JP2010007059A - Pigment dispersant, pigment dispersion composition and photoresist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoresist composition having high dispersibility of a pigment and high developability with an alkali developer and further having high chemical resistance of a cured film, and a pigment dispersion composition and a pigment dispersant for preparing the photoresist. <P>SOLUTION: The pigment dispersant is a polyurethane resin including (A1) one or two of an acidic functional group and a neutralized salt group of the acidic functional group, (A2) one or more of a basic functional group, a neutralized salt group of the basic functional group and a nonionic polar molecular chain, (B) a low-polarity molecular chain, and (C) an active energy ray-curable unsaturated group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pigment dispersant that is suitably used in paints, inks, resists, and the like in which pigments are dispersed, particularly in photoresists that form images by photolithography. The present invention also relates to a photoresist composition suitably used for forming a black matrix in a color filter for a liquid crystal display device and the like, and a pigment dispersion composition used for the preparation thereof.

  A liquid crystal display controls the transmission of incident light by attaching an electrode to a crystal material that becomes liquid crystal and applying a voltage to change the molecular arrangement of the liquid crystal. By combining a reflector and a polarizing plate, images and characters can be displayed. To display. Since liquid crystal displays consume less power, they are widely used as display devices for mobile phones, watches, cameras, various electric devices and the like.

  This color liquid crystal display is a color liquid crystal display in which blue, red, and green color filters are attached to each pixel to create three primary colors of light, and the color change is expressed by controlling the brightness and darkness of each pixel. The color filter forms pixels of three primary colors of red, blue, and green on a transparent substrate, controls the amount of light transmitted through each pixel, and performs color display by color development by adding the three primary colors.

  The color filter is formed with a blocking layer for blocking light between the pixels, that is, a black matrix, in order to prevent light leakage between the pixels and prevent a decrease in contrast and color purity. Yes. The black matrix also has a function of shielding a transistor such as a liquid crystal driving electrode or a TFT (thin film transistor) provided on a substrate facing the color filter. Accordingly, the black matrix is naturally required to have excellent light shielding properties.

  In addition, if the surface smoothness is poor and the layer thickness is large, irregularities may occur when forming a color pattern of the three primary colors, so the black matrix may have a smooth surface and a thin layer thickness. is needed.

  Conventionally, (i) a black matrix made of a metal thin film such as Cr, Ni, Al or the like and (ii) a black matrix made of a black organic resin film in which a black pigment is dispersed have been used as the black matrix. Among these, the black matrix made of the metal thin film (i) has a high degree of light shielding and optical density and excellent resolution, but has a high light reflectance, so that reflection due to reflected light is likely to occur and display quality is impaired. There are difficulties.

  On the other hand, the black matrix comprising the black organic resin film in which the black pigment of (ii) is dispersed has few such difficulties. In particular, since carbon black is a black pigment having excellent blackness, a black matrix composed of a black organic resin film in which carbon black is dispersed has excellent performance.

  A black matrix made of a black organic resin film is formed by photolithography using a photoresist composition made of carbon black, a dispersant, an acrylic monomer, an acrylic oligomer, a resin, a photopolymerization initiator, and the like. That is, by exposing the photoresist composition, the exposed portion is cured, and the unexposed portion is removed with an alkali developer, thereby forming a black matrix made of a black organic resin film. Then, the three primary colors are embedded in the unexposed portion of the black matrix made of the formed black organic resin film, thereby producing a color filter.

  As a photoresist composition using carbon black as a black pigment, for example, JP-A 2000-227654 (Patent Document 1) includes (A) a colorant containing a black pigment, (B) an alkali-soluble resin, and (C). A radiation-sensitive composition for a black resist containing a polyfunctional monomer and (D) a photopolymerization initiator, wherein (A) the colorant is dispersed by a dispersant containing a compound having a urethane bond. A radiation sensitive composition for black resist is disclosed.

  A photoresist composition used for image formation by photolithography, particularly for a color filter for a liquid crystal display device, needs both high dispersibility of carbon black and excellent developability. . That is, after development, there is no residue in the non-exposed part, the alkali solubility of the non-exposed part is high, the non-exposed part is dissolved away with an alkali developer, and the exposed part is not eroded by the alkali developer and cured. Subsequent chemical resistance is required.

  Carbon black that has not been surface-treated has poor dispersibility when blended in an organic solvent or resin, so that it is extremely difficult to form a uniform coating film and is not alkali-soluble. Therefore, in patent document 1, since the compounding quantity of a dispersing agent will increase, there existed a problem that the compounding quantity of carbon black decreased and the light-shielding property became low.

  Therefore, carbon black and base having an acidic functional group on the surface by introducing an acidic group such as sulfonic acid, phosphoric acid, carboxylic acid, phenolic hydroxyl group, etc. on the surface of carbon black and combining this with a basic dispersant. It has been proposed to improve the dispersibility and alkali solubility of carbon black by making a photoresist composition containing a functional dispersant.

For example, in JP-A-2004-198717 (Patent Document 2), (A) average primary particle diameter of 20 to 60 nm, DBP oil absorption of 30 to 100 ml / 100 g, specific surface area of 30 to 150 m ² / g by BET method, particles It contains carbon black having a carboxyl group concentration of 0.2 to 1.0 μmol / m ² on the surface, (B) a copolymer having an amino group and / or a quaternary ammonium salt thereof, and (C) an organic solvent. A carbon black dispersion composition for a color filter black matrix resist is disclosed.

  However, in this case, since the dispersant itself is basic, it does not have alkali solubility. Therefore, by introducing an acidic group into a part of the photocurable resin or monomer, the overall alkali-soluble balance is adjusted, but a part of the carbon black or coating film remains in the unexposed area. However, there was a problem that it could not be wiped out and would cause stains on the color filter. In this case, since the alkali-solubility is borne in the photo-curable resin or monomer, naturally, the alkali-solubility is also expressed in the exposed portion, resulting in poor developability and low chemical resistance. There was a problem of becoming.

JP 2000-227654 A (Claims) JP 2004-198717 A (Claims)

  Accordingly, an object of the present invention is to prepare a photoresist composition having high dispersibility of the pigment and high developability with an alkaline developer, and having high chemical resistance of the cured coating film, and the photoresist. It is an object of the present invention to provide a pigment dispersion composition and a pigment dispersant.

In order to solve the above-described problems in the prior art, the present inventors have conducted extensive research,
(1) (A1) one or two of acidic functional groups and neutralized bases of acidic functional groups, and (A2) basic functional groups, basic functional group neutralized bases and nonionic polar molecular chains A pigment dispersant composed of a polyurethane resin containing one or more of them, (B) a low-polar molecular chain, and (C) an active energy ray-curable unsaturated group is added to a photoresist composition, a pigment High dispersibility and excellent chemical resistance of the cured film,
(2) Furthermore, all or part of the above (A1), (A2), (B) and (C) above constitutes a side chain of the polyurethane resin or binds to the side chain. As a result, the molecules of the polyurethane resin approach a comb tooth shape, a highly polar group or molecular chain has an affinity for the solvent, and the polar molecular chain has an affinity for the pigment particles. Improved dispersibility,
(3) Furthermore, in the polyurethane resin obtained by using the polyol compound having amino group (A2) and the polyol compound having amino group (B) and the amino compound having an amino group as a synthetic raw material for the polyurethane resin, the amino group is a pigment. In order to exhibit ionic affinity with acidic functional groups on the surface, the dispersibility of the pigment is improved,
As a result, the present invention has been completed.

That is, the present invention (1)
(A1) one or two of acidic functional groups and neutralized bases of acidic functional groups;
(A2) one or more of a basic functional group, a neutralized base of a basic functional group, and a nonionic polar molecular chain; and
(B) a low polarity molecular chain;
(C) an active energy ray-curable unsaturated group;
A pigment dispersant comprising a polyurethane resin containing

  The present invention (2) provides a pigment dispersion composition comprising the pigment dispersant of the present invention (1), a pigment, and an organic solvent.

  In addition, the present invention (3) contains the pigment dispersant of the present invention (1), a pigment, an organic solvent, a compound having an active energy ray-curable unsaturated group, and a photopolymerization initiator. The photoresist composition characterized by these is provided.

  According to the present invention, in order to prepare a photoresist composition having a high dispersibility of a pigment and a high chemical resistance of a cured coating film in addition to a high developability with an alkaline developer, and the photoresist. The pigment dispersion composition and the pigment dispersant can be provided.

The pigment dispersant of the present invention is
(A1) one or two of acidic functional groups and neutralized bases of acidic functional groups;
(A2) one or more of a basic functional group, a neutralized base of a basic functional group, and a nonionic polar molecular chain; and
(B) a low polarity molecular chain;
(C) an active energy ray-curable unsaturated group;
It consists of a polyurethane resin containing.

  That is, the pigment dispersant of the present invention is a polyurethane resin having (A1), (A2), (B), and (C) as essential functional groups or molecular chains in one molecule. It is.

  The pigment dispersant of the present invention comprises a polyurethane resin whose main chain is polyurethane, and is bonded to the main chain, or is bonded to the side chain bonded to the main chain, or the main chain is bonded to the main chain. As molecular chains to be constructed, (A1), (A2), (B), and (C) are included.

  The polyurethane resin constituting the pigment dispersant of the present invention contains, as (A1), either the acidic functional group, the neutralized base of the acidic functional group, or both.

The acidic functional group according to (A1) of the pigment dispersant of the present invention is not particularly limited, and is carboxyl group (—COOH), hydroxyl group (—OH), sulfonic acid group (—SO ₃ H), phosphate ester. Groups (including phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triester groups) and the like. Among these, either a carboxyl group or a sulfone group, or a combination of a carboxyl group and a sulfone group is preferable. The acidic functional group may be one type or a combination of two or more types.

