TWI637237B - Photosensitive resin composition, cured product, black matrix and image display device - Google Patents

Abstract

The present invention provides a photosensitive resin composition having excellent dispersibility and capable of forming high-definition fine lines regardless of the color material content ratio in the photosensitive resin composition. The photosensitive resin composition of the present invention contains a coloring material (a), a dispersant (b), a photopolymerization initiator (c), an alkali-soluble resin (d), and a solvent (e), and the dispersant (b) contains Polyurethane dispersant (b-1) with a solvent-based group and an adsorption group; the polyurethane dispersant (b-1) contains a part of the structure represented by formula (i); photopolymerization The initiator (c) contains an oxime ester photopolymerization initiator (c-1).

Description

Photosensitive resin composition, cured product, black matrix, and image display device

The present invention relates to a photosensitive resin composition, a cured product, a black matrix, and an image display device. Specifically, it relates to a photosensitive resin composition which is excellent in dispersibility, developability, and heat resistance and can form high-definition fine lines. The photosensitive resin composition of the present invention has particularly high light-shielding properties, and is suitable for a photosensitive resin composition for a black matrix (hereinafter referred to as "BM") that can form high-definition fine lines. Moreover, this invention relates to the hardened | cured material of this photosensitive resin composition, and its use.

The color filter is usually formed on the surface of a transparent substrate such as glass or plastic to form a black matrix. Then, three or more different colors of pixels such as red, green, or blue are sequentially formed into a stripe or mosaic shape. And other patterns. The pattern size varies depending on the use of the color filter and each color, and is usually about 5 to 700 μm.

As a typical method for producing a color filter, a pigment dispersion method is currently known. When a color filter is manufactured by the pigment dispersion method, a photosensitive resin composition containing a black pigment is first coated on a transparent substrate and then dried, and then subjected to image exposure and development, and then treated at a high temperature of 200 ° C or higher. It hardens, thereby forming BM. This is repeated for each color such as red, green, or blue to form a color filter.

BM is generally arranged in a grid, stripe or mosaic between pixels such as red, green or blue, and has the advantage of improving contrast by suppressing color mixing between pixels. To prevent light leakage. Therefore, a high light-shielding property is required for the BM system.

Furthermore, the edge portions of the pixels of red, green, or blue formed after the formation of the BM are overlapped with this BM, and therefore are affected by the thickness of the BM film, and a step is formed at the overlapping portion. At this overlapping portion, the flatness of the pixel is damaged, unevenness of the liquid crystal lattice gap or disordered liquid crystal alignment occurs, causing a reduction in display capability.

Therefore, in recent years, thinning of the thickness of the BM film is particularly required. In order to exhibit sufficient light-shielding properties even after thinning, there is a tendency to increase the pigment content ratio in the photosensitive resin composition.

On the other hand, in order to save energy and prolong the life of portable batteries, there is a tendency to reduce the output of the backlight. In order to still display images with high brightness under such conditions, thin lines of BM belonging to the light-shielding section are performed. Into.

Furthermore, in recent years, in the liquid crystal display market, the miniaturization of tablets and the like has become mainstream, and the requirements for high resolution have become higher in large TVs. For these reasons, the expectations for the high fineness of BM have also changed. high. In recent years, the line width of BM thin wires has been changed from the conventionally known about 10 μm to about 6 μm currently required.

Generally, when producing a photosensitive resin composition used in a pigment dispersion method, a composition containing a color material, a dispersant, a solvent, and the like is first dispersed by glass beads or the like to prepare a dispersion liquid. Thereafter, this dispersion is stirred and mixed with an alkali-soluble resin, a photopolymerization initiator, or the like to prepare a photosensitive resin composition.

As dispersants for color filters, acrylics, polyurethanes, polyethyleneimines, or polyesters have been proposed. In terms of structure, random, block, or bonded Various types of branches (comb) (for example, Patent Documents 1 to 3).

Among these, a polyurethane-based dispersant can add a compound having a carboxyl group, a secondary amine group, or a thiol group to the terminal by a urethane bond, Therefore, various forms have been developed as dispersants (for example, Patent Documents 4 to 9).

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2002-031713

Patent Document 2: Japanese Patent No. 3509512

Patent Document 3: Japanese Patent No. 3789965

Patent Document 4: Japanese Patent Laid-Open No. 57-162723

Patent Document 5: Japanese Patent Publication No. 2002-503746

Patent Document 6: Japanese Patent Publication No. 2003-506538

Patent Document 7: Japanese Patent Publication No. 2005-538192

Patent Document 8: Japanese Patent Publication No. 2010-511752

Patent Document 9: Japanese Patent Publication No. 2011-514411

The present inventors and others have found that the dispersants described in Patent Documents 1 to 3 cannot be dispersed depending on the type of pigment, or thickened after dispersion, or that adequate dispersion cannot be obtained unless an appropriate one or condition is selected. Effects and other issues. In addition, even if a conventional high-sensitivity initiator is used in these conventional dispersants, it is not possible to form the finer and finer lines that are currently required.

In addition, the dispersants described in Patent Documents 4 to 9 are insufficient to form finer fine lines under the conditions of higher light-shielding conditions currently required, that is, the conditions of higher pigment content.

Therefore, an object of the present invention is to provide superior dispersibility regardless of color. A photosensitive resin composition which can form high-definition fine lines in a material content ratio, and a cured product using the photosensitive resin composition, a black matrix, and an image display device.

The present inventors made intensive research in order to solve the above-mentioned problems, and as a result, they found that by combining a polyurethane dispersant having a specific structure and a high-sensitivity photopolymerization initiator, regardless of the photosensitive resin composition The proportion of the color material in the medium can form the fine and fine thin lines currently required.

The present invention has been achieved based on such findings, and the gist thereof is as follows.

A photosensitive resin composition comprising a coloring material (a), a dispersant (b), a photopolymerization initiator (c), an alkali-soluble resin (d), and a solvent (e), wherein the dispersant ( b) contains a polyurethane dispersant (b-1) having a solvent-based group and an adsorbing group; the polyurethane dispersant (b-1) contains the following formula (i) Partial structure; photopolymerization initiator (c) contains oxime ester photopolymerization initiator (c-1);

[In the formula (i), R ^a represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms which may have a substituent, or a carbon in which the above alkylene group is connected to the above alkylene group. The base of the number 7 ~ 20; * represents the bond base].

2. The photosensitive resin composition according to the above item 1, wherein the polyurethane dispersant (b-1) contains: a structure containing a portion of a solvent-soluble group containing the solvent-soluble group; and a structure containing the adsorbent group. The structure of the adsorption group-containing portion; the structure of the solvent-containing portion and the structure of the absorption portion are formed by the above formula (i) The parts shown are connected.

3. The photosensitive resin composition according to the above item 1 or 2, wherein the polyurethane dispersant (b-1) has a main chain, and the main chain contains a portion represented by the above formula (i) structure.

4. The photosensitive resin composition according to any one of the foregoing paragraphs 1 to 3, wherein the solvent-based system contains at least one of a polyether chain and a polyester chain.

5. The photosensitive resin composition according to any one of the foregoing paragraphs 1 to 4, wherein the adsorption group is selected from the group consisting of a tertiary amine group, a tertiary ammonium salt group, and a nitrogen atom-containing heterocyclic group. At least one.

6. The photosensitive resin composition according to any one of the foregoing paragraphs 2 to 5, wherein the adsorption group-containing partial structure has a partial structure represented by the following formula (1);

[In formula (1), R ¹ represents an alkyl group or an aryl group which may also have a substituent, and R ² and R ³ each independently represent an alkylene group, an alkylene group, or an alkylene group which may also have a substituent; * Indicates bonding base].

7. The photosensitive resin composition according to any one of the foregoing paragraphs 2 to 6, wherein the adsorption group-containing portion structure has a portion of at least one of the following formulae (2-1) to (2-3) structure;

[In formula (2-1), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^γ , R ^δ and R ^ε each independently represent an alkylene group which may also have a substituent, An arylene group which may have a substituent, or a group in which the above-mentioned alkylene group is connected to the above-mentioned aryl group; wherein R ^γ is an alkylene group which may have a substituent, or the above-mentioned alkylene group and the above-mentioned alkylene When the group is connected via a group, at least a part of the methylene group constituting the above-mentioned alkylene group may be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a sulfonium bond, and a sulfonium imine bond. , At least one bond in the group of thiourethane bond, thioether bond, and thioester bond; and R ^γ can also be connected to the adjacent group through the -NH- (C = O)-group. At least any one of the N atoms is urea-bonded together, or amide-bonded via a carbonyl group; * is a bonding group];

[In formula (2-2), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^γ and R ^η each independently represent an alkylene group which may also have a substituent, and may also have An arylene group as a substituent, or a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected; wherein R ^γ and R ^η are each independently an alkylene group which may also have a substituent, or the above-mentioned alkylene group and the above-mentioned When the aryl group is linked, at least a part of the methylene group constituting the above-mentioned alkylene group may be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a fluorene bond, and a fluorene At least one bond in the group of amine bond, thiourethane bond, thioether bond, and thioester bond; and R ^γ and R ^η may also be via -NH- (C = O)-group Urea bonding with at least one of the adjacent N atoms, or amido bonding via a carbonyl group; * is a bonding group];

[In the formula (2-3), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^{γ ′} and R ^δ each independently represent an alkylene group which may also have a substituent, or An arylene group having a substituent, or a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected; wherein R ^{γ ′} is an alkylene group which may have a substituent, or the above-mentioned alkylene group and the above-mentioned alkylene group At the time of the linked group, at least a part of the methylene group constituting the above-mentioned alkylene group may be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, an amidine bond, an amidine bond, At least one bond in the group of thioaminoformate bond, thioether bond, and thioester bond is substituted; R ^{γ '} may also be connected to the adjacent group through a -NH- (C = O)-group. The N atoms are bonded together by urea or amide through carbonyl; R ^{ε ′} represents a direct bond, an alkylene group which may have a substituent, an alkylene group which may also have a substituent, or the above A group in which an alkyl group is connected to the above-mentioned aryl group; R ^ζ represents a hydrogen atom, and an alkyl group or an aryl group which may have a substituent; wherein, when R ^ζ is the above-mentioned alkyl group or the above-mentioned aryl group, its hydrogen atom At least one of them may be substituted by a tertiary amine group or a nitrogen atom-containing heterocyclic group; * is a bonding group].

8. The photosensitive resin composition according to any one of the foregoing items 1 to 7, wherein the oxime ester photopolymerization initiator (c-1) has a carbazolyl group which may be substituted.

9. The photosensitive resin composition according to any one of the preceding paragraphs 1 to 8, wherein the alkali-soluble resin (d) is an alkali-soluble resin (d-1) containing at least one of a carboxyl group and an ethylenically unsaturated group. .

10. The photosensitive resin composition according to the item 9, wherein the alkali-soluble resin (d-1) is an epoxy (meth) acrylate resin.

11. The photosensitive resin composition according to the above item 10, wherein the epoxy (meth) acrylate resin is the following epoxy (meth) acrylate resin (D1-1) and epoxy group (formaldehyde) Base) at least one of acrylate resins (D1-2); (1) adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further An epoxy (meth) acrylate resin (D1-1) obtained by reacting at least one of a polybasic acid and an anhydride thereof; (2) an α, β-unsaturated monocarboxylic acid or an α having a carboxyl group, Epoxy (meth) acrylate resin (D1-2) obtained by adding a β-unsaturated monocarboxylic acid ester to an epoxy resin and further reacting a polyol with at least one of a polybasic acid and an anhydride thereof .

12. The photosensitive resin composition according to any one of the foregoing paragraphs 1 to 11, wherein the average primary particle diameter of the color material (a) is 20 to 100 nm.

13. The photosensitive resin composition according to any one of the preceding paragraphs 1 to 12, wherein the color material (a) contains carbon black.

14. The photosensitive resin composition according to the above item 13, which contains the carbon black in an amount of 40% by mass or more with respect to the total solid content.

15. A cured product obtained by curing the photosensitive resin composition according to any one of the preceding paragraphs 1 to 14.

16. A black matrix containing the hardened material of item 15 above.

17. An image display device comprising the black matrix described in the above item 16.

According to the present invention, it is possible to provide a photosensitive resin composition having excellent dispersibility and capable of forming high-definition fine lines regardless of the color material content ratio in the photosensitive resin composition. The photosensitive resin composition of the present invention is particularly highly light-shielding, and can be used as a photosensitive resin composition for a black matrix capable of forming high-definition fine lines.

10‧‧‧ transparent support substrate

20‧‧‧ pixels

30‧‧‧ Organic protective layer

40‧‧‧ inorganic oxide film

50‧‧‧ transparent anode

51‧‧‧ Hole injection layer

52‧‧‧ Hole transport layer

53‧‧‧Light-emitting layer

54‧‧‧ Electron injection layer

55‧‧‧ cathode

100‧‧‧Organic EL element

500‧‧‧Organic luminous body

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element including a color filter of the present invention.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

In addition, the "(meth) acrylic acid" in the present invention means "acrylic and / or methacrylic acid", and the same applies to "(meth) acrylate" and "(meth) acrylfluorenyl". In addition, "acid (anhydride)" and "(anhydrous) ... acid" mean both an acid and its anhydride.

In the present invention, the "total solid content" means all components other than the solvent contained in the photosensitive resin composition or the ink described later.

In the present invention, the number average molecular weight and weight average molecular weight refer to the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (gel permeation chromatography).

In addition, in the present invention, the "amine value" means an amine value in terms of effective solid content in terms of effective solid content, and is a value shown by the weight of KOH equivalent to the alkali amount per 1 g of the solid content of the dispersant. . The measurement method will be described later. On the other hand, the so-called "acid value" means an acid value in terms of effective solid content conversion without being particularly limited, and is calculated by neutralization titration.

In addition, in this specification, "*" may be used to indicate a bonding group.

In addition, the "polyurethane skeleton" as used in this specification is not limited to the skeleton which consists of a polyurethane, and also includes the concept of the skeleton which consists of a polyurethane urea. Similarly, the so-called "polyurethane dispersant" is not limited to a dispersant having two or more urethane bonds, but also includes a dispersant having two or more urea bonds and a urethane bond. Bond and urea bond dispersant concept.

[Photosensitive resin composition]

The photosensitive resin composition of the present invention contains a color material (a), a specific dispersant (b), a specific photopolymerization initiator (c), an alkali-soluble resin (d), and a solvent (e).

The photosensitive resin composition of the present invention preferably further contains a photopolymerizable monomer, and further contains a thiol, a dispersing aid (pigment derivative), a tackifier, a coatability improver, and a development improver as necessary. , Ultraviolet absorber, antioxidant, surfactant, and other formulation ingredients; usually, each formulation ingredient is used in a state of being dissolved or dispersed in the solvent (e).

The present invention is characterized in that the photosensitive resin composition contains a specific polyurethane dispersant (b-1) as a dispersant, and contains an oxime ester photopolymerization initiator (c-1) as a photopolymerization initiation.剂 (c).

[Dispersant (b)]

The photosensitive resin composition of the present invention is characterized by containing a specific polyurethane dispersant (b-1) as a dispersant (b).

[Polyurethane Dispersant (b-1)]

The polyurethane dispersant (b-1) has a soluble vehicle group and an adsorbing group, and further contains a partial structure represented by the following formula (i).

In the above formula (i), R ^a represents an alkylene group having 1 to 20 carbon atoms, an alkylene group having 6 to 20 carbon atoms which may have a substituent, or a carbon in which the alkylene group is connected to the alkylene group. The base of the number 7 ~ 20; * indicates the bond base.

The carbon number of the alkylene group which may also have a substituent in the above formula (i) is not particularly limited if it is in the range of 1 to 20, preferably 2 or more, more preferably 3 or more, and preferably 15 or less It is more preferably 10 or less, and even more preferably 7 or less. When it is at least the above lower limit value, the dispersibility tends to be good; and when it is at most the above upper limit value, there is a tendency that a high viscosity can be prevented.

The alkylene may be chain or cyclic, and may also be a chain-shaped alkylene and a cyclic alkylene connected through. From the viewpoint of dispersibility, those having at least a ring portion are preferred.

Specific examples of the alkylene group include trimethylene, tetramethylene, pentamethylene, hexamethylene, octyl, decamethylene, cyclohexyl, cyclohexylmethylene, and hexamethylene Cyclohexyl methylene cyclohexyl and the like. From the viewpoint of good dispersion, Preferably it is tetramethylene, pentamethylene, hexamethylene, cyclohexyl, or cyclohexylmethylene cyclohexyl, more preferably pentamethylene, hexamethylene, cyclohexyl, or Cyclohexyl methylene cyclohexyl.

Specific examples of the alkylene group which may have a substituent include the following.

The carbon number of the arylene group which may also have a substituent in the above formula (i) is not particularly limited if it is in the range of 6 to 20, preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less . By making it below the said upper limit, there exists a tendency for high viscosity to be prevented.

Specific examples of the arylene group include the following.

Specific examples of the arylene group having a substituent include the following.

Among them, from the viewpoint of dispersibility, it is preferably represented by the above formula (0-3) base.

The carbon number of the alkylene group which may have a substituent in the above formula (i) and the alkylene group which may also have a substituent is not particularly limited if it is in the range of 7 to 20, and is preferably 8 or more, more preferably 9 or more, and preferably 15 or less, more preferably 14 or less, and even more preferably 13 or less. When it is at least the above lower limit value, the dispersibility tends to be good; and when it is at most the above upper limit value, there is a tendency that a high viscosity can be prevented.

