 ° C. for 6 hours. In this way, a vinyl dispersant (B3) having an average number of succinic acid per molecule of 1.0 was obtained. The solid content ratio in the vinyl dispersant (B3) was 50%.
<< Comparative Production Example 4 (Vinyl Dispersant B4) >>
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. A mixture of 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 in advance. The solution was added dropwise over 2 hours, and then stirred for 3 hours at the same temperature to complete the reaction. In this manner, a vinyl dispersant (B4) having a number average molecular weight of 4000 was obtained. The solid content ratio in the vinyl dispersant (B4) was 50%.
<< Comparative Production Example 5 (Vinyl Dispersant B5) >>
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 isobutyl methacrylate, 18 parts dodecyl methacrylate, 3 parts 2-hydroxyethyl methacrylate, 1 part methacrylic acid, 4 parts methacrylsulfoethyl, 40 parts methoxypropyl acetate, and dimethyl-2,2'-azobisdiisobutyrate 6 A mixed solution in which the parts were mixed uniformly 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, a vinyl dispersant (B5) having a number average molecular weight of 4400 was obtained. The solid content ratio in the vinyl dispersant (B5) was 50%. Only the vinyl dispersant (B5) solution was turbid.
<< Comparative Production Example 6 (Vinyl Dispersant B6) >>
Except that the amount of pyromellitic dianhydride charged in step (D) of Production Example 5 is 0.2 parts, the average number of pyromellitic acid per molecule (ie, the same number as that of Production Example 5) Thus, a vinyl dispersant (B6) having an average number of carboxyl group-containing units (G) of 0.1 was obtained. The solid content ratio in the vinyl dispersant (B6) was 50%.
<< Comparative Production Example 7 (Vinyl Dispersant B7) >>
Except that the amount of pyromellitic dianhydride charged in the step (D) of Production Example 5 is 17.7 parts, the average number of pyromellitic acid per molecule (ie, the same number as that of Production Example 5 (ie, Thus, a vinyl dispersant (B7) having an average number of carboxyl group-containing units (G) of 4.1 was obtained. The solid content ratio in the vinyl dispersant (B7) was 50%.
<< Comparative Production Example 8 (Vinyl Dispersant B8) >>
A reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer is obtained by adding 100 parts of the vinyl resin intermediate (C8) obtained in Production Example 8 in solids, 2.7 parts of succinic anhydride, and dimethyl 0.1 part of benzylamine was added and reacted at 100 ° C. for 6 hours. Thus, a vinyl dispersant (B8) having an average number of succinic acids per molecule of 1.0 was obtained. The solid content ratio in the vinyl dispersant (B8) was 50%.
<< Comparative Production Example 9 (Vinyl Dispersant B9) >>
A vinyl dispersant (B9) was obtained in exactly the same manner as in Step (C) of Production Example 9. The solid content ratio in the vinyl dispersant (B9) was 50%.
<< Comparative Production Example 10 (Vinyl Dispersant B10) >>
Except for changing 2.9 parts of pyromellitic dianhydride in Step (G) of Production Example 15 to 3.8 parts of phthalic anhydride, the same method as in Production Example 15 except that phthalic acid per molecule was A vinyl dispersant (B10) having an average number (that is, an average number of carboxyl group-containing units (G)) of 1.0 was obtained. The solid content ratio in the vinyl dispersant (B10) was 50%.
[Polyester dispersion resin]
<< Production Example of Polyester Dispersion Resin (S1) >>
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added and reacted at 120 ° C. for 2 hours to obtain a polyester-based dispersion resin (S1). The obtained polyester dispersion resin (S1) was a white wax-like solid at room temperature.
[Heat-reactive compound]
Nippon Carbide Corp. Alkoxyalkyl Group-Containing Melamine Compound Nicalak MX-43
Nicarac MX-417, an imino group / methylol group-containing melamine compound manufactured by Nippon Carbide Corporation
Nippon Carbide Corp. alkoxyalkyl group-containing benzoguanamine compound Nicalac SB-401
Nippon Carbide Co., Ltd. imino group / methylol group-containing benzoguanamine compound Nicalak BL-60
Epoxy compound EPPN-201 manufactured by Nippon Kayaku Co., Ltd.
