JP5488859B2 - Pigment-dispersed photosensitive resin composition - Google Patents

Description

  The present invention relates to a pigment-dispersed photosensitive resin composition that is suitably used for image formation by a photolithography method, and particularly suitable for forming a black matrix in a color filter for a liquid crystal display device.

  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 necessary.

  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 pigment-dispersed photosensitive resin composition made of carbon black, a pigment dispersant, an acrylic monomer, an acrylic oligomer, a resin, a photopolymerization initiator, and the like. That is, by exposing the pigment-dispersed photosensitive resin 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.

  Examples of the pigment-dispersed photosensitive resin composition using carbon black as a black pigment include, for example, JP-A 2000-227654 (Patent Document 1), (A) a colorant containing a black pigment, (B) an alkali-soluble resin, (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 resists 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.

  In order to solve the above problem, Japanese Patent Application Laid-Open No. 2007-254694 (Patent Document 3) contains an average of 2 to 10 isocyanate groups in one molecule, and the number per isocyanate group. The isocyanate group in the polyfunctional polyisocyanate compound (a) having an average molecular weight of 100 to 1000 is reacted with the hydroxyl group in the acrylic polymer (b) having a hydroxyl group at the terminal and further having an ethylenically unsaturated group. A photosensitive resin dispersant and a photosensitive pigment dispersion composition containing the dispersant are disclosed. However, in Patent Document 3, since the dispersant itself is three-dimensionally cross-linked, it tends to be agglomerated and it is extremely difficult to maintain the form as the dispersant.

JP 2000-227654 A (Claims) JP 2004-198717 A (Claims) JP 2007-254694 A (Claims)

  Accordingly, an object of the present invention is to provide a pigment-dispersed photosensitive resin composition having a high dispersibility of the pigment and a high developability with an alkali developer, and a high chemical resistance of the cured coating film. It is in.

  As a result of intensive studies to solve the problems in the conventional technology, the present inventors have (1) (A1) one or two of acidic functional groups and neutralized bases of acidic functional groups, (A2) one or more of basic functional groups, neutralized bases of basic functional groups and nonionic polar molecular chains, (B) low polar molecular chains, and (C) active energy ray curability The pigment dispersant, which is a polyurethane resin having an unsaturated group, can impart high dispersibility of acidic carbon black having acidic functional groups and excellent chemical resistance of a cured film to the pigment-dispersed photosensitive resin composition. (2) Further, all or a part of (A1), (A2), (B) and (C) constitutes a side chain of the polyurethane resin or is present in the side chain. Due to the bonding, the polyurethane resin molecules approach the comb teeth. A highly polar group or molecular chain has an affinity for the solvent, and a low polarity molecular chain has an affinity for the pigment particles, so that the dispersibility of the pigment is improved. (3) Furthermore, the synthesis of the polyurethane resin In the polyurethane resin obtained using the (A2) and a polyol compound having an amino group as a raw material and the (B) and a polyol compound having an amino group, the amino group has an ionic affinity with an acidic functional group on the pigment surface. As a result, the present inventors have found that the dispersibility of the pigment is improved and completed the present invention.

That is, the present invention (1) includes pigment (I), pigment dispersant (II), organic solvent (III), alkali-soluble resin (IV), active energy ray-curable compound (V), light A polymerization initiator (VI),
The pigment (I) is an acidic carbon black having an acidic functional group,
The pigment dispersant (II) comprises (A1) one or two of an acidic functional group and an acidic functional group neutralized base; and (A2) a basic functional group, a basic functional group neutralized base, and and one or more of the nonionic polar molecular chain, (B) and the low polar molecules chains, polyurethane resins der having a (C) the active energy ray-curable unsaturated groups,
It is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or active hydrogen,
A part of the compound having the hydroxyl group or active hydrogen is represented by the following general formula (1):

(In General Formula (1), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or a hydrogen atom, and R ¹ and R ² At least one of them is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, where a is 2 to 6, b is 2 to 3, and c is 2 to 4. R ¹ and R ² may be the same or different, and R ³ is represented by the following general formula (2):

(In general formula (2), d is 1-4 and e is 5-30.)
Nonionic polar molecular chain represented by the following general formula (3):

(In general formula (3), f is 1-4, g is 5-30, and {h / (h + g)} <0.2.)
Nonionic polar molecular chain represented by the following general formula (4):

(In general formula (4), i is 5 to 30, and j is 0 to 6.)
Is a nonionic polar molecular chain represented by )
And a compound having a hydroxyl group or active hydrogen represented by the following general formula (5):

(In General Formula (5), R ⁴ and R ⁵ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or a hydrogen atom, and R ⁴ and R ⁵ At least one of them is —C _p H _2p —OH or —C _q H _2q —COO—C _r H _2r —OH, p is 2 to 6, q is 2 to 3, and r is 2 to 4. R ⁴ and R ⁵ may be the same or different, and R ⁶ is represented by the following general formula (6):

(In general formula (6), s is 5-30.)
A low polarity molecular chain represented by the following general formula (7):

(In general formula (7), t is 5-30.)
A low polarity molecular chain represented by the following general formula (8):

(In general formula (8), u is 5-30.)
A low-polar molecular chain represented by:
Polyester, polyether, polycarbonate or polycaprolactone low polarity molecular chain having two or more molecular units having 4 or more carbon atoms as repeating units
It is. )
The present invention provides a pigment-dispersed photosensitive resin composition characterized by being a compound having a hydroxyl group or active hydrogen represented by the formula:

  According to the present invention, it is possible to provide a pigment-dispersed photosensitive resin composition having high dispersibility of pigments and high developability with an alkali developer, and high chemical resistance of a cured coating film. .