The number of the arylene groups having a group through which the above-mentioned alkylene group and the above-mentioned arylene group are connected is not particularly limited if it is 1 or more, and from the viewpoint of dispersibility, it is preferably 2 or more, and more preferably 3 or less. The number of alkylene groups is not particularly limited, but is preferably 3 or less from the viewpoint of dispersibility.

Specifically, for example, one alkylene group which may have a substituent and one alkylene group which may have a substituent are connected; and two alkylene groups which may have a substituent are connected. The alkylene group which has a substituent may be connected to one.

Specific examples of the group in which the above-mentioned alkylene group is connected to the above-mentioned aromatic group include the following.

Among these, from the viewpoint of dispersibility, a base represented by the above formula (0-5) is preferred.

As these alkylene, alkylene, alkylene and alkylene groups are connected via The substituent which the group may have is not particularly limited, and examples thereof include an alkyl group, an aryl group, and an aralkyl group.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a methyl group is preferable from a viewpoint of easy handling or dispersibility.

Among these, from the viewpoint of dispersion, it is more preferable that R ^a is ^{a base} represented by the above formula (0-5), a base represented by the above formula (0-3), or the above formula (0-1 ).

In addition, the polyurethane dispersant (b-1) may be connected to each other via a partial structure shown in the formula (i) above, with a solvent-containing moiety-containing structure described later. Similarly, the adsorption-group-containing partial structures described later may be connected to each other by the partial structure shown in the above formula (i). In addition, a later-described structure containing a compatible solvent group and a later-described structure containing an adsorption group may be connected by a partial structure represented by the above formula (i).

In this way, the polyurethane dispersant (b-1) has a partial structure represented by the above formula (i), so that the structure containing a hydrophilic solvent-based portion and the structure containing an adsorption group can be arranged on a straight line, and It is considered that by expanding the movable region of these partial structures, there is a tendency that the compatibility with the solvent and the adsorption with the pigment can be improved.

The polyurethane dispersant (b-1) preferably has a main chain containing a partial structure represented by the above formula (i). In this way, by adopting a highly linear partial structure shown in the above formula (i) as a partial structure included in the main chain, a solvent-containing moiety can be made. The structure and the structure containing the adsorbing group are arranged on a straight line, and it is considered that by expanding the movable region of the partial structure, the compatibility with the solvent and the adsorption with the pigment tend to be improved.

In addition, in this specification, the main chain which a polyurethane dispersant (b-1) has means the chain connected by two or more urethane bond, and it means the longest chain.

As a preferred embodiment, a form in which the polyurethane skeleton of the main chain has a linear structure can be cited. At this time, the main chain has a linear structure except for the bonding portion with the eluent-based group, the adsorption group, and the bonding portion with the adsorption group. As described above, when the polyurethane skeleton is linear, there is a tendency that the compatibility between the solvent-soluble group and the solvent or the adsorption of the pigment with the adsorbing group becomes favorable. In particular, since the polyurethane skeleton is linear, it tends to promote pigment adsorption and dispersibility by nitrogen atoms of urethane bonds.

The content ratio of the partial structure represented by the above formula (i) in the polyurethane dispersant (b-1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol%. The above, more preferably 10 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less.

Similarly, from the viewpoint of dispersibility, the content ratio of the partial structure represented by the above formula (i) in the polyurethane dispersant (b-1) is preferably 5 mass% or more, and more preferably The content is 10% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less.

(Adsorbing group)

The adsorption group of the polyurethane dispersant (b-1) is not particularly limited. From the standpoint of dispersion, it is preferably at least one selected from the group consisting of a tertiary amine group, a tertiary ammonium salt group, and a nitrogen atom-containing heterocyclic group (hereinafter sometimes abbreviated as "specific adsorption group ").

In addition, when the polyurethane dispersant (b-1) has a main chain, from the viewpoint of dispersibility, the adsorption group is preferably selected from the group consisting of tertiary amines or bonded to the main chain. At least one member selected from the group consisting of amino group, quaternary ammonium salt group, and nitrogen atom-containing heterocyclic group.

The polyurethane dispersant (b-1) preferably contains an adsorption group-containing moiety structure including the above-mentioned adsorption group; as described above, from the viewpoint of dispersibility, it is preferable that the adsorption group-containing moiety structure is mutually, Alternatively, the structure containing the adsorption group-containing portion and the later-described solvent-containing medium-containing portion structure are connected by a portion structure shown in the above formula (i).

(Structure with adsorption base part 1)

The specific partial structure of the structure containing the adsorption group is not particularly limited, and it is preferably a partial structure represented by the following formula (1).

In formula (1), R ¹ represents an alkyl group or an aryl group which may have a substituent, and R ² and R ³ each independently represent an alkylene group, an alkylene group, or an alkylene group which may also have a substituent.

* Indicates a bonded base.

The carbon number of the alkyl group of R ¹ is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. From the viewpoint of dispersibility, methyl, ethyl, propyl, cyclopentyl, or cyclohexyl is preferred, methyl, ethyl, or cyclohexyl is more preferred, and methyl or cyclohexyl is even more preferred .

The number of carbon atoms of the aryl group of R ¹ is not particularly limited, but is usually 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenyl, naphthyl, and the like. From the viewpoint of dispersibility, phenyl is preferred.

The substituents which the alkyl group and aryl group may have are not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as methyl, ethyl, propyl, and cyclohexyl; an aryl group such as phenyl; and benzyl Aralkyl and the like.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a hydroxyl group, a methyl group, or an ethyl group is preferable from a viewpoint of the adsorption force to a pigment.

Further, in the above R ^1, from the viewpoint of dispersibility of the terms, R ¹ is preferably an alkyl group.

The carbon number of the alkylene group in R ² and R ³ is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 7 or less. . If it is in the said range, there exists a tendency for dispersibility to be favorable. Specifically, for example, methylene, ethylene, propyl, butyl, cyclopentyl methylene, cyclohexyl methylene, cyclohexyl ethylene, and cyclohexyl ethylene Base etc. From the viewpoint of dispersibility, methylene, ethylene, or cyclohexylmethylene is preferred, and ethylene is more preferred.

The number of carbon atoms of the arylene aralkylene group (the group in which the arylene group and the arylene group are connected) in R ² and R ³ is not particularly limited, but it is usually 7 or more, preferably 8 or more, and preferably 30 or less. It is more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenylene methylene, phenylene, and phenylene. From the viewpoint of dispersibility, phenylene methylene is preferred.

The carbon number of the arylene group in R ² and R ³ is not particularly limited, but it is usually 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenylene and naphthyl. From the viewpoint of dispersibility, phenylene is preferred.

These alkylene, alkylene, and alkylene substituents are not particularly limited, and examples thereof include hydroxyl groups; carboxyl groups; alkyl groups such as methyl, ethyl, propyl, and cyclohexyl; Aryl groups such as phenyl; aralkyl groups such as benzyl.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 ~ 10. Specific examples include benzyl and the like.

Among these, a hydroxyl group, a methyl group, or an ethyl group is preferable from a viewpoint of suppressing a steric intermolecular barrier.

R ² and R ³ may be the same or different, and are preferably the same from the viewpoint of dispersibility. Among these, from the viewpoint of dispersibility, R ² and R ^{3 are} preferably each independently an alkylene group.

Specific examples of the partial structure represented by the above formula (1) include the following.

In addition, in the partial structure represented by the above formula (1), the formula (1) as a whole becomes an adsorption group containing a tertiary amine group. In addition, by connecting the partial structure shown in the formula (1) with other structures containing an adsorbing group or a part containing a soluble medium group, and connecting the partial structure shown in the formula (i), the formula (1) can be obtained. The adsorption group shown is arranged in the main chain of the polyurethane dispersant (b-1). At this time, * in the above formula (1) represents a bonding group with a carbonyl group of a urethane bond in the polyurethane skeleton of the main chain.

As another example, it is preferable to have a partial structure represented by the following formula (1 ').

[Chemical 13]

In the formula (1 ′), R ¹ to R ³ and * have the same meanings as in the above formula (1). R ^A represents an alkyl group or an aryl group which may have a substituent. X ^- represents a monovalent anion.

As the alkyl group or aryl group of R ^A , those listed as R ¹ can be preferably used.

X ^- is not particularly limited as long as it is a monovalent anion. From the viewpoint of dispersibility, X ^-is preferably a halogen anion such as a chloride anion, or a methyl sulfate anion, more preferably a halogen anion, and even more preferably a chloride anion. . The quaternary ammonium salt group of the formula (1 ') can be obtained by quaternizing the tertiary amine group of the formula (1). In this case, X ^- is an anion derived from a quaternary agent.

In addition, in the partial structure represented by the above formula (1 '), the formula (1') as a whole is an adsorption group containing a fourth-order ammonium salt group. In addition, by connecting the partial structure shown in the formula (1 ') with another partial structure containing an adsorbing group or a partial structure containing an affinity medium, the partial structure shown in the formula (i) can be used to connect the formula (1'). The adsorption group shown is arranged in the main chain of the polyurethane dispersant (b-1).

Moreover, as another specific example, the partial structure shown below is mentioned. The entire structure below becomes an adsorbing group containing a nitrogen atom-containing heterocyclic group. The adsorption group containing a nitrogen atom-containing heterocyclic group exhibits an ionic bond with a pigment and a hydrophobic bond caused by a tightening effect. Therefore, it is considered to exert the same properties as a third-class amine group or a fourth-class ammonium salt group. Effect, showing good pigment adsorption.

In addition, by connecting the partial structure with other adsorbing group-containing partial structures or with an affinity medium-containing partial structure, the partial structure shown in the formula (i) above can be connected, and the adsorbing group shown in the partial structure can be arranged in a polymer structure. In the main chain of the urethane dispersant (b-1).

In the above formula, * represents a bonding group.

(Structure with adsorption base part 2)

As another preferable example, at least one partial structure represented by the following formulae (2-1) to (2-3) is preferable. By having at least one partial structure as shown in the following formulae (2-1) to (2-3), it has a three-dimensional obstacle to alleviate the adsorption portion, and can efficiently adsorb to the pigment by increasing the space freedom of the adsorption portion. Propensity.

In the formula (2-1), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent.

R ^γ , R ^δ and R ^ε each independently represent an alkylene group which may have a substituent, an arylene group which may also have a substituent, or a group in which the above-mentioned alkylene group is connected to the above-mentioned arylene group. Among them, when R ^γ is an alkylene group which may also have a substituent, or at least a part of the methylene group constituting the alkylene group may be selected from the group consisting of the alkylene group and the alkylene group connected through the alkylene group. At least one bond in the group consisting of ester bond, ether bond, urethane bond, urea bond, amidine bond, amidine bond, thiourethane bond, thioether bond, and thioester bond Was replaced. In addition, R ^γ may be urea-bonded together with at least one of the N atoms adjacent to each other via an -NH- (C = O)-group, or amido-bonded through a carbonyl group.

* Is the bonding base.

In formula (2-2), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^γ and R ^η each independently represent an alkylene group which may also have a substituent, and may also have a substituent An arylene group, or a group in which the above-mentioned alkylene group is connected to the above-mentioned alkylene group. Among them, when R ^γ and R ^η are each independently an alkylene group which may have a substituent, or a group in which the alkylene group and the alkylene group are connected, at least a part of the methylene group constituting the alkylene group is also It may be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, an amidine bond, an amidine bond, a thiourethane bond, a thioether bond, and a thioester bond. With at least 1 bond. Further, R ^γ and R ^η may be urea-bonded together with at least one of the N atoms adjacent to each other through an -NH- (C = O)-group, or amido-bonded through a carbonyl group.

* Is the bonding base.

In the formula (2-3), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent.

R ^{γ ′} and R ^δ each independently represent an alkylene group which may have a substituent, an alkylene group which may also have a substituent, or a group in which the aforementioned alkylene group is connected to the aforementioned alkylene group. Among them, when R ^{γ ′} is an alkylene group which may also have a substituent, or at least a part of the methylene group constituting the alkylene group may be selected by selecting the alkylene group which is connected to the alkylene group and the alkylene group via the alkylene group. At least one selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a sulfonium bond, a fluorenimine bond, a thiourethane bond, a thioether bond, and a thioester bond. Key. In addition, R ^{γ ′} may be urea-bonded with an adjacent N atom via an -NH- (C = O)-group, or amido via a carbonyl group.

R ^{ε ′} represents a direct bond, an alkylene group which may have a substituent, an alkylene group which may have a substituent, or a group in which the aforementioned alkylene group is connected to the aforementioned alkylene group.

R ^ζ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may also have a substituent. Among them, when R ^ζ is an alkyl group or an aryl group, at least one of its hydrogen atoms may be substituted by a tertiary amine group or a nitrogen atom-containing heterocyclic group.

* Is the bonding base.

In the above formulae (2-1) to (2-3), the carbon number of the alkyl group of R ^α , R ^β and R ^ζ is not particularly limited, but it is usually 1 or more, preferably 20 or less, and more preferably 10 Below, and even more preferably, it is 2 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. From the viewpoint of dispersibility, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, or a cyclohexyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

The carbon number of the aryl group of R ^α , R ^β and R ^ζ is not particularly limited, but it is usually 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenyl, naphthyl, and the like. From the viewpoint of dispersibility, phenyl is preferred.

R ^α and R ^β may be the same or different, and are preferably the same from the viewpoint of dispersibility.

The substituent which the alkyl group and aryl group may have is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as methyl, ethyl, propyl, and cyclohexyl; an aryl group such as phenyl; and benzyl Aralkyl and the like.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a hydroxyl group, a methyl group, or an ethyl group is preferable from the viewpoint that the adsorption of the pigment is not hindered by an intermolecular steric hindrance.

From the viewpoint of dispersibility, it is preferable that R ^α and R ^β are each independently an alkyl group. From the viewpoint of dispersibility, R ^{ζ is} preferably a hydrogen atom or an alkyl group.

In the above formulae (2-1) to (2-3), the number of carbons of the alkylene group which may have a substituent in R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε', and R ^η is not particularly limited. The limitation is usually 1 or more, preferably 2 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

The alkylene may be chain or cyclic, and may also be a chain-shaped alkylene and a cyclic alkylene connected through. From the viewpoint of dispersibility, a chain-like alkylene is preferred.

Specific examples include methylene, dimethylene, trimethylene, tetramethylene, cyclopentylmethylene, cyclohexylmethylene, cyclohexyldimethylene, and cyclomethylene Hexyltrimethylene and the like. From the viewpoint of dispersibility, methylene, dimethylene, or trimethylene is preferable, and dimethylene or trimethylene is more preferable.

When R ^γ , R ^{γ ′} , R ^δ , R ^ε , R ^{ε ′} and R ^η are alkylene groups which may have a substituent, the specific structures of the above formulae (2-1) to (2-3), Examples include the following structures.

In the above formulae (2-1) to (2-3), R ^γ , R ^{γ ′} , R ^δ , R ^ε , R ^{ε ′} and R ^η may also have an alkylene group which may have a substituent, and may also have a substituent. The number of carbons of the radical to which the aryl group of the base is connected is not particularly limited, but is usually 6 or more, preferably 7 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. The number of alkylene groups is not particularly limited, but is preferably 3 or less from the viewpoint of dispersibility.

Specifically, for example, one alkylene group which may have a substituent and one alkylene group which may have a substituent are connected; two alkylene groups which may have a substituent may be 1 alkylene group having a substituent; 2 alkylene groups which may have a substituent; 2 alkylene groups which may have a substituent; 1 alkylene group which may have a substituent; and The group is a group in which an arylene group which may have a substituent is alternately connected.

Specific examples of the group in which the above-mentioned alkylene group is connected to the above-mentioned aromatic group include the following.

Among these, from the viewpoint of dispersibility, a base represented by the above formula (b3) is preferred.

When at least any one of R ^γ , R ^{γ ′} , R ^δ , R ^ε , R ^{ε ′} and R ^η is a base through which the above-mentioned alkylene group and the above-mentioned aromatic group are connected, the above formula (2-1) ~ Specific structures of (2-3) include the following structures, for example.

Among these, from the viewpoint of dispersibility, it is preferably (2-1-b), (2-2-b), (2-3-b), etc., and R ^γ or R ^{γ '} is The alkylene group which may have a substituent and the alkylene group which may have a substituent are connected. In this case, from the viewpoint of dispersibility, it is preferable that R ^δ , R ^ε , R ^{ε ′,} and R ^η are alkylene groups.

In the above formulae (2-1) to (2-3), the number of carbon atoms of the arylene group which may have a substituent in R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε', and R ^η is not particularly limited. The limitation is usually 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenylene and naphthyl. From the viewpoint of dispersibility, phenylene is preferred.

As a specific structure of the above formulae (2-1) to (2-3) when at least any one of R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε' and R ^η is an aryl group, it may be The following structures are listed, for example.

Among these, from the viewpoint of dispersibility, it is preferably (2-1-c), (2-2-c), (2-3-c), etc., and R ^γ or R ^{γ '} is Fang Fang Ji who.

In the above formulae (2-1) to (2-3), as the alkylene group, alkylene group, alkylene group and alkylene group of R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε' and R ^η The substituents which the group to which the group is linked are not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, and cyclohexyl; aryl groups such as phenyl; aralkyl groups such as benzyl;

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, More preferably, it is 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a methyl group is preferable from a viewpoint of easy handling and dispersibility.