Oxetane compound ETERNACOLL-OXBP manufactured by Ube Industries, Ltd.
Isocyanate compound Death Module BL-4265 manufactured by Sumika Bayer Urethane Co., Ltd.
Nippon Kayaku Co., Ltd. acrylic monomer Kayalad TPA-330
[Leveling agent]
FZ2104 manufactured by Toray Dow Corning
FZ2203 manufactured by Toray Dow Corning
BYK302 made by Big Chemie
[Organic solvent]
Methoxypropyl acetate (PGMAc)
Cyclohexanone Example 1
90 parts of red pigment (A), 10 parts of pigment derivative [RD-1], 134 parts of vinyl dispersant (A1), and 323 parts of organic solvent (PGMAc) are placed in a sand mill and dispersed for 4 hours. Further, a melamine compound (Nicarac MX-43) 40 parts, leveling agent (FZ2104) 2 parts, and organic solvent (PGMAc) 446 parts are mixed in a mixer, pressure filtered with a membrane filter, and a coloring composition for printing having a solid content of 20%. I got a thing.
<< Comparative Example 1 >>
In Example 1, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 1 except that 134 parts of the vinyl dispersant (A1) was replaced with 134 parts of the vinyl dispersant (B1). .
Example 2
90 parts of red pigment (A), 10 parts of pigment derivative [RD-1], 94 parts of vinyl dispersant (A1) and 20 parts of polyester dispersion resin (S1) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (Nicarac MX-43) and 2 parts of a leveling agent (FZ2104). And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 3
90 parts of the red pigment (A), 10 parts of the pigment derivative [RD-1], and 134 parts of the vinyl dispersant (A1) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (Nicarac MX-43) and an epoxy compound (EPPN-201). 20 parts, 2 parts of a leveling agent (FZ2104), and 526 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 2 >>
In Example 3, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 3 except that 134 parts of the vinyl dispersant (A1) was replaced with 134 parts of the vinyl dispersant (B2). .
Example 4
90 parts of red pigment (B), 10 parts of pigment derivative [RD-2] and 134 parts of vinyl dispersant (A1) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, further dispersed by 40 parts of a melamine compound (Nicarac MX-43), an oxetane compound (ETERRNACOLL-OXBP). 20 parts, 2 parts of a leveling agent (FZ2104), and 526 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 3 >>
A colored composition for printing having a solid content of 20% was obtained in the same manner as in Example 4 except that 134 parts of the vinyl dispersant (A1) was replaced with 134 parts of the vinyl dispersant (B3). .
Example 5
90 parts of red pigment (B), 10 parts of pigment derivative [RD-2], 134 parts of vinyl dispersant (A2), and 323 parts of organic solvent (PGMAc) are placed in a sand mill and dispersed for 4 hours. Further, a melamine compound (Nicarac MX-43) 40 parts, isocyanate compound (Desmodur BL-4265) 20 parts, leveling agent (FZ2104) 2 parts and organic solvent (PGMAc) 526 parts are mixed in a mixer and pressurized with a membrane filter. Filtration was performed to obtain a coloring composition for printing having a solid content of 20%.
Example 6
90 parts of a magenta pigment, 10 parts of a pigment derivative [MD-1], 134 parts of a vinyl dispersant (A3), and 323 parts of an organic solvent (PGMAc) are placed in a sand mill and dispersed for 4 hours. Further, a melamine compound (Nicarac MX) -43) 40 parts, 20 parts of acrylic monomer (Kayarad TPA330), 2 parts of leveling agent (FZ2104), and 526 parts of organic solvent (PGMAc) are mixed in a mixer, pressure-filtered with a membrane filter, solid content 20 % Of a coloring composition for printing was obtained.
<< Comparative Example 4 >>
In Example 6, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 6 except that 134 parts of the vinyl dispersant (A3) was replaced with 134 parts of the vinyl dispersant (B4). .
Example 7
90 parts of a magenta pigment, 10 parts of a pigment derivative [MD-1], and 134 parts of a vinyl dispersant (A4) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (Nicarac MX-417) and 2 parts of a leveling agent (FZ2104). And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 8
90 parts of green pigment, 10 parts of pigment derivative [BD-1], and 100 parts of vinyl dispersant (A5) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

