JP2018053141A - Pigment dispersion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersion composition containing a pigment with excellent dispersion stability.SOLUTION: A pigment dispersion composition contains an alkali-soluble resin, a pigment, a pigment dispersant, and a solvent. The alkali-soluble resin has a constitutional unit having a biphenyl group in a side chain, and the pigment dispersant has an acid value of 15 mgKOH/g or less. According to one embodiment, the pigment dispersant has an amine value of 25 mgKOH/g or less.SELECTED DRAWING: None

Description

  The present invention relates to a pigment dispersion composition.

  For example, a color filter used in an image display device such as a liquid crystal display device is usually a photolithographic method after a photosensitive resin composition containing a color material such as a pigment and a photocurable resin is applied to a transparent substrate. Is manufactured by. In recent years, with the demand for higher performance of image display devices, color filters that can contribute to improvements in luminance, contrast, and the like have been demanded. Examples of a method for forming a color filter that can contribute to the improvement of luminance and contrast include a method for refining a pigment as a coloring material in a pigment dispersion composition. However, there is a problem that the dispersion stability deteriorates as the pigment becomes finer.

  The cured product formed from the photosensitive resin composition is not limited to the above-described color filter application, and there is a tendency for fineness and densification to be required, and the pigment contained in the composition is also dispersed. There is a need to refine it with good quality.

JP 2010-168580 A

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

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 includes an alkali-soluble resin, a pigment, a pigment dispersant, and a solvent, and the alkali-soluble resin includes a structural unit having a biphenyl group in a side chain. An acid value is 15 mgKOH / g or less.
In one embodiment, the amine value of the pigment dispersant is 25 mg KOH / 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 includes a structural unit (B) having a ring structure in the main chain.
In one embodiment, the alkali-soluble resin further includes a structural unit having an acid group in the side chain.
In one embodiment, the alkali-soluble resin further includes a structural unit having a carbon double bond in the side chain.

  According to the present invention, a pigment dispersion composition having excellent pigment dispersion stability can be provided.

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 includes 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, by using a combination of 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, the pigment has excellent dispersion stability. Thus, it is possible to obtain a pigment dispersion composition in which pigments hardly aggregate over time. In the present invention, deterioration of dispersibility can be suppressed even if the pigment is made finer.

  In one embodiment, the pigment dispersion composition of the present invention can be used in combination with a polyfunctional monomer and a photopolymerization initiator. The resin composition containing the pigment dispersion composition, the polyfunctional monomer, and the photopolymerization initiator includes, for example, a color filter, a photo spacer, an overcoat, a black matrix, a black column spacer, an ink, and a paint as a photosensitive resin composition. And can be suitably used for a sealant and the like. In the pigment dispersion composition of the present invention, it is possible to make the pigment fine without impairing the dispersibility. Therefore, when the composition is used, a color filter that can contribute to improvement in luminance and contrast is formed. Can do.

B. Alkali-soluble resin As above-mentioned, alkali-soluble resin contains the structural unit which has a biphenyl group in a side chain. When the alkali-soluble resin has the structural unit (A) having a biphenyl group in the side chain, a pigment dispersion composition having excellent pigment dispersion stability can be obtained. Further, when an alkali-soluble resin having a structural unit (A) having a biphenyl group in the side chain is used, a pigment dispersion composition that can be a material for a photosensitive resin composition having an excellent development speed can be obtained. Further, a cured product (for example, a color filter) produced using a pigment dispersion composition containing an alkali-soluble resin having a structural unit (A) having a biphenyl group in the side chain has excellent adhesion to the substrate, and Excellent smoothness. The alkali-soluble resin is typically a (meth) acrylic resin. The (meth) acrylic resin is not particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing at least 10 wt% (mass%) of a (meth) acrylic monomer such as a (meth) acrylic acid ester. First, the monomer composition may contain another monomer copolymerizable with the (meth) acrylic monomer.

  In one embodiment, the alkali-soluble resin may further include a structural unit (B) having a ring structure in the main chain. The alkali-soluble resin may further contain a structural unit (C) having an acid group in the side chain. Moreover, the said alkali-soluble resin may further contain the other structural unit (D) as needed.

