JP6829571B2 - Pigment dispersion composition - Google Patents

Description

The present invention relates to pigment dispersion compositions.

For example, a color filter used in an image display device such as a liquid crystal display device usually has a photosensitive resin composition containing a coloring material such as a pigment and a photocurable resin applied to a transparent substrate, and then a photolithography method or the like. Manufactured by. In recent years, with the demand for higher performance of image display devices, color filters that can contribute to improvement of brightness, contrast, etc. are required. Examples of a method for forming a color filter that can contribute to the improvement of brightness and contrast include a method of miniaturizing a pigment as a coloring material in a pigment dispersion composition. However, there is a problem that the finer the pigment, the worse the dispersion stability.

Not only in the above color filter applications, but also in other applications, the cured product formed by the photosensitive resin composition tends to be required to be finely divided and densified, and the pigment contained in the composition is also dispersed. There is a need for good miniaturization.

Japanese Unexamined Patent Publication No. 2010-168580

The present invention has been made to solve the above problems, and an object of the present invention is to provide a pigment dispersion composition having excellent dispersion stability of a pigment.

式（２）中、ｎ１は１〜１０である。
１つの実施形態においては、上記アルカリ可溶性樹脂が、主鎖に環構造を有する構成単位（Ｂ）をさらに含む。
１つの実施形態においては、上記アルカリ可溶性樹脂が、側鎖に酸基を有する構成単位をさらに含む。
１つの実施形態においては、上記アルカリ可溶性樹脂が、側鎖に炭素二重結合を有する構成単位をさらに含む。 The pigment dispersion composition of the present invention contains an alkali-soluble resin, a pigment, a pigment dispersant, and a solvent, and the alkali-soluble resin contains a structural unit having a biphenyl group in a side chain of the pigment dispersant. The acid value is 15 mgKOH / g or less.
In one embodiment, the amine value of the pigment dispersant is 25 mgKOH / g or less.
In one embodiment, the alkali-soluble resin is a (meth) acrylic resin.
In one embodiment, the structural unit having a biphenyl group in the side chain is a structural unit derived from a monomer represented by the general formula (1) or (2).

In formula (2), n1 is 1-10.
In one embodiment, the alkali-soluble resin further comprises a structural unit (B) having a ring structure in the main chain.
In one embodiment, the alkali-soluble resin further comprises a structural unit having an acid group in the side chain.
In one embodiment, the alkali-soluble resin further comprises a structural unit having a carbon double bond in the side chain.

According to the present invention, it is possible to provide a pigment dispersion composition having excellent dispersion stability of a pigment.

A. Outline of Pigment Dispersion Composition The pigment dispersion composition of the present invention contains an alkali-soluble resin, a pigment, a pigment dispersant, and a solvent. The alkali-soluble resin contains a structural unit having a biphenyl group in the side chain. The pigment dispersant has an acid value of 15 mgKOH / g or less. In the present invention, the dispersion stability of the pigment is extremely excellent by using an alkali-soluble resin containing a structural unit having a biphenyl group in the side chain and a pigment dispersant having an acid value of 15 mgKOH / g or less in combination. It is possible to obtain a pigment dispersion composition in which the pigment does not easily aggregate over time. In the present invention, even if the pigment is made finer, deterioration of dispersibility can be suppressed.

In one embodiment, the pigment dispersion compositions of the present invention can be used in combination with polyfunctional monomers and photopolymerization initiators. The resin composition containing the pigment dispersion composition, the polyfunctional monomer, and the photopolymerization initiator can be used as a photosensitive resin composition, for example, a color filter, a photospacer, an overcoat, a black matrix, a black column spacer, an ink, or a paint. , Can be suitably used as a sealant or the like. In the pigment dispersion composition of the present invention, it is possible to miniaturize the pigment without impairing the dispersibility. Therefore, by using the composition, a color filter that can contribute to the improvement of brightness and contrast can be formed. Can be done.

B. Alkali-soluble resin As described above, the alkali-soluble resin contains a structural unit having a biphenyl group in the side chain. When the alkali-soluble resin has a structural unit (A) having a biphenyl group in the side chain, a pigment dispersion composition having excellent dispersion stability of the pigment can be obtained. Further, by using an alkali-soluble resin having a structural unit (A) having a biphenyl group in the side chain, a pigment dispersion composition that can be used as a material for a photosensitive resin composition having an excellent developing speed can be obtained. Further, a cured product (for example, a color filter) produced by using a pigment dispersion composition containing an alkali-soluble resin having a structural unit (A) having a biphenyl group in a side chain has excellent adhesion to a substrate and has excellent adhesion to a substrate. Also excellent in smoothness. The alkali-soluble resin is typically a (meth) acrylic resin. The (meth) acrylic resin is particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing at least 10% by weight (mass%) of a (meth) acrylic monomer such as (meth) acrylic acid ester. However, the monomer composition may contain other monomers copolymerizable with the (meth) acrylic monomer.

In one embodiment, the alkali-soluble resin may further comprise a structural unit (B) having a ring structure in the main chain. Further, the alkali-soluble resin may further contain a structural unit (C) having an acid group in the side chain. Further, the alkali-soluble resin may further contain another structural unit (D), if necessary.

The alkali-soluble resin can be obtained by polymerizing a monomer composition I containing a monomer (a) having a biphenyl group in the side chain. When the alkali-soluble resin has a structural unit (B) having a ring structure in the main chain, the alkali-soluble resin has a monomer (a) having a biphenyl group in the side chain and a ring structure in the main chain. It can be obtained by polymerizing a monomer composition I containing a monomer (b) and / or a monomer (b') capable of forming a ring structure. The above-mentioned monomer composition I includes a monomer (monomer (c) having an acid group, a monomer (c') into which an acid group can be introduced) and / or other monomers constituting the structural unit (C) having an acid group in the side chain. Other monomers (d) constituting the structural unit (D) may be further contained. In one embodiment, the monomer (a), monomer (c), monomer (c') and / or monomer (d) are (meth) acrylic monomers, preferably acrylic monomers.

B-1. A structural unit having a biphenyl group in the side chain (A)
When the alkali-soluble resin has a structural unit (A) having a biphenyl group in the side chain, a pigment dispersion composition having excellent dispersion stability of the pigment can be obtained. Preferably, the structural unit (A) having a biphenyl group in the side chain is a structural unit derived from a (meth) acrylic monomer.