The neutralizing base of the acidic functional group according to (A1) of the pigment dispersant of the present invention is not particularly limited, and the acidic functional group according to (A1) of the pigment dispersant of the present invention is, for example, hydroxylated. It is a group neutralized with a basic compound such as sodium or ammonium hydroxide. For example, when the acidic functional group is a carboxyl group, -COONa, -COONH _{4 and the} like can be mentioned. The neutralizing base of the acidic functional group may be one type or a combination of two or more types.

  In the pigment dispersant of the present invention, as (A2), the basic functional group, the neutralized base of the basic functional group, the nonionic polar molecular chain, or two or more of these including.

  The basic functional group according to (A2) of the pigment dispersant of the present invention is not particularly limited, and is basic such as an aliphatic amine group, an alicyclic amine group, a heteroalicyclic amine group, and an aromatic amine group. Examples thereof include nitrogen-containing functional groups. The basic functional group may be one kind or a combination of two or more kinds.

  The neutralizing base of the basic functional group according to (A2) of the pigment dispersant of the present invention is not particularly limited, and the basic functional group according to (A2) of the pigment dispersant of the present invention is, for example, hydrochloric acid. And a group neutralized with an acidic compound such as sulfuric acid. The neutralized base of the basic functional group may be one type or a combination of two or more types.

  The nonionic polar molecular chain according to (A2) of the pigment dispersant of the present invention is, for example, a nonionic polar molecule such as a polyoxyalkylene ether molecular chain or a polyoxypropylene ether molecular chain, or a molecular chain of a copolymer thereof. Examples include molecular chains. The nonionic polar molecular chain may be one kind or a combination of two or more kinds. The nonionic polar molecular chain is preferably a polyoxyethylene ether molecular chain having 3 or more oxyethylene ether repeating units, and whether the polyoxyethylene ether molecular chain constitutes the main chain of the pigment dispersant. Or it is preferable that it is a side chain couple | bonded with the principal chain of a pigment dispersant, or its terminal. The number of repeating oxyethylene ether units in the polyoxyethylene ether molecular chain is more preferably 4 or more, and even more preferably 5 or more.

  The nonionic polar molecular chain is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, and {h / (h + g)} <0.25.)
The nonionic polar molecular chain represented by is preferable in that the dispersibility of the pigment is increased.

  d is preferably an integer of 1 to 3. Moreover, it is preferable that e is an integer of 8-30. f is preferably an integer of 1 to 3. Moreover, it is preferable that g is an integer of 8-30. h is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

  In the pigment dispersant of the present invention, the acidic functional group according to (A1) and the neutralized base of the acidic functional group, and the basic functional group according to (A2) and the neutralized base of the basic functional group are dispersed in the pigment dispersion. It may be bonded to the main chain of the polyurethane resin constituting the agent, or may be bonded to the side chain of the polyurethane resin constituting the pigment dispersant. In the pigment dispersant of the present invention, the nonionic polar molecular chain according to (A2) may be bonded to the main chain of the polyurethane resin constituting the pigment dispersant or the terminal thereof, or the pigment dispersant is You may couple | bond with the side chain of the polyurethane resin to comprise, or you may form the principal chain of the polyurethane resin which comprises a pigment dispersant.

  The polyurethane resin constituting the pigment dispersant of the present invention has a low polarity molecular chain (B). The low polar molecular chain (B) is a molecular chain having an alkyl group or alkenyl group derived from oil or fat, a molecular chain having an alkyl group or alkenyl group having 6 or more carbon atoms, or a molecular unit having 4 or more carbon atoms. A molecular chain as a unit, or a molecular chain composed of a rosin skeleton or a hydrogenated rosin skeleton is preferable, and one or a combination of two or more of these may be used. The alkyl group having 6 or more carbon atoms according to the low polarity molecular chain (B) may be linear, branched or cyclic. The molecular chain having a molecular unit having 4 or more carbon atoms as the repeating unit related to the low polar molecular chain (B) may have any of linear, branched or cyclic molecular units. In the present specification, the low polar molecular chain (B) includes reaction residues of the respective low polar molecular chains.

  In the present invention, for example, the molecular unit having 6 carbon atoms may be an alkylene group having 6 carbon atoms, for example, a methyl group bonded to an alkylene group having 5 carbon atoms, Those having a butoxy group bonded to an ethylene group having 2 carbon atoms are also included. That is, it means that the number of carbon atoms in one molecular unit is 6.

  Further, the low polarity molecular chain (B) has the following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a low-polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a low-polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a low-polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a low-polarity molecular chain represented by
A low-polar molecular chain containing a polyester having two or more molecular units having 4 or more carbon atoms as repeating units, or a low-polar molecular chain containing a polyether having two or more molecular units having 4 or more carbon atoms as repeating units A low polarity molecular chain containing a polycarbonate having 2 or more molecular units having 4 or more carbon atoms as repeating units, or a low polarity containing a polycaprolactone having 2 or more molecular units having 4 or more carbon atoms as repeating units Molecular chains are preferred in that the dispersibility of the pigment is increased.

  i is preferably an integer of 6 to 30. Moreover, it is preferable that j is an integer of 0-4. It is preferable that s is an integer of 8-30. Moreover, it is preferable that t is an integer of 8-30. u is preferably an integer of 8 to 30.

  In the pigment dispersant of the present invention, the low polarity molecular chain (B) may be bonded to the main chain of the polyurethane resin constituting the pigment dispersant or the terminal thereof, or the polyurethane resin constituting the pigment dispersant. It may be bonded to the side chain or may form the main chain of the polyurethane resin constituting the pigment dispersant.

The polyurethane resin constituting the pigment dispersant of the present invention has an active energy ray-curable unsaturated group (C).
In this specification, an active energy ray-curable unsaturated group (C) means a group that cures a resin composition containing a pigment dispersant by irradiating active energy rays such as UV light.
Examples of the active energy ray-curable unsaturated group according to (C) of the pigment dispersant of the present invention include unsaturated groups having active energy ray curability such as vinyl group, acryloyl group, and methacryloyl group. In the present specification, the active energy ray-curable unsaturated group (C) includes a reaction residue of an active energy ray-curable unsaturated group.

  In the pigment dispersant of the present invention, the active energy ray-curable unsaturated group may be bonded to the main chain of the polyurethane resin constituting the pigment dispersant or the terminal thereof, or the polyurethane resin constituting the pigment dispersant. The main chain of the polyurethane resin constituting the pigment dispersant may be formed.

  In the pigment dispersant of the present invention, all or part of (A1), (A2), (B), and (C) above constitutes a side chain of the polyurethane resin or side chains. The molecular shape of the polyurethane resin approaches that of a comb, and the polar group or molecular chain (the group or molecular chain according to (A1) or (A2) above) has an affinity for the solvent. And a low-polarity molecular chain (low-polar molecular chain according to the above (B)) has an affinity for pigment particles, and is preferable in terms of improving the dispersibility of the pigment.

In the pigment dispersant of the present invention, all or part of the above (C) is an acryloyl group or a methacryloyl group, and the concentration of the acryloyl group or methacryloyl group is 0.2 to 3 mol / kg. Preferably, it is 0.2 to 2.5 mol / kg, more preferably 0.3 to 2.5 mol / kg.
If the concentration of the acryloyl group or methacryloyl group is less than 0.2 mol / kg, sufficient chemical resistance (solvent resistance) cannot be obtained, and if it exceeds 3 mol / kg, the unsaturated group concentration is high. It becomes too much, and cross-linking increases at the time of curing, so that its workability and adhesion are lowered.

  The pigment dispersant of the present invention is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or an active hydrogen atom, and at least a part of the compound having a hydroxyl group or an active hydrogen atom is represented by the following general formula: Formula (I):

And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (IV):

Pigment dispersant (hereinafter, also referred to as pigment dispersant (1) of the present invention. Details of R ^{1 to} R ⁶ are as described later), which is a compound having a hydroxyl group or an active hydrogen atom represented by It is done. In addition, having an active hydrogen atom means having a group having an active hydrogen atom other than a hydroxyl group and reacting with an isocyanate compound, for example, an amino group.

  The pigment dispersant (1) of the present invention is a polyurethane resin obtained by reacting an isocyanate compound and a compound having a hydroxyl group or an active hydrogen atom as a polymerization raw material for the polyurethane resin.

  All of the isocyanate compounds according to the pigment dispersant (1) of the present invention may be bifunctional isocyanate compounds, or bifunctional isocyanate compounds and trifunctional or higher functional isocyanate compounds or monofunctional isocyanate compounds. Or a combination thereof.

The compound having a hydroxyl group or active hydrogen atom may be a compound (polyfunctional compound) in which all or two or more hydroxyl groups or active hydrogen atoms react with the isocyanate compound, or the isocyanate. A combination of a compound having two or more hydroxyl groups or active hydrogen atoms that react with the compound and a compound having one hydroxyl group or active hydrogen atom that reacts with the isocyanate compound (monofunctional compound) may be used. Examples of the compound having two hydroxyl groups or two active hydrogen atoms that react with the isocyanate compound include compounds represented by the above general formula (I) and general formula (IV).
In the case of a combination of a compound having two or more hydroxyl groups that react with the isocyanate compound and a compound having one hydroxyl group or active hydrogen atom that reacts with the isocyanate compound as a compound having a hydroxyl group or an active hydrogen atom, A compound having one hydroxyl group or one active hydrogen atom that reacts with the isocyanate compound serves as an end of the main chain of the polyurethane resin. A compound having two or more hydroxyl groups or active hydrogen atoms that react with the isocyanate compound is also called a polyol.

In the general formula (I), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ and R ^At least one of ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH. Therefore, either one or both of R ¹ and R ² have a hydroxyl group. a is an integer of 1 to 6, preferably an integer of 2 to 4, b is an integer of 1 to 3, preferably an integer of 1 to 2, and c is an integer of 1 to 4. Yes, preferably an integer of 1 to 3, and R ¹ and R ² may be the same or different.