  The alkali-soluble resin can be obtained by polymerizing the monomer composition I containing the 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 monomer composition I containing monomer (b) and / or monomer (b ′) capable of forming a ring structure. The monomer composition I includes a monomer constituting the structural unit (C) having an acid group in the side chain (monomer having an acid group (c), monomer capable of introducing an acid group (c ′)) and / or other Another monomer (d) constituting the structural unit (D) may further be included. In one embodiment, monomer (a), monomer (c), monomer (c ') and / or monomer (d) are (meth) acrylic monomers, preferably acrylic monomers.

B-1. Structural unit having biphenyl group in side chain (A)
When the alkali-soluble resin has the structural unit (A) having a biphenyl group in the side chain, a pigment dispersion composition having excellent pigment dispersion stability 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 = carbamer , N- (meth) acryloyloxyethyl-m-biphenyl = carbamate, o-phenylphenol glycidyl ether acrylate, o-biphenyloxypropyl (meth) acrylate and the like derived from the monomer (a) having a biphenyl group in the side chain Units are listed. Among these, a structural unit derived from an acrylic monomer is preferable. If an acrylic monomer having no methyl group in the double bond portion is used, a pigment dispersion composition that can be a material of a photosensitive resin composition having a high development rate 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). In addition, you may use the said monomer individually or in combination of 2 or more types.

In formula (2), n1 is 1-10, Preferably it is 1 or 2.

  The content ratio of the structural unit (A) having a biphenyl group in the side chain is preferably 10 to 80 parts by weight, more preferably 15 parts by weight to 100 parts by weight (mass part) of the alkali-soluble resin. 70 parts by weight, more preferably 20 parts by weight to 65 parts by weight. If it is such a range, the effect of this invention will become more remarkable.

  In the monomer composition I forming the 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 monomers in the monomer composition I. Parts by weight, more preferably 30 parts by weight to 70 parts by weight, and still more preferably 40 parts by weight to 65 parts by weight. If it is such a range, the effect of this invention will become more remarkable.

B-2. Constituent units having a ring structure in the main chain (B)
When the alkali-soluble resin has the 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 structural units 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). It is more preferable that it is a structural unit represented by. If an alkali-soluble resin (preferably a (meth) acrylic resin) having a structural unit represented by the general formula (3) is used, 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 structural units represented by the general formulas (6) to (9). Among these, the structural unit represented by the general formula (6) or (9) is preferable.

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

  The structural unit (B) having a ring structure in the main chain can be constituted by the monomer (b) having a ring structure in the main chain. As the monomer (b) having a ring structure in the main chain, for example, maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide N-o-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o- Aromatic substituted maleimides such as methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide; cyclohexylmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide, isopropyl Alkyl-substituted maleimides such as Rumareimido like. Among these, maleimide, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are preferable, benzylmaleimide, phenylmaleimide, and cyclohexylmaleimide are more preferable, and benzylmaleimide is more preferable. The above 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 ′) that can form 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 of the structural unit (B) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight, more preferably 8 parts by weight to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. And more preferably 10 to 25 parts by weight.

  In the monomer composition I forming the alkali-soluble resin, the content of the monomer (b) having a ring structure in the main chain is preferably 5 to 50 parts by weight with respect to 100 parts by weight of all monomers in the monomer composition I. Parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight. The content of the monomer (b ′) capable of forming a ring structure in the monomer composition I forming the alkali-soluble resin is preferably 5 parts by weight with respect to 100 parts by weight of all monomers in the monomer composition I. It is -50 weight part, More preferably, it is 8 weight part-30 weight part, More preferably, it is 10 weight part-25 weight part.