As described above, when R ^γ , R ^{γ ′,} and R ^η are each independently an alkylene group which may have a substituent, or a group in which the alkylene group and the alkylene group are connected, the subalkylene group is constituted. At least a part of the methyl group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a fluorene amine bond, a fluorene imine bond, a thiourethane bond, a thioether bond, and a sulfur At least one bond in the group of ester bonds is substituted. Among these, from the viewpoint of dispersibility, preferred linkages include those in which at least a part of the methylene group constituting the above-mentioned alkylene group is substituted with a urethane bond or an ester bond.

Specific structures of the above formulae (2-1) to (2-3) at this time include, for example, the following structures.

[Chemical 22]

Especially from the viewpoint of dispersibility, it is preferable that R ^γ of the above formula (2-1) is a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected and constitute a part of the methylene group of the alkylene group. It is the one represented by the above formula (2-1-d ') substituted by a urethane bond.

From the viewpoint of dispersibility, it is preferable that R ^γ and R ^{η in the} above formula (2-2) are alkylene groups, and that at least a part of the methylene groups constituting at least any of the alkylene groups is as follows: The above formula (2-2-d) or (2-2-d ') is substituted by an ester bond.

From the viewpoint of dispersibility, the formula (2-3) in which any of R ^{γ ′} , R ^δ and R ^{ε ′ in} the above formula (2-3) is an unsubstituted alkylene group is preferred. -a) like those. In addition, R ^{γ ′} of the above formula (2-3) is preferably an alkylene group, or a group in which the aforementioned alkylene group is connected to the aforementioned aromatic group, and the methylene group constituting the alkylene group is preferably used. One part is one of the above formula (2-3-d) or (2-3-d ') substituted by a urethane bond, a thiourethane bond, an ester bond, or a thioether bond.

As described above, R ^γ may be urea-bonded together with at least one of the N atoms adjacent to each other via an -NH- (C = O)-group, or amido-bonded through a carbonyl group.

In particular, from the viewpoint of dispersibility, it is preferable that R ^γ of the above formula (2-1) together with the N atom bonded to R ^δ and R ^ε be urea bond via the -NH- (C = O)-group. Knot. Specific examples of the above formulae (2-1) and (2-2) include the following structures.

In addition, as described above, R ^{γ ′} may be urea-bonded with an adjacent N atom via an -NH- (C = O)-group, or amido-bond via a carbonyl group. Specific examples of the above formula (2-3) include the following structures.

Similarly, R ^η may be urea-bonded with an adjacent N atom via an -NH- (C = O)-group, or amidine via a carbonyl group. Specific examples of the above formula (2-2) include the following structures.

[Chemical 25]

When R ^ζ is an alkyl group or an aryl group, at least one of its hydrogen atoms may be substituted by a tertiary amine group or a nitrogen atom-containing heterocyclic group. Specific examples of the above formula (2-3) include the following structures.

In the above formulae (2-1) to (2-3), from the viewpoint of dispersibility, the following are preferred.

In the above formula (2-1), R ^{γ is} preferably a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected; in this case, it is preferable that at least a part of the methylene group constituting the above-mentioned alkylene group is via an amine group. Ethyl formate bond is substituted, or urea bond is carried out together with adjacent N atom via -NH- (C = O)-group. In this case, R ^δ and R ^{ε are} preferably alkylene groups. As such a specific example, the following formula (2-1-e) is mentioned.

[Chemical 27]

Further, in the above formula (2-1), R ^{γ is} preferably an alkylene group; in this case, at least a part of the methylene group constituting the alkylene group is preferably substituted by an ester bond. In this case, R ^δ and R ^{ε are} preferably alkylene groups. As such a specific example, the following formula (2-1-d) is mentioned.

In the above formula (2-2), R ^{γ is} preferably a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected; in this case, it is preferable that at least a part of the methylene group constituting the above-mentioned alkylene group is by Substituted by urethane bond or urea bond with adjacent N atom via -NH- (C = O)-group. In this case, R ^{η is} preferably an alkylene group. As such a specific example, the following formula (2-2-e) is mentioned.

In the above formula (2-2), R ^{γ is} preferably an alkylene group; in this case, it is preferable that at least a part of the methylene group constituting the alkylene group is substituted by an ester bond. In this case, R ^{η is} preferably an alkylene group. As such a specific example, the following formula (2-2-d) is mentioned.

[Chemical 30]

In the above formula (2-2), R ^{γ is} preferably an alkylene group. In this case, R ^{η is} preferably an alkylene group; at least a part of the methylene group constituting the alkylene group is preferably substituted by an ester bond. Such a specific example is given by the following formula (2-2-d ').

In the above formula (2-3), R ^{γ ′} and R ^{δ are} preferably alkylene groups, and R ^{ε ′ is} preferably a direct bond or an alkylene group; in this case, R ^{ζ is} preferably a hydrogen atom. As such a specific example, the following formula (2-3-a) is mentioned.

Furthermore, in the above formula (2-3), R ^{γ ′ is} preferably a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected; in this case, it is preferably at least a part of the methylene group constituting the above-mentioned alkylene group. Substituted by a urethane bond and / or a thiourethane bond. In this case, R ^{δ is} preferably an alkylene group, and R ^{ε ′ is} preferably directly bonded. R ^{ζ is} preferably a hydrogen atom. As such a specific example, the following equation (2-3-d) can be mentioned.

[Chemical 33]

In the above formula (2-3), R ^{γ ′ is} preferably an alkylene group; at this time, it is preferable that at least a part of the methylene group constituting the alkylene group is replaced by an ester bond and a thioether bond. . In this case, R ^{δ is} preferably an alkylene group, and R ^{ε ′ is} preferably a direct bond. R ^{ζ is} preferably a hydrogen atom. As such a specific example, the following formula (2-3-d ') is mentioned.

In addition, R ^α , R ^β , N and R ^γ in the above formula (2-1) become an adsorption group containing a tertiary amine group. Similarly, R ^α , R ^β , N and R ^γ in the above formula (2-2) become an adsorption group containing a tertiary amine group. In addition, R ^α , R ^β , N and R ^{γ ′} in the above formula (2-3) are adsorbing groups containing a tertiary amine group. In these cases, * in the formula represents a bonding group in the polyurethane skeleton with a carbonyl group of a urethane bond or a urea bond.

In addition, the partial structure shown in the above formula (i) is obtained by combining the partial structure shown in the above formulae (2-1) to (2-3) with other structures containing an adsorbing group or a structure containing a soluble solvent group. The connection can be made by binding the adsorption group contained in the formulae (2-1) to (2-3) and the main chain of the polyurethane dispersant (b-1).

In addition, as another preferable example, it is preferable to have a partial structure represented by the following formulae (2-1 ') to (2-3').

[Chemical 35]

In the formula (2-1 '), R ^α to R ^ε and * have the same meanings as those in the formula (2-1). R ^A and X ^- have the same meanings as those in formula (1 ').

In the formula (2-2 '), R ^α to R ^η and * have the same meanings as those in the formula (2-2). R ^A and X ^- have the same meanings as those in formula (1 ').

In the formula (2-3 '), R ^α ~ R ^ζ and * have the same meanings as in the formula (2-3). R ^A and X ^- have the same meanings as those in formula (1 ').

Moreover, as another specific example, the partial structure shown below is mentioned. In the following partial structure, a heterocyclic group containing a nitrogen atom becomes an adsorbing group.

[Chemical 38]

In the above formula, * represents a bonding group.

Rather than having a specific adsorption group in the polyurethane backbone of the main chain, it is preferably a pendant type in which the polyurethane is present in the backbone of the main chain in a side chain type. The nitrogen atom in the particularly preferred adsorption group is bonded by at least one atom via the closest atom on the main polyurethane skeleton. That is, it is preferably an adsorption group bonded to the main chain.

More preferably, the nitrogen atom in the specific adsorption group is at least 2 atoms separated by the closest atom on the polyurethane backbone of the main chain. The nitrogen atom of the radical is at least 3 atoms separated by the closest atom on the polyurethane backbone of the main chain.

The nitrogen atom in the adsorbing group is preferably separated by 20 atoms or less from the closest atom on the polyurethane skeleton of the main chain, and more preferably by 10 atoms or less. Hereinafter, the number of atoms between the closest atom on the polyurethane skeleton of this main chain and the nitrogen atom of a specific adsorbing group may be referred to as "the number of intervening atoms".

For example, when having a partial structure of the above formula (2-3-a), the nitrogen atom in the adsorbing group is as follows, with one carbon atom separated by a methine group in the polyurethane skeleton. Carbon atomist.

(Content ratio of the structure containing the adsorption group)

The polyurethane dispersant (b-1) can be used, for example, as the one having the above-mentioned structure containing an adsorbing group portion, one having one type of the structure containing the above adsorption group portion, or two or more types.

For example, all the adsorption groups can be made into a partial structure containing a third-order amine group, and all the adsorption groups can be similarly made into a partial structure containing a fourth-order ammonium salt group, or all the adsorption groups can be made into a Partial structure of heterocyclic group.

From the viewpoint of dispersibility and compatibility, it is preferred that all the adsorbing groups are tertiary amine groups. In this case, it is possible to prepare one having two or more tertiary amine groups. From the viewpoint of the viewpoint, it is preferable to have one kind of tertiary amine group, and it is more preferable to have a tertiary amine group-containing partial structure selected from any one of the above formulae (1) and (2-1) to (2-3). Still more preferably, it has a tertiary amine group-containing partial structure represented by formula (2-1).

On the other hand, from the viewpoint of the development solubility of the alkali developer, it is preferable that all the adsorbing groups are quaternary ammonium salt groups. Among them, the level 4 ammonium salt can be prepared by level 4 ammonium saltation of the level 3 amine group by the level 4 agent. However, if the level 4 ammonium saltation is performed on all the level 3 amine groups, there are Since a lot of impurities of chemical agents tend to be generated, from the viewpoint of suppressing the generation of impurities, most of the tertiary amine groups remain, and the tertiary amine groups and the tertiary ammonium salt groups coexist.

Therefore, it is preferable to have both a tertiary amine group and a tertiary ammonium salt group as an adsorption group. From the viewpoint of efficiency of production, it is more preferable to select from the combination of the above formulae (1) and (1 '). , The combination of the above formulae (2-1) and (2-1 '), the combination of the above formulae (2-2) and (2-2'), and the above formulae (2-3) and (2-3 ') Any one of the combinations; more preferably a combination of the above formulae (2-1) and (2-1 ').

In the case of having both a tertiary amine group and a tertiary ammonium salt group, the content ratio is not particularly limited. From the standpoint of dispersibility, the partial structure containing a tertiary ammonium salt group is relative to a tertiary amine group The content of the partial structure is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and more preferably 99 mol% or less, more preferably 95 mol. Earn% or less, more preferably 80 mole% or less, still more preferably 60 mole% or less, particularly preferably 40 mole% or less, and most preferably 30 mole% or less.

Similarly, from the viewpoint of dispersibility, the content ratio of the structure containing the adsorption group portion in the polyurethane dispersant (b-1) is preferably 5% by mass or more, and more preferably 10% by mass or more. And more preferably 20% by mass or more, and more preferably 90% by mass Below, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less.

The content ratio of the specific adsorption group is preferably 0.001 mol or more, more preferably 0.01 mol or more, and still more preferably 0.05 mol relative to 100 g of the polyurethane dispersant (b-1). Above the ears, and preferably below 0.8 moles, more preferably below 0.4 moles, even more preferably below 0.2 moles. Hereinafter, the ratio of the specific adsorption group to 100 g of the polyurethane dispersant (b-1) is referred to as a specific adsorption group content, and is expressed in a unit of "Mole / 100 g".

(Solvent-based)

Polyurethane dispersant (b-1) contains a hydrophilic vehicle group. The kind of the hydrophilic vehicle group which the polyurethane dispersant (b-1) has is not specifically limited if it shows the compatibility with a solvent. From the viewpoint of dispersibility, the soluble vehicle group preferably contains at least one of a polyether chain and a polyester chain. When the polyurethane dispersant (b-1) has a main chain, from the viewpoint of dispersibility, the more compatible solvent group preferably contains at least one of a polyether chain and a polyester chain. , And those who are bonded to the main chain.

Polyurethane dispersant (b-1) preferably has a structure containing a hydrophilic solvent-containing moiety containing the above-mentioned solvent-soluble medium group; as described above, from the viewpoint of dispersibility, it is preferably a structure containing a hydrophilic solvent-containing moiety. The structures of the adsorption-group-containing partial structure and the solvent-containing medium-containing partial structure are connected to each other by the partial structure shown in the above formula (i).

There is no particular limitation on the specific partial structure of the partial structure containing the solvent-based group, and the partial structures shown by the following formulae (3-1) to (3-3) are preferred. In the formulae (3-1) to (3-3), R ^θ and the O atom are lyophilic mediators, and other than that, they are bonding portions with the solitary mediators.

[Chemical 40]

In the formula (3-1), R ^θ represents a polyether chain and / or a polyester chain.

R ^γ , R ^δ and R ^ε each independently represent an alkylene group which may have a substituent, an arylene group which may also have a substituent, or a group in which the above-mentioned alkylene group is connected to the above-mentioned arylene group. Among them, when R ^γ is an alkylene group which may also have a substituent, or at least a part of the methylene group constituting the alkylene group may be selected from the group consisting of the alkylene group and the alkylene group connected through the alkylene group. At least one bond in the group consisting of ester bond, ether bond, urethane bond, urea bond, amidine bond, amidine bond, thiourethane bond, thioether bond, and thioester bond Was replaced. In addition, R ^γ may be urea-bonded with an adjacent N atom via an -NH- (C = O)-group, or amido-bond via a carbonyl group.

In addition, R ^γ may be urethane-bonded with an adjacent O atom via an -NH- (C = O)-group, or ester-bonded via a carbonyl group.

* Indicates a bonded base.

In the formula (3-2), R ^θ represents a polyether chain and / or a polyester chain.

R ^γ and R ^η each independently represent an alkylene group which may have a substituent, an alkylene group which may also have a substituent, or a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected. Among them, when R ^γ and R ^η are each independently an alkylene group which may have a substituent, or a group in which the alkylene group and the alkylene group are connected, at least a part of the methylene group constituting the alkylene group is also It may be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, an amidine bond, an amidine bond, a thiourethane bond, a thioether bond, and a thioester bond. Of at least 1 bond. In addition, R ^γ and R ^η may be urea-bonded together with an adjacent N atom via an -NH- (C = O)-group, or amido via a carbonyl group.

In addition, R ^γ may be urethane-bonded with an adjacent O atom via an -NH- (C = O)-group, or ester-bonded via a carbonyl group.

* Indicates a bonded base.

In the formula (3-3), R ^θ represents a polyether chain and / or a polyester chain.

R ^{γ ′} and R ^δ each independently represent an alkylene group which may have a substituent, an alkylene group which may also have a substituent, or a group in which the aforementioned alkylene group is connected to the aforementioned alkylene group. Among them, when R ^{γ ′} is an alkylene group which may also have a substituent, or at least a part of the methylene group constituting the alkylene group may be selected by selecting the alkylene group which is connected to the alkylene group and the alkylene group via the alkylene group. At least one selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a sulfonium bond, a fluorenimine bond, a thiourethane bond, a thioether bond and a thioester bond Key.

In addition, R ^{γ ′} may be urethane-bonded with an adjacent O atom via an -NH- (C = O)-group, or may be ester-bonded via a carbonyl group.

R ^{ε ′} represents a direct bond, an alkylene group which may have a substituent, an arylene group which may also have a substituent, or a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected.

R ^{ζ ′} represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may also have a substituent. When R ^{ζ ′} is an alkyl group which may have a substituent or an aryl group which may also have a substituent, at least one of its hydrogen atoms may be substituted by R ^θ -OR ^{γ '} -.

* Indicates a bonded base.

The number of carbons of the alkylene group which may also have a substituent among R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε' and R ^η is not particularly limited, but it is usually 1 or more, preferably 2 or more, and It is preferably 20 or less, more preferably 15 or less, and even more preferably 7 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, cyclopentylmethylene, and cyclohexyl Methylene, cyclohexyldimethylene, cyclohexyltrimethylene, etc .; from the viewpoint of dispersibility, dimethylene, trimethylene, tetramethylene, pentamethylene, Or hexamethylene, more preferably trimethylene, tetramethylene or pentamethylene.

In the above formulae (3-1) to (3-3), the carbon of the above-mentioned alkylene group and the above-mentioned alkylene group of R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε' and R ^η are connected The number is not particularly limited, but it is usually 6 or more, preferably 7 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. The number of alkylene groups is not particularly limited, but is preferably 3 or less from the viewpoint of dispersibility.

Specifically, for example, one alkylene group which may have a substituent and one alkylene group which may have a substituent are connected; two alkylene groups which may have a substituent may be One alkylene group having a substituent is connected; two alkylene groups which may have a substituent are connected via one alkylene group which may have a substituent. Specific examples of the group in which the above-mentioned alkylene group is connected to the above-mentioned aromatic group include groups represented by the above formulae (b1) to (b5).

The number of carbons of the arylene group which may also have a substituent in R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^ε', and R ^η is not particularly limited, but it is usually 6 or more, and preferably 30 or less, more It is preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenylene and naphthyl. From the viewpoint of dispersibility, phenylene is preferred.