In the general formula (I), R ³ represents the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these.

  d is preferably an integer of 1 to 3. Moreover, it is preferable that e is an integer of 8-30. f is preferably an integer of 1 to 3. Moreover, it is preferable that g is an integer of 8-30. h is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

In the general formula (IV), R ⁴ and R ⁵ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ⁴ and R at least one of the ^five _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH. Therefore, either one or both of R ⁴ and R ⁵ have a hydroxyl group. p is an integer of 1 to 6, q is an integer of 1 to 3, r is an integer of 1 to ^4, and R ⁴ and R ⁵ may be the same or different.
p is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. Moreover, q is preferably an integer of 2 to 3. Furthermore, r is preferably an integer of 2 to 4, and more preferably an integer of 2 to 3.

In the general formula (IV), R ⁶ represents the following general formula (V)

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (8), u is an integer of 5-30.)
Or a low-polar group containing a polyester having two or more molecular units having 4 or more carbon atoms as repeating units, or a molecular unit having 4 or more carbon atoms as a repeating unit. A low-polar group containing a polyether having two or more, a low-polar group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as a repeating unit, or a repeating unit having a molecular unit having 4 or more carbon atoms As a low polar group containing polycaprolactone having two or more.
i is preferably an integer of 6 to 30. Moreover, it is preferable that j is an integer of 0-4. It is preferable that s is an integer of 8-30. Moreover, it is preferable that t is an integer of 8-30. u is preferably an integer of 8 to 30.
The pigment dispersant of the present invention comprises a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (I) and the bifunctional compound represented by the general formula (IV). In some cases, the ratio of the structural unit derived from the general formula (I) to the structural unit derived from the general formula (IV) in the polyurethane resin (the structural unit derived from the general formula (I): the general formula (IV) The derived structural unit) is preferably 1: 0.1 to 0.1: 1, more preferably 1: 0.3 to 0.3: 1, and 1: 0.5 to 0.00. More preferably, it is 5: 1.

  Moreover, since the pigment dispersant (1) of the present invention has (A1) and (C) in addition to (A2) and (B), a hydroxyl group or an active hydrogen atom to be reacted with the isocyanate compound is added. Among the compounds having a hydroxyl group or an active hydrogen atom other than a compound having a hydroxyl group or an active hydrogen atom represented by the general formula (I) and a compound having a hydroxyl group or an active hydrogen atom represented by the general formula (IV) All or a part of the compounds are “the compound having (A1) the hydroxyl group or active hydrogen atom” and “the compound having (C) the hydroxyl group or active hydrogen atom”. . In the pigment dispersant (1) of the present invention, the compound having a hydroxyl group or an active hydrogen atom represented by the general formula (I) as the compound having the hydroxyl group or active hydrogen atom to be reacted with the isocyanate compound, A compound having a hydroxyl group or an active hydrogen atom represented by formula (IV), “a compound having (A1) the hydroxyl group or active hydrogen atom”, and “the hydroxyl group or activity having (C)” A compound having a hydroxyl group or an active hydrogen atom other than the “compound having a hydrogen atom” can be used.

  When the pigment dispersant of the present invention is made of a polyurethane resin obtained by reacting an isocyanate compound with the compound represented by the above general formula (I) and the compound represented by the general formula (IV), In the polyurethane resin, the compound represented by the general formula (I) gives a nonionic polar molecular chain represented by the general formulas (II) to (III), and is represented by the general formula (IV). The compound imparts a low-polar molecular chain represented by general formulas (V) to (VIII). For this reason, in the polyurethane resin obtained by reacting the isocyanate compound with the compound represented by the general formula (I) and the general formula (IV), it is represented by the general formula (I) and the general formula (IV). (A1), (A2) and a low-polar molecular chain (B) related to a polar group or a polar molecular chain, and the polar molecular chain (A1), (A2) and the low-polar molecular chain ( B) improves the affinity for an organic solvent and the affinity for a pigment, respectively, and (A1), (A2) and a low number of polar groups or polar molecular chains as side chains with respect to the main chain of the molecular chain. By having a comb-shaped structure having a polar molecular chain (B), it is considered that the above-mentioned affinity can be effectively exhibited and the pigment can be suitably dispersed. In addition, the amino group or amide group contained in the structural unit derived from the general formula (I) or the structural unit derived from the general formula (IV) exhibits weak ionic affinity with the acidic functional group on the pigment surface. Therefore, it is considered that the pigment can be suitably dispersed.

  A polyurethane resin obtained by reacting the bifunctional compound represented by the general formula (I) and the bifunctional compound represented by the general formula (IV) can be produced by a method described later.

As the pigment dispersant of the present invention, the resin is a polyurethane resin obtained by reacting an isocyanate compound with a bifunctional compound having a hydroxyl group or an active hydrogen atom, and the bifunctional compound having a hydroxyl group or an active hydrogen atom. At least a part of the following general formula (IX):

(In General Formula (IX), R ⁷ and R ⁸ are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ⁷ and R 8 ^At least one of ⁸ is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ⁷ and R ⁸ may be the same or different, and R ⁹ is represented by the following general formula (X):

(In general formula (X), d is an integer of 1-4, and e is an integer of 5-30.)
A nonionic polar molecular chain-containing group represented by )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (XI):

(In General Formula (XI), R ¹⁰ and R ¹¹ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ¹⁰ and R 11 at least one of the ¹¹ _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, and R ⁴ and R ⁵ may be the same or different, and R ¹² represents the following general formula (XII):

(In general formula (XII), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
It is a low polar molecular chain containing group represented by these. )
What is a compound which has a hydroxyl group or an active hydrogen atom represented by these is preferable.

  Preferred ranges and more preferred ranges for a, b, c, d, e, p, q, r, i, and j are the same as those described above.

  The pigment dispersant of the present invention comprises a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI). In some cases, the ratio of the structural unit derived from the general formula (IX) to the structural unit derived from the general formula (XI) in the polyurethane resin (the structural unit derived from the general formula (IX): The derived structural unit) is preferably 1: 0.2 to 0.2: 1, more preferably 1: 0.3 to 0.3: 1, and 1: 0.5 to 0.00. More preferably, it is 5: 1.

  When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the general formula (XI) is used as the pigment dispersant, the isocyanate compound is all difunctional. May be a combination of a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound or a monofunctional isocyanate compound.

  When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the general formula (XI) is used as the pigment dispersant, the general formula (IX) and A monofunctional compound having one hydroxyl group or one active hydrogen atom that reacts with an isocyanate compound may be used together with the bifunctional compound represented by the general formula (XI). In this case, the monofunctional compound having one hydroxyl group or one active hydrogen atom that reacts with the isocyanate compound forms the terminal portion of the main chain of the polyurethane resin.

When a polyurethane resin obtained by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI) is used as the pigment dispersant, this polyurethane is used. The resin is a compound in which the bifunctional compound represented by the general formula (IX) imparts a nonionic polar molecular chain-containing group represented by the general formula (X), and the compound represented by the general formula (XI) However, it provides a low polar molecular chain-containing group represented by the general formula (XII).
For this reason, in the polyurethane resin formed by reacting an isocyanate compound with the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI), the above general formula (IX) is used. And the bifunctional compound represented by the general formula (XI) gives (A2) and the low polar molecular chain (B) related to the polar molecular chain.
The polyurethane resin obtained by reacting the bifunctional compound represented by the general formula (IX) and the bifunctional compound represented by the general formula (XI) can be prepared by a method described later.

  Among the pigment dispersants of the present invention, the polyurethane resin is obtained by reacting an isocyanate compound with a compound having a hydroxyl group or an active hydrogen atom, and 2 of the compounds having a hydroxyl group or an active hydrogen atom. Compound having bifunctional hydroxyl group or active hydrogen atom having (A1), (A2), (B) or (C) as a side chain with respect to the total number of moles of the compound having functional hydroxyl group or active hydrogen atom It is preferable that the mol% of the total mol of the polymer is 10 to 100 mol% in that the dispersibility of the pigment becomes high. That is, paying attention to a compound having a bifunctional hydroxyl group or an active hydrogen atom among compounds having a hydroxyl group or an active hydrogen atom used in producing the pigment dispersant of the present invention, the bifunctional hydroxyl group or active hydrogen atom is used. A compound having a bifunctional hydroxyl group or active hydrogen atom having (A1) as a side chain, a bifunctional hydroxyl group or active hydrogen having (A2) as a side chain, relative to the total number of moles of compounds having A compound having an atom, a bifunctional hydroxyl group having (B) as a side chain or an active hydrogen atom, and a bifunctional hydroxyl group or active hydrogen atom having (C) as a side chain The ratio of the total number of moles of the compound is preferably 10 to 100 mol% in terms of increasing dispersibility of the pigment, and more preferably 25 to 80 mol. The bifunctional hydroxyl group having Y as a side chain or a compound having an active hydrogen atom is a bifunctional hydroxyl group or active hydrogen such that, when polymerized, Y becomes a side chain of the polyurethane resin. A compound having an atom.

  A hydroxyl group or a bifunctional compound having an active hydrogen atom containing (A1) or (A2) in the side chain, and a hydroxyl group containing a low polarity molecular chain (B) in the side chain The ratio of the total number of moles with the bifunctional compound having an active hydrogen atom is preferably 20 to 90% by mole, and preferably 25 to 85% by mole, based on the total of the bifunctional compound having a hydroxyl group or an active hydrogen atom. More preferably, it is more preferably 30 to 80 mol%.

  Further, the side of (A1) or (A2) related to the polar group or polar molecular chain with respect to the number of moles of the bifunctional compound having a hydroxyl group or active hydrogen atom comprising the low polarity molecular chain (B) in the side chain. Ratio of the number of moles of a bifunctional compound having a hydroxyl group or active hydrogen atom contained in the chain (having a hydroxyl group or active hydrogen atom comprising (A1) or (A2) relating to the polar group or polar molecular chain in the side chain) The number of moles of the bifunctional compound / the number of moles of the bifunctional compound having a hydroxyl group or an active hydrogen atom comprising the low-polar molecular chain (B) in the side chain is preferably 2/8 to 8/2. It is more preferably 3/7 to 7/3, and further preferably 4/6 to 6/4.