The pigment-dispersed photosensitive resin composition of the present invention comprises a pigment (I), a pigment dispersant (II), an organic solvent (III), an alkali-soluble resin (IV), and an active energy ray-curable compound (V). And a photopolymerization initiator (VI),
The pigment (I) is an acidic carbon black having an acidic functional group,
The pigment dispersant (II) comprises (A1) one or two of an acidic functional group and an acidic functional group neutralized base; and (A2) a basic functional group, a basic functional group neutralized base, and A polyurethane resin having one or more of nonionic polar molecular chains, (B) a low polar molecular chain, and (C) an active energy ray-curable unsaturated group.
It is a pigment-dispersed photosensitive resin composition.

  The pigment (I) according to the pigment-dispersed photosensitive resin composition of the present invention is an acidic carbon black having an acidic functional group. The acidic carbon black having an acidic functional group is a carbon black whose surface is modified with an acidic functional group or a neutralized base of the acidic functional group. In other words, the acidic carbon black having an acidic functional group is one having the acidic functional group on the surface or a part of the acidic functional group neutralized with a basic compound.

  The acidic functional group bonded to the acidic carbon black having the acidic functional group or the neutralized base of the acidic functional group is an acidic functional group or acidic functional group according to the pigment dispersant (II) of the present invention described later. Same as Japanese base. Among these, as the acidic functional group relating to the acidic carbon black having the acidic functional group, a combination of a carboxyl group and a hydroxyl group is preferable.

  In the acidic carbon black having an acidic functional group, as the carbon black that is a pigment before the functional group is introduced, channel black, roller black, carbon black produced by a contact method called disk black, gas furnace black, Examples thereof include carbon black produced by a furnace method called oil furnace black, thermal black, carbon black produced by a thermal method called acetylene black, etc. Of these, furnace black having excellent productivity is preferable.

In order to obtain a carbon black having an acidic functional group introduced therein by introducing an acidic functional group into the carbon black before introducing the functional group, the carbon black before introducing the functional group is brought into contact with free oxygen at a high temperature. Oxidizing with ozone, oxidizing with ozone, NO ₂ , treating with bromine and water under normal pressure or under pressure, oxidizing with oxidizing solution such as nitric acid or sulfuric acid, Moreover, the method of introduce | transducing a carboxyl group or a hydroxyl group to carbon black before this functional group introduction | transduction is mentioned by oxidation methods, such as combining these and oxidizing with hydrogen peroxide. 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.

  And, since the acidic carbon black having an acidic functional group has an acidic functional group on the surface, as a pigment of a pigment-dispersed photosensitive resin composition for forming a black matrix, the light-shielding property and the alkali developability are excellent. ,preferable.

The average primary particle diameter of the acidic carbon black having acidic functional groups 50nm or less, STSA specific surface area of ^{30 m} 2 / g or more, DBP oil absorption of 80 cm ^3/100 g or less, and an acid value of 1.0~20KOHmg / g It is preferable that The average primary particle diameter of the acidic carbon black having an acidic functional group is particularly preferably 20 to 50 nm, the STSA specific surface area is particularly preferably 30 to 130 m ² / g, and the DBP oil absorption is 40 to 80 cm ^3. / 100 g is particularly preferable, and the acid value is particularly preferably 3.0 to 10 KOH mg / g.
If the average primary particle size of the acidic carbon black having acidic functional groups exceeds 50 nm, the average particle size of the carbon black when dispersed in the solvent increases, and the blackness and light shielding power of the black matrix decrease. easy. Further, when the STSA specific surface area of the acidic carbon black having an acidic functional group is less than 30 m ² / g, the average particle size of the carbon black when dispersed in a solvent is increased, and the blackness and lightness of the black matrix are increased. Shielding power tends to be low. DBP oil absorption of the acidic carbon black having acid functional groups is more than 80 cm ^3/100 g, when mixed with the resin, the viscosity is increased, easily smoothness of the light-shielding layer is impaired. If the acidic carbon black having an acidic functional group has an acid value of less than 1.0 KOHmg / g, it tends to agglomerate. On the other hand, if it exceeds 20 KOHmg / g, the compatibility with the polyurethane resin tends to be low and the viscosity increases. It becomes easy to do.
The STSA specific surface area is an external specific surface area measured using nitrogen gas, and ASTM D6556 “Standard Test Methods for Carbon Black-External Surface Area” using an automatic specific surface area measurement device (Gemini 2375, manufactured by Shimadzu Corporation). It is a value measured according to the method described in “by Multipoint Nitrogen Adsorption”. As another specific surface area, there is a total specific surface area to be measured up to the pores of the carbon black. However, in the present invention, the total specific surface area to be measured up to the pores not much related to the penetration of the solvent into the carbon black is not appropriate. Not shown by external specific surface area.
Moreover, the primary average particle diameter was calculated | required by the arithmetic average by an electron microscope based on ASTMD3849.

The pigment dispersant (II) according to the pigment-dispersed photosensitive resin composition 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;
A polyurethane resin having

  That is, the pigment dispersant (II) is a pigment dispersant having (A1), (A2), (B), and (C) as essential components in one molecule.

  Since the pigment dispersant (II) has an active energy ray-curable unsaturated group in the molecule, the curability of the exposed portion can be increased, and the development contrast is improved. A cured film having high chemical resistance can be obtained.

  The pigment dispersant (II) is 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. (A1), (A2), (B), and (C) are included.