150 parts of the coating pigment and 350 parts of an organic solvent (PGMAc) are mixed in a mixer, and further dispersed in a sand mill, and further 40 parts of a benzoguanamine compound (Nicarac SB-401) and 2 parts of a leveling agent (FZ2104). , And 418 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 5 >>
In Example 8, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 8 except that 100 parts of the vinyl dispersant (A5) was replaced with 100 parts of the vinyl dispersant (B5). .
Example 9
90 parts of a green pigment, 10 parts of a pigment derivative [BD-1], and 100 parts of a vinyl dispersant (A6) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

150 parts of the coating pigment and 350 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a benzoguanamine compound (Nicarac SB-401) and an epoxy compound (EPPN-201). 20 parts, 2 parts of a leveling agent (FZ2104), and 498 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 10
90 parts of a green pigment, 10 parts of a pigment derivative [BD-1], and 100 parts of a vinyl dispersant (A7) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

150 parts of the coating pigment and 350 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further dispersed by 40 parts of a benzoguanamine compound (Nicalac SB-401) and an oxetane compound (ETERRNACOLL-OXBP). 20 parts, 2 parts of a leveling agent (FZ2104), and 498 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 11
90 parts of a yellow pigment, 10 parts of a pigment derivative [YD-1], and 134 parts of a vinyl dispersant (A8) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a benzoguanamine compound (Nicarac SB-401), an isocyanate compound (Desmodur BL- 4265) 20 parts, leveling agent (FZ2104) 2 parts, and organic solvent (PGMAc) 526 parts were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 6 >>
In Example 11, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 11 except that 134 parts of the vinyl dispersant (A8) was replaced with 134 parts of the vinyl dispersant (B6). .
Example 12
90 parts of a yellow pigment, 10 parts of a pigment derivative [YD-1], and 134 parts of a vinyl dispersant (A9) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of a benzoguanamine compound (Nicarac SB-401), an acrylic monomer (Kayarad TPA-330). ) 20 parts, leveling agent (FZ2104) 2 parts, and organic solvent (PGMAc) 526 parts were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 13
90 parts of a blue pigment, 10 parts of a pigment derivative [BD-1], and 134 parts of a vinyl dispersant (A10) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a benzoguanamine compound (Nicalac BL-60) and 2 parts of a leveling agent (FZ2104). And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 7 >>
In Example 13, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 1 except that 134 parts of the vinyl dispersant (A10) was replaced with 134 parts of the vinyl dispersant (B7). .
Example 14
90 parts of a blue pigment, 10 parts of a pigment derivative [BD-1], and 134 parts of a vinyl dispersant (A11) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of an epoxy compound (EPPN-201), 2 parts of a leveling agent (FZ2104), And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 8 >>
In Example 14, a colored composition for printing having a solid content of 20% was obtained in the same manner as in Example 14 except that 134 parts of the vinyl dispersant (A11) was replaced with 134 parts of the vinyl dispersant (B8). .
Example 15
90 parts of a blue pigment, 10 parts of a pigment derivative [BD-1], and 134 parts of a vinyl dispersant (A12) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, and further dispersed in a sand mill. Further, 40 parts of an oxetane compound (ETERRNACOLL-OXBP), 2 parts of a leveling agent (FZ2104), And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 16
90 parts of a cyan pigment, 10 parts of a pigment derivative [BD-1], and 134 parts of a vinyl dispersant (A13) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of an isocyanate compound (Desmodur BL-4265), leveling agent (FZ2104) 2 And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 17
90 parts of a cyan pigment, 10 parts of a pigment derivative [BD-1], and 134 parts of a vinyl dispersant (A14) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of an acrylic monomer (Kayarad TPA-330), 2 parts of a leveling agent (FZ2104). And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 9 >>
In Example 17, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 17 except that 134 parts of the vinyl dispersant (A14) was replaced with 134 parts of the vinyl dispersant (B9). .
Example 18
90 parts of violet pigment, 10 parts of pigment derivative [VD-1], and 134 parts of vinyl dispersant (A15) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (cyclohexanone) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (MX-43), 2 parts of a leveling agent (FZ2104), And 446 parts of an organic solvent (cyclohexanone) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
Example 19
90 parts of violet pigment, 10 parts of pigment derivative [VD-1], and 134 parts of vinyl dispersant (A16) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (PGMAc) are mixed in a mixer, and further dispersed in a sand mill, and further 40 parts of a melamine compound (MX-43), 2 parts of a leveling agent (FZ2208), And 446 parts of an organic solvent (PGMAc) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Comparative Example 10 >>
In Example 19, a coloring composition for printing having a solid content of 20% was obtained in the same manner as in Example 19 except that 134 parts of the vinyl dispersant (A16) was replaced with 134 parts of the vinyl dispersant (B10). .
Example 20
90 parts of black pigment, 10 parts of pigment derivative [BLD-1], and 134 parts of vinyl dispersant (A17) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (cyclohexanone) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (MX-43), 2 parts of a leveling agent (FZ2208), And 446 parts of an organic solvent (cyclohexanone) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Example 21 >>
90 parts of black pigment, 10 parts of pigment derivative [BLD-1], and 134 parts of vinyl dispersant (A18) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