Among these, from the viewpoint of dispersibility, it is preferable that R ^γ and R ^{γ ′} are an alkylene group, an alkylene group, or a group in which the aforementioned alkylene group and the aforementioned alkylene group are connected; preferably, R ^δ , R ^ε , R ^{ε ′} and R ^η are alkylene groups.

In the above formulae (3-1) to (3-3), R ^γ , R ^{γ ′} , R ^δ , R ^ε , R ^{ε ′,} and R ^η may have an alkylene group which may have a substituent, or may have a substituent. The aryl group of the radical, the substituent which the above-mentioned alkylene group and the above-mentioned alkylene group may be connected to are not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, and cyclohexyl; phenyl and the like Aryl; aralkyl, etc. of benzyl.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, in terms of ease of handling and dispersibility, an alkyl group is preferred, and a methyl group is more preferred.

As described above, when R ^γ , R ^{γ ′,} and R ^η are each independently an alkylene group which may have a substituent, or a group in which the alkylene group and the alkylene group are connected, the subalkylene group is constituted. At least a part of the methyl group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a fluorene amine bond, a fluorene imine bond, a thiourethane bond, a thioether bond, and a sulfur At least one bond in the group of ester bonds is substituted.

Among these, from the viewpoint of dispersibility, as preferable bonds, R ^γ may include urethane bonds or ester bonds; R ^{γ ′} may include thiourethane bonds and amines. Urethane bond or ester bond. In addition, R ^η is preferably unsubstituted. In particular, from the viewpoint of dispersibility, it is preferable that R ^γ of the above formulae (3-1) and (3-1) is an alkylene group, or a group in which the aforementioned alkylene group and the aforementioned aromatic group are connected and constitute A part of its methylene group is substituted by a urethane bond or an ester bond. Specific examples thereof include the following.

In addition, in the above formula (3-3), R ^{γ ′} is a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected, and a part of the methylene group constituting the alkylene group is via urethane Bond and / or thiourethane bond substitution. Specific examples thereof include the following.

In addition, as described above, R ^γ and R ^η may be independently bonded to each other via a -NH- (C = O)-group with an adjacent N atom, or to a amide bond through a carbonyl group.

Among these, from the viewpoint of dispersibility, it is preferable that R ^γ is urea-bonded together with the adjacent N atom via the -NH- (C = O)-group as a preferred bond. ; And, in R ^η , those which are not bonded with the adjacent N atom are preferable.

In addition, R ^γ and R ^{γ ′} may be independently bonded to each other via an -NH- (C = O)-group with an adjacent O atom, or through an carbonyl group to perform esterification. Bonding.

In particular, from the viewpoint of dispersibility, R ^{γ in the} above formulae (3-1) and (3-2) is preferably an alkylene group or an arylene group, and is via an -NH- (C = O)-group. Urea bonding is performed with adjacent N atoms. In addition, it is preferable to perform urethane bonding with an adjacent O atom via an -NH- (C = O)-group, or to perform ester bonding via a carbonyl group. Specific examples thereof include the following.

In the above formula (3-3), R ^{γ ′} is a group in which the above-mentioned alkylene group and the above-mentioned alkylene group are connected, and a part of the methylene group constituting the alkylene group is thioaminoformate. Ester bond substitution, or urea bonding with an adjacent O atom via the -NH- (C = O)-group. Specific examples thereof are listed below.

[Chemical 46]

R ^ζ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may also have a substituent. However, when R ^{ζ ′} is an alkyl group or an aryl group, at least one of its hydrogen atoms may be substituted by R ^θ -OR ^{γ '} -.

The carbon number of the alkyl group in R ^{ζ ′} is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 20 or less, more preferably 10 or less, and even more preferably 6 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. From the viewpoint of dispersibility, methyl, ethyl, propyl, cyclopentyl, or cyclohexyl is preferred, methyl, ethyl or cyclohexyl is more preferred, and methyl or cyclohexyl is even more preferred.

The carbon number of the aryl group of R ^{ζ ′} is not particularly limited, but it is usually 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable. Specific examples include phenyl, naphthyl, and the like. From the viewpoint of dispersibility, phenyl is preferred.

The substituent which the alkyl group and aryl group may have is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as methyl, ethyl, propyl, and cyclohexyl; an aryl group such as phenyl; and benzyl Aralkyl and the like.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples can be listed Examples are methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a hydroxyl group, a methyl group, or an ethyl group is preferable from the viewpoint of suppressing the blocking of the adsorption of the pigment.

And the ^R ζ ^'in terms of a viewpoint of dispersibility, ^{R ζ'} is preferably a hydrogen atom.

Examples of the polyether chain of R ^θ include those represented by the following formula (3-4). Examples of the polyester chain include those represented by the following formula (3-5) or (3-6).

In the above formula (3-4), R ^b represents an alkyl group which may have a substituent, and R ^c represents an alkylene group which may also have a substituent. n represents an integer from 1 to 100. * Indicates a bonding group with an adjacent O atom.

In the above formulae (3-5) and (3-6), R ^{b ′} represents an alkyl group which may have a substituent, and R ^{c ′} represents an alkylene group which may also have a substituent. n represents an integer from 1 to 100. * Indicates a bonding group with an adjacent O atom.

The carbon number of the alkyl group of R ^b is not particularly limited, but is usually 1 or more, and preferably 50 or less, more preferably 10 or less, and even more preferably 6 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. From the viewpoint of dispersibility, methyl, ethyl, propyl, or butyl is preferred, methyl or ethyl is more preferred, and methyl is even more preferred.

The substituent which the alkyl group may have is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as methyl, ethyl, propyl, and cyclohexyl; an aryl group such as phenyl; and an arane group such as benzyl Base etc.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a hydroxyl group, a methyl group, or an ethyl group is preferable from the viewpoint of a benefit to alkali developability, or a benefit to substrate adhesion.

The number of carbons of the alkylene group in R ^c is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 7 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

Specifically, for example, methylene, ethylene, propyl, isopropyl, butylene, cyclopentylmethylene, cyclohexylmethylene, cyclohexylethylene, and Cyclohexyl and propyl. From the viewpoint of dispersibility, methylene, ethylidene, propylidene, isopropylidene, or butylidene is preferred, and ethylidene, propylidene, or butylidene is more preferred Isopropyl.

The substituent which the alkylene group may have is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as methyl, ethyl, propyl, and cyclohexyl; an aryl group such as phenyl; and an arane group such as benzyl Base etc.

The carbon number of the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, and cyclohexyl.

Moreover, the carbon number of the said aryl group is not specifically limited, It is preferably 6-20, More preferably, it is 6-10. Specific examples include phenyl and naphthyl.

The carbon number of the aralkyl group is not particularly limited, but is preferably 7 to 20, and more preferably 7 to 10. Specific examples include benzyl and the like.

Among these, a hydroxyl group, a methyl group, or an ethyl group is preferable from the viewpoint of a benefit to alkali developability, or a benefit to substrate adhesion.

n is an integer of 1 to 100, but from the viewpoint of dispersibility, it is preferably 4 or more, more preferably 6 or more, and more preferably 60 or less, and more preferably 40 or less.

The carbon number of the alkyl group of R ^{b ′} is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 50 or less, and more preferably 40 or less.

The carbon number of the alkyl group of R ^{b ′} may also be changed depending on the polarity of the solvent (e) contained in the photosensitive resin composition. When the solvent (e) is a polar solvent, the carbon number of the alkyl group of R ^{b ′} is preferably 1 or more and 12 or less. On the other hand, when the solvent (e) is a non-polar solvent, the carbon number of the alkyl group of R ^{b ′} is preferably 9 or more and 30 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

Specifically, when the solvent (e) is a polar solvent, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, and nonane-1-yl are preferred. , Decane-1-yl, undecane-1-yl, or dodecane-1-yl.

When the solvent (e) is a non-polar solvent, octyl, nonane-1-yl, decane-1-yl, undecane-1-yl, dodecane-1-yl, and tridecane are preferred. 1-yl, tetradecane-1-yl, pentadec-1-yl, fluoren-1-yl or triadec-1-yl.

In the case of a polar solvent such as propylene glycol methyl ether acetate, decane-1-yl, undecane-1-yl, dodecane-1-yl, or tridecane-1 is preferred. -base.

The substituent which the alkyl group may have is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as methyl, ethyl, propyl, and cyclohexyl; an aryl group such as phenyl; and an arane group such as benzyl Base etc. From the standpoint of a benefit to alkali developability or a close adhesion to a substrate, a hydroxyl group, a methyl group, or an ethyl group is preferred.

The carbon number of the alkylene group in R ^{c ′} is not particularly limited, but it is usually 1 or more, preferably 2 or more, and preferably 50 or less, more preferably 35 or less, and still more preferably 26 or less.

In addition, the carbon number of the alkylene group of R ^{c ′} may be changed depending on the polarity of the solvent (e) contained in the photosensitive resin composition. When the solvent (e) is a polar solvent, the carbon number of the alkyl group of R ^{c ′} is preferably 1 or more and 8 or less. On the other hand, when the solvent (e) is a non-polar solvent, the carbon number of the alkyl group of R ^{c ′} is preferably 9 or more and 26 or less. If it is in the said range, there exists a tendency for dispersibility to be favorable.

Specifically, when the solvent (e) is a polar solvent, it is preferably methylene, ethylene, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, or Octyl (or octamethylene).

When the solvent (e) is a non-polar solvent, it is preferably octamethylene, decamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecyl methylene Methylene, pentamethylene, fluorene methylene, or trimethylene. Depending on the polarity of the solvent, it is better The combination of these.

In the case of a polar solvent such as propylene glycol methyl ether acetate, propylene, butyl, pentyl or hexyl is preferred.

As such, a polyester chain represented by the above formula (3-5) or (3-6) as R ^{θ can} be cited, but from the viewpoint of ease of synthesis, it is preferably represented by the above formula (3-5) By.

In addition, in the case where the polyurethane dispersant (b-1) has a main chain, the formulae (3-1) to (3-3) are an affinity medium group bonded to the main chain, where * in the formula represents Bonding group with carbonyl group of urethane bond or urea bond in polyurethane backbone of main chain.

(Content ratio of the solvent-based group)

The polyurethane dispersant (b-1) can be used, for example, as the one having the above-mentioned solvent-containing-medium-group-containing structure, or as the one having one of the above-mentioned hydrophilic-medium-group-containing structure, or two or more of them. In particular, when having a structure containing a hydrophilic solvent-containing moiety having a polyether chain and a structure containing a hydrophilic solvent-containing moiety having a polyester chain at the same time, the dispersion effect is further increased, which is preferable.

The mass ratio of the structure of the hydrophilic-medium-containing part having a polyester chain to the structure of the hydrophilic-medium-containing part having a polyether chain is preferably 1/99 or more, more preferably 3/97 or more, and still more preferably 5 / 95 or more, and preferably 99/1 or less, more preferably 97/3 or less, and even more preferably 95/5 or less.

From the viewpoint of dispersibility, the polyurethane dispersant (b-1) preferably has a partial structure selected from any one of the above formulae (3-1) to (3-3), and more preferably has Partial structure shown by formula (3-1).

Similarly, from the viewpoint of dispersibility, the content ratio of the hydrophilic vehicle-group-containing portion structure in the polyurethane dispersant (b-1) is preferably 5% by mass or more, It is more preferably 10% by mass or more, even more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, most preferably 50% by mass or more, and more preferably 90% by mass or less It is more preferably 80% by mass or less, and even more preferably 70% by mass or less.

The polyurethane dispersant (b-1) may have other functional groups in addition to the solvent-soluble group and the adsorbing group. Examples of the other functional group include an active energy ray-curable unsaturated group. Specific examples include unsaturated groups such as a vinyl group, an acrylfluorenyl group, and a methacrylfluorenyl group.

In this way, it is considered that by having an active energy ray-curable unsaturated group, the sensitivity tends to be increased when a photosensitive composition is formed; on the other hand, it is considered that these functional groups react to cause gelation during dispersion From the viewpoint of pigment dispersion in consideration of stability over time, it is preferable that the active energy ray-hardening unsaturated group is not included.

(Reason for effectiveness) <Dispersion improvement effect>

The polyurethane dispersant (b-1) used in the present invention is characterized by containing a partial structure represented by the above formula (i). By including the partial structure shown in the above formula (i), a solvent-soluble or ionic group, especially a structure containing a lyophilic medium group or an absorbing-group-containing structure can be arranged on a straight line, and the compatibility with the solvent is considered to be improved. And the adsorption of the whole pigment. In addition, the nitrogen atom in the urethane bonding site also contributes to the adsorption of the pigment, and it is considered that the multiplying effect with the adsorption group makes the pigment adsorption more favorable.

In particular, in the case where the hydrophilic solvent group is a group containing a polyether chain and / or a polyester chain, the solvent and the solvent (e) in the photosensitive resin composition are compatible with each other and spread in the solvent. The pigment will agglomerate, and it will become a three-dimensional obstacle. The tendency to prevent the function of pigment aggregation.

In addition, if the polarity of the polyether chain and the polyester chain is constituted in such a manner that the polarity of the solvent or the polarity of the alkali-soluble resin (d) or the photopolymerizable monomer described later is incorporated in the photosensitive resin composition, the chain portion is easier for the solvent The effect of medium expansion and steric hindrance becomes larger, and there is a tendency of good dispersion.

Particularly preferred are both a hydrophilic vehicle group with a polyether chain and a hydrophilic vehicle group with a polyester chain. It can be considered that by having these two, it is easy to adjust the polarity of the solvent-based group to match the polarity of the solvent. The tendency to keep the dispersed state stably after time.

Furthermore, the adsorption group is preferably a polyurethane skeleton far from the main chain. It is considered that when the specific adsorption group is kept away from the linear polyurethane frame, the steric hindrance at the time of pigment adsorption is reduced, and the pigment adsorption tends to be further improved.

<Formation of high fine lines due to improvement in resistance to alkali development treatment and heat resistance>

By using a photosensitive resin composition containing a polyurethane dispersant (b-1), a high-definition color filter for use in a tablet computer, a high-definition display, etc. can be produced, especially for alkalis. In the step of development or high-temperature processing, fine high-fine lines can be formed stably.

In order to form fine fine lines stably, the shape of the fine lines must be formed stably during alkali development, and the shape of the thin lines must be kept stable during the subsequent hardening step by a high-temperature heat treatment of 200 ° C or higher.

It is considered that the photosensitive resin composition containing a polyurethane dispersant (b-1) has a resistance to an alkali developer due to strong adsorption between the pigment and the dispersant. It is high, so when the alkali is developed after ultraviolet irradiation, the fine thin lines that are temporarily formed are even in the case of further immersion in the alkali developing solution, the fine threads can still prevent the developing solution from penetrating to the part that is closely adhered to the substrate. It can prevent the occurrence of indentation, peeling, and deformation of the wedge shape caused by erosion. In addition, it is considered that even when the high-temperature treatment is performed at 200 ° C. or higher for hardening after development, the adsorption between the pigment and the dispersibility is not weakened and the thermal deformation is small, so that the fine fine line shape can be stably maintained.

It is considered that the polyurethane dispersant (b-1) has a partial structure represented by the above formula (i), and therefore, as described above, it is easily adsorbed to the entire pigment, and is bonded to a urethane bond or an adsorption group. The strong adsorption between the part and the pigment can coat the pigment.

In particular, when a compatible solvent group is used which contains a polyether chain and / or a polyester chain, the compatible solvent group has a function of expanding toward the outer side of the pigment, and is soluble in alkali in the step of manufacturing a color filter. The resin and the photopolymerizable monomer crosslinked by ultraviolet rays tend to be compatible and entangled.

In this way, it is considered that the resistance to the alkali developer and the resistance to high-temperature processing can be improved by the pigment adsorption and solvent affinity of the polyurethane dispersant (b-1). In particular, it is effective in a photosensitive resin composition in which it is difficult for ultraviolet rays to reach a deep part, and the hardening of the deep part is weak, and the content ratio of pigments such as carbon black is high.

In particular, the oxime ester photopolymerization initiator (c-1), which has both light absorption and free radical generation as a photopolymerization initiator (c) to be described later, has a high sensitivity in a small amount, and In the case where the urethane dispersant (b-1) is used in combination, it is considered that the photopolymerizable monomer or the alkali-soluble resin can promote cross-linking caused by ultraviolet irradiation, and these are dispersed with the polyurethane The entanglement between the solvent-soluble solvent groups becomes stronger, improves the alkali-resistant developing property and heat resistance, and forms a fine and fine line shape stably.

Especially when using resins which contain more aromatic rings as alkali soluble In the case of flexible resins, due to the high heat resistance and high alkali resistance of the aromatic ring, or a large three-dimensional obstacle, the heat resistance and alkali resistance are also improved, and finer particles can be formed more stably. Thin line shape tendency.

Furthermore, when a light-shielding agent such as carbon black is used, when the average primary particle diameter is small, the polyurethane dispersant (b-1) is more likely to absorb pigment, and the alkali-resistant developing property and heat resistance are more improved. It tends to form a fine fine line shape more stably.

When the polyurethane dispersant (b-1) contains both a hydrophilic solvent group having a polyether chain and a hydrophilic solvent group having a polyester chain, these are easily dissolved with a polymer-based alkali-soluble resin or borrowed. Photopolymerizable monomers crosslinked by ultraviolet rays are compatible with each other and are more likely to be entangled, so there is a tendency to improve the resistance to alkali developing solution and the resistance to high temperature processing.