  The pigment dispersant (II) has, 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 (II) is not particularly limited, and carboxyl group (—COOH), hydroxyl group (—OH), sulfonic acid group (—SO ₃ H), phosphoric acid Examples include ester groups (including phosphoric acid monoesters, phosphoric acid diesters, and phosphoric acid triester groups). 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 (II) is not particularly limited, and the acidic functional group according to (A1) of the pigment dispersant of the present invention is, for example, water. It is a group neutralized with a basic compound such as sodium oxide 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.

  The pigment dispersant (II) is, as (A2), any one of the basic functional group, the neutralized base of the basic functional group, the nonionic polar molecular chain, or two of these Have the above.

  The basic functional group according to (A2) of the pigment dispersant (II) is not particularly limited, and is a base such as an aliphatic amine group, an alicyclic amine group, a heteroalicyclic amine group, or an aromatic amine group. Nitrogen-containing functional groups and the like. 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 (II) is not particularly limited, and the basic functional group according to (A2) of the pigment dispersant of the present invention is, for example, , A group neutralized by an acidic compound such as hydrochloric acid or sulfuric acid. The neutralized base of the basic functional group may be one kind or a combination of two or more kinds.

  The nonionic polar molecular chain according to (A2) of the pigment dispersant (II) is, for example, a nonion such as a polyoxyalkylene ether molecular chain or a polyoxypropylene ether molecular chain, or a molecular chain of a copolymer thereof. System polar molecular chains. The nonionic polar molecular chain may be one kind or a combination of two or more kinds. And, the nonionic polar molecular chain is a polyoxyethylene ether molecular chain having 4 or more oxyethylene ether repeating units, and constitutes the main chain of the pigment dispersant, or the main chain of the pigment dispersant or the terminal thereof. A side chain to be bonded is preferred.

  Further, the nonionic polar molecular chain has the following general formula (2):

(In general formula (2), d is 1-4 and e is 5-30.)
Nonionic polar molecular chain represented by the following general formula (3):

(In general formula (3), f is 1-4, g is 5-30, and {h / (h + g)} <0.2.)
Nonionic polar molecular chain represented by the following general formula (4):

(In general formula (4), i is 5 to 30, and j is 0 to 6.)
The nonionic polar molecular chain represented by is preferable in that the dispersibility of the pigment becomes high.

  In the pigment dispersant (II), the acidic functional group of (A1) and the neutralized base of the acidic functional group, and the basic functional group of (A2) and the neutralized base of the basic functional group are pigments. It may be bonded to the main chain of the dispersant, or may be bonded to the side chain of the pigment dispersant. In the pigment dispersant (II), the nonionic polar molecular chain may be bonded to the main chain of the pigment dispersant or the terminal thereof, or may be bonded to the side chain of the pigment dispersant. Alternatively, it may constitute the main chain of the pigment dispersant.

  The pigment dispersant (II) has the 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. It is a molecular chain having a repeating unit, or a molecular chain composed of a rosin skeleton or a hydrogenated rosin skeleton, 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 as a repeating unit the molecular unit having 4 or more carbon atoms according to the low polarity molecular chain (B) may have any of linear, branched or cyclic molecular units.

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

The low polar molecular chain (B) has the following general formula (6):

(In general formula (6), s is 5-30.)
A low polarity molecular chain represented by the following general formula (7):

(In general formula (7), t is 5-30.)
A low polarity molecular chain represented by the following general formula (8):

(In general formula (8), u is 5-30.)
A low polar molecular chain represented by the formula: a low polar molecular chain comprising a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units, and a polyether having 2 or more molecular units having 4 or more carbon atoms as repeating units Low polarity molecular chain, low polarity molecular chain consisting of polycarbonate having 2 or more molecular units having 4 or more carbon atoms as repeating units, or low polarity consisting of 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.

  In the pigment dispersant (II), the low polarity molecular chain (B) may be bonded to the main chain of the pigment dispersant or the terminal thereof, or may be bonded to the side chain of the pigment dispersant. Alternatively, it may constitute the main chain of the pigment dispersant.

  The pigment dispersant (II) has the active energy ray-curable unsaturated group (C). The active energy ray-curable unsaturated group according to (C) of the pigment dispersant (II) is an unsaturated group having the active energy ray-curable property such as a vinyl group, an acryloyl group, or a methacryloyl group.

  In the pigment dispersant (II), the active energy ray-curable unsaturated group may be bonded to the main chain of the pigment dispersant or the terminal thereof, or may be bonded to the side chain of the pigment dispersant. Alternatively, it may constitute the main chain of the pigment dispersant.

  In the pigment dispersant (II), all or part of the (A1), the (A2), the (B), and the (C) constitutes a side chain of the polyurethane resin or the side. The molecules of the polyurethane resin approach the comb tooth shape, and the polar group or molecular chain has affinity for the solvent, and the low polarity molecular chain has affinity for the pigment particles. Since it has, it is preferable at the point which the dispersibility of a pigment improves.

  In the pigment dispersant (II), all or part of the (C) is an acryloyl group or a methacryloyl group, and the concentration of the acryloyl group or the methacryloyl group is 0.2 to 3 mol / kg. It is particularly preferably 0.3 to 2.5 mol / kg.

The pigment dispersant (II) is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or active hydrogen,
A part of the compound having the hydroxyl group or active hydrogen is represented by the following general formula (1):

And a compound having a hydroxyl group or active hydrogen represented by the following general formula (5):

And a pigment dispersant (hereinafter, also referred to as pigment dispersant (II-1)) which is a compound having a hydroxyl group or active hydrogen represented by the formula (1). In addition, having this active hydrogen means having a group which reacts with an isocyanate compound other than a hydroxyl group, for example, an amino group.