167 parts of the coating treatment pigment and 390 parts of an organic solvent (cyclohexanone) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (MX-43), 2 parts of a leveling agent (BYK302), And 446 parts of an organic solvent (cyclohexanone) were added and mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.
<< Example 22 >>
90 hours of black pigment, 10 parts of pigment derivative [BLD-1], 94 parts of vinyl dispersant (A19), 20 parts of polyester dispersion resin (S1), and 343 parts of organic solvent (PGMAc) are placed in a sand mill for 4 hours. Dispersion, 40 parts of melamine compound (Nicalak MX-43), 2 parts of leveling agent (BYK302) and 446 parts of organic solvent (PGMAc) are mixed in a mixer, filtered under pressure with a membrane filter, solid content 20% of the coloring composition for printing was obtained.
<< Comparative Example 11 >>
90 parts of black pigment, 10 parts of pigment derivative [BLD-1], and 134 parts of vinyl dispersant (A1) were uniformly stirred to obtain a mixture. When the mixture was put into two rolls heated to 60 ° C. and kneaded for 10 minutes, the solvent was volatilized to form a sheet. Further, 50 parts of an organic solvent (PGMAc) was added, and the two rolls were heated to 80 ° C. and kneaded. During the dispersion, the solvent volatilized and the heated kneaded product became an elastic solid. The obtained solid was cooled and pulverized to obtain a coated pigment.

 167 parts of the coated pigment and 390 parts of an organic solvent (cyclohexanone) are mixed in a mixer, further dispersed in a sand mill, and further 40 parts of a melamine compound (MX-43) and 438 parts of an organic solvent (cyclohexanone). And mixed. Finally, pressure filtration was performed with a membrane filter to obtain a coloring composition for printing having a solid content of 20%.

[Evaluation of the physical properties]
The viscosity and storage stability of the colored compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 11 were evaluated by the following methods. Moreover, using the thin film printing apparatus shown in FIG. 1 for the colored compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 11, the dry coating film thickness is 1 to 2 μm on the glass substrate. The anilox roll was appropriately exchanged for printing, and the transferability duration and precision pattern formation were evaluated by the following methods. The results are shown in Tables 1 to 3. In Tables 1 to 3, the numerical value in the “vinyl dispersant” column indicates the solid content, and the numerical value in the “organic solvent” column indicates the content in the generated colored composition.
(1) Viscosity A viscosity (η: mPa · s) at a shear rate of 100 (1 / s) was measured with a dynamic viscoelasticity measuring apparatus.
<Evaluation criteria>
○: η <30
×: 30 ≦ η
(2) Storage stability Viscosity was measured after heating in a 45 ° C oven for 7 days.
<Evaluation criteria>
○: Thickening rate is less than 10% compared to the viscosity before heating. X: Thickening rate is 10% or more compared to the viscosity before heating. (3) Transferability duration The transfer from the blanket cylinder to the substrate is the same substrate. In the case of transferring the image on the blanket, a waiting time is generated on the blanket cylinder. For this reason, the transferability duration after the colored composition was transferred to the blanket cylinder was measured.
<Evaluation criteria>
○: Interfacial peeling transfer can be performed on the substrate for 3 minutes or more.