式（２）中、ｎ１は１〜１０であり、好ましくは１または２である。 Examples of the structural unit (A) having a biphenyl group in the side chain include biphenyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate (ethoxylated o-phenylphenol (meth) acrylate), and o-biphenyloxyethoxy. Ethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) acrylate , M-biphenyloxy-2-hydroxypropyl (meth) acrylate, N- (meth) acryloyloxyethyl-o-biphenyl = carbamate, N- (meth) acryloyloxyethyl-p-biphenyl = carbamate, N- (meth) Examples thereof include structural units derived from the monomer (a) having a biphenyl group on the side chain such as acryloyloxyethyl-m-biphenyl = carbamate, o-phenylphenol glycidyl ether acrylate, and o-biphenyloxypropyl (meth) acrylate. Of these, it is a constituent unit derived from an acrylic monomer. If an acrylic monomer having no methyl group in the double bond portion is used, a pigment dispersion composition that can be used as a material for a photosensitive resin composition having a high development speed can be obtained. In one embodiment, the structural unit (A) having a biphenyl group in the side chain is a structural unit derived from the monomer (a) represented by the general formula (1) or (2). More preferably, the structural unit (A) having a biphenyl group in the side chain is a structural unit derived from the monomer (a) represented by the general formula (2). The above-mentioned monomers may be used alone or in combination of two or more.

In formula (2), n1 is 1 to 10, preferably 1 or 2.

The content ratio of the structural unit (A) having a biphenyl group in the side chain is preferably 10 parts by weight to 80 parts by weight, and more preferably 15 parts by weight to 100 parts by weight with respect to 100 parts by weight (mass part) of the alkali-soluble resin. It is 70 parts by weight, more preferably 20 parts by weight to 65 parts by weight. Within such a range, the effect of the present invention becomes more remarkable.

In the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (a) having a biphenyl group in the side chain is preferably 20 parts by weight to 80 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is a part by weight, more preferably 30 parts by weight to 70 parts by weight, and further preferably 40 parts by weight to 65 parts by weight. Within such a range, the effect of the present invention becomes more remarkable.

B-2. Structural unit (B) having a ring structure in the main chain
When the alkali-soluble resin has a structural unit (B) having a ring structure in the main chain, a resin having high solubility in alkali can be obtained.

Examples of the structural unit (B) having a ring structure in the main chain include a structural unit having a maleimide structure, an N-substituted maleimide structure, a lactone ring structure, a glutaric anhydride structure, a maleic anhydride structure, and the like. Of these, a maleimide structure or an N-substituted maleimide structure is preferable. By using an alkali-soluble resin having a structural unit having a maleimide structure or an N-substituted maleimide structure in the main chain, a resin having high solubility in alkali can be obtained. Specifically, the structural unit (B) having a ring structure in the main chain is preferably at least one selected from the structural units represented by the general formulas (3) to (5), and the general formula (3). ) Is more preferable. By using an alkali-soluble resin (preferably (meth) acrylic resin) having a structural unit represented by the general formula (3), a pigment dispersion composition capable of forming a cured product having high strength can be obtained.

式（６）〜（９）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６はそれぞれ独立して、水素原子または炭素数が１〜３０の直鎖状もしくは分岐状のアルキル基であり、好ましくは水素原子または炭素数が１〜１０の直鎖状もしくは分岐状のアルキル基であり、より好ましくは水素原子または炭素数が１〜５の直鎖状もしくは分岐状のアルキル基であり、さらに好ましくはメチル基である。 The structural unit (B) having a ring structure in the main chain may be at least one selected from the structural units represented by the general formulas (6) to (9). Of these, it is a structural unit represented by the general formula (6) or (9).

In formulas (6) to (9), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently linear or branched with hydrogen atoms or 1 to 30 carbon atoms. It is an alkyl group, preferably a linear or branched alkyl group having 1 to 10 hydrogen atoms or carbon atoms, and more preferably a linear or branched alkyl group having 1 to 5 hydrogen atoms or carbon atoms. It is a group, more preferably a methyl group.

The structural unit (B) having a ring structure in the main chain may be composed of the monomer (b) having a ring structure in the main chain. Examples of the monomer (b) having a ring structure in the main chain include maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, NO-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, and Np-hydroxyphenylmaleimide. , NO-Chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, NO- Aromatic substituted maleimides such as methoxyphenyl maleimide, Nm-methoxyphenyl maleimide, Np-methoxyphenyl maleimide; alkyl substituted maleimides such as cyclohexyl maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, isopropyl maleimide and the like. Be done. Of these, maleimide, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are preferable, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are more preferable, and benzylmaleimide is more preferable. The above-mentioned monomers may be used alone or in combination of two or more.

式（１０）および（１１）中、Ｒ^１、Ｒ^２およびＲ^３は上記で説明したとおりである。 As the monomer constituting the structural unit (B) having a ring structure in the main chain, a monomer (b') capable of forming a ring structure by an intramolecular cyclization step may be used. According to the monomer (b'). The structural units represented by the general formulas (6) to (9) are formed. Examples of the monomer (b') include 1,6-dienes represented by the general formula (10) or (11).

In formulas (10) and (11), R ¹ , R ² and R ³ are as described above.

The content ratio of the structural unit (B) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight, and more preferably 8 parts by weight to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. Yes, more preferably 10 to 25 parts by weight.

In the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (b) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is a part by weight, more preferably 8 parts by weight to 30 parts by weight, and further preferably 10 parts by weight to 25 parts by weight. Further, in the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (b') capable of forming a ring structure is preferably 5 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition I. It is ~ 50 parts by weight, more preferably 8 parts by weight to 30 parts by weight, and further preferably 10 parts by weight to 25 parts by weight.

B-3. Constituent unit (C) having an acid group in the side chain
Preferably, the alkali-soluble resin has a structural unit (C) having an acid group in the side chain. If the alkali-soluble resin has a structural unit (C) having an acid group in the side chain, a pigment dispersion composition that can be used as a material for a photosensitive resin composition having excellent alkali developability can be obtained. Examples of the monomer (monomer (c) having an acid group) constituting the structural unit (C) having an acid group in the side chain include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and itaconic acid. Monomers having a carboxyl group such as acid and ω-carboxy-polycaprolactone monoacrylate; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride can be mentioned. Of these, (meth) acrylic acid is preferable. These monomers may be used alone or in combination of two or more.