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

  The isocyanate compound according to the pigment dispersant (II-1) may be a bifunctional isocyanate compound, or a bifunctional isocyanate compound and a trifunctional or higher functional isocyanate compound or a monofunctional isocyanate. A combination with a compound may also be used.

  The compound having a hydroxyl group or active hydrogen related to the pigment dispersant (II-1) may be a compound (polyfunctional compound) having all two or more hydroxyl groups or active hydrogens that react with the isocyanate compound. Alternatively, a combination of a compound having two or more hydroxyl groups or active hydrogen that reacts with the isocyanate compound and a compound having one hydroxyl group or active hydrogen that reacts with the isocyanate compound (monofunctional compound) may be used. 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 that reacts with the isocyanate compound as the compound having the hydroxyl group or active hydrogen, the isocyanate A compound having one hydroxyl group or active hydrogen that reacts with the compound serves as an end of the main chain of the polyurethane resin. A compound having two or more hydroxyl groups or active hydrogens that react with the isocyanate compound is also called a polyol.

In the general formula (1), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or a hydrogen atom, and R ¹ and R ² At least one of them 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 2 to 6, b is 2 to 3, c is 2 to 4, and R ¹ and R ² may be the same or different.

In the general formula (1), R ³ represents the following general formula (2):

(In general formula (2), d is 1-4 and e is 5-30.)
Nonionic polar molecular chain represented by the following general formula (3):

(In general formula (3), f is 1-4, g is 5-30, and {h / (h + g)} <0.2.)
Nonionic polar molecular chain represented by the following general formula (4):

(In general formula (4), i is 5 to 30, and j is 0 to 6.)
Is a nonionic polar molecular chain represented by

In the general formula (5), ^{R 4} and ^{R _5,} -C _p H _{2p -OH,} a _{-C q H 2q -COO-C r} H 2r -OH or a hydrogen atom, and, ^{R 4} and ^{R 5} at least one of _is a -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 2-6, q is 2-3, r is 2-4, and R ⁴ and R ⁵ may be the same or different.

In the general formula (5), R ⁶ represents the following general formula (6):

(In general formula (6), s is 5-30.)
A low polarity molecular chain represented by the following general formula (7):

(In general formula (7), t is 5-30.)
A low polarity molecular chain represented by the following general formula (8):

(In general formula (8), u is 5-30.)
A low polar molecular chain represented by the formula: a low polar molecular chain comprising a polyester having 2 or more molecular units having 4 or more carbon atoms as repeating units, and a polyether having 2 or more molecular units having 4 or more carbon atoms as repeating units Low polarity molecular chain, low polarity molecular chain consisting of polycarbonate having 2 or more molecular units having 4 or more carbon atoms as repeating units, or low polarity consisting of polycaprolactone having 2 or more molecular units having 4 or more carbon atoms as repeating units It is a molecular chain.

  Moreover, since this pigment dispersant (II-1) has (A1) and (C) in addition to (A2) and (B), the hydroxyl group or active hydrogen to be reacted with the isocyanate compound is reduced. Of the compounds having all of the compounds having the hydroxyl group or active hydrogen other than the compounds having the hydroxyl group or active hydrogen represented by the general formula (1) and the compounds having the hydroxyl group or active hydrogen represented by the general formula (5) Alternatively, a part of them is “(A1) the compound having the hydroxyl group or active hydrogen” and “the compound having the hydroxyl group or active hydrogen having (C)”. In the pigment dispersant (I-1), as the compound having a hydroxyl group or active hydrogen to be reacted with the isocyanate compound, a compound having a hydroxyl group or active hydrogen represented by the general formula (1), the general formula ( 5) a compound having a hydroxyl group or active hydrogen, “a compound having (A1) the hydroxyl group or active hydrogen”, and “a compound having the hydroxyl group or active hydrogen having (C)” A compound having a hydroxyl group or active hydrogen other than "" can be used.

  The pigment dispersant (II-1) is a compound having a hydroxyl group or active hydrogen represented by the general formula (1) as a compound having the hydroxyl group or active hydrogen to be reacted with the isocyanate compound, and the general formula (5). ), A compound having a hydroxyl group or active hydrogen is used, and therefore the pigment dispersant has an amino group. In the pigment-dispersed photosensitive resin composition of the present invention, acidic carbon black having the acidic functional group is used as the pigment, and the amino group in the pigment dispersant (II-1) is the acidic functional group. It exhibits an ionic affinity with the acidic functional group in the acidic carbon black or the neutralized base of the acidic functional group, thereby increasing the dispersibility of the pigment.

  Of the pigment dispersant (II), it is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or active hydrogen, and the bifunctional hydroxyl group or activity of the compound having the hydroxyl group or active hydrogen. The mol% of the total mole of the compound having a bifunctional hydroxyl group or active hydrogen having (A1), (A2), (B) or (C) as a side chain with respect to the total mole of the compound having hydrogen, It is preferable that it is 20-100 mol% at the point from which the dispersibility of this pigment becomes high. That is, paying attention to the bifunctional hydroxyl group or active hydrogen compound among the compounds having the hydroxyl group or active hydrogen used in producing the pigment dispersant (II), the bifunctional hydroxyl group or active hydrogen is used. A compound having a bifunctional hydroxyl group or active hydrogen 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 the compound having A compound having a bifunctional hydroxyl group or active hydrogen having (B) as a side chain, and a compound having a bifunctional hydroxyl group or active hydrogen having (C) as a side chain The ratio of the number of moles is preferably 20 to 100% by mole because the dispersibility of the pigment is enhanced. The compound having a bifunctional hydroxyl group or active hydrogen having Y as a side chain means a bifunctional hydroxyl group or active hydrogen such that Y becomes a side chain of a polyurethane resin when polymerized. The compound which has.