 Δ: Interfacial peeling transfer to the substrate is possible for 1 minute or more and less than 3 minutes.

X: Interfacial peeling transfer to the substrate is possible for less than 1 minute.
(4) Precision pattern formability Continuous printing of a straight line having a line width of 50 μm was performed to observe the linear shape.
<Evaluation criteria>
○: A good linear pattern can be continuously printed.

 Δ: The linear pattern is distorted in about 30 continuous printings.

 X: The linear pattern is distorted in about 10 continuous printings.

本発明のビニル系分散剤を用いていない比較例１〜１１では、着色組成物は高粘度かつ保存安定性が悪く、印刷インキとして用いた場合、転写性持続時間が短く、精密なパターンを形成することが困難であった。また、レベリング剤を用いていない比較例１１では、着色組成物をシリコーンブランケットに均一に塗布することができず、転写性持続時間評価、及び精密パターン形成性評価を行うことができなかった。

In Comparative Examples 1 to 11 in which the vinyl dispersant of the present invention is not used, the colored composition has a high viscosity and poor storage stability, and when used as a printing ink, the transferability is short and a precise pattern is formed. It was difficult to do. Moreover, in the comparative example 11 which does not use a leveling agent, a coloring composition could not be apply | coated uniformly to a silicone blanket, and transferability duration evaluation and precision pattern formation evaluation could not be performed.

The colored composition of the present invention has a low viscosity and good storage stability, and when used as a printing ink, it has a long transfer duration and can form a precise pattern. In addition, by using the coloring composition of the present invention, it is possible to produce a high-performance color filter substrate, package, outdoor signboard, or the like much more efficiently than the conventional method.

It is explanatory drawing which showed the thin film printing apparatus used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Dispenser 2 Doctor 3 Anilox roll 4 Plate cylinder 5 Letterpress 6 Silicone rubber blanket cylinder 7 Substrate 8 Printing table 9 Coloring composition

Claims (28)

A printing coloring composition comprising a vinyl dispersant comprising a vinyl polymer, a pigment, and a leveling agent,
The vinyl polymer main chain (A) contains 0.3 to 3.0 average carboxyl group-containing units (G) represented by the following general formula (1) per molecule of the vinyl polymer. A coloring composition for printing, comprising:

General formula (1)

{In general formula (1),
R ¹ is a hydrogen atom or a methyl group,
X ¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ² is a group represented by the general formula: — (— R ^a1 —O—) _m1 −,
(In the formula, 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.)
X ³ is a group represented by the general formula: — (— C (═O) —R ^b1 —O—) _m2 −,
( ^Rb1 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.)
Y ¹ is a group represented by the following general formula (2) or a group represented by the following general formula (3).

General formula (2)

[In general formula (2),
(I) a combination in which one of A ^{1 to} A ³ is a hydrogen atom and the other two are —C (═O) OH;
(Ii) One of A ^{1 to} A ³ is —C (═O) OR ^c (wherein R ^c is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Iii) ^{one of} A ^{1 to} A ³ is a group represented by the following general formula (2a), and the other two are a combination of —C (═O) OH, or
(Iv) ^Three of A ^{1 to} A ³ are —C (═O) OH, and k is 1 or 2. ]
General formula (2a)

[In general formula (2a),
X ²¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ²² is a group represented by the general formula: — (— R ^a21 —O—) _m21 −.
(In the formula, R ^a21 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m21 is an integer of 1 to 50.)
X ²³ is a group represented by the general formula: — (— C (═O) —R ^b21 —O—) _m22 −,
(R ^b21 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m22 is an integer of 0 to 20.)
Z ²¹ is a vinyl polymer main chain (B) containing a group represented by the following general formula (21), wherein the vinyl polymer main chain (A) and the vinyl polymer main chain (B) Can be the same main chain, or each can be a different main chain. ]
Formula (21)

(In the general formula (21), R ²¹ is a hydrogen atom or a methyl group.)