Furthermore, when the polyether chain is an alkylene oxide having a long chain, it is more compatible with alkali-soluble resins or photopolymerizable monomers, and is easily entangled, so the alkali resistance and heat resistance are improved, and it is better. .

In addition, the adsorption group is preferably a polyurethane skeleton far from the main chain. By keeping the adsorption group away from the polyurethane skeleton of the main chain, the steric hindrance of the adsorption group when adsorbed on the pigment is reduced, and the polyurethane dispersant (b-1) easily absorbs the pigment. Furthermore, there is a tendency that the resistance to an alkali developer and the resistance to a high-temperature treatment increase.

[Manufacturing Method of Polyurethane Dispersant (b-1)]

The polyurethane dispersant (b-1) is produced using, for example, a diisocyanate compound. As the adsorbing group, a compound having two hydroxyl groups, an imine group, or a thiol group and a functional group that reacts with an isocyanate group, and one or more adsorbing groups that do not react with the isocyanate group (hereinafter sometimes referred to as For "adsorption group introduction compound") and obtain.

The above-mentioned adsorption group introduction compound reacts with the diisocyanate compound to be bonded to form a polyurethane skeleton with a linear structure. The adsorption group contained in the adsorption group-introducing compound is an adsorption group that adsorbs a pigment belonging to the color material (a) in the photosensitive resin composition.

Depending on the structure of the specific adsorption group introduced into the compound described above, the adsorption group may be contained in the polyurethane skeleton, and may form a bond with the main chain of the polyurethane skeleton. In the case of a pendant adsorption group of a polyurethane skeleton of a chain.

Although the urethane bond in the polyurethane skeleton of the polyurethane dispersant (b-1) is also adsorbed on the pigment, it further has an adsorption group adsorbed on the surface of the pigment, and When it is incorporated into a polyurethane skeleton or becomes a side chain of a polyurethane skeleton to form a pendant adsorption group, it exhibits better pigment adsorption. When the adsorption group is a hanging type adsorption group, it is preferred that the three-dimensional obstacle during pigment adsorption is small. These details will be described later.

The hydrophilic vehicle group contained in the polyurethane dispersant (b-1) is obtained by using a compound having two hydroxyl groups, imine groups, or thiol groups only at one end thereof, and combining the two groups with The isocyanate group reacts to be bonded to the polyurethane skeleton.

The polyether chain of the preferred solvent vehicle group contained in the polyurethane dispersant (b-1) is obtained by using a compound having only two hydroxyl groups, imine groups, or thiol groups at one end. These two groups are reacted with an isocyanate group to be bonded to a polyurethane skeleton. When the other terminal has a group that reacts with an isocyanate, it is preferred that the group is substituted with an alkyl group so that the group does not react with the isocyanate group.

In this way, by bonding to the diisocyanate compound only at one end, the It is bonded in such a manner that the polyurethane skeleton of the main chain is extended in the form of a side chain (hereinafter referred to as the "lateral direction"), and a polyether side chain that is a solvent-based group can be formed. Details about these will be described later.

Similarly, the preferred polyester chain contained in the soluble vehicle group is also reacted with an isocyanate group by using a compound having only two hydroxyl groups, imine groups, or thiol groups at one end. Instead, it can be bonded to a polyurethane skeleton. When the other terminal has a group which reacts with an isocyanate, it is preferred that the group does not react with the isocyanate group by substitution.

In this way, by bonding to the diisocyanate compound only at the single end, and bonding it in the lateral direction from the polyurethane skeleton of the main chain, a polyester side chain of an affinity vehicle can be formed. Details about these will be described later.

[Compounds (b-a), (b-b), (b-c) constituting the polyurethane dispersant (b-1)]

The polyurethane skeleton that becomes the main chain of the polyurethane dispersant (b-1) is preferably substantially linear in nature. As the polyisocyanate compound for forming the linear polyurethane skeleton, it is preferable to use a diisocyanate compound (b-a) having two isocyanate groups as described above.

The above-mentioned diisocyanate compound (ba) is introduced into the compound (bb) with an adsorption group having two functional groups that react with an isocyanate group and having one or more adsorption groups, and having an isocyanate group at only one end. The compound (bc) having two functional groups reacted and containing a solvent-soluble group can be bonded to obtain a urethane skeleton having a linear structure belonging to the main chain, a solvent-soluble group bonded to the main chain, and Adsorbent-based polyurethane dispersant (b-1).

Polyurethane dispersant (b-1) is based on polyurethane skeleton Graft polymer having a backbone polymer and a hydrophilic vehicle as a branch polymer; preferably a backbone polymer having a linear polyurethane backbone in the backbone polymer, or a polymer bonded to the backbone Specific adsorption groups.

[Compound (b-a); a diisocyanate compound constituting a polyurethane skeleton]

The diisocyanate compound (ba) is preferably toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexane diisocyanate (HDI), α, α-tetramethylxylene diisocyanate (TMXDI ), Diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), or dicyclohexylmethane-4 , 4'-diisocyanate (HMDI) and other diisocyanate compounds, or a mixture of these diisocyanate compounds.

Among these, any one of TDI, IPDI, and MDI is preferred, and TDI and / or MDI is more preferred. As the diisocyanate compound (b-a), a diisocyanate compound other than the above specific examples may be used.

The lower left is exemplified by several compounds of the diisocyanate compound (b-a), whereby the polyurethane dispersant (b-1) can be introduced into the lower right part of the structure.

In the above formula, * represents a bonding group with an oxygen atom in a urethane bond or a nitrogen atom in a urea bond.

In addition to the above, if it is a diisocyanate compound having two isocyanates, it can also be used as a diisocyanate compound (ba) for introducing a linear polyurethane structure into a polyurethane dispersant (b-1). .

[Compound (b-b); a compound having two functional groups reacting with isocyanate and having at least one adsorption group]

The adsorption group contained in the polyurethane dispersant (b-1) is for forming a polyurethane skeleton with the diisocyanate compound (ba), and may have a functional group 2 that reacts with the isocyanate group. Each adsorption group was obtained by introducing a compound (bb).

As a functional group which reacts with an isocyanate group, a hydroxyl group or an imine group is preferable. As specific examples when the functional group has two functional groups, the case where one is a hydroxyl group and the other is an imino group is preferable, or the case where both are both a hydroxyl group; and more preferably, both are a hydroxyl group.

In the case where the compound (b-b) has a basic group in addition to the functional group that reacts with the isocyanate group, it is preferable that the basic group is a person that does not react with the isocyanate group. Examples of the compound having such a basic group include an aliphatic tertiary amine, a hindered aromatic amine, and an alicyclic or aromatic nitrogen heterocyclic compound. Examples of the hindered aromatic amine include aniline having a sterically hindered group at the 2-position and / or 6-position thereof.

With the urethane bond and / or urea bond caused by the compound (bb) and the diisocyanate compound (ba), the above formula (1), (2-1), (2-2) or ( Part of the structure shown in 2-3) was introduced into the polyurethane dispersant (b-1).

Partial structure shown by formula (1) can be introduced into polyurethane dispersion Examples of the compound (b-b) of the agent (b-1) include those in which the two functional groups that react with the isocyanate group are both hydroxyl groups. These two hydroxyl groups are urethane-bonded to two isocyanate groups of the diisocyanate compound (b-a). Specific examples will be described later.

The compound (bb) which can introduce a part of the structure represented by the formula (2-1) into the polyurethane dispersant (b-1). Examples of the two functional groups that react with the isocyanate group are hydroxyl groups. . These two hydroxyl groups are urethane-bonded to two isocyanate groups of the diisocyanate compound (b-a). Specific examples will be described later.

The partial structure represented by the formula (2-2) can be introduced into the compound (bb) of the polyurethane dispersant (b-1). Examples of the partial structure represented by the formula (2-2) are listed below. An imine group having a bond between a N atom and a hydrogen atom, and a hydroxyl group having a bond between a N atom and a hydrogen atom. The imine group and the hydroxyl group, and the two isocyanate groups of the diisocyanate compound (b-a) are urea-bonded and urethane-bonded, respectively. Specific examples will be described later.

The compound (bb) which can introduce a part of the structure represented by the formula (2-3) into the polyurethane dispersant (b-1). Examples of the two functional groups which react with the isocyanate group are hydroxyl groups. . These two hydroxyl groups are urethane-bonded to two isocyanate groups of the diisocyanate compound (b-a). Specific examples will be described later.

[Compound (b-b) for introducing a partial structure represented by formula (1)]

When the compound (bb) is a compound in which a part of the structure represented by the formula (1) is introduced into the polyurethane dispersant (b-1), the two hydroxyl groups of the compound (bb) and the diisocyanate compound are used. The bonding of the two isocyanates in (ba) allows the tertiary amine structure of the entire partial structure shown in formula (1) to be incorporated into the polyurethane skeleton.

Specific examples of this case include N-methyldiethanolamine (NMDA) and N-phenyldiethanolamine (NPDA).

For example, with the compounds exemplified in the lower left, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1). This corresponds to a partial structure shown in the above formula (1). In addition, as long as it has a partial structure represented by formula (1) and has a hydroxyl group at its terminal, it can also be applied to the synthesis of a polyurethane dispersant (b-1). In addition, by using a thiol group, an amine group, or the like in place of a hydroxyl group, a similar polyurethane compound can be obtained.

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

[Compound (b-b) for introducing a partial structure represented by formulas (2-1) to (2-3)]

The compound (bb) is introduced into the adsorbing group by introducing a part of the structure represented by the above formula (2-1), (2-2), or (2-3) into the polyurethane dispersant (b-1). In the case of a compound, the two functional groups that react with the isocyanate group of the compound (bb) and the isocyanate group of the diisocyanate compound (ba) are bonded to form the formulae (2-1) and (2) belonging to the adsorbing group. -2) or (2-3), R ^α , R ^β , N, and R ^γ (R ^{γ ′} ) exist away from the polyurethane skeleton.

The adsorption group is introduced into the compound (bb), and a part of the structure represented by the formula (2-1), (2-2) or (2-3) can be introduced into the polyurethane dispersant (b-1) The compound is based on the above <dispersibility improvement effect> and <alkali-resistant developer improvement and heat resistance improvement Formation of high fine lines> The reasons described above are preferred.

It is preferable to introduce a partial structure represented by the formula (2-1), (2-2), or (2-3) into the adsorption group of the polyurethane dispersant (b-1) into the compound (bb). It has a hydroxyl group and / or an imine group, and is bonded to two isocyanate groups of the diisocyanate compound (ba) through a urethane bond and / or a urea bond to form a polyurethane skeleton.

At this time, the N atom, R ^δ and R ^ε (R ^{ε '} ), O, R ^η , and C atom in the partial structure represented by formula (2-1), (2-2), or (2-3) It is incorporated into the polyurethane skeleton, but the R ^α , R ^β , N, and R ^γ (R ^{γ ′} ) adsorbing groups belonging to the tertiary amine are bonded to the polyurethane skeleton. Away from the polyurethane backbone. As a result, the nitrogen atom of the tertiary amine is at least one atom separated by the closest atom on the polyurethane skeleton.

In this way, the tertiary amine having a polyurethane skeleton structured from a linear structure of the main chain is far away and is bonded in the horizontal direction, which tends to have a better adsorption function on the pigment surface. The tertiary amine may be partially or completely quaternized to form a quaternary ammonium salt.

Examples of the fourth-order ammonium salts include those belonging to R ^α , R ^β , R ^A , N ⁺ and R ^α in a partial structure represented by the formula (2-1 ′), (2-2 ′), or (2-3 ′). Adsorption group for R ^γ (R ^{γ '} ).

At this time, the above-mentioned adsorption group is separated from the polyurethane skeleton by being bonded to the polyurethane skeleton, and as a result, the nitrogen atom system of the fourth-order ammonium salt is composed of the polyurethane skeleton. The closest atom is separated by at least 1 atom.

Specific examples of the compounds in which these adsorption groups are introduced into the compound (bb) and the partial structure represented by the formula (2-1) can be introduced into the polyurethane dispersant (b-1) include the following However, if it contains a partial structure represented by formula (2-1) and has two functional groups that react with an isocyanate group at its terminal, it can also be applied to a polyurethane dispersant ( b-1).

Part of the structure shown in formula (2-1) is composed of at least one tertiary amine. And a compound (b-b1) having one hydroxyl group and one hydroxyl group. The specific reaction is shown below.

First, the hydroxyl group of the compound (b-b1) is reacted with one isocyanate group of a compound containing two isocyanate groups, such as toluene diisocyanate. Next, another isocyanate group is reacted with a secondary amine group in a compound containing one secondary amine group and at least two reactive hydroxyl groups, such as diethanolamine. Thereby, two hydroxyl groups can be introduced into the compound (b-b1).

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure shown in the above formula (2-1).

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

Moreover, a compound having a partial structure introduced by the formula (2-1) can also be obtained by the following method. Specifically, a compound having at least one tertiary amine group and an ethylenically unsaturated group, and a secondary amine such as diethanolamine and a compound containing one secondary amine group and at least two reactive hydroxyl groups are used. Based on Michael's bonus.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure shown in the above formula (2-1).

[Chemical 51]

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

Moreover, a compound having a partial structure introduced by the formula (2-1) can also be obtained by the following method. For example, a compound having a tertiary amine group and one hydroxyl group can be reacted with a compound having an isocyanate group and an acryloxy group, and a urethane bond can be formed between the hydroxyl group and the isocyanate group. A method of introducing an unsaturated group into an amine-based compound and subjecting it to a secondary amine group of diethanolamine by Michael addition. In this way, two hydroxyl groups can also be introduced.

In addition, as the compound having a partial structure introduced by the formula (2-1), there are the following compounds. With the compounds exemplified in the lower left, the structures exemplified in the lower right can be introduced into the polyurethane dispersant (b-1). This also corresponds to a partial structure shown in the above formula (2-1). In addition, if it contains a partial structure represented by formula (2-1) and has two hydroxyl groups at its ends, it can also be applied to the synthesis of a polyurethane dispersant (b-1).

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

In addition, a compound having a partial structure introduced by the formula (2-2) can be obtained by the following method. Specifically, it is based on a tertiary amine in dimethylaminopropylamine, etc. Among the compounds having a primary group and one primary amine group, a compound having one hydroxyl group and an ethylenically unsaturated group such as hydroxyethyl acrylate can be obtained by Michael addition. Thus, a compound having an imine group and a hydroxyl group obtained by the Michael addition of an ethylenically unsaturated group and a primary amine group was obtained.

Similarly, a compound having one hydroxyl group and a primary amine group such as monoethanolamine and a compound having one tertiary amine group and an ethylenically unsaturated group such as 2- (dimethylamino) -ethyl acrylate and the like are used. The Michael addition of the compound can also obtain a compound having a tertiary amine group adsorption group, a hydroxyl group, and an imine group.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure shown in the above formula (2-2). Moreover, if it contains a partial structure shown by the said Formula (2-2), and has a hydroxyl group and an imine group in the terminal, it can also be used for a polyurethane dispersant (b-1).

In the above formula, * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton of the main chain; and * adjacent to a nitrogen atom represents polymerization with a main chain A bonding group between carbonyl groups of a urea bond in a urethane skeleton.

In addition, as the compound having a partial structure represented by the formula (2-3), there are the following compounds. For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This is equivalent to the partial structure shown in the above formula (2-3) Made.

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

In addition, if it contains a partial structure represented by the above formula (2-3) and its terminal has two hydroxyl groups, it can be applied to the synthesis of a polyurethane dispersant (b-1).

For example, a compound that replaces two hydroxyl groups of the above-mentioned compound and has substituted two primary and / or secondary amine groups can also be applied to the synthesis of a polyurethane dispersant (b-1). In addition, compounds containing one or more specific adsorbing groups and replacing two primary and / or secondary amine groups may also be used in the synthesis of the polyurethane dispersant (b-1). In addition, the compound (bb-1) having only one hydroxyl group can be introduced into the polyurethane dispersant (b-1- by reacting with thioglycerol and having a partial structure represented by formula (2-3). 1).

Specific reaction examples are as follows. First, a hydroxyl group of the compound (b-b1) is reacted with one isocyanate group of a compound containing two isocyanates, such as toluene diisocyanate.

Next, the other isocyanate group is reacted with an active thiol group of a compound containing one active thiol group and at least two active hydroxyl groups, such as thioglycerin. Thereby, two hydroxyl groups can be introduced into the compound (b-b1).

For example, the compounds The powder exemplified below is introduced into the powder (b-1). This corresponds to a partial structure shown in the above formula (2-3).

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

[Compound (b-b) for introducing a nitrogen atom-containing heterocyclic group]

By using a heterocyclic compound containing a nitrogen atom as the compound (b-b), it is possible to impart a good pigment adsorption function to the polyurethane dispersant (b-1). Specific examples of the compound for introducing the nitrogen atom-containing heterocyclic group when the heterocyclic group containing such a nitrogen atom is incorporated into the polyurethane skeleton and the structure to be introduced are as follows: By.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. In addition, a compound in which two functional groups that react with an isocyanate group are directly bonded to a heterocyclic position at a heterocyclic ring, or a compound having a heterocyclic position bonded to the heterocyclic ring through 1 to 10 atoms can also be used.

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

When the nitrogen atom-containing heterocyclic group is separated from at least one atom by a polyurethane skeleton of the main chain, the following compounds can be used. For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left.