  The production method of the pigment dispersant (II) is not particularly limited, and a known method is used.

  The pigment dispersant (II) includes, for example, a polyol (a1) having one or two of the acidic functional group and a neutralized base of the acidic functional group, the basic functional group, and the basic functional group. A polyol (a2) having one or more of the group neutralizing base and the nonionic polar molecular chain, a polyol (b) having the low polar molecular chain (B), and the active energy ray curing It can be obtained by reacting a compound (c) having a polymerizable unsaturated group and a hydroxyl group with a difunctional or higher functional 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, the polyol (a1) having one or two of the acidic functional group and a neutralized base of the acidic functional group as a side chain, the basic functional group, and the basic functional group as a side chain By using the polyol (a2) having one or more of the neutralizing base and the nonionic polar molecular chain, and the polyol (b) having the low polar molecular chain (B) as a side chain, (A1), (A2), and (B) are preferable in that a pigment dispersant in which the side chain is extended to the 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 that reacts with the isocyanate compound (d) and having (A1) reacts with the isocyanate compound (d). A monool having one hydroxyl group or active hydrogen and having (A2) (monofunctional compound) or a monool having one hydroxyl group or active hydrogen that reacts with the isocyanate compound (d) and having (B) ( Monofunctional compounds) can also be used in combination.

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

As (a1), a carboxyl group (—COOH), a hydroxyl group (—OH), a sulfonic acid group (—SO ₃ H), a phosphoric acid ester group (phosphoric monoester, phosphoric diester, phosphoric triester group) And a polyol compound having one or two or more of acidic functional groups such as sulfuric acid esters and groups in which they are neutralized with a basic compound. More specifically, as (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) propio Acid, 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 (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, 4-hydroxybutyl acrylate; dimethylaminoethylamine, diethylaminoethylamine, Diamine consisting of tertiary amine such as dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine and the like and primary amine, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, Michael addition reactants of hydroxyalkyl acrylates such as 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 (a2), as the polyol compound (a2) having a nonionic polar molecular chain, a nonionic polar molecular chain such as a polyoxyethylene ether chain or a polyoxyethylene ether-polyoxypropylene ether glycol copolymer molecular chain is used. 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; Block copolymer diol in which polyoxyethylene ether chain accounts for 60 mol% or more of 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.
Further, as (a2), the following general formula (11):

(In General Formula (11), R ⁸ is an alkyl group having 4 to 27 carbon atoms, and w + x is 5 to 50.)
The diol represented by these is mentioned.

As (a2), an alkoxypolyoxyethylene ether acrylate such as methoxypolyoxyethylene ether acrylate having three or more polyoxyethylene ether repeating units and a dialkanolamine such as diethanolamine or dipropanolamine are mixed with Michael. Examples of diols obtained by addition reaction include diols having a polar molecular chain in the molecular side chain.
In addition, as the (a2) for introducing a nonionic molecular side chain having three or more oxyethylene ether repeating units as a side chain of the polyurethane resin, a hydroxyl group or active hydrogen represented by the general formula (1) is used. The compound which has is mentioned. And the compound which has a hydroxyl group or active hydrogen represented by the said General formula (1) is preferable at the point from which the dispersibility of a pigment becomes high.

  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 two 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 the polyester polyol (b), one or more of the following polyols and polyol synergistic components and one or more of polybasic acids and their anhydrides undergo a condensation reaction. Can be obtained.

  Examples of the polyol having a molecular unit of 4 or more as a raw material of 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.

  Examples of the polyol synergistic component that is a raw material of the polyester polyol (b) include 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 that 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.

  There are also 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 polyol and polyester polyol (b). As an example of polyester polyol (b).

  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 bd R-15HT and R-45T (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 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 (b), as 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 (9):

(In the general formula (9), R ⁷ 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, for example, the following general formula (10):

(In the general formula (10), R ⁷ 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 (12):

(In general formula (12), v is 4 to 27.)
In particular, those having v of 11, 17, and 21 are preferred.

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

  Examples of (c) include a compound having a vinyl group or (meth) acryloyl group and a hydroxyl group having active energy ray curability.

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

Examples of the compound (c) having a (meth) acryloyl group and a hydroxyl group include monohydroxyacryl methacrylate, monohydroxytriacrylate, monohydroxypentaacrylate, and dihydroxymono (meth) acrylate.
Further, compounds 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 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.

The molar ratios of (a1), (a2), (b), (c), and (d) are respectively [a1], [a2], [b], [c], [d], the first reaction of reacting (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. In addition, the dispersant of the present invention in which the active energy linear unsaturated group is side chain or terminal can be obtained.
Moreover, an unsaturated group can be introduce | transduced in a molecular chain by using the polyol which has unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group, with this (b).

  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.

  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 above reaction is carried out without 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.

  Examples of the organic solvent (III) relating to the pigment-dispersed photosensitive resin 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, and 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-dimethylsulfoxide and the like.