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

  As a monomer constituting the structural unit (C) having an acid group in the side chain, a monomer (c ′) capable of introducing an acid group may be used. The monomer (c ′) is a monomer that enables addition of 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. And monomers having a group. These monomers may be used alone or in combination of two or more. The post-treatment for imparting acid groups varies depending on the type of monomer (c ′) used, but when a monomer (c ′) having a hydroxyl group is used, for example, succinic anhydride, tetrahydrophthalic anhydride, etc. An acid anhydride such as maleic anhydride may be added. When the 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 acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride) may be added to a hydroxyl group generated after adding an acid such as acrylic acid. Further, when the 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 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 with respect to 100 parts by weight of the alkali-soluble resin. More preferably 15 to 45 parts by weight.

  The content ratio of the monomer (c) having an acid group is preferably 15 to 60 parts by weight, more preferably 20 to 50 parts by weight, in the monomer composition I that forms an alkali-soluble tree. And more preferably 20 to 45 parts by weight. Further, the content ratio of the monomer (c ′) capable of introducing an acid group in the monomer composition I forming the alkali-soluble resin is preferably 15 parts by weight to 60 parts by weight, and more preferably 20 parts by weight to 50 parts by weight. Parts 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 other structural unit (D). As other structural units, the structural unit (D1) having two or more oxyalkylene groups in the side chain, the monomer (a), the monomer (a ′), the monomer (b), the monomer (c) and / or the monomer ( and a structural unit (D2) derived from other monomer (d2) polymerizable with c ′).

(Structural unit (D1) having two or more oxyalkylene groups in the side chain)
When the alkali-soluble resin has a structural unit (D1) having two or more oxyalkylene groups in the side chain, it becomes a material for a photosensitive resin composition capable of forming a color filter having a high crosslinking density and a high breaking strength. The resulting pigment dispersion composition can be obtained. Also, a pigment dispersion composition that is particularly excellent in pigment dispersibility can be obtained. When the alkali-soluble resin having the structural unit (D1) and a polyfunctional monomer described later (preferably a polyfunctional monomer having no oxyalkylene group) are combined to constitute a photosensitive resin composition, the above effect is obtained. 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。 As a structural unit (D1) which has a 2 or more oxyalkylene group in a side chain, the structural unit represented by General formula (12) is mentioned, for example.

In formula (12), R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. 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. And 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 still more preferably a linear alkyl group having 1 to 5 carbon atoms, A phenyl group or a biphenyl group, particularly preferably a methyl group, a phenyl group or a biphenyl group. In addition, the alkyl group, the alkenyl group, and the 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) can contain one or more oxyalkylene groups. x represents an integer of 0-2. y represents 0 or 1; n2 represents the average addition mole number of an oxyalkylene group and is 2 or more, preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 15. When n2 is within such a range, a pigment dispersion composition that can be a material for a photosensitive resin composition that can form 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 a monomer (d1) having two or more oxyalkylene groups in the side chain. Examples of the monomer (d1) include ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO 4 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, methoxy polypropylene glycol (meth) acrylic Over DOO, nonylphenoxy polyethyleneglycol (meth) acrylate (EO4-17 moles), nonylphenoxy polypropylene glycol (meth) acrylate (PO5 mol), EO-modified cresol (meth) acrylate (EO2 mol), and the like. These monomers may be used alone or in combination of two or more. In the present specification, for example, “EO2 mole”, “PO5 mole” and the like represent the average number of moles added of the oxyalkylene group.

  The content ratio of the structural unit (D1) having two or more oxyalkylene groups in the side chain is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.8 parts per 100 parts by weight of the alkali-soluble resin. 5 parts by weight to 5 parts by weight.

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

(Constitutional unit (D2) derived from other monomer (d2))
The structural unit (D2) derived from the other monomer (d2) includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth). Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl ( (Meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl ethylene glycol (meth) acrylate, metho Cypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, biphenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate (Meth) acrylic acid esters such as tricyclodecyloxyethyl (meth) acrylate, nonylphenoxyethylene glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( (Meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, -Butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl (meth) acrylamide, N, N-dimethyl ( (Meth) acrylic amides such as (meth) acrylamide, aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene, butadiene or substituted butadiene compounds such as butadiene and isoprene, ethylene, propylene, vinyl chloride Ethylene or substituted ethylene compound such as acrylonitrile; monomers vinyl esters such as vinyl acetate (d2) include structural units derived from. These monomers may be used alone or in combination of two or more.