In addition, a compound containing two functional groups that react with a ring of a heterocyclic compound containing a nitrogen atom and an end of one side chain bonded through 1 to 20 atoms with an isocyanate group can also be used.

[Chemical 57]

The * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton; the * adjacent to a nitrogen atom represents an atom in a polyurethane skeleton A bonding group between carbonyl groups of a urea bond.

These compounds can also be obtained by the same method as the partial structure shown by the above formula (2-1) or (2-2). In addition, the case where the part of the tertiary amine group corresponding to the partial structure represented by the above formula (2-3) is a heterocyclic compound containing a nitrogen atom is also effective, and can be applied to polyurethane Dispersant (b-1).

In these cases, the heterocyclic compound containing a nitrogen atom of the compound (b-b) is formed as a pendant type adsorbed by a polyurethane skeleton away from at least one atom. Attachment. Polyurethane compounds (b-1-1) containing this pendant adsorption group are formed based on the above-mentioned <dispersibility improvement effect> and <alkaline-resistant developing solution improvement and heat resistance improvement due to the formation of high fine lines > The reason described above is preferred.

The adsorption group introducing compound (b-b) used for the synthesis of the polyurethane dispersant (b-1) can also be obtained by other known general methods.

[Method of Introducing Grade 4 Ammonium Salt]

As a method for introducing a fourth-order ammonium salt group into the polyurethane dispersant (b-1), for example, first, by using the formula (2-1) to (2-3), The partially structured compound shown is a method in which a tertiary amine group is introduced into a polyurethane dispersant (b-1), and then the tertiary amine group is quaternized using any known quaternary agent.

Preferred grade 4 agents are alkyl halides, aralkyl halides, dialkyl sulfates, dialkyl carbonates or epoxides. Particularly preferred grade 4 agents are dimethyl sulfate, benzyl chloride or styrene oxide. Part of the tertiary amine group can be partially salified with quaternary ammonium, or all tertiary amine groups can be hydrolyzed with tertiary ammonium.

These tertiary amine groups may form salts with any known organic acid compound. Preferred organic acid compounds include organic sulfonic acid compounds such as vinyl sulfonic acid, organic phosphonium compounds such as dimethyl propylene ethoxyethyl phosphate, and phenylphosphonic acid.

[Compound (b-c); a compound having two functional groups reacting with an isocyanate group at a single terminal and containing a compatible vehicle group]

The main chain of the polyurethane skeleton in the polyurethane dispersant (b-1), and the side chain of the affinity vehicle group bonded in the lateral direction to the side thereof can be made only by Compound containing at the single end a hydrophilic solvent group having two functional groups that react with an isocyanate group (b-c) obtained by reacting with the diisocyanate compound (b-a).

As the two functional groups reacting with the isocyanate group of the compound (bc), a hydroxyl group and / or an imine group are preferred, and one is a hydroxyl group and the other is an imine group, or both are hydroxyl groups. Even more preferably, the two are hydroxyl groups.

The following is a case where the hydrophilic vehicle group of the polyurethane dispersant (b-1) contains a polyether chain and / or a polyester chain, and particularly has the formulae (3-1) to (3-3) above. The structure of the part shown is described in detail.

By the urethane bond or the urea bond of the compound (bc) and the diisocyanate compound (ba), the part represented by the above formula (3-1), (3-2) or (3-3) The structure was introduced into a polyurethane dispersant (b-1).

The two functional groups capable of reacting with the isocyanate group in the compound (bc) in which the partial structure represented by the formula (3-1) is introduced into the polyurethane dispersant (b-1), and These two hydroxyl groups are urethane-bonded to two isocyanate groups of the diisocyanate compound (ba). Specific examples will be described later.

The compound (bc) capable of introducing a part of the structure represented by the formula (3-2) into the polyurethane dispersant (b-1), and the two functional groups that react with the isocyanate group are an imine group and a hydroxyl group. The imine group is urea-bonded with the isocyanate group, and the hydroxyl group is urethane-bonded with the isocyanate group. Specific examples will be described later.

The two functional groups capable of reacting with the isocyanate group of the compound (bc) in which the partial structure represented by the formula (3-3) is introduced into the polyurethane dispersant (b-1) are both hydroxyl groups. Two hydroxyl groups are bonded to two isocyanate groups of the diisocyanate compound (ba). Specific examples will be described later.

Next, the compound (b-c) for introducing a solvent-compatible group into the polyurethane dispersant (b-1) will be described.

If the compound (bc) contains functional groups that react with isocyanate groups at both ends, the functional groups are bonded to other residual isocyanate groups during the synthesis of the polyurethane dispersant (b-1). On the other hand, there is a possibility that the formation of the side chain of the linear polyurethane skeleton in the lateral direction of the side bond may be prevented. Therefore, it is preferable that the compound (b-c) does not contain a functional group which reacts with an isocyanate group other than a single terminal.

Therefore, when the functional group which reacts with an isocyanate group at the opposite end of the two functional groups which reacts with an isocyanate group has a functional group which reacts with an isocyanate group, it is preferable that the hydroxyl group etc. are substituted so that it may not react with an isocyanate group. More preferably, the hydrogen atom of the hydroxy group is substituted with an alkyl group to form an alkoxy group.

Particularly preferred is an alkyl group in which a hydrogen atom of the hydroxyl group is substituted with an alkyl group having 1 to 50 carbon atoms. The alkyl group may be an arbitrary branched alkyl group or a cycloalkyl group, or an aryl group or an aralkyl group may be introduced instead of the alkyl group.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 6 carbon atoms such as a cyclopropyl group and a cyclohexyl group. The aryl group is preferably an aryl group having 6 to 10 carbon atoms such as a naphthyl group or a phenyl group which may be substituted by a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

The aralkyl group is preferably a 2-phenethyl group or a benzyl group substituted by a halogen atom, an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

The chain length of the terminal alkyl group of the compound containing a polyether chain and / or polyester chain can be appropriately selected depending on the nature of the solvent (e) contained in the photosensitive resin composition. For example, when the solvent (e) is a polar organic solvent, the above-mentioned terminal alkyl group may preferably be a linear or branched alkyl group having 1 to 12 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

When the polyurethane dispersant (b-1) contains a polyether side chain, from the viewpoint of being easily available from the market, it is preferred that the terminal alkyl group is an alkyl group having 1 to 4 carbon atoms. More preferred is methyl. On the other hand, when the (e) solvent is a non-polar organic solvent, the carbon number of the terminal alkyl group is preferably 8 or more.

The portion of the polyalkylene oxide chain of the polyether chain (which does not contain a terminal alkyl group) contained in the soluble vehicle group is preferably a polyalkylene oxide having 2 to 4 carbon atoms. The content of the polyalkylene oxide contained in the polyalkylene oxide having 2 to 4 carbon atoms is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 20 in terms of substrate adhesion. Mass% or less, and even more preferably, it does not contain polyalkylene oxide.

The polyalkylene oxide chain part having 2 to 4 carbon atoms can also be obtained by (co) polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide, or from tetrahydrofuran. In the case of copolymerization, it may be a random copolymer or a block copolymer. The polyalkylene oxide portion may be a straight chain or a branched chain.

From the viewpoint of improving the stability of dispersion over time, the polyalkylene oxide is preferably polypropylene oxide. From the viewpoint of improving dispersibility, the polyether chain contained in the hydrophilic vehicle group of the polyurethane dispersant (b-1) is preferably an alkyl group having 1 to 10 carbon atoms as a terminal alkyl group. Those having a polyalkylene oxide having 2 to 4 carbon atoms; in this case, the terminal alkyl group is more preferably a methyl group or a butyl group.

The polyester chain belonging to the solvent-soluble group is preferably obtained from a hydroxycarboxylic acid or a lactone containing 1 to 26 carbon atoms. The type of the hydroxycarboxylic acid is appropriately selected depending on the nature of the solvent (e) contained in the photosensitive resin composition.

When (e) the solvent is a polar organic solvent, the hydroxycarboxylic acid preferably contains a maximum of 8 carbon atoms; when the organic medium is a non-polar organic liquid, the hydroxycarboxylic acid preferably contains more than 8 carbon atoms.

The polyester chain is preferably obtained from two or more different hydroxycarboxylic acids or their lactones in order to contribute to the solubility of the organic medium. Hydroxycarboxylic acids can be saturated or unsaturated And may be straight or branched.

Examples of suitable hydroxycarboxylic acids are glycolic acid, lactic acid, 5-hydroxyvaleric acid, 6-hydroxyhexanoic acid, ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecane Acid, 5-hydroxydecanoic acid and 4-hydroxydecanoic acid.

Examples of suitable lactones are β-propiolactone and δ-valerolactone and ε-caprolactone optionally substituted with an alkyl group having 1 to 6 carbon atoms. For example, β-methyl-δ-valerolactone, δ-valerolactone, ε-caprolactone, 2-methyl, 3-methyl, 4-methyl-, 5-third butyl, 7- Methyl-4,4,6-trimethyl and 4,6,6-trimethyl-εcaprolactone and mixtures thereof.

Polyester chains derived from δ-valerolactone and ε-caprolactone are particularly preferred.

The lateral side chains of the polyether chain and / or the polyester chain which belong to the solvent-based group may be composed of a single monomer or may be composed of a plurality of monomer components. Moreover, a polyether chain may contain a polyester part, Conversely, a polyester chain may contain a polyether part.

The number average molecular weight of the hydrophilic vehicle-based polyether chain and / or polyester chain in the polyurethane dispersant (b-1) is preferably 10,000 or less, more preferably 4,000 or less, and even more preferably 2,500 the following. The number average molecular weight of the polyether chain and / or polyester chain is preferably 300 or more, more preferably 600 or more, and even more preferably 800 or more. When it is below the above-mentioned upper limit value, the adhesiveness of the substrate tends to be improved, and when it is above the above-mentioned lower limit value, the dispersibility tends to be improved.

Next, a method of introducing two functional groups that react with an isocyanate group at the single terminal of the polyether chain and / or polyester chain of the compound (b-c) will be described.

There are several methods for introducing two functional groups that react with the isocyanate group of the compound (b-a) at the single terminal of the polyether chain and / or polyester chain. As a result, the above polyether chain and / or polyester chain are bonded to a diisocyanate compound (ba) by two functional groups at a single end to form a main chain belonging to a polyurethane skeleton, and can form a polymer Ether chain and And / or a side chain of a hydrophilic medium of a polyester chain.

In the case where the side chain of the solvent-compatible group in the horizontal direction contains a polyether chain, the compound (bc) containing a solvent-containing polyether chain preferably has two hydroxyl groups which react with an isocyanate group at one end, or 1 hydroxyl group and 1 imino group. The hydroxyl and imino groups are preferably separated by a maximum of 6 carbon atoms. In the case where the compound (b-c) contains two hydroxyl groups which react with an isocyanate group, these are preferably separated by a maximum of 17 atoms.

As a method of introducing two functional groups at one terminal as one functional group reacting with an isocyanate group of a compound (bc) containing a polyether chain, a method of introducing two hydroxyl groups into the compound (bb) is used. The same way.

Specific examples of the compound (b-b) for introducing a partial structure represented by the formula (3-1) into the polyurethane dispersant (b-1) include the followings. In addition, if it contains a partial structure represented by the formula (3-1) and its terminal has two hydroxyl groups, it can be applied to the synthesis of a polyurethane dispersant (b-1).

First, a hydroxyl group at the other end of a polyalkylene oxide chain having a carbon number of 2 to 4 which is alkyl-etherified at one end is reacted with one isocyanate group of a compound containing two isocyanate groups, such as toluene diisocyanate. Next, the other isocyanate group is reacted with a secondary amine group of a compound containing one secondary amine group and at least two active hydroxyl groups, such as diethanolamine. Thereby, two hydroxyl groups can be introduced into the single terminal of the polyalkylene oxide chain.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to the chemical structure represented by the formula (3-1).

[Chem 58]

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

A compound having a partial structure represented by the above formula (3-1) can also be obtained by the following method. As a method of introducing two hydroxyl groups into the single terminal of the compound (b-c) containing a polyether chain, there is also a method of subjecting diethanolamine to polyaddition in poly (alkylene oxide) acrylate. Specific examples are as follows.

With the compounds exemplified in the lower left, the structures exemplified in the lower right can be introduced into the polyurethane dispersant (b-1). This corresponds to a partial structure shown in the above formula (3-1).

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

Moreover, when it has a partial structure shown by Formula (3-2), it can also be obtained by the following method.

In the case where the two functional groups at the single terminal of the compound (bc) containing a polyether chain react with an isocyanate group are one hydroxyl group and one imine group, it is also applied to the compound (bb) and one introduced The method of the hydroxyl group and one imine group is the same method. Specifically, it is a compound having one hydroxyl group such as hydroxyethyl acrylate and an ethylenically unsaturated group, and a compound having one primary amine group at the end of a polyalkylene oxide chain. The thing is obtained by Michael addition. Thereby, one hydroxy group in the imine group and the hydroxy acrylate obtained by the Michael addition of an ethylenically unsaturated group and an amine group can be obtained.

Similarly, a compound having an alkylene oxide chain and an ethylenically unsaturated group, such as a compound having one hydroxyl group and a primary amine group, such as monoethanolamine, or an acrylate ester-bonded to an alkylene oxide chain, is used. It can also be added to the solvent of the alkylene oxide and the hydroxyl and imine groups which react with the isocyanate group. Such compounds are as follows.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure represented by the formula (3-2). In addition, if it contains a partial structure represented by formula (3-2) and has one hydroxyl group and one imine group, it can also be applied to the synthesis of a polyurethane dispersant (b-1).

An * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton of the main chain; an * adjacent to a nitrogen atom represents a polycarbamic acid to the main chain A bonding group between carbonyl groups of a urea bond in an ester backbone.

In addition, in the case of a structure corresponding to a partial structure represented by the above formula (3-3), it also has an effective effect and can be applied to the synthesis of a polyurethane dispersant (b-1-1).

The partially introduced compound represented by the above formula (3-3) is a compound having two hydroxyl groups at one end. The partial structure represented by the above formula (3-3) is obtained by using, for example, a polyether having one hydroxyl group at a terminal, a diisocyanate compound, and thioglycerin. Its specific The reaction examples are as follows.

First, a hydroxyl group of a polyether having one hydroxyl group at a terminal is reacted with one isocyanate group of a compound containing two isocyanates, such as toluene diisocyanate. Next, another isocyanate group is reacted with an active thiol group of a compound containing one active thiol group and at least two active hydroxyl groups, such as thioglycerin. This makes it possible to obtain a compound having two hydroxyl groups introduced into a single end of the polyether.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure shown in the above formula (3-3).

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

The compound in which the structure represented by the above formula (3-3) is introduced into the polyurethane dispersant (b-1) is a compound having two hydroxyl groups at one end, but the above formula (3-3) The compound shown in the figure has two oxygen atoms substituted by two primary and / or secondary amine groups. It can also be used as a synthetic for polyurethane dispersant (b-1). Compound (bc).

The compound (bc) which is used in the synthesis of a polyurethane-based dispersant (b-1) containing a polyester chain as the solvent medium is preferably at one end of the compound containing a polyester chain and contains an isocyanate group. The two hydroxyl groups of the reaction. The hydroxyl groups are preferably at most 17 atoms apart. The two hydroxy special systems are separated by more than 5 atoms.

In either the case where the terminal of the polyester chain is a hydroxyl group or the case where it is a carboxyl group, two hydroxyl groups which react with an isocyanate group can be introduced to a single terminal.

When the terminal of the polyester chain is a hydroxyl group, it can be produced by polymerizing one or a plurality of hydroxycarboxylic acids or their lactones in the presence of a hydroxyl-containing compound that is a chain-stop compound described later.

The polyester obtained by using a hydroxyl-containing compound of a chain-stopping compound described later is preferably one represented by the following formula (4).

R ⁹ O (OC-AO) _w H (4)

In the formula (4), w is 5 to 150, R ⁹ is an alkyl group having 1 to 50 carbon atoms, and A is an alkylene group having 1 to 26 carbon atoms or an alkylene group having 2 to 26 carbon atoms.

When a compound of the formula (4) is introduced at the single terminal with two hydroxyl groups which react with an isocyanate group, the same method as the method described above for introducing two hydroxyl groups into the single terminal of a polyether can be used.

In addition, when a compound of the formula (4) is introduced at one end with one hydroxyl group and one imine group to react with an isocyanate group, the above-mentioned one hydroxyl group and one subgroup can be introduced at the single end of the polyether. The method of the amino group is the same.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure shown in the above formula (3-1) or a partial structure shown in the formula (3-2). In addition, if a functional group containing a partial structure represented by the above formula (3-1) or a partial structure represented by the formula (3-2) and having a hydroxyl group or an imine group that reacts with an isocyanate group at the terminal is included, Two can be used for polyurethane dispersant (b-1).

[Chem 62]

An * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton of a main chain; an * adjacent to a nitrogen atom represents a polyamine group to a main chain A bonding group between carbonyl groups of a urea bond in a formate backbone.

In addition, it has an effective effect even in a structure corresponding to a partial structure shown in the above formula (3-3), and it can be applied to a polyurethane dispersant (b-1).

A structure corresponding to a structure containing a partial structure shown in the formula (3-3) above the polyester chain, and a structure corresponding to a structure containing a partial structure shown in the formula (3-3) above the polyether chain can also be applied. The same construction.

For example, the compounds The powder exemplified below is introduced into the powder (b-1). This corresponds to a partial structure shown in the above formula (3-3).