  The alkali-soluble resin (IV) according to the pigment-dispersed photosensitive resin composition of the present invention is a resin that dissolves in an alkali developer during alkali development, and is usually used as an alkali-soluble resin in the photosensitive resin composition. If it is possible, it will not be restrict | limited. Examples of the alkali-soluble resin (IV) include an alkali having an acidic functional group introduced into the molecule, which is obtained by reacting an acid anhydride with an acrylate having an epoxy resin skeleton disclosed in Japanese Patent Publication No. 56-40329. Examples thereof include soluble epoxy resin acrylates. The alkali-soluble resin (IV) includes a copolymer of a monomer having a carboxyl group such as acrylic acid and methacrylic acid, and methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, styrene and the like. Can be mentioned.

  The active energy ray-curable compound (V) according to the pigment-dispersed photosensitive resin 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, etc. Without being limited, for example, compounds that are usually used as an active energy ray-curable resin, monomer, or oligomer of a photosensitive resin composition can be mentioned. Examples of the active energy ray-curable compound (V) 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 (V) include (meth) acrylate oligomers such as urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers. These may be used in combination of two or more.

  Moreover, as this active energy ray hardening compound (V), as monofunctional (meth) acrylate, for example, methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, isooctyl, nonyl, dodecyl, hexadecyl, octadecyl, Having a substituent such as cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclopentenyloxyethyl ( (Meth) acrylate; 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 (V) include polyfunctional (meth) acrylates such as 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane diethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene Di (meth) acrylate such as glycol, tripropylene glycol and polypropylene glycol, di (meth) acrylate of tris (2-hydroxyethyl) isocyanurate, 4 mol or more of ethylene oxide or propylene oxide per 1 mol of neopentyl glycol Di (meth) acrylate of diol obtained by adding a bisphenol, 2 mol of ethylene oxide or propylene oxide obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, 3 mol or more per mole of trimethylolpropane Diol or tri (meth) acrylate of triol obtained by adding ethylene oxide or propylene oxide, and di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, Methylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, poly (meth) acrylate of dipentaerythritol, ethylene oxide modified phosphoric acid (meth) acrylate, ethylene oxide modified , Alkylphosphoric acid (meth) acrylate and the like, and these may be used in combination of two or more.

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

  The photopolymerization initiator (VI) according to the pigment-dispersed photosensitive resin composition of the present invention is not particularly limited as long as it is a photopolymerization initiator usually used for a photosensitive resin composition. Examples of the photopolymerization initiator (VI) include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6- Trimethylbenzoyldiphenylethoxyphosphine 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) -phenylphospho Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are preferably used, and other molecular cleavage types include 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 Also used in combination with -4'-methyl-diphenyl sulfide It may be.

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

  In addition, the pigment-dispersed photosensitive resin composition of the present invention further comprises acrylic resin, methacrylic resin, phenol resin, melamine resin, xylene resin, diallyl phthalate resin, cryptal resin, epoxy resin, alkylbenzene resin, polyester resin, polyvinyl alcohol resin. It is possible to contain a resin having excellent heat resistance or fluidity.

  Moreover, the pigment dispersion photosensitive resin composition of this invention can contain a dispersion stability adjuvant, an inhibitor, a coating-film smoothing adjuvant, and other additives as needed.

  In the pigment-dispersed photosensitive resin composition of the present invention, for example, first, the pigment (I) and the pigment dispersant (II) are added to the organic solvent (III) and mixed by a homogenizer device such as a bead mill. A pigment dispersion is prepared by dispersing the pigment (I) in the organic solvent (III) with the pigment dispersant (II), and then the pigment dispersion, alkali-soluble in the organic solvent (III). Resin (IV), the active energy ray-curable compound (V) and the photopolymerization initiator (VI) are added, and if necessary, a dispersion stability aid, an inhibitor, a coating film smoothing aid, and other additives. Is added and mixed.

  The content of the pigment (I) in the pigment-dispersed photosensitive resin 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 (II) is preferably 2 to 100 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of the pigment (I), and the alkali-soluble component. The content of the resin (IV) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the pigment (I), and the content of the active energy ray-curable compound (V) is the pigment (I). ) Preferably it is 5 to 20 parts by weight with respect to 100 parts by weight, and the content of the photopolymerization initiator (VI) is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the pigment (I). Particularly preferred is 3 to 12 parts by weight.

  The pigment-dispersed photosensitive resin composition of the present invention is used as a pigment-dispersed photosensitive resin composition that forms a cured coating film by photolithography. In particular, the pigment-dispersed photosensitive resin composition of the present invention is suitably used as a pigment-dispersed photosensitive resin composition for forming a black matrix for a color filter of a color liquid crystal display.

  As a method for forming a black matrix using the pigment-dispersed photosensitive resin composition of the present invention, for example, after applying the pigment-dispersed photosensitive resin composition of the present invention to a substrate, a black matrix is formed by photolithography. Method, the pigment-dispersed photosensitive resin composition of the present invention is applied to a substrate by printing, spin coating, etc., dried, then mask-adhered, exposed, and then alkali-developed to form an arbitrary image on the substrate The method of forming a black matrix by the lithography method to perform is mentioned.

  The pigment-dispersed photosensitive resin composition of the present invention can provide a cured film having high dispersibility of the pigment (I), high developability with an alkaline developer, and excellent chemical resistance.

  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 acidic carbon black-1>
STSA specific surface area ^{50 m} 2 / g, DBP oil absorption of 62cm ³ / 100g, the carbon black 100g of an average primary particle diameter of 36 nm, were placed in an ozone treatment unit, an ozone generator (Nippon Ozone Co., IOT-4A6) by The gas was oxidized for 2 hours under conditions of a generated voltage of 200 V and an ozone generation amount of 5 mg / s, and gas phase oxidation treatment with ozone was performed to obtain acidic carbon black-1 (TK-1). The acid value of the TK-1 was 3.5 KOH mg / g.