As the monomer constituting the structural unit (C) having an acid group in the side chain, a monomer (c') into which an acid group can be introduced may be used. The monomer (c') is a monomer capable of imparting an acid group after polymerization. Examples of the monomer (c') include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and an isocyanate such as 2-isocyanatoethyl (meth) acrylate. Examples include a monomer having a group. These monomers may be used alone or in combination of two or more. The post-treatment for imparting an acid group differs depending on the type of monomer (c') used, but when a monomer (c') having a hydroxyl group is used, for example, succinic anhydride and tetrahydrophthalic anhydride , An acid anhydride such as maleic anhydride may be added. When a monomer (c') having an epoxy group is used, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol is added, or (meth). An acid anhydride (for example, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride) may be added to the hydroxyl group generated after the addition of an acid such as acrylic acid. When a monomer (c') having an isocyanate group is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

The content ratio of the structural unit (C) having an acid group in the side chain is preferably 10 parts by weight to 60 parts by weight, more preferably 15 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. Yes, more preferably 15 to 45 parts by weight.

The content ratio of the monomer (c) having an acid group in the above-mentioned monomer composition I for fat-forming an alkali-soluble tree is preferably 15 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 50 parts by weight. Yes, more preferably 20 parts by weight to 45 parts by weight. Further, in the above-mentioned monomer composition I for forming an alkali-soluble resin, the content ratio of the monomer (c') into which an acid group can be introduced is preferably 15 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 50 parts by weight. It is a part by weight, more preferably 20 parts by weight to 45 parts by weight.

B-4. Other structural units (D)
The alkali-soluble resin may further have another structural unit (D). Other structural units include a structural unit (D1) having two or more oxyalkylene groups in the side chain, the above-mentioned monomer (a), monomer (a'), monomer (b), monomer (c) and / or monomer ( Examples thereof include a structural unit (D2) derived from another monomer (d2) that can be polymerized with c').

(Constituent unit (D1) having two or more oxyalkylene groups in the side chain)
Since the alkali-soluble resin has a structural unit (D1) having two or more oxyalkylene groups in the side chain, it can be used as a material for a photosensitive resin composition capable of forming a color filter having high crosslink density and high breaking strength. The pigment dispersion composition to be obtained can be obtained. In addition, a pigment dispersion composition having particularly excellent pigment dispersibility can be obtained. When an alkali-soluble resin having a structural unit (D1) and a polyfunctional monomer described later (preferably a polyfunctional monomer having no oxyalkylene group) are combined to form a photosensitive resin composition, the above effect is obtained. This is especially noticeable.

式（１２）中、Ｒ^７、Ｒ^８およびＲ^９はそれぞれ独立して、水素原子またはメチル基であり、好ましくは水素原子である。Ｒ^１０は、炭素数が１〜２０の直鎖状もしくは分岐状のアルキル基、炭素数が２〜２０の直鎖状もしくは分岐状のアルケニル基または炭素数が６〜２０の芳香族炭化水素基であり、好ましくは水素原子、炭素数が１〜２０の直鎖状のアルキル基、炭素数が２〜２０の直鎖状のアルケニル基または炭素数が６〜２０の芳香族炭化水素基であり、より好ましくは炭素数が１〜１０の直鎖状のアルキル基または炭素数が６〜１２の芳香族炭化水素基であり、さらに好ましくは炭素数が１〜５の直鎖状のアルキル基、フェニル基またはビフェニル基であり、特に好ましくはメチル基、フェニル基またはビフェニル基である。なお、アルキル基、アルケニル基および芳香族炭化水素基は、置換基を有していてもよい。ＡＯは、オキシアルキレン基を表す。ＡＯで表されるオキシアルキレン基の炭素数は２〜２０であり、好ましくは２〜１０であり、より好ましくは２〜５であり、さらに好ましくは２である。構成単位（Ｄ１）は１種または２種以上のオキシアルキレン基を含み得る。ｘは０〜２の整数を表す。ｙは０または１を表す。ｎ２は、オキシアルキレン基の平均付加モル数を表し、２以上であり、好ましくは２〜１００であり、より好ましくは２〜５０であり、さらに好ましくは２〜１５である。ｎ２がこのような範囲であれば、基材との密着性に優れるカラーフィルターを形成し得る感光性樹脂組成物の材料となり得る顔料分散組成物を得ることができる。 Examples of the structural unit (D1) having two or more oxyalkylene groups in the side chain include the structural unit represented by the general formula (12).

In formula (12), R ⁷ , R ⁸ and R ⁹ are independently hydrogen atoms or methyl groups, preferably hydrogen atoms. R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. It is preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. , More preferably a linear alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms. It is a phenyl group or a biphenyl group, and particularly preferably a methyl group, a phenyl group or a biphenyl group. The alkyl group, alkenyl group and aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The oxyalkylene group represented by AO has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2. The structural unit (D1) may contain one or more oxyalkylene groups. x represents an integer from 0 to 2. y represents 0 or 1. n2 represents the average number of moles of the oxyalkylene group added, and is 2 or more, preferably 2 to 100, more preferably 2 to 50, and even more preferably 2 to 15. When n2 is in such a range, a pigment dispersion composition that can be used as a material for a photosensitive resin composition capable of forming a color filter having excellent adhesion to a substrate can be obtained.

The structural unit (D1) having two or more oxyalkylene groups in the side chain is composed of the monomer (d1) having two or more oxyalkylene groups in the side chain. Examples of the monomer (d1) include ethoxylated o-phenylphenol (meth) acrylate (EO2 mol), phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO4 mol), and methoxypolyethylene glycol (meth) acrylate. (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2-ethylhexyldiethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (EO4-17 mol), nonylphenoxypolyethylene glycol (meth) acrylate (PO5 mol), EO-modified cresol (meth) Examples thereof include acrylate (2 mol of EO). These monomers may be used alone or in combination of two or more. In the present specification, for example, notations such as "EO 2 mol" and "PO 5 mol" represent the average number of moles of oxyalkylene groups added.

The content ratio of the structural unit (D1) having two or more oxyalkylene groups in the side chain is preferably 0.1 part by weight to 10 parts by weight, more preferably 0 parts by weight, based on 100 parts by weight of the alkali-soluble resin. It is 5 parts by weight to 5 parts by weight.

In the above-mentioned monomer composition I for forming the alkali-soluble resin, the content ratio of the monomer (d1) having two or more oxyalkylene groups in the side chain is preferably 1 part by weight to 10 parts by weight, more preferably 2 parts by weight. ~ 5 parts by weight.