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

When the terminal of the polyester chain is a carboxyl group, it can be produced by polymerizing one or a plurality of hydroxycarboxylic acids or their lactones in the presence of a carboxyl-containing compound which is a chain-stopping compound described later.

The polyester obtained using a carboxyl-containing compound of a chain-stopping compound described later is preferably one represented by the following formula (5).

R ⁹ CO (OA-CO) _w OH (5)

In formula (5), R ⁹ , A and w are the same as defined in the above formula (4).

Polyesters of formula (4) and / or (5) generally use one or more hydroxycarboxylic acids in an inert environment and in the presence of an esterification catalyst at 50 to 250 ° C. It is produced by reacting a hydroxy compound or a carboxyl group-containing compound together. Typical process conditions are described in International Publication No. 2001/80987.

When a compound of the above formula (5) is introduced at one terminal into two hydroxyl groups that react with an isocyanate group, the compound of the formula (5) is reacted with a glycol such as ethylene glycol or propylene glycol to convert it to a monohydroxy compound. The obtained monohydroxy derivative is carried out in the same manner as in the compound of the formula (4).

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by using the compound exemplified in the lower left. This corresponds to a partial structure shown in the above formula (3-1) or a partial structure shown in the formula (3-2).

In addition, if a functional group containing a partial structure represented by the above formula (3-1) or a partial structure represented by the formula (3-2) and having a hydroxyl group or an imine group that reacts with an isocyanate group at the terminal is included, only Two can be used in the synthesis of polyurethane dispersant (b-1).

[Chemical 64]

In the above formula, * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton of a main chain; and * adjacent to a nitrogen atom represents a main chain Bonding group between carbonyl groups of urea bond in the polyurethane frame.

In addition, it also has an effective effect in a structure corresponding to a partial structure shown in the above formula (3-3), and can be applied to the synthesis of a polyurethane dispersant (b-1).

A structure corresponding to a structure containing a partial structure shown in the formula (3-3) above the polyester chain, and a structure corresponding to a structure containing a partial structure shown in the formula (3-3) above the polyether chain can also be applied. The same construction.

In addition, as a method for introducing a functional group that reacts with an isocyanate group at the end of a polyether chain and / or a polyester chain, other known methods may be used. For example, there is also a polyether chain or a polyester chain having one hydroxyl group at a single end, and a compound having an isocyanate group and an acryloxy group can be reacted to form a polyether chain by urethane bonding. Or a method in which an unsaturated group is introduced into a single terminal of a compound of a polyester chain, and this is subjected to Michael addition with diethanolamine. By this method, it is also possible to introduce two hydroxyl groups at a single end of a polyether chain or a polyester chain.

A main chain having a polyurethane skeleton, a side chain belonging to a soluble vehicle group, which has a polyether chain and / or a polyester chain bonded to the side, and a polyurethane having a specific adsorption group The ester compound (b-1-1) is within a range that does not affect its characteristics, and can also react a polyacrylate and / or polyolefin having two functional groups that react with an isocyanate group at a single terminal to obtain.

When two functional groups reacting with an isocyanate group are introduced into the single end of polyacrylic acid and / or polyolefin, it is a method applied to the introduction of two hydroxyl groups at the ends of the above polyether chain or polyester chain or the introduction of one hydroxyl group and The method is the same for one imino group.

In addition, when synthesizing a polymer of polyacrylate and / or polyolefin, it can be obtained by using a polymerization initiator having two hydroxyl groups or a dihydroxy functional chain shifting agent such as thioglycerin.

By the reaction between the polyacrylate and / or polyolefin having two functional groups which react with an isocyanate group at one terminal as described above, and the reaction between the isocyanate group of the diisocyanate compound (ba), a bond to the polymer can be formed. Polyurethane and / or polyolefin chains in the lateral direction of the urethane skeleton.

[Any other structure that the polyurethane dispersant (b-1) may also contain]

Polyurethane dispersant (b-1), on the other hand, may contain a structure introduced by the urethane reaction and urea reaction of the following compounds (bd), (be), (bf) .

‧Compound (b-d): One or more compounds having two functional groups that react with an isocyanate group.

‧Compound (b-e): One or two or more compounds that contain one functional group that reacts with an isocyanate group and function as a chain stopper.

‧Compound (b-f): One or more compounds containing one isocyanate group and acting as a chain stopper.

The structures from these compounds (bd), (be), (bf) are obtained by bringing these compounds (bd), (be), (bf) together with compounds (ba), (bb), (bc) Reaction, and can be introduced into the polyurethane skeleton of the polyurethane dispersant (b-1).

More specifically, the structure from the compound (bd) can be introduced into the polyurethane skeleton, and the structure from the compounds (be) and (bf) can be introduced into both ends of the polyurethane skeleton. .

The compound (b-d) preferably contains only two functional groups that react with an isocyanate group.

The preferred functional group of the compound (b-d) is an amine group or a hydroxyl group, more preferably a diamine or a diol, and even more preferably a diol. The compound (b-d) is mainly used as a chain extender for changing the solubility of the polyurethane polymer. The number average molecular weight of the compound (b-d) is not particularly limited, but is preferably 32 to 3,000.

Examples of preferred diamines are ethylenediamine, 1,4-butanediamine and 1,6-hexanediamine. Examples of preferred diols are 1,6-hexanediol, 1,4-cyclohexanedimethanol (CHDM), 1,2-dodecanediol, 2-phenyl-1,2-propanediol, 1 , 4-benzenedimethanol, 1,4-butanediol and neopentyl glycol.

The diol may also be a polyether such as poly (C2 ~ 4-alkanediol), polyester, or polyacrylic acid diol. The polyalkanediol may also be a random or block homopolymer or copolymer containing repeated ethyleneoxy, propyleneoxy or buteneoxy groups including a mixture thereof.

Several compounds (b-d) are exemplified in the lower left, whereby the lower right part of the structure can be introduced into the polyurethane compound (b-1-1).

[Chem 65]

In the above formula, * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton of a main chain; and * adjacent to a nitrogen atom represents a main chain Bonding group between carbonyl groups of urea bond in the polyurethane frame.

Moreover, if there are only two functional groups which react with an isocyanate group, the compound (b-d) which introduce | transduces the said partial structure into a polyurethane dispersant (b-1) can be used.

The polyurethane skeleton in the polyurethane dispersant (b-1) preferably has a linear character in nature. However, there may be cases where a polyol or a polyisocyanate having a functional valence greater than 2 exists in any of the components depending on the impurity type, and a small amount of branch structure may be introduced.

As disclosed below, the chain-stopping compound belonging to the compound (b-e) is a monofunctional compound having one functional group that reacts with an isocyanate group. The monofunctional group of the compound (b-e) is preferably an amine group or a hydroxyl group. The compound (b-e) is bonded to the end of the polyurethane skeleton of the main chain of the polyurethane dispersant (b-1), and becomes a terminal group.

Preferred chain-stop compounds include the same polyalkylene oxide monoalkyl ethers and polyalkylene oxide monoalkyl groups as those used in the compound (bc) constituting the polyurethane dispersant (b-1). Etheramine or a polyester compound in which the terminal group of the compound represented by the above formula (4) is a hydroxyl group.

The compound (b-e) is exemplified in the lower left, so that it can be dispersed in polyurethane The lower right part of the agent (b-1) is introduced.

In the above formula, * represents a bonding group with a carbonyl group of an urethane bond in the polyurethane skeleton of the main chain.

Moreover, if there is only one functional group which reacts with an isocyanate group at a single terminal, it can be used as a compound (b-e) which can introduce the said partial structure into a polyurethane dispersant (b-1).

From the viewpoint of dispersibility and dispersion stability over time, the compound (be) is preferably one which contains a polyether chain and / or a polyester chain as a compatible solvent group. In addition, if it has only one hydroxyl group and one A compound having a primary amine group, a secondary amine group, or a thiol group has a chain-stopping effect and can be used as a compound (be).

As the above-mentioned compound (be), it is possible to substitute a compound having a hydrophilic vehicle group of a polyether chain and / or a polyester chain, and within a range that does not affect the effect of the polyurethane dispersant (b-1), Polyacrylates or polyolefins having the same structure can also be applied.

The monoisocyanate compound of the compound (b-f) also functions as a chain stop compound, and is bonded to both ends of a linear polyurethane skeleton belonging to the main chain of the polyurethane dispersant (b-1). Specific examples of the monoisocyanate compound of the compound (b-f) include phenyl isocyanate, but if it remains, it may be necessary to perform a post-treatment. In this case, it is preferable to perform chain stop by the compound (b-e).

[Synthesis of Polyurethane Dispersant (b-1)]

The typical amount of raw materials used in the synthesis of the polyurethane dispersant (b-1) is 10 to 50 based on the total mass of the raw materials of the polyurethane dispersant (b-1). Compound (ba) by mass, Compound (bb) from 1 to 24 percent by mass, Compound (bc) from 10 to 80 percent by mass, Compound (bd) from 0 to 25 percent by mass, Compound (be from 0 to 50 percent by mass) ), And 0-20% by mass of the compound (bf).

The mass ratio of the compound (bc) constituting the lateral side chain in the polyurethane dispersant (b-1) and the compound (be) constituting both ends of the polyurethane skeleton is preferred. The total mass of the raw materials of the polyurethane dispersant (b-1) is 35% or more.

Compound (b-c) and compound (b-e) The compounds containing a polyester chain may be separate, but it is preferable to contain both. The mass ratio of the compound containing a polyether chain to the compound containing a polyester chain is based on the total mass of the compound (bc) and the compound (be), preferably 1:99 to 99: 1, more preferably 3:97 ~ 97: 3, and more preferably 5: 95 ~ 95: 5.

The polyurethane dispersant (b-1) contains polyether chains and polyester chains as a solvent medium. When a tablet computer or a high-line color filter BM is formed, the alkali development is performed during the formation process. The liquid resistance or the resistance during high-temperature processing becomes better, so it is preferable. In addition, when the adsorption group of the polyurethane dispersant (b-1) is a specific adsorption group bonded to the main chain, since the specific adsorption group is well adsorbed to the pigment, it is easy to take in It is particularly good because it is a pigment that is resistant or resistant to high temperature processing.

Polyurethane dispersant (b-1) may be prepared according to any formula known in the art. Known method for modulation. Generally speaking, the polyurethane dispersant (b-1) is under substantially anhydrous conditions, in an inert environment at a temperature of generally 0 to 130 ° C, in the presence of any inert solvent, and optionally In the presence of a catalyst, one or two or more diisocyanate compounds (ba) can be obtained by reacting at least one or two or more compounds (bb) and one or two or more compounds (bc). .

In addition, one or a plurality of compounds (bd) acting as a chain extender and any one or a plurality of compounds acting as a chain stop compound belonging to the compound (be) and the compound (bf) may be arbitrarily combined together. Implement the reaction.

The inert environment may be performed by any one of inert gases, and nitrogen is preferred.

The preparation of the polyurethane dispersant (b-1) can be carried out in the presence of a catalyst. A particularly good catalyst is a tin complex of a fatty acid such as dibutyltin dilaurate (DBTDL) or a tertiary amine.

In the synthesis of the polyurethane dispersant (b-1), the ratio of the mole number of the functional group that reacts with the isocyanate group and the isocyanate group is adjusted in the entire compound reacted during the synthesis, and Various products are formed.

In one case, the total number of moles of the isocyanate groups in the compound (ba) can be compared with the compounds (bb), (bc) and, if necessary, reacted with the isocyanate groups of the compounds (bd), (be) The total molar number of functional groups is small. At this time, any terminal isocyanate group reacts, and there is a tendency that the unreacted terminal isocyanate group does not remain.

Alternatively, the total number of moles of isocyanate groups provided by compound (ba) and any compound (bf) may be smaller than those of compounds (bb), (bc), and (bd), (be The total number of functional groups for which the isocyanate group of) reacts Count more. At this time, the obtained polyurethane compound (b-1-1) tends to become a prepolymer containing a residual isocyanate group.

Therefore, this prepolymer can be carried out with other chain extenders such as compound (bd) and / or a chain stop compound belonging to compound (be) before dissolving in a different solvent with a different prepolymer. reaction.

When a prepolymer containing a residual isocyanate group is present, the chain extension reaction can be performed by water itself. Alternatively, it can be carried out by a polyol, an amine-alcohol, a first or second aliphatic, alicyclic, aromatic, or heterocyclic polyamine, especially a diamine, hydrazine or substituted hydrazine.

Examples of the chain extender include the following chain extenders having two or more functional groups that react with an isocyanate group. However, in order to maintain a linear urethane skeleton, it is preferable to have a chain extender having an isocyanate group. There are only two chain extenders for the functional groups in the reaction.

Commonly used chain extenders include, for example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, cyclohexanediamine, piperidine 2-methylpiperazine , Phenylenediamine, toluenediamine, xylenediamine, 4,4'-methylenebis (2-chloroaniline), 3,3'-dichloro-4,4'-biphenyldiamine, 2, 6-diaminopyridine, 4,4'-diaminodiphenylmethane, methanediamine, m-xylylenediamine, isophoronediamine, hydrazine, dimethylhydrazine, etc. Wait.

As the chain extender used in the synthesis of the polyurethane dispersant (b-1) having a linear polyurethane skeleton, it is preferred to have only two functional groups that react with isocyanate groups. Chain extender, particularly preferred is hexamethylenediamine.

The chain extension reaction can be performed at any one of high temperature, low temperature, and room temperature. The preferred temperature is about 5 ~ 95 ° C.

Prepolymer method for preparing polyurethane dispersant (b-1) In this case, in order to control the molecular weight of the obtained polyurethane dispersant (b-1), the amounts of the chain extender and the chain stopper can be adjusted.

When the molar number of the functional group that reacts with the isocyanate group in the chain extender is almost equal to the molar number of the free isocyanate group in the prepolymer, the molecular weight tends to be high. In order to obtain a low molecular weight polyurethane dispersant (b-1), a chain stopper may be used in a reaction with a polyurethane prepolymer in combination with a chain extender and a chain stopper. Increase and so on.

In order to control the viscosity, an inert solvent may be added before, during, or after the formation of the polyurethane dispersant (b-1) or its prepolymer. Preferred solvents include, for example, acetone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, diglyme, N-methylpyrrolidone, butyl acetate, and methyl acetate. Oxypropyl, ethyl acetate, ethylene glycol diacetate and propylene glycol diacetate, alkyl ethers of ethylene glycol acetate and propylene glycol acetate, toluene, xylene, and tertiary butanol, and two Stereotactic alcohols such as acetol. More preferred vehicles are ethyl acetate, butyl acetate, methoxypropyl acetate, and N-methylpyrrolidone.

[Physical Properties of Polyurethane Dispersant (b-1)]

From the viewpoint of dispersibility, the amine value in 1 g of the solid content of the polyurethane dispersant (b-1) is preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more. From the viewpoint of dispersibility, it is preferably 180 mgKOH / g or less, more preferably 110 mgKOH / g or less, and even more preferably 70 mgKOH / g or less.

The number-average molecular weight of the polyurethane dispersant (b-1) is preferably 2,000 or more, more preferably 3,000 or more, particularly preferably 4,000 or more from the viewpoint of dispersion effect, and it is easily dispersed and low. From the viewpoint of viscosity, preferably 50,000 Below, more preferably below 40,000, even more preferably below 30,000, and particularly preferably below 20,000.

In addition, with respect to 100 g of the polyurethane dispersant (b-1), the soluble vehicle group is preferably 0.001 mol or more, more preferably 0.005 mol or more, even more preferably 0.01 mol or more, and particularly preferably It is 0.02 mol or more; more preferably 0.5 mol or less, more preferably 0.2 mol or less, even more preferably 0.1 mol or less, and particularly preferably 0.08 mol or less. Hereinafter, the proportion of the soluble vehicle group is expressed in the unit of "Morgen / 100g" based on the content of the soluble vehicle group.

Among them, the so-called "molle root" of the solvent-based group refers to a value obtained by dividing the filling amount of the solvent-based raw material by the number-average molecular weight during the packing during synthesis. In addition, using the "molle root" of the solvent-based group, a value equivalent to 100 g of the solid content of the filling amount other than the catalyst was defined as "molle root / 100 g" of the solvent-based group.

<Other embodiments>

As another embodiment of the polyurethane dispersant (b-1) of the present invention, those having a non-straight chain, that is, a main chain with a divergent structure, that is, at least 3 in the main chain, are listed. More than one branch.

In this embodiment, as will be described later, except for the case where the main chain has at least three or more branch structures that branch, the polyurethane skeleton of the main chain is close to a linear structure, as described below. The structure of the embodiment is considered to have good dispersibility in the photosensitive resin composition. In alkali development during patterning or high-temperature treatment at 200 ° C or higher, it is considered that the oxime ester photopolymerization initiator (c-1) and the alkali-soluble resin (d) are combined to multiply alkali resistance and heat resistance. Improved sexually, which can form high finesse Thin line.

If the main chain of the polyurethane dispersant (b-1) of this embodiment has a branch structure other than the bonding portion with the solvent medium group, the adsorption group and the bonding portion with the adsorption group, It is not particularly limited; examples of the branched structure include a partial structure represented by the following general formula (ii).

In the above formula (ii), R ^e represents a trivalent alcohol compound residue, and * represents a bonding group. The term “alcohol compound residue” means a residue from which a hydrogen atom has been removed from the total hydroxyl group of the alcohol compound.