<Preparation of acidic carbon black-2>
STSA specific surface area ^50m 2 / g, DBP oil absorption of 62cm ³ / 100g, an average primary particle size in place of the carbon black 100g of 36 nm, STSA specific surface area ^54m 2 / g, DBP oil absorption of 50 cm ³ / 100g, an average primary particle size Was performed in the same manner as in the preparation of acidic carbon black-1, except that the carbon black was 100 g of 38 nm. Thus, acidic carbon black-2 (TK-2) was obtained. The acid value of the TK-2 was 4.5 KOHmg / g.

<Preparation of acidic carbon black-3>
STSA specific surface area ^{50 m} 2 / g, DBP absorption 62cm ³ / 100g, the carbon black 100g of an average primary particle diameter of 36 nm, was added to the peroxodisulfuric acid aqueous solution of sodium 1500ml concentration 0.05mmol / g, 0.12s ^{- 1. The} mixture was stirred and mixed for 10 hours under the conditions of a reaction temperature of 60 ° C. and subjected to liquid phase oxidation. After the oxidation treatment, the carbon black dispersion was purified and removed with an ultrafiltration membrane (AHP-1010 manufactured by Asahi Kasei Co., Ltd., molecular weight cut off 50000), filtered, dried, and acid carbon black-3 (TK-3) was obtained. The acid value of the TK-3 was 9.5 KOH mg / g.

<Carbon black-4>
STSA specific surface area ^50m 2 / g, DBP absorption 62cm ^3/100 g, average primary particle size of carbon black 36 nm, and a carbon black -4 (TK-4).

<Preparation of acidic carbon black-5>
STSA specific surface area ^50m 2 / g, DBP absorption 62cm ³ / 100g, an average primary particle size in place of the carbon black 100g of 36 nm, STSA specific surface area 130m ² / g, DBP absorption 104cm ³ / 100g, an average primary particle size Was made in the same manner as in the preparation of acidic carbon black-3 except that the carbon black was 100 g of 20 nm to obtain acidic carbon black-5 (TK-5). The acid value of the TK-5 was 25.4 KOH mg / g.

<Synthesis of polyurethane dispersant 1>
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 nonvolatile content of 48.0% by weight, 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.

<Synthesis of polyurethane dispersant 2>
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 nonvolatile content of 48.3% by weight, 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%.

<Comparison dispersant>
Solsperse 44000 (hereinafter also referred to as Dispersant S): manufactured by Lubrizol, acid value 12 KOH mg / g, nonvolatile content 50%

(Examples 1-4, Comparative Examples 1-3)
<Preparation of carbon black dispersion composition>
Carbon black in an amount shown in Table 1, a dispersant (in terms of solid content), t-butyl hydroquinone (tBHQ), and propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent, using a TK homomixer manufactured by PRIMIX, After pre-dispersing for 30 minutes, 1 mmφ zirconia beads were used and dispersed for 2 hours in a dyno mill KDL type manufactured by Willy et Bacofen, to obtain a pigment dispersion (Table 1).

<Production of pigment-dispersed photosensitive resin composition>
35 parts of the pigment dispersion obtained above, 10 parts of methacrylic acid / methyl methacrylate copolymer (25/75, Mw 20000), 7 parts of bisphenol A type epoxy acrylate resin (Mw 3000), 7 parts of trimethylolpropane triacrylate, Icargacure (907) (polymerization initiator manufactured by Ciba Specialty Chemicals) 3 parts, 9-phenylacridine (manufactured by Nippon Steel Chemical Co., Ltd.) 2 parts, 4,4′-bisdiethylaminobenzophenone (Hodogaya Chemical EAB-F) 1 Part, 35 parts of propylene glycol monomethyl ether acetate was pre-dispersed for 30 minutes with a TK homomixer manufactured by PRIMIX, then kneaded for 2 hours with a 3-roll mill manufactured by Inoue Seisakusho, and then filtered with a filter having a pore size of 2 μm. A pigment-dispersed photosensitive resin composition was obtained.

<Viscosity and particle size of pigment-dispersed photosensitive resin composition>
The viscosity and particle size of the pigment-dispersed photosensitive resin composition obtained above were measured. Moreover, in order to confirm dispersion stability, it stored at 40 degreeC in the airtight container, and the viscosity and the particle size were measured also after 4 weeks.
For measuring the viscosity, an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-20L) was used to measure the viscosity at a temperature of 25 ° C.
In addition, for measuring the particle size, a heterodyne laser Doppler type particle size distribution analyzer (UPA model 9340 manufactured by Microtrac Co., Ltd.) is used, and propylene glycol monomethyl ether acetate is used as a solvent for viscosity adjustment, and a pigment-dispersed photosensitive resin composition From the particle size distribution curve of the carbon black particle aggregate, the 50% cumulative frequency value (volume basis) was determined as the average particle size, and the 99% cumulative frequency value (volume basis) as the maximum particle size.
In addition, 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 2.

<Formation of black matrix>
The pigment-dispersed photosensitive resin composition produced as described above was applied onto a glass substrate having a clean surface with a thickness of 1 mm using a slit coater, dried at 120 ° C. for 2 minutes, and then photopolymerized. A black color composition layer was formed.
Next, UV irradiation was performed under the condition of 340 J / cm ^{2 with} an exposure apparatus I Inverter Grandage ECS-401GX manufactured by Eye Graphics Co., Ltd., through a mask having a line width of 20 μm (the width of the portion to become a black matrix was 20 μm). Thereafter, spray development was performed with a 0.25% aqueous solution of potassium carbonate at 25 ° C. for 60 seconds, and then post-baked in an oven at 200 ° C. for 30 minutes to form a black matrix. The results are shown in Table 2.