  The total amount of the bifunctional compound having a hydroxyl group or active hydrogen atom comprising the active energy ray-curable unsaturated group (C) in the side chain is such that the active energy ray-curable unsaturated group concentration of the entire resin is 0. The amount is preferably 3 to 3.0 equivalents / kg, more preferably 0.4 to 2.5 equivalents / kg, and 0.5 to 2.0 equivalents / kg. More preferably, the amount.

  The method for producing the pigment dispersant of the present invention is not particularly limited, and a known method is used.

  The pigment dispersant of the present invention includes, for example, a polyol (a1) having one or two (A1) of the acidic functional group and the neutralized base of the acidic functional group, the basic functional group, and the basic functional group. A polyol (a2) having one or more (A2) of a neutralized base of a group and a nonionic polar molecular chain, a polyol (b) having the low polar molecular chain (B), and the active energy It is obtained by reacting a compound (c) having a linear curable unsaturated group (C) and a hydroxyl group with a difunctional or higher isocyanate compound (d). This method is preferable in that (a1), (a2) and (b) can be connected in a block manner via (d). In this method, a polyol (a1) having one or two of the acidic functional group and a neutralized base of the acidic functional group as a side chain, a basic functional group as a side chain, and neutralization of a basic functional group By using the polyol (a2) having one or more of the base and nonionic polar molecular chains, and the polyol (b) having a low polar molecular chain (B) as a side chain, the above (A1), (A2) and (B) are preferable in that a pigment dispersant extending as a side chain in a comb tooth shape is obtained. In addition, the polyol which has Y as a side chain refers to the polyol from which Y becomes a side chain of a polyurethane resin when it superposes | polymerizes. In addition to the polyol compound, a monool (monofunctional compound) having one hydroxyl group or active hydrogen atom that reacts with the isocyanate compound (d) and having (A1), reacts with the isocyanate compound (d). A monool (monofunctional compound) having (A2) and one hydroxyl group or active hydrogen atom which reacts with the isocyanate compound (d) and having (B) A monool (monofunctional compound) can also be used in combination.

  The acidic functional group in (a1) corresponds to the acidic functional group (A1) of the pigment dispersant of the present invention, and the neutralizing base of the acidic functional group in (a1) is the pigment of the present invention. It corresponds to the neutralized base of the acidic functional group (A1) of the dispersant, the basic functional group in (a2) corresponds to the basic functional group (A2) of the pigment dispersant of the present invention, and The neutralized base of the basic functional group in (a2) corresponds to the neutralized base of the basic functional group in (A2) of the pigment dispersant of the present invention, and the nonionic polar molecular chain in (a2) above is This corresponds to the nonionic polar molecular chain (A2) of the pigment dispersant of the present invention. Further, the low polar molecular chain in (b) corresponds to the low polar molecular chain (B) of the pigment dispersant of the present invention. Moreover, the active energy ray-curable unsaturated group in the above (c) corresponds to the active energy ray-curable unsaturated group of (C) of the pigment dispersant of the present invention.

As the above (a1), as a polyol compound (a1) having an acidic functional group, a carboxyl group (—COOH), a hydroxyl group (—OH), a sulfonic acid group (—SO ₃ H), a phosphoric acid ester group (phosphoric acid mono group) Examples include polyol compounds having one or more of acidic functional groups such as esters, phosphoric acid diesters, phosphoric acid triester groups, and sulfuric acid esters, and groups in which they are neutralized with a basic compound. .
More specifically, as the above (a1), trimethylolpropane monophosphate ester, trimethylolpropane monosulfate ester, polyester diol in which at least a part of the dibasic acid component is sodium sulfosuccinic acid or sodium sulfoisophthalic acid, Diaminocarboxylic acids such as lysine, cystine and 3,5-diaminocarboxylic acid, 2,6-dihydroxybenzoic acid, 3,5 dihydroxybenzoic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2, 2-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, carboxyl group-containing polycaprolactone diol, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (Hydroxypropyl) propi Phosphate, 2,2-bis-dihydroxy alkanoic acids such as (hydroxymethyl) butanoic acid, caprolactone adducts of dihydroxy alkanoic acids and the like. Moreover, what neutralized these acidic functional groups with the basic compound is mentioned.

Examples of the (a2) include compounds having a hydroxyl group and a basic nitrogen-containing group such as dialkanolamines as the polyol compound (a2) having the basic functional group.
More specifically, examples of the polyol compound (a2) having a basic functional group include N-monoalkyl dialkanolamines such as N-methyldiethanolamine, N-ethyldiethanolamine, and N-methylpropanolamine, N, N -Cationic diols such as dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide;
Michael addition reaction product of dimethylaminoethyl acrylate and dialkanolamine such as diethanolamine and dipropanolamine;
Michael addition reaction of monoalkylamines such as ethylamine and butylamine and hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate;
Diamine consisting of tertiary amine and primary amine such as dimethylaminoethylamine, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, etc. and primary amine, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Michael addition reaction products of hydroxyalkyl acrylates such as 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate;
Compounds consisting of heterocyclic amines and primary amines such as N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethyl-4-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine and 2 -Michael addition reaction products of hydroxyalkyl acrylates such as hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and 4-hydroxybutyl acrylate.

As the above (a2), the polyol compound (a2) having a nonionic polar molecular chain may be a nonionic polar molecular chain such as a polyoxyethylene ether chain or a polyoxyethylene ether-polyoxypropylene ether glycol copolymer molecular chain. The polyol compound which has.
More specifically, as the polyol compound (a2) having a nonionic polar molecular chain, polyoxyethylene ether having three or more polyoxyethylene ether repeating units obtained by adding ethylene oxide to dibasic acid or diols. Diol;
A block copolymer diol in which the polyoxyethylene ether chain occupies 60 mol% or more of the block copolymer diol of polyoxypropylene ether glycol or polyoxybutylene ether glycol and polyoxyethylene ether;
A block copolymer diol polymer diol in which the polyoxyethylene ether chain occupies 60 mol% or more, a block copolymer diol of polyoxyethylene ether, and the like are typical diols having a polar group in the molecular main chain.
Moreover, as said (a2), the following general formula:

(In General Formula (11), R ¹³ is an alkyl group having 4 to 27 carbon atoms, w and x are positive integers, and w + x is 5 to 50.)
The diol represented by these is mentioned.

Moreover, as said (a2), alkoxy polyoxyethylene ether acrylates, such as methoxy polyoxyethylene ether acrylate which has a 3 or more polyoxyethylene ether repeating unit, and dialkanolamines, such as diethanolamine or dipropanolamine, are Michael. Examples of diols obtained by addition reaction include diols having a polar molecular chain in the molecular side chain.
The above (a2) for introducing a nonionic molecular side chain having three or more oxyethylene ether repeating units as a side chain of the polyurethane resin includes a hydroxyl group or active hydrogen represented by the general formula (I). A compound having an atom is exemplified. And the compound which has the hydroxyl group or active hydrogen atom represented by the said general formula (I) is preferable at the point from which the dispersibility of a pigment becomes high.

As such a polyol compound (a2) having a nonionic polar molecular chain, the following general formula (I):
(Where R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and at least one of R ¹ and R ² one _is -C _a H 2a -OH or _{-C b H 2b -COO-C c} H 2c -OH, a is an integer from 1 to 6, b is an integer of 1 to 3, c is 1 to 4 And R ¹ and R ² may be the same or different, and R ³ is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, h is a positive integer, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these. )
The bifunctional compound represented by these can be mentioned.

  The more preferable ranges and further preferable ranges of the above a, b, c, d, e, f, g, and h are the same as the above-described ranges.

Moreover, as a polyol compound (a2) which has a nonionic polar molecular chain, following general formula (IX):

(In General Formula (IX), R ⁷ and R ⁸ are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ⁷ and R 8 ^At least one of ⁸ is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ⁷ and R ⁸ may be the same or different, and R ⁹ is represented by the following general formula (X):

(In general formula (X), d is an integer of 1-4, and e is an integer of 5-30.)
A nonionic polar molecular chain-containing group represented by )
And a bifunctional compound represented by the formula:

  The more preferable ranges and further preferable ranges of the above a, b, c, d, and e are the same as the above-described ranges.

  As described above, the compound represented by the general formula (I) and the compound represented by the above (IX) are, for example, methoxy polyoxyethylene ether acrylate having 5 to 30 polyoxyethylene ether repeating units, It can be prepared by Michael addition reaction with dialkanolamine such as diethanolamine and dipropanolamine.

  Examples of (b) include polymer polyols having two or more molecular units having 4 or more carbon atoms as repeating units. Examples of the polymer polyol (b) include polyester polyol, polycarbonate diol, and polyether polyol. Examples of the polymer polyol (b) include polymer diols such as butadiene diol. The polymer polyol (b) includes a polymer diol of a compound having a rosin skeleton or a hydrogenated rosin skeleton. The molecular weight of the polymer polyol (b) is preferably 500 to 3000 in terms of number average molecular weight.

  The polymer polyol (b) preferably has 2 or more molecular units each having a carbon number of each molecular unit of 4 or more and an average number of carbon atoms of all molecular units of 6 or more as a repeating unit. Is.

  As said polyester polyol (b), 1 type (s) or 2 or more types of the following polyols and polyol synergistic components, and 1 type (s) or 2 or more types among polybasic acids and their anhydrides undergo a condensation reaction. Can be obtained.

  Examples of the polyol having a molecular unit of 4 or more, which is a raw material for the polyester polyol (b), include cyclohexane-1,4-dimethanol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol. 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexyldimethanol, castor oil-modified diol, castor oil-modified polyol, and the like.

  The polyol synergistic component which is a raw material of the polyester polyol (b) includes alkyl monoglycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, decyl glycidyl ether and stearyl glycidyl ether, and alkyls. One type or two or more types of monoepoxy compounds such as glycidyl ester (product name: Cardura E10: manufactured by Shell Japan) are listed.