  The content of the structural unit (D2) is preferably 0 to 55 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. Parts 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 monomer by any appropriate method. Examples of the polymerization method include a solution polymerization method.

  The monomer composition can include 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; dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more. The polymerization concentration when polymerizing the monomer composition is preferably 5 wt% (mass%) to 90 wt%, more preferably 5 wt% to 50 wt%, and even more preferably 10 wt% to 50 wt%. % By weight.

  The monomer composition can include any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-amyl peroxy-2. Organic peroxides such as ethylhexanoate and 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 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 with respect to 100 parts by weight of the total monomer in the monomer composition.

  The monomer composition can include any suitable chain transfer agent. Examples of the chain transfer agent include monofunctional thiol compounds such as n-dodecyl mercaptan and β-mercaptopropionic acid; bifunctional thiol compounds such as mercapto-modified polysiloxane at both ends; and side-chain polyfunctional mercapto whose side chain is mercapto-modified. Examples thereof 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 with respect to 100 parts by weight of the total monomer 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 3,000 to 200,000, more preferably a value measured by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent. It is 4,000-100,000, More preferably, it is 5,000-50,000. If it is such a range, heat resistance can be ensured and the pigment dispersion composition which has a viscosity suitable for coating-film formation can be obtained.

  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 further preferably 30 mgKOH / g to 150 mgKOH / g. Within such a range, it is possible to obtain a pigment dispersion composition that can be a material for a photosensitive resin composition that can form a color filter that has excellent alkali developability, little 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 which has structural unit (E) which has a carbon double bond in a side chain In one embodiment, the said alkali-soluble resin has a structural unit (E) which has a carbon double bond in a side chain. If alkali-soluble resin has the structural unit (E) which has a carbon double bond in a side chain, it can form the color filter which is excellent in intensity | strength, and can become the material of the photosensitive resin composition with 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 of 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 heavy 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 is a compound having an epoxy group and a double bond, an isocyanate group and a double bond. Or the like. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinyl. Examples include benzyl glycidyl ether and 4-hydroxybutyl acrylate glycidyl ether. 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 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 obtaining the alkali-soluble resin having the structural unit (E) having a carbon double bond in the side chain, after polymerizing the monomer composition, the compound having the carbon double bond is added to the obtained resin. The carbon double bond is preferably an ethylenically unsaturated double bond. Any appropriate method can be adopted as a method for adding a 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 part or all (preferably part) of the acid group of the structural unit (C) having an acid group in the side chain. Thus, the 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% with respect to 100 parts by weight of the alkali-soluble resin after polymerization (that is, the alkali-soluble resin before adding the compound having a carbon double bond). Part or more, more preferably 10 parts by weight or more, still more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. If it is such a range, the pigment dispersion composition which can become the photosensitive resin composition excellent in exposure sensitivity can be obtained. If such a photosensitive resin composition is used, a dense cured coating film can be formed, and a color filter having excellent substrate adhesion and high strength can be formed. In addition, if 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 the solubility in an alkali developer is excellent. Can be obtained. The upper limit of the amount of the compound having a carbon double bond is preferably 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin after polymerization (that is, the alkali-soluble resin before adding the compound having a carbon double bond). It is 150 weight part or less, More preferably, it is 100 weight part or less, More preferably, it is 80 weight part 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. The pigment pigment, any suitable pigment may be used. The pigment may be an organic pigment or an inorganic pigment. Examples of organic pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, Metal complex, diketopyrrolopyrrole, etc.), dye lake pigments and the like. Examples of inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium-based, chrome vermilion, nickel titanium, Chromium titanium, yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc., black pigment (carbon black, bone black, graphite, iron black, titanium black) Etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) and the like. The pigment may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc. according to the purpose and application.

  The number average primary particle size of the pigment may be any appropriate particle size depending on the type of pigment. The number average primary particle size of the pigment is preferably 100 nm or less, and 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, pigment dispersibility is improved, and a pigment having a small particle size can be used.