General formula (3)

[In general formula (3),
(V) one of A ^{5 to} A ⁷ is a hydrogen atom and the other two are a combination of —C (═O) OH;
(Vi) one of A ^{5 to} A ⁷ is —C (═O) OR ^d (where R ^d is an alkyl group having 1 to 18 carbon atoms), and the other two are — A combination of C (= O) OH,
(Vii) one of A ^{5 to} A ⁷ is a group represented by the following general formula (3a) and the other two are a combination of —C (═O) OH, or
(Viii) three of A ^{5 to} A ⁷ are —C (═O) OH;
R ² is a direct bond, —CH ₂ —, —O—, —C (═O) —, —C (═O) OCH ₂ CH ₂ OC (═O) —, —C (═O) OCH (OC (═O) CH ₃ ) CH ₂ OC (═O) —, —SO ₂ —, —C (CF ₃ ) ₂ —,
The group represented by the following formula (81) or the group represented by the following formula (82). ]
General formula (3a)

[In general formula (3a),
X ³¹ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ³² is a group represented by the general formula — (— R ^a31 —O—) _m31 −;
(In the formula, R ^a31 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m31 is an integer of 1 to 50.)
X ³³ has the general formula - (- C (= O) -R b31 -O-) m32 - with a group represented by
(R ^b31 is a linear or branched alkylene group having 4 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms, and m32 is an integer of 0 to 20.)
Z ³¹ is a vinyl polymer main chain (C) containing a group represented by the following general formula (31), the vinyl polymer main chain (A), the vinyl polymer main chain (C), Can be the same main chain, or each can be a different main chain. ]
General formula (31)

(In the general formula (31), R ³¹ is a hydrogen atom or a methyl group.)

Formula (81)

Formula (82)

}
Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is
A ^{1 to} A ³ are a group represented by the general formula (2) which is the combination (i), or
A ⁵ to A ⁷ are a group represented by combination (v) a is Formula (3), colored composition according to claim 1. Y ^{1 of the} carboxyl group-containing unit (G) represented by the general formula (1) is
A ^{1 to} A ³ are a group represented by the general formula (2) which is the combination (iii), or
A ⁵ to A ⁷ are a group represented by combination (vii) a is Formula (3), colored composition according to claim 1. Y ¹ carboxyl group-containing unit (G) represented by the general formula (1) is a group represented by the general formula (2), the colored composition according to any one of claims 1 to 3. The coloring composition according to any one of claims 1 to 4, wherein the vinyl polymer comprises a vinyl dispersant represented by the following general formula (4).

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 —C (═O) —X ⁷ —R ⁷ (where X ⁷ is —O— or —NH—, and R ⁷ is a hydrogen atom or the number of carbon atoms. 1 to 18 linear or branched alkyl groups, and R ⁷ may have an aromatic group as a substituent).
X ⁴ is —C (═O) O—, —C (═O) NH—, —O—, —OC (═O) — or —CH ₂ O—,
X ⁵ is a group represented by the formula: — (— R ^a2 —O—) _m3 −;
(In the formula, 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.)
X ⁶ is a group represented by the formula: — (— C (═O) —R ^b2 —O—) _m4 −,
(In the formula, R ^b2 is a linear or branched alkylene group having 4 to 8 carbon atoms, and m4 is an integer of 0 to 20.)
I is a crosslinkability represented by a group represented by the following general formula (51), the following general formula (52), the following general formula (53), the following general formula (54), or the following general formula (55). A functional group-containing unit (I),
p1, p2, p3, and p4 represent the average number of each structural unit per molecule of the vinyl-based dispersant,
p1 is 0.3 or more and 3.0 or less,
p2 is 0 or more and 180 or less,
p3 is 6 or more and 250 or less,
p4 is 0 or more and 180 or less.
A main chain containing a carboxyl group-containing unit (G) in formula (4), a hydroxyl group-containing unit (J) containing —X ⁴ —X ⁵ —X ⁶ —H, and —C (R ⁵ ) (R ⁶ ) —. The arrangement of the structural unit (K) and the crosslinkable functional group-containing unit (I) can be included in a random type or a block type,
The carboxyl group-containing unit (G), the hydroxyl group-containing unit (J), the main chain constituent unit (K), and the crosslinkable functional group-containing unit (I) contained in the general formula (4) are represented by the general formula (4 In the vinyl polymer main chain represented by (1), it is indicated that they are contained in an arbitrary order, and when they are present in plural, they can be the same or different from each other.
]