  The polybasic acids and their anhydrides, which are raw materials for the polyester polyol (b), include aliphatic dibasic acids such as adipic acid, azelaic acid, sebacic acid and dimer acid, and their anhydrides, dodecenyl anhydride. Aromatic polybasic acids such as acid, phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride and their anhydrides, hydrophthalic anhydride and dimethyl-1,4-cyclohexanedicarboxylic acid And anhydrides thereof.

  Polyester polyols obtained by ring-opening addition polymerization of monomers having a lactone ring such as ε-caprolactone and β-methyl-δ-valerolactone starting from a hydroxyl-terminated compound such as the above-mentioned polyol or polyester polyol (b) are also polyesters. An example of the polyol (b) is mentioned.

  As the polycarbonate diol (b), diols such as 1,6 hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol were used as raw materials. Examples include polycarbonate diol.

  Examples of the polyether polyol (b) include polyether polyols in which propylene oxide, tetrahydrofuran, or butylene oxide is added using bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, or the like as starting materials.

  As the butadiene diol (b), the following general formula:

(In the formula, k = 0.2, l = 0.2, m = 0.6. N represents a positive integer.)
Polybutadiene diols Poly bdR-15HT, R-45HT (made by Idemitsu Kosan Co., Ltd.), polyisoprene diol Poly ip (made by Idemitsu Kosan Co., Ltd.) represented by the following general formula:

(In the formula, n represents a positive integer.)
Α, ω-polybutadiene glycol G-1000, G-2000, G-3000 (manufactured by Nippon Soda Co., Ltd.) and the like represented by

  Examples of the polymer diol (b) of the compound having the rosin skeleton or the hydrogenated rosin skeleton include Pine Crystal D-6011 and D-6240 (manufactured by Arakawa Chemical Industries).

  Examples of (b) include diols having an alkyl group derived from fats and oils such as polyester polyol, polycarbonate diol and ether polyol, and diols having an alkyl group having 4 or more carbon atoms such as butadiene diol.

  As the above (b), as the polyol (b) having an alkyl group or alkenyl group having 6 or more carbon atoms, cyclohexane-1,4-dimethanol, 1,6-hexanediol, 3-methyl-1,5-pentane Molecular chains such as diol, 2-ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, etc. Diols having hydroxyl groups at both ends; Diols having an alkyl group or alkenyl group having 6 or more carbon atoms via an ester group as a side chain, such as the following general formula:

(However, R ¹⁴ is an alkyl group or alkenyl group having 6 or more carbon atoms.)
A diol having an alkyl group or alkenyl group having 6 or more carbon atoms via an ether group as a side chain, such as the following general formula:

(However, R ¹⁴ is an alkyl group or alkenyl group having 6 or more carbon atoms.)
The diol represented by these is mentioned.

As (b), the following general formula:

(However, v is an integer of 4 to 27, and is preferably any one of 11, 17, and 21)
The diol represented by these is mentioned.

  Examples of (b) include compounds having a hydroxyl group or an active hydrogen atom represented by the general formula (5). And among this (b), the compound which has a hydroxyl group or active hydrogen atom represented by the said General formula (5) is preferable.

Moreover, as diol (b) which has a low polar molecular chain (B), following general formula (IV)

In the bifunctional compound represented by R ⁴ and R ⁵ , —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ⁴ and At least one of R ⁵ is —C _p H _2p —OH or —C _q H _2q —COO—C _r H _2r —OH, p is an integer of 1 to 6, q is an integer of 1 to 3, r is an integer of 1 to 4, R ⁴ and R ⁵ may be the same or different, and R ⁶ is represented by the following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a low-polar group containing a polyester having two or more molecular units having 4 or more carbon atoms as repeating units, or a molecular unit having 4 or more carbon atoms as a repeating unit. A low-polar group containing a polyether having two or more, a low-polar group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as a repeating unit, or a repeating unit having a molecular unit having 4 or more carbon atoms As a low polar group containing polycaprolactone having two or more. )
The bifunctional compound represented by these can be mentioned.

  More preferable ranges and further preferable ranges of p, q, r, i, j, s, t, and u are the same as those described above.

Moreover, as diol (b) which has a low polar molecular chain (B), following general formula (XI):

(In General Formula (XI), R ¹⁰ and R ¹¹ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or an active hydrogen atom, and R ¹⁰ and R 11 at least one of the ¹¹ _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, and R ⁴ and R ⁵ may be the same or different, and R ¹² represents the following general formula (XII):

(In general formula (XII), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
It is a low polar molecular chain containing group represented by these. )
And a bifunctional compound represented by the formula:

  More preferable ranges and further preferable ranges of p, q, r, i, and j are the same as those described above.

  The compound represented by the general formula (IV) or the compound represented by the above (XI) is obtained by reacting, for example, an alkylphenyl polyoxyethylene ether acrylate with a dialkanolamine such as diethanolamine or dipropanolamine. Can be produced.

  As said (c), the compound which has a vinyl group or (meth) acryloyl group which has active energy ray curability, and a hydroxyl group is mentioned.

  Examples of the compound (c) having a vinyl group and a hydroxyl group include monohydroxyethyl vinyl ether, monohydroxybutyl vinyl ether, cyclohexanedimethanol monohydroxylovinyl ether, and diethylene glycol monovinyl ether.

Examples of the compound (c) having a (meth) acryloyl group and a hydroxyl group include monohydroxyacryl methacrylate, monohydroxytriacrylate, monohydroxypentaacrylate, and dihydroxymono (meth) acrylate.
Further, a compound obtained by addition polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or ε-caprolactone may be used.

  Examples of the monohydroxyacryl methacrylate relating to the compound (c) having the (meth) acryloyl group and the hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples thereof include monohydroxy mono (meth) acrylate, glycerin di (meth) acrylate, and light ester G-201P (manufactured by Kyoeisha Chemical).

  Examples of the monohydroxytriacrylate according to the compound (c) having the (meth) acryloyl group and hydroxyl group include pentaerythritol triacrylate.

  Examples of the monohydroxypentaacrylate related to the compound (c) having the (meth) acryloyl group and hydroxyl group include dipentaerythritol pentaacrylate.

  Examples of the dihydroxy mono (meth) acrylate according to the compound (c) having the (meth) acryloyl group and hydroxyl group include glycerin mono (meth) acrylate.

  Further, (c) includes (meth) acryloyl groups obtained by reacting a compound having a (meth) acryloyl group and an isocyanate group with dialkanolamines such as diethanolamine and dipropanolamine at a low temperature of 40 ° C. or lower. A diol compound having one hydroxyl group and two hydroxyl groups in the same molecule can be mentioned. When these are used, a (meth) acryloyl group can be introduced into the molecular side chain.

  Examples of (d) include aliphatic diisocyanates such as 1,6 hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate; trimers of the aliphatic diisocyanate; low molecular triols and the fat Aliphatic polyisocyanates such as adducts of aromatic isocyanates, or alicyclic rings such as isophorone diisocyanate, hydrogenated MDI, hydrogenated tolylene diisocyanate, methylcyclohexylene diisocyanate, isopropylidenecyclohexyl-4,4′-diisocyanate and norbornene diisocyanate Diisocyanates; trimers of the alicyclic diisocyanates; alicyclic polyisocyanates such as adducts of low-molecular triols and the alicyclic isocyanates; or xylylene diene Araliphatic diisocyanates such as socyanates; trimers of xylylene diisocyanate; aromatic cycloaliphatic polyisocyanates such as adducts of low-molecular triols and araliphatic isocyanates, or 4,4′-diphenylmethane diisocyanate, tolylene diene Aromatic diisocyanates such as isocyanate; triphenylmethane triisocyanate; trimers of the aromatic diisocyanate; aromatic polyisocyanates such as adducts of low molecular triols and aromatic isocyanates, or polymethylene polyphenyl isocyanate, etc. Trifunctional or higher polyisocyanate or Cosmonate LL (Mitsui Chemicals, Inc .: carbodiimidized 4,4′-diphenylmethane diisocyanate and 4,4′-diphenylmethane diisocyanate Mixture) or sulfonates, or CARBODILITE V-05 (Nisshinbo Industries, Ltd.: terminal aliphatic having polycarbodiimide group polyisocyanate compound) polyisocyanate compounds having carbodiimide groups, such as and the like. These may be used alone or in combination of two or more.

  Below, the polyol (a1) having one or two of the acidic functional group and the neutralized base of the acidic functional group, the basic functional group, the neutralized base of the basic functional group, and the nonionic system Polyol (a2) having one or more polar molecular chains, polyol (b) having the low polar molecular chain (B), compound having the active energy ray-curable unsaturated group and hydroxyl group A method for producing the dispersant of the present invention by reaction of (c) with a bifunctional or higher functional isocyanate compound (d) is exemplified.

(1) When using only a diol compound having one or more active energy ray-curable unsaturated groups and one hydroxyl group in the same molecule as the compound (c) having an active energy ray-curable unsaturated group and a hydroxyl group, The molar ratios of (a1), (a2), (b), (c), and (d) are set to [a1], [a2], [b], [c], [d], the first reaction of reacting the above (a1), (a2), (b) and (d) under the following reaction conditions, obtain.
First stage reaction conditions: {([a1] + [a2] + [b]) / [d]} ≦ 1
Next, a second-stage reaction is performed in which the obtained isocyanate group-terminated urethane resin is reacted with (c) such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. The dispersant of the present invention having an active energy linear unsaturated group at its end can be obtained.

  Furthermore, in the first stage reaction, the reaction is carried out as ([a1] + [a2] + [b]) / [d] ≦ 1, and once the isocyanate group-terminated polyurethane resin is obtained, the second stage reaction is performed. As a compound (c) containing one or more active energy ray-curable unsaturated groups and one hydroxyl group with respect to the isocyanate group of the isocyanate group-terminated polyurethane resin, such as N, N′-dimethylethanolamine By reacting with N, N′-dialkylalkanolamine, a polyurethane resin having an amine terminal and an active energy ray-curable unsaturated group terminal can be obtained.