(Constituent unit (D2) derived from other monomer (d2))
The structural unit (D2) derived from the other monomer (d2) is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth). Acrylamide, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl ( Meta) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl ethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) Acrylamide, biphenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, nonylphenoxy (Meta) acrylic acid esters such as ethylene glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acryloylmorpholin (morpholino (meth) acrylate), ( Meta) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-t-butyl (meth) acrylamide, N-t- Octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (Meta) Acrylamides such as (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, etc. Acrylamide or substituted butadiene compounds such as butadiene, isoprene, ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile; constituent units derived from a monomer (d2) such as vinyl esters such as vinyl acetate. These monomers may be used alone or in combination of two or more.

The content ratio of the structural unit (D2) is preferably 0 parts by weight to 55 parts by weight, more preferably 5 parts by weight to 50 parts by weight, and further preferably 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. It is a part by weight to 45 parts by weight.

B-5. Polymerization of Alkali-Soluble Resin The alkali-soluble resin can be obtained by polymerizing a monomer composition containing the above-mentioned monomer by any suitable method. Examples of the polymerization method include a solution polymerization method.

The monomer composition may contain any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl. Examples include esters such as acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethylsulfoxide and the like. These solvents may be used alone or in combination of two or more. The polymerization concentration when polymerizing the above-mentioned monomer composition is preferably 5% by weight (mass%) to 90% by weight, more preferably 5% by weight to 50% by weight, and further preferably 10% by weight to 50% by weight. Weight%.

The monomer composition may contain any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amylperoxy-2. Organic peroxides such as -ethylhexanoate, t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate). The content ratio of the polymerization initiator is preferably 0.1 parts by weight to 15 parts by weight, more preferably 0.2 parts by weight to 10 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition.

The monomer composition may include any suitable chain transfer agent. Examples of the chain transfer agent include monofunctional thiol compounds such as n-dodecyl mercaptoethanol and β-mercaptopropionic acid; bifunctional thiol compounds such as both-terminal mercapto-modified polysiloxane; side chain polyfunctional mercapto having mercapto-modified side chains. Examples include modified polysiloxane. The content ratio of the chain transfer agent is preferably 0.1 parts by weight to 15 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition.

The polymerization temperature when the alkali-soluble resin is polymerized by the solution polymerization method is preferably 40 ° C. to 150 ° C., more preferably 60 ° C. to 130 ° C.

The alkali-soluble resin may be a random copolymer or a block copolymer.

The weight average molecular weight of the alkali-soluble resin is preferably a value measured by gel permeation chromatography (GPC) in a tetrahydrofuran (THF) solvent, preferably 3,000 to 200,000, more preferably. It is 4,000 to 100,000, more preferably 5,000 to 50,000. Within such a range, it is possible to obtain a pigment dispersion composition having heat resistance and an appropriate viscosity for forming a coating film.

The acid value of the alkali-soluble resin is preferably 20 mgKOH / g to 300 mgKOH / g, more preferably 25 mgKOH / g to 200 mgKOH / g, and even more preferably 30 mgKOH / g to 150 mgKOH / g. Within such a range, it is possible to obtain a pigment dispersion composition that can be used as a material for a photosensitive resin composition capable of forming a color filter having excellent alkali developability, less generation of development residue, and excellent adhesion. it can.

The content of the alkali-soluble resin in the pigment dispersion composition of the present invention is preferably 1% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, based on the total solid content of the composition. is there.

B-6. Alkali-soluble resin having a structural unit (E) having a carbon double bond in the side chain In one embodiment, the alkali-soluble resin has a structural unit (E) having a carbon double bond in the side chain. If the alkali-soluble resin has a structural unit (E) having a carbon double bond in the side chain, it can form a color filter having excellent strength and can be a material for a photosensitive resin composition having high exposure sensitivity. A pigment dispersion composition can be obtained. The structural unit (E) having a carbon double bond in the side chain is composed of a part or all (preferably a part) of the acid group of the structural unit (C) having an acid group in the side chain as a reaction point. It can be obtained by adding a compound having a double bond.

When the acid group of the structural unit (C) having an acid group in the side chain is a carboxyl group, the compound having a carbon double bond includes a compound having an epoxy group and a double bond, and an isocyanate group and a double bond. Compounds and the like can be used. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxide cyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinyl. Benzyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether and the like can be mentioned. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate. When the acid group of the structural unit (C) having an acid group in the side chain is a carboxylic acid anhydride group, a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.

When an alkali-soluble resin having a structural unit (E) having a carbon double bond in the side chain is obtained, the above-mentioned monomer composition is polymerized, and then the compound having the above-mentioned carbon double bond is added to the obtained resin. As the carbon double bond, an ethylenically unsaturated double bond is preferable. Any suitable method can be adopted as the method for adding the compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond is reacted with a part or all (preferably a part) of the acid group of the structural unit (C) having an acid group in the side chain. By adding this, a structural unit (E) having a carbon double bond in the side chain can be formed.

The addition amount of the compound having a carbon double bond is preferably 5 parts by weight with respect to 100 parts by weight of the alkali-soluble resin after the polymerization (that is, the alkali-soluble resin before adding the compound having a carbon double bond). It is 10 parts by weight or more, more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. Within such a range, a pigment dispersion composition that can be a photosensitive resin composition having excellent exposure sensitivity can be obtained. By using such a photosensitive resin composition, it is possible to form a dense cured coating film and to form a color filter having excellent substrate adhesion and high strength. Further, when the addition amount of the compound having a carbon double bond is within the above range, a photosensitive resin composition in which hydroxyl groups are sufficiently generated by the addition of the compound having a carbon double bond and has excellent solubility in an alkaline developer can be obtained. Obtainable. The upper limit of the addition amount of the compound having a carbon double bond is preferably with respect to 100 parts by weight of the alkali-soluble resin after the polymerization (that is, the alkali-soluble resin before the compound having a carbon double bond is added). It is 150 parts by weight or less, more preferably 100 parts by weight or less, and further preferably 80 parts by weight or less.

Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.