  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, particularly preferably. 100 nm or less. The particle size can be measured using a dynamic light scattering particle size distribution measuring device.

  The pigment dispersion composition was prepared, and the change rate of the number average secondary particle size of the pigment after 7 days in an environment of 40 ° C. with respect to the initial particle size (particle size after 7 days / initial particle size) is Preferably it is 150% or less, More preferably, it is 130% or less, More preferably, it is 110% or less, Especially preferably, it is 105% or less, Most preferably, it is less than 100%. The lower limit of the change rate is, for example, 90%. In the present invention, the pigment dispersion is excellent in stability, and aggregation of the pigment 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 still more 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. If a pigment dispersion composition having a high pigment content is used, a thin color filter filter can be formed while having desired characteristics.

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

  Any appropriate pigment dispersant may be used as the pigment dispersant as long as the effects of the present invention are obtained. In one embodiment, an anionic dispersant, a nonionic dispersant, a cationic dispersant, a polymer (resin type) dispersant, or the like is used as the pigment dispersant. Among these, a polymer (resin type) dispersant is preferable.

  Specific examples of the polymer (resin type) dispersant include, for example, a polyacrylic polymer, a polyether polymer, a polyester polymer, a polyurethane polymer, a polyphosphate ester polymer, a polyethyleneimine polymer, a polyallylamine polymer, Polymers composed of monomers having amino groups and macromonomers, polyoxyethylene alkyl ether polymers, polyoxyethylene diester polymers, polyether phosphate polymers, polyester phosphate polymers, sorbitan aliphatic ester polymers, Aliphatic modified polyester polymers and the like can be mentioned. In addition, as a polymer (resin type) dispersant, polycarboxylic acid ester such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, Polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide and salt formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, (meth) acrylic acid -Styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct etc It 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 trade names “Disperbyk-103”, “Disperbyk-108”, “Disperbyk-109”, “Disperbyk-112”, “Disperbyk-116”, “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”, “Disperbyk-2070”, “Disperbyk-2096”, “Disperbyk-2150”, BYK-9077 ”; trade names“ Asperper PB822 ”,“ Asperper PN411 ”manufactured by Ajinomoto Co., Inc .; Trade names “Disparon DA-375” and “Disparon ED-251” manufactured by Enomoto Kasei Co., Ltd .; trade names “Nusperse 657NA” manufactured by Elementis, Inc .; trade names “TEG Disper650”, “TEG Disper652” manufactured by TEGO Examples thereof include “TEG Disper 662C”, “TEG Disper 670”, “TEG Disper 710”, “TEG Disper 740W”, “TEG Disper 752W”, and the like. Among these, from the viewpoint 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 preferred.

  In addition, 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 property with a dispersion medium, or the anchor chain is compatible with the anchor chain. A resin having a soluble chain having a block structure 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 still more preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. 50 parts by weight, particularly preferably 20 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 still more preferably 10 parts by weight to 100 parts by weight of the pigment. 50 parts by weight.

E. Solvent The pigment dispersion composition 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, 3-methoxy Esters such as butyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Chloroform, dimethyl sulfoxide, and the like Can be mentioned. The amount of the solvent can be set to any appropriate 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, and more preferably in a proportion of 60% by weight to 90% by weight.

F. Additives The pigment dispersion composition of the present invention may contain any appropriate additive as required. Examples of additives include fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, quantum dots, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers , Antioxidants, ultraviolet 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. And hollow fine particles.

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

G-1. Multifunctional monomer The photosensitive resin composition may contain a polyfunctional monomer. Examples of the polyfunctional monomer include polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) 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, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate , Tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, trifunctional (meth) acrylates such as tris (hydroxyethyl) isocyanurate tri (meth) acrylate; these monomers are modified with caprolactone or alkylene Examples thereof include oxide-modified polyfunctional monomers. Among them, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Tris (hydroxy) isocyanurate tri (meth) acrylate and the like are preferred. If these polyfunctional monomers are used, a color filter having a high crosslinking density can be obtained because of the large number of functional groups. In the present invention, as described above, a binder polymer having an oxyalkylene group is used. On the other hand, 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, 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. More preferably, it is 30 to 120 parts by weight, and particularly preferably 35 to 100 parts by weight.