General formula (51):

[Wherein R ⁵¹ represents a hydrogen atom or a methyl group;
T ¹ is a group represented by the following formula (83), formula (84), or formula (85);
Formula (83)

Formula (84)

Formula (85)

(R ^a51 and R ^b51 are each a linear or branched alkylene group having 1 to 8 carbon atoms.)
T ² is a group represented by the following formula (86), formula (87), or formula (88).
Formula (86)

(R ^c51 and R ^d51 are each a linear or branched alkylene group having 1 to 8 carbon atoms, or R ^c51 and R ^d51 are integrated to form a cyclic structure having 3 to 8 carbon atoms. Represents.)
Formula (87)

(R ^e51 , R ^f51 , and R ^g51 are each a hydrogen atom or a linear or branched alkylene group having 1 to 8 carbon atoms.)
Formula (88)

(N51 is an integer of 1-8.)
]
Formula (52):

[Wherein R ⁵² represents a hydrogen atom or a methyl group;
R ^a52 is a linear or branched alkylene group having 1 to 8 carbon atoms,
R ^b52 is a linear or branched alkyl group having 1 to 8 carbon atoms. ]
Formula (53):

[Wherein, R ⁵³ represents a hydrogen atom or a methyl group. ]
Formula (54):

[ ^Wherein , R ⁵⁴ and R ^c54 each represent a hydrogen atom or a methyl group,
R ^a54 and R ^b54 are each a linear or branched alkylene group having 1 to 8 carbon atoms. ]
Formula (55):

[ ^Wherein , R ⁵⁵ and R ^d55 each represent a hydrogen atom or a methyl group,
X ^a55 is —C (═O) O—, —C (═O) ^NH— , ^—O— , —OC (═O) — or —CH ₂ O—,
X ^b55 is a group represented by the formula: — (— R ^b55 —O—) _m55 −;
(In the formula, R ^b55 is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms, and m55 is an integer of 1 to 50.)
X ^c55 is a group represented by the formula: — (— C (═O) —R ^c55 —O—) _n55 —,
( ^Wherein R ^c55 is a linear or branched alkylene group having 4 to 8 carbon atoms, and n55 is an integer of 0 to 20)
T ⁵ is a group represented by the following formula (89), formula (90), or formula (91).
Formula (89)

Formula (90)

Formula (91)