C. Pigment As the pigment, any suitable pigment can be used. The pigment may be an organic pigment or an inorganic pigment. Examples of organic pigments include azo pigments, phthalocyanine pigments, and polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindolin, dioxazine, thioindigo, anthraquinone, quinophthalone, etc. Metal complex type, diketopyrrolopyrrole type, etc.), dye lake type pigment and the like. Examples of inorganic pigments include white / extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chromium vermillion, nickel titanium, etc.). Chromium titanium, yellow iron oxide, red iron oxide, zinc chromate, lead tan, ultramarine, dark blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigments (carbon black, bone black, graphite, iron black, titanium black, etc.) Etc.), bright material pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc oxide, strontium sulfide, strontium aluminate, etc.) and the like. The pigment may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc., depending on the purpose and application.

The number average primary particle size of the pigment may be any suitable particle size depending on the type of pigment. The number average primary particle size of the pigment is preferably 100 nm or less, more preferably 50 nm or less. The lower limit of the number average primary particle size of the pigment is, for example, 10 nm. In the present invention, by containing the alkali-soluble resin, the dispersibility of the pigment is improved, and it becomes possible to use a pigment having a small particle size.

The number average secondary particle size (initial particle size) of the pigment immediately after preparing the pigment dispersion composition is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, and particularly preferably 120 nm or less. It is 100 nm or less. The particle size can be measured using a dynamic light scattering type particle size distribution measuring device.

The rate of change (particle size after 7 days / initial particle size) of the number average secondary particle size of the pigment after 7 days in an environment of 40 ° C. after preparing the pigment dispersion composition is It is preferably 150% or less, more preferably 130% or less, further preferably 110% or less, particularly preferably 105% or less, and most preferably less than 100%. The lower limit of the rate of change is, for example, 90%. In the present invention, the stability of pigment dispersion is excellent, and the aggregation of pigments over time can be effectively suppressed.

The content ratio of the pigment is preferably 30 parts by weight to 500 parts by weight, more preferably 80 parts by weight to 450 parts by weight, and further preferably 100 parts by weight to 400 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. Parts, particularly preferably 200 parts by weight to 350 parts by weight. In the present invention, since the pigment can be added with good dispersibility, the content ratio of the pigment can be increased. By using a pigment dispersion composition having a high pigment content, it is possible to form a color filter having a desired property but having a thin thickness.

D. Pigment Dispersant The acid value of the pigment dispersant is 15 mgKOH / g or less, preferably 13 mgKOH / g or less, more preferably 10 mgKOH / g or less, still more preferably 8 mgKOH / g or less, and most preferably. Is 5 mgKOH / g or less. Within such a range, a pigment dispersion composition having excellent pigment dispersion stability can be obtained. The method for measuring the acid value will be described later.

The amine value of the pigment dispersant is preferably 25 mgKOH / g or less, more preferably 20 mgKOH / g or less, and even more preferably 15 mgKOH / g or less. Within such a range, a pigment dispersion composition having more excellent dispersion stability can be obtained. The method for measuring the amine value will be described later.

As the pigment dispersant, any suitable pigment dispersant can be used as long as the effects of the present invention can be obtained. In one embodiment, as the pigment dispersant, an anionic dispersant, a nonionic dispersant, a cationic dispersant, a polymer (resin type) dispersant and the like are used. Of these, a polymer (resin type) dispersant is preferable.

Specific examples of the polymer (resin type) dispersant include polyacrylic polymers, polyether polymers, polyester polymers, polyurethane polymers, polyphosphate ester polymers, polyethyleneimine polymers, and polyallylamine polymers. Polymers composed of monomers having amino groups and macromonomers, polyoxyethylene alkyl ether-based polymers, polyoxyethylene diester-based polymers, polyether phosphoric acid-based polymers, polyester phosphoric acid-based polymers, sorbitan aliphatic ester-based polymers, Examples thereof include aliphatic modified polyester polymers. Further, as a polymer (resin type) dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts, Polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, salts thereof, (meth) acrylic acid. -Sterethane copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester-based, modified polyacrylate, ethylene oxide / polypropylene oxide adduct Etc. may be used. As the copolymer, a block copolymer is preferably used.

Among the above dispersants, acrylic polymers, block copolymers, and urethane polymers are preferably used.

A commercially available product may be used as the dispersant. Specific examples of commercially available products include the product names "Disperbyk-103", "Disperbyk-108", "Disperbyk-109", "Disperbyk-112", "Disperbyk-116", and "Disperbyk-130" manufactured by Big Chemie Japan. , "Disperbyk-161", "Disperbyk-162", "Disperbyk-163", "Disperbyk-164", "Disperbyk-166", "Disperbyk-167", "Disperbyk-168", "Disperbyk-170" "Disperbyk-171", "Disperbyk-182", "Disperbyk-183", "Disperbyk-185", "Disperbyk-184", "Disperbyk-2000", "Disperbyk-2050", "Discerbyk-2050" -2096 "," Disperbyk-2150 ", BYK-9077"; Ajinomoto's product names "Ajispar PB822", "Ajisper PN411"; Kusumoto Kasei's product names "Disparon DA-375", "Disparon ED-251" "; Product name" Nusperth 657NA "manufactured by Elementis; Product name" TEG Disper 650 "," TEG Disper 652 "," TEG Disper 662C "," TEG Disper 670 "," TEG Disper 710 "," TEG Disper 710 "," TEG Disper 670 " Examples thereof include "TEG Disper 752W". Among them, from the viewpoints of heat resistance, electrical reliability, and dispersibility, "Disperbyk-161", "Disperbyk-162", "Disperbyk-163", "Disperbyk-164", "Disperbyk-166", "Disperbyk-167" , "Disperbyk-168", "Disperbyk-170", "Disperbyk-171", "Disperbyk-182", "Disperbyk-183", "Disperbyk-185", "Disperbyk-184", "Disperbyk-2000" "Disparon ED-251" is preferable.

Further, as a structure, a resin having a graft structure in which the main chain is an anchor chain having an interaction site with a pigment and the graft chain is a compatible chain having an interaction with a dispersion medium, or a phase with an anchor chain. A resin having a block structure of soluble chains is particularly preferably used.

The content ratio of the pigment dispersant is preferably 5 parts by weight to 100 parts by weight, more preferably 10 parts by weight to 70 parts by weight, and further preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. It is 50 parts by weight, particularly preferably 20 parts by weight to 40 parts by weight.

The content ratio of the pigment dispersant is preferably 2 parts by weight to 80 parts by weight, more preferably 5 parts by weight to 60 parts by weight, and further preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the pigment. It is 50 parts by weight.