G-2. Photopolymerization initiator The photosensitive resin composition may further contain a photopolymerization initiator. Any appropriate photopolymerization initiator may be used as the photopolymerization initiator. Examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone. Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinop Α-aminoketones such as pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-hydroxy-1- {4- [4- (2-hydroxy- Α-hydroxyketones such as 2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one; 1,2-octanedione, 1- [4- (phenylthio)-, 2- ( O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and other oximes; acylphosphine Examples thereof include oxides and xanthones. 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 with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. is there.

  Further, in addition to the photopolymerization initiator, a photopolymerization initiation assistant may be used in combination. Photopolymerization initiation assistants can also be used in combination. Specific examples of the photopolymerization initiation assistant include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate, 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa Electric Works, Karenz MT (registered trademark) NR1), trimethylolpropane tris (trifunctional thiol compounds such as 3-mercaptopropionate; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto) (Butylate) (Showa Denko Co., Ltd., Karenz MT (registered trademark) PE1) and other tetrafunctional thiol compounds; difunctional thiol compounds such as dipentaerythritol hexakis (3-propionate)

  The said photosensitive resin composition may further contain arbitrary appropriate other additives as needed. Examples of other additives include fillers such as aluminum hydroxide, talc, clay, barium sulfate, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents, lubricants, plasticizers, and antioxidants. Agent, ultraviolet absorber, flame retardant, polymerization inhibitor, thickener, organic fine particles, inorganic fine particles (zinc oxide, silicon oxide, zirconia, titanium), porous fine particles such as silica, hollow fine particles such as silica Etc.

  Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. The evaluation methods in the examples are as follows.

(1) Weight average molecular weight: Mw
GPC (HLC-8220GPC, manufactured by Tosoh Corporation) was used as an eluent, and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) was used as a column for the measurement.
(2) Solid content About 0.3 g of the copolymer solution prepared in the production example was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Thereafter, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Corp.), it was dried at 140 ° C. for 3 hours, then allowed to cool in a desiccator, and the weight was measured. From the weight loss, the weight of the solid content (resin) of the polymer solution was calculated.
(3) Acid value Acid value of alkali-soluble resin: 1.5 g of the copolymer solution prepared in 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 aqueous KOH solution. . Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was determined from the solid content concentration (mgKOH / g).
Acid value of the pigment dispersant: 1.5 g of the 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 aqueous KOH solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of pigment dispersant was determined from the solid content concentration (mgKOH / g).
(4) Amine value A sample (pigment dispersant non-volatile content) of 5 g was precisely weighed and dissolved by adding 50 ml of ethanol and 1 ml of bromophenol blue reagent, and titrated until the liquid turned green with 0.5 mol / L hydrochloric acid. The amine value was calculated according to the following formula (mgKOH / g).
Amine number = 28.05 × b / c
b: Amount of 0.5 mol / L hydrochloric acid consumed by titration (ml)
c: Sample amount (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 shaken with a paint shaker for 3 hours. After 3 hours, the pigment-dispersed resin composition and the zirconia beads were separated, and then 64 g of zirconia beads having a diameter of 0.5 mm were added, followed by further shaking for 3 hours with a paint shaker. Thereafter, the pigment-dispersed resin composition and zirconia beads were separated, added with 64 g of 0.3 mm zirconia beads, and further shaken with a paint shaker for 3 hours. After the dispersion treatment, the pigment-dispersed resin composition and zirconia beads were separated.
After the treatment, the pigment particle size (median diameter) in the pigment-dispersed resin composition was measured with a dynamic light scattering particle size distribution measuring device (LB-500, manufactured by Horiba, Ltd.). The pigment particle size immediately after dispersion was compared with the pigment particle size after storage at 40 ° C. for 7 days.
(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 rotational viscometer (TVE22LT, manufactured by Toki Sangyo Co., Ltd.). The viscosity immediately after dispersion was compared with the viscosity after storage for 7 days at 40 ° C.