(2) When a diol compound having one or more active energy ray-curable unsaturated groups and two hydroxyl groups in the same molecule is used as the compound (c) having an active energy ray-curable unsaturated group and a hydroxyl group For example, ([a1] + [a2] + [b] + [c]) / [d] ≧ 1, and a hydroxyl-terminated polyurethane resin can be obtained by a one-step reaction.

(3) Further, as the compound (c) having an active energy ray-curable unsaturated group and a hydroxyl group, a diol compound having one or more active energy ray-curable unsaturated groups and two hydroxyl groups is used to form a first step. In this reaction, the reaction is carried out as ([a1] + [a2] + [b] + [c]) / [d] ≦ 1 to obtain an isocyanate group-terminated polyurethane resin. ,
(3-1) The isocyanate group of the above-mentioned isocyanate group-terminated polyurethane resin is reacted with any diol selected from diol (a1), diol (a2) and diol (b) to give a hydroxyl-terminated polyurethane resin or (reaction Or if the total number of moles of diol (a1), diol (a2), and diol (b) to be used is not sufficient as compared with the number of terminal isocyanate groups) to obtain an isocyanate group-terminated polyurethane resin,
(3-2) To the isocyanate group of the isocyanate group-terminated polyurethane resin,
As the compound (c) having an active energy ray-curable unsaturated group and a hydroxyl group, one or more active energy ray-curable unsaturated groups and a compound (c) containing one hydroxyl group are reacted to form a double bond at the terminal portion. To obtain a polyurethane resin having
(3-3) Compound (c) containing one or more active energy ray-curable unsaturated groups and one hydroxyl group in the isocyanate group of the isocyanate group-terminated polyurethane resin, such as N, N′-dimethylethanolamine It is also possible to react with a N, N′-dialkylalkanolamine to obtain a polyurethane resin having an amine terminal and an active energy ray-curable unsaturated group terminal.

  Moreover, in the method shown to said (1)-(3), it is unsaturated in a molecular chain by using the polyol which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, with diol (b). Groups can be introduced.

  If necessary, the isocyanate group of the isocyanate group-terminated polyurethane resin may be reacted with an N, N′-dialkanolamine such as N, N′-dimethylethanolamine to make the terminal group an amine. it can.

  If necessary, the molecular chain can be extended by reacting the isocyanate group-terminated polyurethane resin with diol, amine, amino alcohol, or the like.

  The reactions (1) to (3) are carried out in the absence of a solvent or in an organic solvent. Examples of the reaction solvent include known arbitrary solvents that do not react with an isocyanate group, and a solvent having few impurities such as moisture, base, and strong acid is preferable. The reaction temperature is preferably 40 to 120 ° C. If the reaction temperature is too low, the reaction time becomes long, and if the reaction temperature is too high, the isocyanate may increase in quantity.

  In the above reaction, any known catalyst can be used as necessary. Examples of the catalyst include tin-based catalysts such as dibutyltin disuccinate, dibutyltin dilaurate, and stannous octylate, and amine-based urethane catalysts such as triethylenediamine, diazabicycloundecene (DBU), and DBU salts.

  The pigment dispersant of the present invention is suitably used as a dispersant for dispersing a pigment in a pigment dispersion composition or a photoresist composition. The pigment dispersant of the present invention is a pigment dispersant capable of providing a cured film having high dispersion performance of the pigment, high developability with an alkaline developer, and excellent chemical resistance. In particular, the pigment dispersant of the present invention is excellent in dispersibility of carbon black, particularly carbon black having an acidic functional group or a neutralized base of an acidic functional group.

  The pigment dispersion composition of the present invention contains the pigment dispersant of the present invention, a pigment, and an organic solvent. In the pigment dispersion composition of the present invention, the pigment is dispersed in an organic solvent by the pigment dispersant of the present invention.

  Examples of the pigment according to the pigment dispersion composition of the present invention include inorganic pigments such as carbon black, titanium oxide, and iron oxide, insoluble azo pigments, soluble azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, isoindoline pigments, and benzimidazolones. Organic pigments such as pigments, pyranthrone pigments, thioindigo pigments, and quinophthalone pigments, or surface modified pigments that have been surface modified by bonding acidic functional groups or neutralizing bases of acidic functional groups to the surfaces of these pigments It is done. Among these pigments, carbon black includes carbon black produced by a contact method called channel black, roller black, and disk black, carbon black produced by a furnace method called gas furnace black, and oil furnace black, and thermal black. And carbon black produced by a thermal method called acetylene black.

  The surface-modified pigment according to the pigment dispersion composition of the present invention is a pigment whose surface is modified with the acidic functional group or the neutralized base of the acidic functional group. In other words, the surface-modified pigment has an acidic functional group on the surface, or is obtained by neutralizing all or part of the acidic functional group with a basic compound.

  The acidic functional group or the neutralized base of the acidic functional group bonded to the surface-modified pigment is the same as the acidic functional group or the neutralized base of the acidic functional group according to the dispersant of the present invention. Of these, the acidic functional group relating to the surface-modified pigment is preferably a combination of a carboxyl group and a hydroxyl group.

  As an example of the surface modified pigment, the surface modified pigment in which the pigment is carbon black will be described.

  In the surface-modified pigment, carbon black, which is a pigment before the functional group is introduced, includes carbon black, gas furnace black, and oil furnace black produced by a contact method called channel black, roller black, and disk black. Examples thereof include carbon black produced by a so-called furnace method, thermal black, carbon black produced by a thermal method called acetylene black, etc. Among these, furnace black having excellent productivity is preferable.

Introducing an acidic functional group into carbon black before the introduction of the functional group, the carbon black having the acidic functional group introduced therein, that is, as a method of obtaining the surface modified pigment, the carbon black before the introduction of the functional group, Oxidation by contact with free oxygen at high temperature, oxidation with oxidants such as ozone and NO ₂ , treatment under normal pressure or pressure with bromine and water, oxidation properties such as nitric acid and sulfuric acid And a method of introducing a carboxyl group or a hydroxyl group into carbon black before the introduction of the functional group by an oxidation method such as oxidation with a solution of the above, or a combination thereof, or oxidation with hydrogen peroxide. It is done. Moreover, as a method of introducing an acidic functional group such as a carboxyl group, a sulfone group, and a phosphoric acid group into the carbon black before the introduction of the functional group other than the oxidation method, a diazo coupling method can be mentioned. Examples of the carbon black introduced with the acidic functional group or the carbon black in which a part or all of the acidic functional group is neutralized with a basic compound include CAB-O-JET200 and CAB-O-JET300 manufactured by Cabot Specialty. And water dispersible carbon black such as CAB-O-JET400.

  Examples of the organic solvent according to the pigment dispersion composition of the present invention include propylene glycol monomethyl ether acetate, methoxybutyl acetate, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, benzene, chloroform, dichloromethane, ethyl acetate, Methyl lactate, ethyl lactate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methanol, ethanol, propanol, butanol, tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyl sulfoxide etc. are mentioned.

  The pigment dispersion composition of the present invention is obtained by adding the pigment and the pigment dispersant of the present invention to the organic solvent, mixing the mixture with a homogenizer such as a bead mill, and dispersing the pigment in the organic solvent.

In the pigment dispersion composition of the present invention, the pigment content is appropriately selected, but is preferably 3 to 30% by weight, more preferably 4 to 20% by weight.
Further, in the pigment dispersion composition of the present invention, the content of the pigment dispersant is appropriately selected, but is preferably 3 to 30% by weight, and more preferably 4 to 20% by weight.

  And among the pigment dispersion composition of the present invention, as the pigment, a pigment dispersion composition using carbon black or carbon black surface-modified with the acidic functional group or a neutralized base of the acidic functional group, It is preferably used as a carbon black dispersion composition for preparing a photoresist composition for producing a black matrix.

  The photoresist composition of the present invention is a photoresist composition containing the pigment dispersant of the present invention, a pigment, an organic solvent, an active energy ray-curable compound, and a photopolymerization initiator.

  Examples of the pigment and the organic solvent according to the photoresist composition of the present invention include the same pigments and organic solvents as the pigment dispersion composition of the present invention.

  The active energy ray-curable compound according to the photoresist composition of the present invention is a resin, monomer, or oligomer that is cured by irradiation with infrared rays, ultraviolet rays, electron beams, X-rays, and the like, and is not particularly limited. Usually, the active energy ray curable resin of a photoresist composition, the compound used as a monomer or an oligomer are mentioned. Examples of the active energy ray-curable compound include a resin, monomer or oligomer having a (meth) acryloyl group, or a resin, monomer or oligomer having a vinyl group. Specifically, examples of the active energy ray-curable compound (I) include (meth) acrylate oligomers such as urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, These may be used in combination of two or more.

  Examples of the active energy ray-curable compound include monofunctional (meth) acrylates such as methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl and benzyl. (Meth) acrylates having substituents such as methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl N-vinyl pyrrolidone; N-vinyl caprolactam; N-methyl morpholine, etc. may be mentioned, and these may be used in combination of two or more.

  Examples of the active energy ray-curable compound include polyfunctional (meth) acrylates such as 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. -Pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tri Di (meth) acrylate such as propylene glycol and polypropylene glycol, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 mol or more of ethylene oxide or propylene oxide in 1 mol of neopentyl glycol Di (meth) acrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, 3 mol or more of ethylene per 1 mol of trimethylolpropane Diol or tri (meth) acrylate of triol obtained by adding oxide or propylene oxide, di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylolpropane Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, poly (meth) acrylate of dipentaerythritol, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified Kirurin acid (meth) acrylate and the like, which may be two or more in combination.

  Examples of the active energy ray-curable compound include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers as (meth) acrylate oligomers. These may be used alone or in combination of two or more.