E. Solvents The pigment dispersion compositions of the present invention may contain any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxy. Esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, ethylbenzene; chloroform, dimethyl sulfoxide, etc. Can be mentioned. The amount of solvent can be set to any suitable amount depending on the desired viscosity of the pigment dispersion composition. For example, the solvent is preferably contained in the pigment dispersion composition in a proportion of 50% by weight to 90% by weight, more preferably in a proportion of 60% by weight to 90% by weight.

F. Additives The pigment dispersion compositions of the present invention may optionally include any suitable additive. Additives include, for example, fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, quantum dots, defoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers. , Antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners, organic fine particles, inorganic fine particles (zinc oxide, silicon oxide, zirconia, titanium), porous fine particles such as silica, silica, etc. Hollow fine particles and the like can be mentioned.

G. Photosensitive Resin Composition In one embodiment, a photosensitive resin composition containing the pigment dispersion composition and a polyfunctional monomer is provided.

G-1. Polyfunctional Monomer The photosensitive resin composition may contain a polyfunctional monomer. Examples of the polyfunctional monomer include polyfunctional aromatic vinyl-based monomers such as divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and trimethyl propanedi. (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Di (Meta) Acrylate, Dipentaerythritol Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate , Tripenta erythritol tetra (meth) acrylate, tripenta erythritol penta (meth) acrylate, tripenta erythritol hexa (meth) acrylate, tripenta erythritol hepta (meth) acrylate, tripenta erythritol octa (meth) acrylate, tris (hydroxyethyl) ) Polyfunctional (meth) acrylates such as tri (meth) acrylates of isocyanurate; polyfunctional monomers obtained by caprolactone-modified or alkylene oxide-modified these monomers can be mentioned. Of these, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tri (meth) acrylate of tris (hydroxyethyl) isocyanurate is preferable. By using these polyfunctional monomers, a color filter having a high crosslink density can be obtained because the number of functional groups is large. In the present invention, the binder polymer having an oxyalkylene group is used as described above, while the polyfunctional monomer may or may not have an oxyalkylene group. Preferably, a polyfunctional monomer having no oxyalkylene group is used.

The content ratio of the polyfunctional monomer is preferably 5 parts by weight to 200 parts by weight, and more preferably 10 parts by weight to 150 parts by weight with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. It is more preferably 30 parts by weight to 120 parts by weight, and particularly preferably 35 parts by weight to 100 parts by weight.

G-2. Photopolymerization Initiator The photosensitive resin composition may further contain a photopolymerization initiator. Any suitable photopolymerization initiator can be used as the photopolymerization initiator. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether and their alkyl ethers; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 2-benzyl-2-dimethyl Α-Aminoketones such as amino-1- (4-morpholinophenyl) -butanone-1; 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl}- Α-Hydroxyketones such as 2-methyl-propan-1-one; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and other oximes; acylphosphine oxides and xanthones and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.

The content ratio of the photopolymerization initiator is preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. is there.

Further, a photopolymerization initiator may be used in combination with the photopolymerization initiator. A plurality of combinations of photopolymerization initiators can also be used. Specific examples of the photopolymerization initiator include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate and 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa). Trifunctional thiol compounds such as Karenz MT (registered trademark) NR1) and trimethylol propanthris (3-mercaptopropionate) manufactured by Denkosha; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). Butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PE1) and other tetrafunctional thiol compounds;

The photosensitive resin composition may further contain any suitable other additives, if desired. Other additives include, for example, fillers such as aluminum hydroxide, talc, clay, barium sulfate, defoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, antioxidants. Agents, UV absorbers, flame retardants, polymerization inhibitors, thickeners, organic fine particles, inorganic fine particles (zinc oxide, silicon oxide, talconia, titanium), porous fine particles such as silica, hollow fine particles such as silica And so on.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The evaluation method in the examples is as follows.

(1) Weight average molecular weight: Mw
It was measured using GPC (HLC-8220GPC, manufactured by Tosoh Corporation) using THF as an eluent and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) on the column, and calculated in terms of standard polystyrene.
(2) Solid content About 0.3 g of the copolymer solution prepared in the production example was weighed in an aluminum cup, about 1 g of acetone was added to dissolve the solution, and then the solution was naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC CORPORATION), the mixture was dried at 140 ° C. for 3 hours, allowed to cool in a desiccator, and weighed. The weight of the solid content (resin) of the polymer solution was calculated from the weight loss.
(3) Acid value Acid value of alkali-soluble resin: 1.5 g of the copolymer solution prepared in the production example was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N KOH aqueous solution. .. The titration was carried out using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of the polymer was determined from the solid content concentration (mgKOH / g).
Acid value of pigment dispersant: 1.5 g of pigment dispersant was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N KOH aqueous solution. The titration was carried out using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of the pigment dispersant was determined from the solid content concentration (mgKOH / g).
(4) Amine Value A sample (nonvolatile component of pigment dispersant) was precisely weighed, 50 ml of ethanol and 1 ml of bromophenol blue reagent were added to dissolve the sample, and the solution was titrated with 0.5 mol / L hydrochloric acid until the solution turned green. The amine value was calculated by the following formula (mgKOH / g).
Amine value = 28.05 x b / c
b: Amount of 0.5 mol / L hydrochloric acid consumed by titration (ml)
c: Amount of sample (g)
(5) Pigment particle size 64 g of zirconia beads having a diameter of 1.0 mm were added to the pigment dispersion compositions obtained in Examples and Comparative Examples, and the mixture was shaken with a paint shaker for 3 hours. After 3 hours, the pigment-dispersed resin composition and the zirconia beads were separated, then 64 g of zirconia beads having a diameter of 0.5 mm were added, and the mixture was shaken with a paint shaker for another 3 hours. Then, the pigment-dispersed resin composition and the zirconia beads were separated, 64 g of 0.3 mm zirconia beads were added, and the mixture was further shaken with a paint shaker for 3 hours. After the dispersion treatment, the pigment-dispersed resin composition and the zirconia beads were separated.
After the above treatment, the pigment particle size (median diameter) in the pigment-dispersed resin composition was measured by a dynamic light scattering type particle size distribution measuring device (LB-500, manufactured by Horiba Seisakusho). The pigment particle size immediately after dispersion and the pigment particle size after storage at 40 ° C. for 7 days were compared.
(6) Viscosity measurement of pigment-dispersed resin composition The viscosity of the pigment-dispersed resin composition at 25 ° C. was measured with a cone plate type rotational viscometer (TVE22LT, manufactured by Toki Sangyo). The viscosity immediately after dispersion was compared with the viscosity after storage at 40 ° C. for 7 days.