[Production 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, 15 g of benzylmaleimide (BzMI), 32 g of acrylic acid (AA), 1 mol ethoxylated phenylphenol acrylate (trade name “HRD-01”, manufactured by Nippon Distillation Co., Ltd., hereinafter HRD- 53), t-butyl peroxy-2-ethylhexanoate (trade name “Perbutyl (registered trademark) O”, manufactured by NOF Corporation, hereinafter also referred to as “PBO”), propylene glycol methyl ether acetate (PGMEA) 42 g and 18 g of propylene glycol monomethyl ether (PGME) were added and mixed with stirring. Further, 2.0 g of dodecyl mercaptan (nDM), 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 41 g of glycidyl methacrylate (GMA) in the reaction vessel, 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 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-1) containing 38.6 weight% of alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 15000, 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 2-9.

[Production Example 2]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of BzMI, 21 g of AA, and 64 g of HRD-01, 2 g of PBO, and 40 g of PGMEA were added as a monomer composition into the monomer dropping tank, and mixed with 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 mixed with stirring.
After charging PGMEA 100g into the reaction vessel and replacing with nitrogen, the reaction vessel was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 as a catalyst, and 21 g of PGMEA were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-2) containing 39.4 weight% of alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 27000, 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.

[Production Example 3]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 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 PGME were added as a monomer composition into the monomer dropping tank and mixed with stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-3) containing 38.5 weight% of 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.

[Production Example 4]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 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 PGME were added as a monomer composition into the monomer dropping tank and mixed with stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 69 g of GMA, 0.3 g of topanol as a polymerization inhibitor, and 0.5 g of DMBA, 19 g of PGMEA, and 8.5 g of PGME were charged in a reaction vessel and reacted at 110 ° C. for 1 hour and 115 ° C. for 8 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-4) containing 39.0 weight% of 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.

[Production Example 5]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of BzMI, 32 g of AA, and HRD-01, 2 g of PBO, 42 g of PGMEA, and 18 g of PGME were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, nDM5.0g, PGMEA18.2g and PGME7.8g were thrown into the chain transfer agent dripping tank as a chain transfer agent solution, and it stirred and mixed.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-5) containing 38.5 weight% of 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.

[Production 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, 15 g of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD), 32 g of AA, 53 g of HRD-01, 2 g of PBO, 42 g of PGMEA and 18 g of PGME were used as the monomer composition. The mixture was stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-6) containing 38.5 weight% of 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.

[Production Example 7]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 15 g of (α-allyloxymethyl) methyl acrylate (AMA), 53 g of AA32, and HRD-01, 2 g of PBO, 42 g of PGMEA, and 18 g of PGME were stirred and mixed. Further, 2.0 g of nDM, 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-7) containing 38.6 weight% of 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.

[Production Example 8]
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in a monomer dropping tank, as a monomer composition, 15 g of BzMI, AA 32 g, 50 g of HRD-01, methoxypolyethylene glycol (400) acrylate (trade name “Light Acrylate 130A” manufactured by Kyoeisha Chemical Co., Ltd., hereinafter also referred to as 130A) 3 g, PBO 2 g , 42 g of PGMEA and 18 g of PGME were added and mixed with stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-8) containing 38.7 weight% of alkali-soluble resin (acrylic resin). The weight average molecular weight (Mw) of the alkali-soluble resin (acrylic resin) was 14800, 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.

[Production 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 PGME were added as a monomer composition to the monomer dropping tank and mixed with stirring. Further, 2.0 g of nDM, 18.2 g of PGMEA, and 7.8 g of PGME were added as a chain transfer agent solution into the chain transfer agent dropping tank, and mixed with stirring.
The reaction vessel was charged with 98 g of PGMEA and 42 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized 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 added dropwise over 180 minutes while maintaining the temperature at 90 ° C. PBO 0.5g was added 30 minutes after the completion of the dropping. After another 30 minutes, the temperature of the reaction vessel was raised to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and bubbling of 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 a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution (A-9) containing 38.8 weight% of 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 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 mg KOH / g, nonvolatile 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 And 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 R1. The obtained pigment dispersion composition R1 was subjected to the evaluations (5) and (6). The results are shown in Table 2.