  The photopolymerization initiator according to the photoresist composition of the present invention is not particularly limited as long as it is usually a photopolymerization initiator used in a photoresist composition. Examples of the photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl. Ethoxyphosphine oxide, 6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methyl) -Benzyl) -1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxy Id, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are preferably used, and as other molecular cleavage type, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl Ether, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and 2-methyl-1 -(4-Methylthiophenyl) -2-morpholinopropan-1-one or the like may be used in combination, and benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl which are hydrogen abstraction type photopolymerization initiators -4'-methyl-diphenyl sulfide etc. Good.

  In addition, amines may be added to the photopolymerization initiator as a sensitizer or for the purpose of improving surface curability. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis (diethylamino) ) Amines that do not cause an addition reaction with the alkali-soluble resin and the active energy ray-curable compound, such as benzophenone, may be used in combination. Of course, it is preferable that the photopolymerization initiator and the sensitizer are excellent in solubility in the active energy ray-curable compound and do not inhibit the transmittance of the active energy ray.

  Moreover, the photoresist composition of this invention can contain alkali-soluble resin further as needed. The alkali-soluble resin is a resin that dissolves in an alkali developer during alkali development, and is not particularly limited as long as it is usually used as an alkali-soluble resin of a photoresist composition. Examples of the alkali-soluble resin include an alkali-soluble epoxy obtained by reacting an acid anhydride with an acrylate having an epoxy resin skeleton disclosed in Japanese Patent Publication No. 56-40329 and having an acidic functional group introduced in the molecule. Examples thereof include acrylate having a resin skeleton.

  The content of the pigment in the photoresist composition of the present invention is preferably 1.5 to 15% by weight, particularly preferably 3 to 10% by weight. Further, the content of the pigment dispersant of the present invention is preferably 20 to 200 parts by weight, particularly preferably 30 to 150 parts by weight, based on 100 parts by weight of the pigment, and the active energy ray-curable compound. Is preferably 10 to 50 parts by weight with respect to 100 parts by weight of the pigment, and the content of the photopolymerization initiator is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the pigment. Particularly preferred is 3 to 12 parts by weight.

  In addition, the photoresist composition of the present invention further has heat resistance such as acrylic resin, methacrylic resin, phenol resin, melamine resin, xylene resin, diallyl phthalate resin, cryptal resin, epoxy resin, alkylbenzene resin, polyester resin, polyvinyl alcohol resin, etc. Resin excellent in property or fluidity can be contained.

  The photoresist composition of the present invention can contain a dispersion stability aid, an inhibitor, a coating film smoothing aid, and other additives as necessary.

  The photoresist composition of the present invention is preferably produced using the pigment dispersion composition of the present invention. For example, in the photoresist composition of the present invention, the pigment dispersion composition of the present invention, the active energy ray-curable compound and the photopolymerization initiator are added to the organic solvent, and if necessary, the alkali-soluble resin, It is manufactured by adding and mixing a dispersion stability aid, an inhibitor, a coating film smoothing aid, and other additives.

  The photoresist composition of the present invention is used as a photoresist composition for forming a cured coating film by photolithography. In particular, the photoresist composition of the present invention is suitably used as a photoresist composition for forming a black matrix for a color filter of a color liquid crystal display.

  Examples of a method for forming a black matrix using the photoresist composition of the present invention include, for example, a method of forming a black matrix by photolithography after applying the photoresist composition of the present invention to a substrate, and a photo of the present invention. The resist composition is applied to the substrate by printing, spin coating, etc., dried, then mask adhesion, exposure, and then alkali development to form a black matrix by a lithography method that forms an arbitrary image on the substrate. The method of doing is mentioned.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention. In addition, the part in an Example and a comparative example and the numerical value in a table | surface represent a weight part.

<Preparation of carbon black-1 surface-modified with acidic functional groups>
STSA specific surface area ^35m 2 / g, carbon black 100g of DBP absorption 115cm ³ / 100g, was added to the peroxodisulfuric acid aqueous solution of sodium 3000ml of concentration 0.1 N, 0.12 s ^-1, in the conditions of reaction temperature 60 ° C. The mixture was stirred for 10 hours and liquid phase oxidized. After the oxidation treatment, the carbon black dispersion was purified and removed by ultrafiltration membrane (AHP-1010 manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 50000), filtered, dried, and surfaced with acidic functional groups. Modified carbon black-1 (TK-1) was obtained. The amount of carboxyl groups of the TK-1 was 124 μmol / g.

<Preparation of surface-modified carbon black-2 with acidic functional group>
STSA specific surface area ^35m 2 / g, in place of the carbon black 100g of DBP absorption 115cm ³ / 100g, except that the STSA specific surface area ^42m 2 / g, DBP absorption 135 cm ³ / 100g carbon black 100g of acidic functional groups The carbon black-2 (TK-2) surface-modified with an acidic functional group was obtained in the same manner as in the preparation of carbon black-1 having introduced thereinto. The amount of carboxyl groups of the TK-2 was 283 μmol / g.

The carboxyl group amount was measured by the following method.
2 g of carbon black was put into 50 ml of 0.976 N sodium hydrogen carbonate aqueous solution, shaken for about 6 hours, carbon black was filtered and separated, and the filtrate was neutralized and titrated with 0.05 mol / L sodium hydroxide. The amount of carboxyl groups formed on the carbon black surface was measured.

Example 1
<Synthesis of polyurethane dispersant>
11.2 parts of N-diethanolamine, 250 parts of propylene glycol monomethyl ether acetate, and 8.2 parts of Karenz MOI are added to a flask equipped with stirring, dry nitrogen, a blowing tube, and a cooling tube at 25 ° C. while stirring. The mixture was heated up to 40 ° C. and stirred for 2 hours. Next, 48.6 parts of light acrylate 130A (methoxypolyoxyethylene ether acrylate: manufactured by Kyoeisha Chemical Co., Ltd., bromine number 34.9Br / 100 g) was added, and the temperature was raised to 80 ° C. and reacted for 4 hours. Subsequently, it is cooled to 60 ° C., castor oil diol HS-2G-150R (manufactured by Toyokuni Oil) 54.2 parts, Kuraray polyester diol P-2050 (number average molecular weight 2066, Kuraray Co., Ltd.) 183 parts, Pine Crystal D-6011 (Arakawa Chemical Co., Ltd.) 25 parts, dimethylol butanoic acid 21 parts, 1,6-hexamethylene diisocyanate 45 parts, isophorone diisocyanate 69 parts, and propylene glycol monomethyl ether acetate 83 parts were added and reacted at 60 ° C. for 5 hours. Next, 22 parts of light acrylate G-201P (manufactured by Kyoeisha Chemical Co., Ltd.) having a hydroxyl group and a (meth) acryloyl group in the molecule, 7.9 parts of N-dimethylaminoethanol, 0.1 part of dibutyltin laurate, 0.3 part of methoquinone Then, 167 parts of propylene glycol monomethyl ether acetate was added and reacted at 70 ° C. for 5 hours to obtain a polyurethane dispersant ASP-1. The ASP-1 had a (meth) acryloyl group concentration of 0.47 meq / g, an acid value of 16 KOH mg / g, and an amine value of 9.9 mg / g.
At this time, among the compounds having all hydroxyl groups used in the reaction, the polyol having (A1) as the side chain and the polyol having (A2) as the side chain are 51 mol% in total, and the polyol having (B) as the side chain is 14 0.5 mol%, the polyol having (C) as a side chain was 11 mol%, and the polyol having (B) as a main chain was 23.5 mol%. The polyol having the molecular chain Z as the main chain refers to a polyol that, when polymerized, the molecular chain Z becomes the main chain of the polyurethane resin.

(Example 2)
<Synthesis of polyurethane dispersant>
19.6 parts of N-diethanolamine, 250 parts of propylene glycol monomethyl ether acetate and 7.6 parts of Karenz MOI were added at 25 ° C. with stirring to a flask equipped with stirring, dry nitrogen, a blowing tube, and a cooling tube, The mixture was heated up to 40 ° C. and stirred for 2 hours. Next, 45 parts of light acrylate 130A (methoxypolyoxyethylene ether acrylate: manufactured by Kyoeisha Chemical Co., Ltd., bromine number 34.9Br / 100 g), 17.7 parts of light acrylate NP-4EA (nonylphenyl polyoxyethylene ether acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) The mixture was heated to 80 ° C. and reacted for 4 hours. Subsequently, it is cooled to 60 ° C., 60 parts of castor oil diol HS-2G-150R (manufactured by Toyokuni Seiyaku), 163 parts of Kuraray polyester diol P-2050 (number average molecular weight 2066, manufactured by Kuraray Co., Ltd.), 29.1 dimethylolbutanoic acid Part, 49.5 parts of 1,6-hexamethylene diisocyanate, 76.4 parts of isophorone diisocyanate and 83 parts of propylene glycol monomethyl ether acetate were added and reacted at 60 ° C. for 5 hours. Next, 23.4 parts of light acrylate G-201P (manufactured by Kyoeisha Chemical Co., Ltd.) having a hydroxyl group and a (meth) acryloyl group in the molecule, 9.1 parts of N-dimethylaminoethanol, 0.1 part of dibutyltin laurate, 0.1 part of methoquinone. 3 parts and 167 parts of propylene glycol monomethyl ether acetate were added and reacted at 70 ° C. for 5 hours to obtain a polyurethane dispersant ASP-2. The ASP-2 had a (meth) acryloyl group concentration of 0.49 meq / g, an acid value of 22 KOH mg / g, and an amine value of 11.5 mg / g.
At this time, among all the polyols used in the reaction, the polyol having (A1) as the side chain and the polyol having (A2) as the side chain are 54.1 mol% in total, and the polyol having (B) as the side chain is 22 mol%. The polyol having (C) as a side chain was 9 mol%, and the polyol having (B) as a main chain was 14.5 mol%.