<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 2.

・ 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 2.

-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 2.

As shown in Table 2, Examples 1 to 4 have the same viscosity, average particle size, and maximum particle size as Comparative Example 1, and exhibit the same dispersibility as the Comparative Example developed as a dispersant for carbon black. I understand that. A high blackness is also a visa that dispersibility is excellent. By comparing the stains in the unexposed areas of the examples and comparative examples, it can be seen that the combination of acidic carbon black and a dispersant having an acidic group is superior in alkali solubility and developability compared to the comparative examples. The curability of the exposed part compared with the example and the comparative example by MEK rubbing shows the resistance of the coating film that dissolves or swells with methyl ethyl ketone in the case where the pigment dispersant has an active energy ray-curable unsaturated group. It is known that the pigment dispersant is superior to an example having no active energy ray-curable unsaturated group. From the above, it can be seen that the present invention can provide high dispersibility and excellent developability of carbon black.
Comparative Example 2 is an example in which ordinary carbon black that is not surface acidic is used, but it can be seen that the viscosity and particle size increase after 4 weeks and the dispersion stability is poor. Comparative Example 3 is an example in which carbon black having a DBP oil absorption amount deviating from Claim 3 was used, but the compatibility with the polyurethane resin deteriorated and the viscosity increased. Also, the dispersibility is poor, and the blackness is low because the smoothness of the light shielding layer is impaired.

Claims (6)

Pigment (I), pigment dispersant (II), organic solvent (III), alkali-soluble resin (IV), active energy ray-curable compound (V), and photopolymerization initiator (VI) Contains,
The pigment (I) is an acidic carbon black having an acidic functional group,
The pigment dispersant (II) comprises (A1) one or two of an acidic functional group and an acidic functional group neutralized base; and (A2) a basic functional group, a basic functional group neutralized base, and and one or more of the nonionic polar molecular chain, (B) and the low polar molecules chains, polyurethane resins der having a (C) the active energy ray-curable unsaturated groups,
It is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or active hydrogen,
A part of the compound having the hydroxyl group or active hydrogen is represented by the following general formula (1):

(In General Formula (1), R ¹ and R ² are —C _a H _2a —OH, —C _b H _2b —COO—C _c H _2c —OH, or a hydrogen atom, and R ¹ and R ² At least one of them is —C _a H _2a —OH or —C _b H _2b —COO—C _c H _2c —OH, where a is 2 to 6, b is 2 to 3, and c is 2 to 4. Yes, R ¹ and R ² may be the same or different.
R ³ represents the following general formula (2):

(In general formula (2), d is 1-4 and e is 5-30) Nonionic polar molecular chain represented by the following general formula (3):

(In general formula (3), f is 1-4, g is 5-30, {h / (h + g)} <0.2), or a nonionic polar molecular chain represented by the following general formula (4 ):

(In general formula (4), i is 5-30, j is 0-6). )
And a compound having a hydroxyl group or active hydrogen represented by the following general formula (5):

(In General Formula (5), R ⁴ and R ⁵ are —C _p H _2p —OH, —C _q H _2q —COO—C _r H _2r —OH, or a hydrogen atom, and R ⁴ and R ⁵ At least one of them is —C _p H _2p —OH or —C _q H _2q —COO—C _r H _2r —OH, p is 2 to 6, q is 2 to 3, and r is 2 to 4. R ⁴ and R ⁵ may be the same or different, and R ⁶ is represented by the following general formula (6):

(In general formula (6), s is 5-30.)
A low polarity molecular chain represented by the following general formula (7):

(In general formula (7), t is 5-30.)
A low polarity molecular chain represented by the following general formula (8):

(In general formula (8), u is 5-30.)
A low-polar molecular chain represented by:
Polyester, polyether, polycarbonate, or polycaprolactone low-polar molecular chain having two or more molecular units having 4 or more carbon atoms as repeating units. )
A pigment-dispersed photosensitive resin composition, which is a compound having a hydroxyl group or active hydrogen represented by the formula: The average primary particle size of the acidic carbon black having an acidic functional group is 50nm or less, STSA specific surface area of ^{30 m} 2 / g or more, DBP oil absorption of 80 cm ^3/100 g or less, and an acid value of 1.0~20KOHmg / g The pigment-dispersed photosensitive resin composition according to claim 1, wherein   All or part of (A1), (A2), (B) and (C) of the pigment dispersant (II) is a side chain of the polyurethane resin or bonded to the side chain. The pigment-dispersed photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is dispersed.   The pigment-dispersed photosensitive resin composition according to any one of claims 1 to 3, wherein the (A1) of the pigment dispersant (II) is a carboxyl group. The pigment according to any one of claims 1 to 4, wherein the (A2) of the pigment dispersant (II) is a polyoxyethylene ether molecular chain having four or more oxyethylene ether repeating units. A dispersed photosensitive resin composition . The pigment dispersant (II) is a polyurethane resin obtained by reacting an isocyanate compound with a compound having a hydroxyl group or active hydrogen,
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 among the compounds having the hydroxyl group or active hydrogen. The pigment-dispersed photosensitive resin composition according to any one of claims 1 to 5 , wherein the mol% of the total number of moles of the compound having a bifunctional hydroxyl group or active hydrogen is 20 to 100 mol%.