[Examples 2-9, Comparative Examples 1-6]
Pigment dispersion composition R2 in the same manner as in Example 1 except that the copolymer solution and the pigment dispersant shown in Table 2 were used instead of the copolymer solution (A-1) and the pigment dispersant byk2000. ~ R15 was obtained. The copolymer solution was used so that 3.5 g of an alkali-soluble resin was blended. The obtained pigment dispersion compositions R2 to 15 were subjected to the 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 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: 3.25 g of 4 mg KOH / g, non-volatile content 1.3 g), 4.8 g of pigment (manufactured by Heubach, trade name “CI Pigment Green 36”, hereinafter referred to as PG36), and pigment (manufactured by Lanxess, trade name) “CI Pigment Yellow 150” (hereinafter referred to as PY150) is weighed out in a 225 ml container and diluted with PGMEA so that the non-volatile content is 20% by weight to obtain a pigment dispersion composition G1. It was. The obtained pigment dispersion composition G1 was subjected to the evaluations (5) and (6). The results are shown in Table 3.

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

[Example 18]
9.07 g of the 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) : 3.25 g of 4 mg KOH / g, non-volatile content 1.3 g), 1.6 g of pigment (manufactured by Clariant, trade name “CI Pigment Violet 23”, hereinafter referred to as PV23), and pigment (manufactured by BASF, 6.4 g of the trade name “CI Pigment Blue 15: 6” (hereinafter referred to as PB15: 6) is weighed into a 225 ml container, diluted with PGMEA to a non-volatile content of 20% by weight, and pigment Dispersion composition B1 was obtained. The obtained pigment dispersion composition B1 was subjected to the evaluations (5) and (6). The results are shown in Table 4.

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

[Example 26]
9.07 g of the 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 mg KOH / g, non-volatile content 1.3 g) 2.17 g and pigment (Orion Engineered Carbons, trade name “Printex 45”, hereinafter referred to as PT45) 8.0 g are 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 K1. The obtained pigment dispersion composition K1 was subjected to the evaluations (5) and (6). The results are shown in Table 5.

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

[Example 34]
9.07 g of the 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 mg KOH / 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 A pigment dispersion composition W1 was obtained by weighing into a 225 ml container and diluting with PGMEA so that the non-volatile content concentration was 20% by weight. The obtained pigment dispersion composition W1 was subjected to the evaluations (5) and (6). The results are shown in Table 6.

[Examples 35 to 41, Comparative Examples 16 to 18]
Pigment dispersion composition W2 was prepared in the same manner as in Example 26 except that the copolymer solution and the pigment dispersant shown in Table 2 were used in place of the copolymer solution (A-1) and the pigment dispersant byk164. ~ W11 was obtained. The copolymer solution was used so that 3.5 g of an alkali-soluble resin was blended. The obtained pigment dispersion compositions W2 to 11 were subjected to the 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 pigment dispersion stability.

Claims (7)

An alkali-soluble resin, a pigment, a pigment dispersant, and a solvent,
The alkali-soluble resin includes a structural unit having a biphenyl group in the side chain;
The acid value of the pigment dispersant is 15 mgKOH / g or less,
Pigment dispersion composition.   The pigment dispersion composition according to claim 1, wherein the amine value of the pigment dispersant is 25 mg KOH / 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 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.   The pigment dispersion composition according to any one of claims 1 to 4, wherein the alkali-soluble resin further comprises a structural unit (B) having a ring structure in the main chain.   The pigment dispersion composition according to any one of claims 1 to 5, wherein the alkali-soluble resin further comprises a structural unit having an acid group in a side chain. The pigment dispersion composition according to any one of claims 1 to 6, wherein the alkali-soluble resin further comprises a structural unit having a carbon double bond in a side chain.