[Manufacturing Example 1]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, as the monomer composition, 15 g of benzyl maleimide (BzMI), 32 g of acrylic acid (AA), 1 molethoxylated phenylphenol acrylate (trade name "HRD-01", manufactured by Nippon Distillery Co., Ltd., hereinafter HRD- (01) 53 g, t-butyl peroxy-2-ethyl hexanoate (trade name "Perbutyl (registered trademark) O", manufactured by Nippon Oil & Fats Co., Ltd., hereinafter also referred to as PBO) 2 g, propylene glycol methyl ether acetate (PGMEA) 42 g and 18 g of propylene glycol monomethyl ether (PGME) were added and mixed by stirring. Further, 2.0 g of dodecyl mercaptan (nDM), 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, in the reaction vessel, 41 g of glycidyl methacrylate (GMA), 0.3 g of 6-tert-butyl-2,4-xylenol (trade name "Topanol", manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and dimethylbenzyl as a catalyst. 0.5 g of amine (DMBA) was charged and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-1) containing 38.6% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 15,000, and the acid value was 70 mgKOH / g. The production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution are shown in Table 1 together with Production Examples 2 to 9.

[Manufacturing Example 2]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 64 g of BzMI, 21 g of AA and 64 g of HRD-01, 2 g of PBO and 40 g of PGMEA were put into the monomer dropping tank and mixed by stirring. Further, 0.5 g of nDM and 10 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
After charging 100 g of PGMEA into the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 14 g of GMA, 0.3 g of topanol as a polymerization inhibitor, 0.5 g of DMBA and 21 g of PGMEA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-2) containing 39.4% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 27,000, and the acid value was 97 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 3]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 43 g of BzMI, 42 g of AA and 43 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank and mixed by stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-3) containing 38.5% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 16000, and the acid value was 125 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 4]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 43 g of BzMI, 42 g of AA and 43 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank and mixed by stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 69 g of GMA, 0.3 g of topanol as a polymerization inhibitor, 0.5 g of DMBA as a catalyst, 19 g of PGMEA and 8.5 g of PGMEA were charged in a reaction vessel, and the reaction was carried out at 110 ° C. for 1 hour and 115 ° C. for 8 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-4) containing 39.0% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 18200, and the acid value was 45 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 5]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 53 g of BzMI, 32 g of AA and 53 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank and mixed by stirring. Further, 5.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-5) containing 38.5% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 10400, and the acid value was 69 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 6]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, dimethyl-2, 2'-[oxybis (methylene)] bis-2-propenoate (MD) 15 g, AA 32 g, HRD-01 53 g, PBO 2 g, PGMEA 42 g and PGME 18 g were added as the monomer composition. It was charged and mixed with stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-6) containing 38.5% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 15200, and the acid value was 70 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 7]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of (α-allyloxymethyl) methyl acrylate (AMA), 32 g of AA, 53 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were added to the monomer dropping tank as a monomer composition, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-7) containing 38.6% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 14900, and the acid value was 71 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 8]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, 15 g of BzMI, 32 g of AA, 50 g of HRD-01, 3 g of methoxypolyethylene glycol (400) acrylate (trade name "Light Acrylate 130A" manufactured by Kyoeisha Chemical Co., Ltd., hereinafter also referred to as 130A), 2 g of PBO as the monomer composition. , PGMEA 42 g and PGME 18 g were added, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-8) containing 38.7% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 14,800, and the acid value was 71 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Manufacturing Example 9]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 32 g of AA, 68 g of cyclohexyl methacrylate (CHMA), 2 g of PBO, 42 g of PGMEA and 18 g of PGMEA were put into the monomer dropping tank as the monomer composition, and the mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA and 7.8 g of PGMEA were added as a chain transfer agent solution into the chain transfer agent dropping tank, and the mixture was stirred and mixed.
98 g of PGMEA and 42 g of PGMEA were charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel became stable at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were each added dropwise over 180 minutes, keeping the temperature at 90 ° C. 30 minutes after the completion of the dropping, 0.5 g of PBO was added. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA as a catalyst were charged in the reaction vessel and reacted at 110 ° C. for 1 hour and at 115 ° C. for 7 hours. Then, the mixture was cooled to room temperature to obtain a copolymer solution (A-9) containing 38.8% by weight of an alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 15500, and the acid value was 72 mgKOH / g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), and acid value of the copolymer solution.

[Example 1]
9.07 g of the above copolymer solution (A-1) (that is, 3.5 g of resin) and a pigment dispersant (manufactured by Big Chemie Japan, trade name "DISPERBYK-2000", acid value: 0 mgKOH / g, amine value : 4 mgKOH / g, non-volatile content: 1.3 g, hereinafter referred to as byk2000) 3.25 g, and pigment (manufactured by Ciba Specialty Chemicals, trade name "CI Pigment Red 254", hereinafter referred to as PR254) 8.0 g Was weighed in a 225 ml container and diluted with PGMEA so that the non-volatile content concentration became 20% by weight to obtain a pigment dispersion composition R1. The obtained pigment dispersion composition R1 was subjected to the above evaluations (5) and (6). The results are shown in Table 2.

[Examples 2-9, Comparative Examples 1-6]
The pigment dispersion composition R2 is the same as in Example 1 except that the copolymer solution and the pigment dispersant shown in Table 2 are used instead of the copolymer solution (A-1) and the pigment dispersant byk2000. ~ R15 was obtained. The copolymer solution was used so as to contain 3.5 g of an alkali-soluble resin. The obtained pigment dispersion compositions R2 to 15 were subjected to the above evaluations (5) and (6). The results are shown in Table 2.
In Table 2, "byk164" is a trade name "DISPERBYK-164" (acid value: 0 mgKOH / g, amine value: 18 mgKOH / g) manufactured by Big Chemie Japan. "Byk2001" is a trade name "ISPERBYK-2001" (acid value: 19 mgKOH / g, amine value: 29 mgKOH / g) manufactured by Big Chemie Japan. "Byk110" is a trade name "DISPERBYK-110" (acid value: 53 mgKOH / g, amine value: 0 mgKOH / g) manufactured by Big Chemie Japan.