Polymer Dispersant of Comparative Example BYK-9076 (hereinafter also referred to as Dispersant B): Byk Chemie, amine value 44 KOH mg / g, acid value 38 KOH mg / g
Solsperse 44000 (hereinafter also referred to as Dispersant S): manufactured by Lubrizol, acid value 12 KOH mg / g, nonvolatile content 50%

(Examples 3-6, Comparative Examples 1-4)
<Preparation of carbon black dispersion composition>
Carbon black in an amount shown in Table 1 and Table 2, a dispersant, and propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent are placed in a glass bottle together with 1 mmφ zirconia beads, dispersed in a paint shaker for 2 hours, and pigment dispersed. Compositions were obtained (Tables 1 and 2).

(Examples 7 to 10, Comparative Examples 5 to 8)
<Preparation of Epoxy Resin Skeleton Acrylate Having Carboxyl Group Obtained by Reacting Acid Anhydride with Epoxy Resin Skeleton Acrylate described in Japanese Patent Publication No. 56-40329>
Charge 776 parts of lipoxy SP-1509 (made by Showa Polymer), 0.4 part of methoquinone, 219 parts of hexahydrophthalic anhydride, and 2 parts of triphenylphosphine into a flask equipped with a stirrer, an air blowing tube and a reflux condenser, and take 1 hour. The temperature was raised to 90 ° C., and then the temperature was raised to 110 ° C. over 3 hours to carry out the reaction to obtain an epoxy resin acrylate acrylate having a carboxyl group. The acid value of the acrylate of the epoxy resin skeleton having a carboxyl group was 105 KOHmg / g.
Next, in the flask containing the reaction solution, the temperature of the reaction solution is 70 ° C. or less. Further, 100 parts of neopentyl glycol diacrylate, 250 parts of trimethylolpropane triacrylate, 50 parts of dipentaerythritol tetraacrylate, propylene glycol monomethyl ether 2600 parts of acetate and 80 parts of a photopolymerization initiator Icargacure (R) 907 (manufactured by Ciba Specialty Chemicals) were added in order, and the mixture was stirred until the photopolymerization initiator was completely dissolved to obtain a diluted resin solution F.

<Manufacture of photoresist composition>
As shown in Tables 3 and 4, 40 parts of the pigment dispersion compositions CBB-1 to CBB-8, 40 parts of the diluted resin liquid F, and 20 parts of propylene glycol monomethyl ether acetate are stirred and mixed to form a photoresist. A composition was obtained.

<Viscosity of photoresist composition>
The viscosity at a temperature of 298K was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-20L). When the viscosity was 20 to 50 mPas, it was “◯”, and when it exceeded 50 Pas, it was “x”. The results are shown in Table 5.

<Particle size of carbon black in the photoresist composition>
The measurement was performed using a heterodyne laser Doppler type particle size distribution analyzer (manufactured by Microtrack, UPA model 9349). The measurement was determined from the particle size distribution curve of the carbon black particle aggregate in the photoresist composition with the 50% cumulative frequency value as the average particle size and the 99% cumulative frequency value as the maximum particle size. In the measurement, propylene glycol monomethyl ether acetate was used as a solvent for adjusting the viscosity. The results are shown in Table 5.

<Formation of black matrix>
The photoresist composition produced as described above was applied on a borosilicate glass substrate having a thickness of 0.6 mm at a rotational speed of 0.06 s ⁻¹ using a spin coater, and then applied on a hot plate having a temperature of 393 K. For 120 seconds. Next, ultraviolet rays were irradiated under the condition of 200100 mJ / cm ² by an exposure apparatus (manufactured by USHIO INC.) Through a mask having a line width of 20 μm (the width of the portion to become a black matrix was 20 μm). Thereafter, the film was immersed in a developer FHD-5 manufactured by Fuji Film Olin Co., Ltd., washed with a shower at a flow rate of 8.33 cm ³ / s and a discharge pressure of 0.098 MPa, and developed to remove the black resin layer in the non-exposed area. Finally, it was heated on a hot plate with a surface temperature of 523 K for 1 hour to form a black matrix. The results are shown in Table 5.

<Evaluation of black matrix>
-Dirt on unexposed area Dirt after unexposed area development was observed with an optical microscope. “O” when no dirt is seen, “△” when slight dirt is seen at the interface between the exposed area and the unexposed area, and “X” when dirt is seen in the unexposed area. " The results are shown in Table 5.

・ Exposed area curability MEK rubbing test: A cotton swab dipped in a methyl ethyl ketone (MEK) placed on an electronic balance with a UV cured coating, and pressed at a load of 100 g at a speed of 1 reciprocation per second, 20 to 20 Rub the same part at a distance of 30 mm for 5 reciprocations, and observe peeling of the coating film.
MEK rubbing was performed 5 times. When the cured coating film was not removed at all, “◯” was given. When the surface was removed, “△” was given, and when the ground was reached, “x” was given. The results are shown in Table 5.

-Blackness Measure the transmission optical density (OD value) using a Macbeth densitometer (manufactured by Colmogen, RD-927) to determine the optical density per 1 μm of film thickness. And less than 3.5 was defined as “x”. The results are shown in Table 5.

  As shown in Table 5, since the viscosity is lower than that of the comparative example, it can be seen that the example is superior in dispersibility than the comparative example. In other words, the pigment dispersants of the examples have superior dispersibility than the dispersants of the comparative examples developed as carbon black dispersants. In addition, it can be seen that the examples have excellent dispersibility because the average particle diameter and the maximum particle diameter are the same as or lower than those of the comparative examples. Moreover, since an Example has high blackness, it turns out that it is excellent in a dispersibility from a comparative example. The examples were found to be superior in alkali solubility by combining the pigment dispersant of the present invention with carbon black having an acidic functional group, and better in developability than the comparative examples. Moreover, the sclerosis | hardenability of the exposure part compared by the MEK rubbing test has shown the tolerance of the coating film which melt | dissolves or swells with methyl ethyl ketone, and an Example is a dispersing agent which does not have an active energy ray-curable unsaturated group. It was found that the curability was excellent as compared with the comparative example.

Claims (10)

(A1) one or two of acidic functional groups and neutralized bases of acidic functional groups;
(A2) one or more of a basic functional group, a neutralized base of a basic functional group, and a nonionic polar molecular chain; and
(B) a low polarity molecular chain;
(C) an active energy ray-curable unsaturated group;
A pigment dispersant comprising a polyurethane resin containing   All or part of (A1), (A2), (B), and (C) is a side chain of the polyurethane resin or is bonded to a side chain. The pigment dispersant according to claim 1.   The pigment dispersant according to claim 1 or 2, wherein (A1) is a carboxyl group.   The pigment dispersant according to any one of claims 1 to 3, wherein (A2) is a polyoxyethylene ether molecular chain having three or more oxyethylene ether repeating units. The polyurethane resin is obtained by reacting an isocyanate compound with a compound having a hydroxyl group or an active hydrogen atom,
At least a part of the compound having a hydroxyl group or an active hydrogen atom is represented by the following general formula (I):

(In the general formula (I), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or an active hydrogen atom, and R ¹ and R 2 ^At least one of ² is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, a is an integer of 1 to 6, b is an integer of 1 to 3, Is an integer of 1 to 4, R ¹ and R ² may be the same or different, and R ³ is represented by the following general formula (II):

(In general formula (II), d is an integer of 1 to 4, and e is an integer of 5 to 30.)
Or a group containing a nonionic polar molecular chain represented by the following general formula (III):

(In general formula (III), f is an integer of 1 to 4, g is an integer of 5 to 30, and {h / (h + g)} <0.25.)
It is group containing the nonionic polar molecular chain represented by these. )
And a compound having a hydroxyl group or an active hydrogen atom represented by the following general formula (IV):

(In the general formula (IV), ^{R 4} and ^{R _5,} -C _p H _{2p -OH,} a _{-C q H 2q -COO-C r} H 2r -OH or an active hydrogen atom, and, ^{R 4} and R at least one of the ^five _is -C _p H 2p -OH or _{-C q H 2q -COO-C r} H 2r -OH, p is an integer from 1 to 6, q is an integer of 1 to 3, r Is an integer of 1 to 4, R ⁴ and R ⁵ may be the same or different, and R ⁶ is represented by the following general formula (V):

(In general formula (V), i is an integer of 4 to 30, and j is an integer of 0 to 6.)
Or a group containing a low polar molecular chain represented by the following general formula (VI):

(In general formula (VI), s is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VII):

(In general formula (VII), t is an integer of 5 to 30.)
Or a group containing a low polar molecular chain represented by the following general formula (VIII):

(In general formula (VIII), u is an integer of 5 to 30.)
Or a group containing a low-polar molecular chain represented by
A low polar group comprising a polyester having two or more molecular units having 4 or more carbon atoms as repeating units,
A low-polar group containing a polyether having two or more molecular units having 4 or more carbon atoms as repeating units,
It is a low polar group containing a polycarbonate having two or more molecular units having 4 or more carbon atoms as repeating units, or a low polar group containing a polycaprolactone having two or more molecular units having 4 or more carbon atoms as repeating units. )
The pigment dispersant according to any one of claims 1 to 4, which is a compound having a hydroxyl group or an active hydrogen atom represented by formula (1). It is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or an active hydrogen atom,
It has (A1), (A2), (B) or (C) as a side chain with respect to the total number of moles of the compound having a bifunctional hydroxyl group or active hydrogen atom in the compound having the hydroxyl group or active hydrogen atom. The pigment dispersant according to any one of claims 1 to 5, wherein the mole% of the total number of moles of the compound having a bifunctional hydroxyl group or active hydrogen atom is 10 to 100 mole%.   A pigment dispersion composition comprising the pigment dispersant according to claim 1, a pigment, and an organic solvent.   The pigment dispersion composition according to claim 7, wherein the pigment is carbon black having an acidic functional group or a neutralized base of an acidic functional group.   It contains the pigment dispersant according to any one of claims 1 to 6, a pigment, an organic solvent, a compound having an active energy ray-curable unsaturated group, and a photopolymerization initiator. A photoresist composition.   The photoresist composition according to claim 9, wherein the pigment is carbon black having an acidic functional group or a neutralized base of an acidic functional group.