(R ^e55 and R ^f55 are each a linear or branched alkylene group having 1 to 8 carbon atoms.)]
 The coloring composition as described in any one of Claims 1-5 whose number average molecular weights of a vinyl polymer are 500 or more and 40000 or less. Vinyl polymer
(A) 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 dianhydride (M4) is produced. Process,
(B) It is manufactured by the manufacturing method including the process of copolymerizing the ethylenically unsaturated monomer and other ethylenically unsaturated monomer obtained at a process (A). The coloring composition as described in any one of 6. Vinyl polymer
(C) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group with another ethylenically unsaturated monomer,
(D) It is manufactured by a manufacturing method including a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) with a hydroxyl group of the copolymer obtained in the step (C). The coloring composition as described in any one of Claims 1-6. Vinyl polymer
(E) While the ethylenically unsaturated monomer (h) having a hydroxyl group is copolymerized with another ethylenically unsaturated monomer, a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride ( The coloring composition as described in any one of Claims 1-6 manufactured by the manufacturing method with which M4) is made to react. Vinyl polymer
(F) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having a carboxyl group;
(G) In the copolymer obtained in step (F), an ethylenically unsaturated compound having an epoxy group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic acid dianhydride (M4) may be used simultaneously or The coloring composition according to claim 5, which is produced by a production method including a step of reacting in an arbitrary order. Vinyl polymer
(H) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group and an ethylenically unsaturated monomer having an epoxy group;
(I) a step of reacting an ethylenically unsaturated compound having a carboxyl group with the epoxy group of the copolymer obtained in step (H),
(J) It is produced by a production method comprising a step of reacting a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) with the hydroxyl group of the copolymer obtained in the step (I). The coloring composition according to claim 5. Vinyl polymer
(K) a step of copolymerizing an ethylenically unsaturated monomer (h) having a hydroxyl group,
(L) An ethylenically unsaturated compound having an isocyanate group and a tricarboxylic acid anhydride (M3) or a tetracarboxylic dianhydride (M4) are simultaneously added to the hydroxyl group of the copolymer obtained in the step (K). Or the coloring composition of Claim 5 which is manufactured by the manufacturing method including the process made to react in arbitrary orders. Vinyl polymer
(M) 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 dianhydride (M4) is produced. Process,
(N) a step of copolymerizing the ethylenically unsaturated monomer obtained in step (M) (provided that an unreacted hydroxyl group remains);
(O) Coloring according to claim 5, which is produced by a production method including a step of reacting an ethylenically unsaturated compound having an isocyanate group with the hydroxyl group of the copolymer obtained in step (N). Composition. Vinyl polymer
(P) 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 dianhydride (M4) is produced. Process,
(Q) A step of copolymerizing the ethylenically unsaturated monomer obtained in step (P) with an ethylenically unsaturated monomer having a carboxyl group,
(R) The colored composition according to claim 5, which is produced by a production method comprising a step of reacting an ethylenically unsaturated compound having an epoxy group with the copolymer obtained in step (Q). .  The coloring composition according to any one of claims 7 to 14, wherein the tricarboxylic acid anhydride (M3) or the tetracarboxylic dianhydride (M4) is trimellitic acid anhydride or pyromellitic acid anhydride.  The coloring composition according to any one of claims 1 to 15, further comprising a thermoreactive compound.  The thermoreactive compound is composed of a melamine compound, a benzoguanamine compound, a carbodiimide compound, an epoxy compound, an oxetane compound, a phenol compound, a benzoxazine compound, a blocked carboxylic acid compound, a blocked isocyanate compound, an acrylate monomer, and a silane coupling agent. The coloring composition of Claim 16 which is 1 type, or 2 or more types of compounds chosen from the group.  The coloring composition according to any one of claims 1 to 17, further comprising a binder resin.  The colored composition according to claim 18, wherein the binder resin is a thermoplastic resin.  The coloring composition according to any one of claims 1 to 19, further comprising a pigment derivative. The coloring composition of Claim 20 whose pigment derivative is a compound represented by General formula (5).
General formula (5)
G ^1- (E) q (5)
(In the formula, G ¹ is a chromogenic compound residue,
E is a basic substituent, an acidic substituent, or a neutral substituent;
q is an integer of 1 to 4. )  The pigment derivative is at least one basic derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. The coloring composition according to claim 21.  The coloring composition according to any one of claims 1 to 22, further comprising an organic solvent.  The coloring composition as described in any one of Claims 1-23 whose content of a pigment is 1 to 30 weight% with respect to coloring composition total weight.  The coloring composition as described in any one of Claims 1-24 whose weight ratio of a pigment and a vinyl-type dispersing agent is 100: 3-100: 150.  The coloring composition as described in any one of Claims 1-25 whose viscosity in 25 degreeC is 2-40 mPa * s.  The coloring composition as described in any one of Claims 1-26 which is an object for color filter substrates.  A color filter substrate carrying a printed layer comprising the colored composition according to any one of claims 1 to 27 on a substrate.

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