[Example 10]
9.07 g of the above copolymer solution (A-1) (that is, 3.5 g of resin), pigment dispersant (manufactured by Big Chemie Japan, trade name "DISPERBYK-2000", acid value: 0 mgKOH / g, amine value: 4 mgKOH / g, non-volatile content 1.3 g) 3.25 g, pigment (manufactured by Heubach, trade name "CI Pigment Green 36", hereinafter referred to as PG36) 4.8 g, and pigment (manufactured by Lanxes, trade name) 3.2 g of "CI Pigment Yellow 150" (hereinafter referred to as PY150) is weighed in a 225 ml container and diluted with PGMEA so that the non-volatile content concentration becomes 20% by weight to obtain a pigment dispersion composition G1. It was. The obtained pigment dispersion composition G1 was subjected to the above evaluations (5) and (6). The results are shown in Table 3.

[Examples 10 to 17, Comparative Examples 7 to 9]
The pigment dispersion composition G2 is the same as in Example 10 except that the copolymer solution and the pigment dispersant shown in Table 2 are used instead of the copolymer solution (A-1) and the pigment dispersant byk2000. ~ R11 was obtained. The copolymer solution was used so as to contain 3.5 g of an alkali-soluble resin. The obtained pigment dispersion compositions G2 to 11 were subjected to the above evaluations (5) and (6). The results are shown in Table 3.

[Example 18]
9.07 g of the above copolymer solution (A-1) (that is, 3.5 g of resin) and a pigment dispersant (manufactured by Big Chemie Japan, trade name "DISPERBYK-2000", acid value: 0 mgKOH / g, amine value : 4 mgKOH / g, non-volatile content 1.3 g) 3.25 g, pigment (manufactured by Clariant, trade name "CI Pigment Violet 23", hereinafter referred to as PV23) 1.6 g, pigment (manufactured by BASF, Weigh 6.4 g of the product name "CI Pigment Blue 15: 6" (hereinafter referred to as PB 15: 6) in a 225 ml container, dilute with PGMEA so that the non-volatile content concentration becomes 20% by weight, and pigment. The dispersion composition B1 was obtained. The obtained pigment dispersion composition B1 was subjected to the above evaluations (5) and (6). The results are shown in Table 4.

[Examples 19 to 25, Comparative Examples 10 to 12]
The pigment dispersion composition B2 is the same as in Example 18 except that the copolymer solution and the pigment dispersant shown in Table 2 are used instead of the copolymer solution (A-1) and the pigment dispersant byk2000. ~ B11 was obtained. The copolymer solution was used so as to contain 3.5 g of an alkali-soluble resin. The obtained pigment dispersion compositions B2 to 11 were subjected to the above evaluations (5) and (6). The results are shown in Table 4.

[Example 26]
9.07 g of the above copolymer solution (A-1) (that is, 3.5 g of resin) and a pigment dispersant (manufactured by Big Chemie Japan, trade name "DISPERBYK-164", acid value: 0 mgKOH / g, amine value : 18 mgKOH / g, non-volatile content 1.3 g) 2.17 g and pigment (manufactured by Orion Engineered Carbons, trade name "Printex 45", hereinafter referred to as PT45) 8.0 g are weighed in a 225 ml container. The pigment dispersion composition K1 was obtained by diluting with PGMEA so that the non-volatile content concentration was 20% by weight. The obtained pigment dispersion composition K1 was subjected to the above evaluations (5) and (6). The results are shown in Table 5.

[Examples 27 to 33, Comparative Examples 13 to 15]
The pigment dispersion composition K2 is the same as in Example 26, except that the copolymer solution and the pigment dispersant shown in Table 2 are used instead of the copolymer solution (A-1) and the pigment dispersant byk164. ~ B11 was obtained. The copolymer solution was used so as to contain 3.5 g of an alkali-soluble resin. The obtained pigment dispersion compositions K2 to 11 were subjected to the above evaluations (5) and (6). The results are shown in Table 5.

[Example 34]
9.07 g of the above copolymer solution (A-1) (that is, 3.5 g of resin) and a pigment dispersant (manufactured by Big Chemie Japan, trade name "DISPERBYK-182", acid value: 0 mgKOH / g, amine value : 13 mgKOH / g, non-volatile content 1.3 g, hereinafter referred to as byk182) 3.02 g and pigment (manufactured by Ishihara Sangyo Co., Ltd., trade name "titanium oxide TTO-51", hereinafter referred to as TTO-51) 8.0 g. , Weighed in a 225 ml container and diluted with PGMEA so that the non-volatile content concentration became 20% by weight to obtain a pigment dispersion composition W1. The obtained pigment dispersion composition W1 was subjected to the above evaluations (5) and (6). The results are shown in Table 6.

[Examples 35 to 41, Comparative Examples 16 to 18]
The pigment dispersion composition W2 is the same as in Example 26, except that the copolymer solution and the pigment dispersant shown in Table 2 are used instead of the copolymer solution (A-1) and the pigment dispersant byk164. ~ W11 was obtained. The copolymer solution was used so as to contain 3.5 g of an alkali-soluble resin. The obtained pigment dispersion compositions W2 to 11 were subjected to the above evaluations (5) and (6). The results are shown in Table 6.

As is clear from Tables 2 to 6, the pigment dispersion composition of the present invention is excellent in the dispersion stability of the pigment.

Claims (5)

Contains an alkali-soluble resin, a pigment, a pigment dispersant, and a solvent.
The alkali-soluble resin has a structural unit (A) having a biphenyl group in the side chain, a structural unit (B) having a ring structure in the main chain, a structural unit (D1) having two or more oxyalkylene groups in the side chain, and a side chain. Containing a structural unit having a carbon double bond (E) in the chain,
The acid value of the pigment dispersant is 15 mgKOH / g or less.
The structural unit (A) having a biphenyl group in the side chain is a structural unit derived from a monomer represented by the general formula (1) or (2).
The pigment dispersion composition: in which the structural unit (B) having a ring structure in the main chain is at least one selected from the structural units represented by the general formulas (3) to (9).

In equation (2), n1 is 1-10:

In formulas (6) to (9), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently linear or branched with hydrogen atoms or 1 to 30 carbon atoms. It is an alkyl group. The pigment dispersion composition according to claim 1, wherein the amine value of the pigment dispersant is 25 mgKOH / g or less. The pigment dispersion composition according to claim 1 or 2, wherein the alkali-soluble resin is a (meth) acrylic resin. The pigment dispersion composition according to any one of claims 1 to 3, wherein the alkali-soluble resin further contains a structural unit having an acid group in the side chain. The pigment dispersion composition according to any one of claims 1 to 4, wherein the number average primary particle size of the pigment is 100 nm or less.