The carbon number of the trivalent alcohol compound residue in the formula (ii) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 100 or less, more preferably It is 50 or less, and even more preferably 10 or less. When it is set to the above lower limit value or more, there is a tendency that the branched structure can be expanded well. When it is set to the above upper limit value or less, the dispersibility tends to be good.

Specific examples of the trivalent alcohol compound residue include trimethylolethane, trimethylolpropane, 1,2,3-propanetriol, 1,3,5-pentanetriol, and 1,5 , 10-Decanetriol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,3,5-trihydroxybenzene, and a polyamine with 3 hydroxyl groups at the end Residues of alcohol compounds such as alkylene oxide compounds. From the standpoint of well-diffused divergence, trimethylolethane, trimethylolpropane, 1,2,3- The residue of an alcohol compound of glycerol and 1,3,5-pentanetriol is more preferably an residue of an alcohol compound of trimethylolethane, trimethylolpropane or 1,2,3-glycerol.

Specific examples of the more preferable trivalent alcohol compound residue include the following.

Among these, from the viewpoint of having a well-diffused ambiguity, R ^{e is more} preferably an alcohol compound residue of trimethylolethane or trimethylolpropane.

In addition, the main chain of the polyurethane dispersant (b-1) of the present embodiment may contain direct bonds other than the bonding portion with the solvent medium group, the adsorption group, and the bonding portion with the adsorption group. Chain construction. As the linear structure, a partial structure shown in the above formula (i) can be preferably used.

At this time, the ratio of the linear structure and the divergent structure contained in the main chain is not particularly limited. The divergent structure is preferably 1% by mass or more, and more preferably 5% by mass or more, relative to the total of the linear structure and the divergent structure. It is preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less.

By setting it to the above lower limit value or more, the affinity of the solvent caused by the polyester structure part or the polyether structure part tends to be improved; and by setting it to be less than the above upper limit value, it is possible to reduce the three-dimensional obstacle. The tendency to efficiently adsorb to pigments.

Further, regarding the specific urethane dispersant (b-1) of the present embodiment, the specific adsorption group, the content ratio of the adsorption group, the specific compatibility vehicle group, the content ratio of the compatibility vehicle group, and the physical properties may be preferable. Use the above.

The method for producing a polyurethane dispersant (b-1) according to this embodiment is the same as that described above except that a small amount of a trifunctional or higher monomer is used in the urethane formation reaction. The method is the same. By using tri- or more functional monomers, several branch points are formed in the main chain.

Examples of the tri- or more-functional monomer used herein include a polyol, a polyamine, or a polyisocyanate, preferably a polyol or a polyamine, and particularly preferably a polyol.

Since the polyurethane dispersant (b-1) of this embodiment tends to gel easily, it is preferable to synthesize | combine so that it does not gel. From this viewpoint, the number average molecular weight of the polyurethane dispersant (b-1) is preferably 40,000 or less, and more preferably 30,000 or less. On the other hand, the number average molecular weight of the polyurethane dispersant (b-1) is preferably at least 3,000 or more, and more preferably at least 5,000 or more, from the viewpoint of a dispersion effect.

The polyurethane dispersant (b-1) of this embodiment can be synthesized by using the compounds (b-a ') and (b-d') instead of the compounds (ba) and (bd) in the above method. .

[Compound (b-a '): Polyisocyanate compound]

If the polyisocyanate compound (b-a ') contains a compound having three or more isocyanate groups, the polyurethane skeleton can be made into a divergent structure, but the divergence is preferably low.

The polyisocyanate compound (b-a ') includes not only a compound having three or more isocyanate groups, but also the diisocyanate compound (b-a). When a compound containing three or more functional groups that react with an isocyanate group is used as the compound (b-d ') described later, the polyisocyanate compound (b-a') may be a compound containing only a diisocyanate compound.

The average number of functional groups of the polyisocyanate compound (b-a ') is preferably 2.0 The above is preferably 2.5 or less, and more preferably 2.2 or less. When a compound containing three or more functional groups that reacts with an isocyanate group is used as the compound (b-d '), the average number of functional groups of the polyisocyanate compound (b-a') is particularly preferably 2.0.

Here, the average number of functional groups refers to a mixture of compounds having different numbers of functional groups, and the average value of the number of functional groups thereof is calculated by the following formula.

The average number of functional groups = [((the number of functional groups) x (the number of moles of the compound with the number of functional groups)])] / (the total number of moles of the compound)

The compound (b-a ') having an average number of functional groups is the same as the compound (b-a).

[Compound (b-d '): a compound having three or more functional groups that reacts with an isocyanate group and imparting a differentiated structure to a polyurethane skeleton]

The compound (bd) has two or more functional groups that react with an isocyanate group and forms a linear polyurethane skeleton. However, the compound (b-d ') contains at least one compound that reacts with an isocyanate group. A compound having three or more functional groups can introduce a divergent structure into the polyurethane skeleton of the main chain.

The compound (b-d ') may be a mixture of a compound having two functional groups that reacts with an isocyanate group, and a mixture with three or more compounds having a functional group that reacts with an isocyanate group. At this time, the average number of functional groups that react with the isocyanate group of the compound (b-d ') is preferably 2.01 or more, more preferably 2.1 or more, and preferably 4 or less, more preferably 3 or less.

Compound (b-d ') having three or more functional groups capable of reacting with isocyanate groups, and polyurethane dispersion caused by the compounds Specific examples of the partial structure of the agent (b-1) are as follows.

Examples of the low-molecular-weight polyol having three or more hydroxyl groups include trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the polyamine having three or more amine groups include diethyltriamine, gins (2-aminoethyl) amine, and triethylenetetramine.

In addition, by using a compound having 3 or 4 hydroxyl groups to synthesize a polyalkylene glycol or polymerize a lactone, it is preferable to obtain an oligomeric triol or tetraol having a number average molecular weight of 200 to 2,000. A polymer compound can also be used as the compound (b-d '). The compound (b-d ') is preferably a compound having a low molecular weight of three hydroxyl groups.

Specific examples of the compound having three or more functional groups that react with an isocyanate group among the compounds (b-d ') are shown in the lower left. This allows them to be used in the polyurethane dispersant (b-1). Import the lower right part of the structure.

[Chemical 69]

In the above formula, * adjacent to an oxygen atom represents a bonding group with a carbonyl group of an urethane bond in a polyurethane skeleton of a main chain; and * adjacent to a nitrogen atom represents a main chain The bonding group between carbonyl groups of the urea bond in the polyurethane skeleton; the * adjacent to the sulfur atom means the bonding group with the thiourea bond in the polyurethane skeleton of the main chain.

Moreover, if it is a compound which has three or more hydroxyl groups and / or a primary and secondary amine group, it can also be used as a compound (b-d ').

The number average molecular weight of the compound (b-d ') is preferably 32 to 3,000. These compounds may be used alone or in combination.

Next, for compounds (b-a '), (b-b), (b-c), (b-d'), (b-e) The amount of the isocyanate group and the amount of the functional group which reacts with the isocyanate group in the will be described.

The isocyanate group in the polyurethane dispersant (b-1) of this embodiment is basically caused by the compound (b-a '). In contrast, the functional group that reacts with an isocyanate group is caused by the compounds (b-b), (b-c), (b-d '), and (b-e). The amount of these functional groups is preferably used in the same manner as described below.

{(b-a ') number of isocyanate groups} × {mole number of (b-a')} = {number of functional groups that react with isocyanate groups in (bb)} × {mole number of (bb) } + {Number of functional groups reacting with isocyanate group in (bc)} × {Mole number of (bc)} + {Number of functional groups reacting with isocyanate group in (b-d ')} × {(b Moore number of -d ')} + {Number of functional groups reacting with isocyanate group in (be)} × {Mole number of (be)}

Among them, when the compound of (b-a ') to (b-e) is a mixture, the average number of functional groups of the functional groups of the mixture and the total mole number of the mixture are used.

The preferable structure of the polyurethane dispersant (b-1) of the present embodiment can be obtained by using the following compounds.

‧Number of isocyanate groups in (b-a '): 2

‧Number of functional groups reacting with isocyanate group in (b-b): 2

‧Number of functional groups to react with isocyanate group in (b-c): 2

‧Number of functional groups reacting with isocyanate groups in (b-d '): Contains a mixture of 2 and 3 or more, and the average number of functional groups is at least 2.

‧Functional group for reaction with isocyanate group in (b-e): 1

The branching structure of the polyurethane dispersant (b-1) of this embodiment is preferably low. The so-called low degree is represented by the following definition. First, Yu and Yi Among the functional groups that react with a cyanate group, the average number of functional groups of the compounds (b-b), (b-c), and (b-d ') other than the compound (b-e) that functions as a chain stopper is considered. This is defined as "the average number of functional groups which react with an isocyanate group other than a chain stopper".

`` Average number of functional groups that react with isocyanate groups other than a chain stopper '' = A / B

Among them, A and B are as follows.

A = {Number of functional groups reacting with isocyanate group in (bb)} × {Mole number of (bb)} + {Number of functional groups reacting with isocyanate group in (bc)} × {Motion of (bc) Ear number} + {Number of functional groups reacting with isocyanate group in (b-d ')} × {Mole number of (b-d')}

B = (Mole number of (b-b)) + {Mole number of ((b-c)} + {Mole number of ((b-d ')}

The polyurethane dispersant (b-1) of the present embodiment can be a polyurethane compound having an "average number of functional groups that react with isocyanate groups other than the chain stopper" greater than two. In order to make the "average number of functional groups reacting with isocyanate groups other than the chain stopper" larger than 2, it is preferable that the average number of functional groups using compounds reacting with isocyanate groups of the compound (b-d ') is larger than two. Therefore, the compound (b-d ') should just be a compound containing at least 3 or more functional groups which react with an isocyanate group.

The functional group that reacts with the isocyanate group of the compound (b-d ') is preferably a hydroxyl group or an amine group, and particularly preferably a hydroxyl group. The compound (b-d ') may also be a mixture of several compounds.

The "average number of functional groups that react with isocyanate groups other than the chain stopper" is preferably more than 2.0 and 3.0 or less. The "average number of functional groups that react with an isocyanate group other than a chain stopper" is preferably 2.6 or less, and more preferably 2.4 Hereinafter, it is more preferably 2.3 or less.

The "average number of functional groups that react with isocyanate groups other than the chain stopper" is preferably low. By reducing the "average number of functional groups that react with isocyanate groups other than the chain stopper" to a low degree, it is possible to suppress the entanglement caused by the entanglement of the polyurethane dispersant (b-1) itself. The compatibility between the alkali-soluble resin or the photopolymerizable monomer in the solvent or the photosensitive resin composition tends to deteriorate. In addition, it is possible to prevent the steric hindrance from increasing due to the entanglement of the dispersant, and it is possible to suppress the deterioration of the adsorption of the pigment. Thereby, the dispersibility in a solvent, the alkali-resistant developer resistance at the time of formation of a thin line, and the heat resistance at the time of high-temperature processing are good, and there exists a tendency which can fully exhibit the effect of this invention.

Moreover, the number average molecular weight of the polyurethane dispersant (b-1) of this embodiment is preferably 3,000 or more, more preferably 5,000 or more, and preferably 40,000 or less, and more preferably 30,000 or less.

<Other dispersants>

The dispersant (b) in the photosensitive resin composition of the present invention contains at least the above-mentioned polyurethane dispersant (b-1), but does not affect the use of the polyurethane dispersant (b) -1) Within the range of the effects of the present invention obtained, a dispersant (b-2) other than the polyurethane dispersant (b-1) may be used in combination.

As the other dispersant (b-2), a polymer dispersant is preferred. In terms of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or such a base; Tertiary amine; quaternary ammonium; pyridine, pyrimidine or pyridine High molecular dispersants with functional groups such as heterocyclic groups containing nitrogen atoms. Among them, particularly preferred is a level 1, 2 or 3 amine group; a level 4 ammonium salt; pyridine, pyrimidine or pyridine Etc. is a polymeric dispersant having a basic functional group such as a nitrogen atom-containing heterocyclic group.

Examples of other polymer dispersants that can be used in combination include, for example, urethane-based dispersants, acrylic dispersants, and polyethyleneimine-based dispersants other than the polyurethane dispersant (b-1). Agent, polyallylamine dispersant, dispersant containing monomer having amine group and macromonomer, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant Agents, polyester phosphoric acid-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified polyester-based dispersants.

Specific examples of such other dispersants that can be used in combination include EFKA [registered trademark, the same applies hereinafter]. EFKA CHEMICALS BV (EFKA). ], Disperbyk (registered trademark, the same below. Made by BYK Chemie.), DISPARLON (registered trademark, the same below. Made by Kusumoto Kasei), SOPSPERSE (registered trademark, the same below: made by Lubrizol Corporation.), KP (Shin-Etsu Chemical Industry Co., Ltd.) Company), Polyflow or Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, the same below. Ajinomoto Fine-techno company.), Etc.

More specifically, for example, EFKA-4046, -4047 (manufactured by BASF), Disperbyk-111, 161, -162, -163, -166, -167, -182, -2000, -2001 (BYK Chemie (Manufactured by the company), DISPARLON DA-7301, ED-701 (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE-22000, -24000, -28000 (manufactured by Lubrizol), Flowlen KDG-2400 (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper-PB -821, -881 (manufactured by Ajinomoto Fine-techno), and the like.

These polymer dispersants may be used in combination with only one kind of polyurethane dispersant (b-1), or may be used in combination of two or more kinds.

Among these other dispersants, urethane-based polymer dispersants other than the polyurethane-based dispersant (b-1) having a basic functional group and / or propylene are preferred. The enoic acid-based polymer dispersant, especially the urethane-based polymer dispersant. A polymer dispersant having a basic functional group and having a polyester and / or polyether bond is also preferred.

Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include, for example, a polyisocyanate compound having three or more isocyanate groups, such as a toluene diisocyanate trimer, having Weight obtained by reacting a compound having one or two hydroxyl groups and a compound having a number-average molecular weight of 300 to 10,000 or a compound having a chain extension group and a compound having one active hydrogen and a tertiary amine group in the same molecule A dispersion resin with an average molecular weight of 1,000 to 200,000.

In such a resin, the introduction amount of a compound having active hydrogen and a tertiary amine group in the same molecule is preferably controlled within a range of 1 to 100 mgKOH / g based on the amine value after the reaction. A more preferable range is 5 to 95 mgKOH / g.

Examples of such commercially available dispersants include Disperbyk-161, -162, -163, -166, -167, -182 (by BYK Chemie), or EFKA-4046, -4047 (by BASF, etc.).

In the present invention, the amine valence is a value represented by the number of mg of KOH corresponding to the acid value when the basic amine group is neutralized and titrated with an acid; specifically, it is measured by the following method. If the amine value is lower than the above range, the dispersing ability tends to decrease, and if it exceeds the above range, the developability tends to decrease.

<Method for measuring amine value>

The amine valence is represented by the mass of alkali and equivalent KOH per 1 g of the solid content of the dispersant sample without the solvent, and can be measured by the following method.

In a 100mL beaker, weigh 0.5 ~ 1.5g of the dispersant sample and dissolve it in 50mL acetic acid. Using an automatic titration device with a pH electrode, this solution was neutralized and titrated with a 0.1 mol / L HClO ₄ (perchloric acid) acetic acid solution. The inflection point of the titration pH curve was used as the end point of the titration, and the amine value was obtained from the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)

[Where: W: the dispersant sample weighing amount [g], V: the titration end point of the titration [mL], and S: the solid content concentration [mass%] of the dispersant sample. ]

[Photopolymerization initiator (c)]

The photopolymerization initiator (c) contained in the photosensitive resin composition of the present invention is characterized by containing at least an oxime ester photopolymerization initiator (c-1).

<Oxime ester photopolymerization initiator (c-1)>

In the present invention, the reason why the oxime esters belonging to the oxime derivatives (oxime-based and ketoxime-based compounds) are effective as the photopolymerization initiator (c) is as follows.

That is, the specific polyurethane dispersant (b-1) used as the dispersant (b) in the present invention is a photosensitive resin composition, and an oxime ester photopolymerization initiator (c -1) When used as a photopolymerization initiator (c), when making a color filter, etc., it can be easily formed by improving the resistance to an alkali developer and suppressing thermal deformation in the subsequent high-temperature hardening treatment. The fine and fine lines required by the market.

The urethane dispersant (b-1) used in the present invention, as described above, ingests pigment at the position of the adsorption group or the urethane skeleton, and is contained in the polyester chain or polyester chain. The part and the resin or monomer in the photosensitive resin composition are compatible with each other and entangled, and thereafter, the resin or monomer of the photosensitive resin composition is subjected to photopolymerization initiator (c) by ultraviolet rays. Alkali development and heat resistance Improved even more. It is considered that this effect is further enhanced by using a polyurethane dispersant (b-1) and an oxime ester photopolymerization initiator (c-1) together.

In particular, at the side of the thin line pattern where the ultraviolet light is blocked by the mask during the exposure of the substrate and the thin line pattern that are hard to reach by ultraviolet rays, or the ultraviolet light, the oxime ester photopolymerization initiator (c-1 ) Coexistence with the polyurethane dispersant (b-1) can multiply improve the effects of the resistance of the alkali developing solution and the heat resistance, and can easily form high-fine fine lines.

In addition, the oxime ester photopolymerization initiator (c-1) has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates free radicals in its structure. It is stable, and a small amount of photosensitive resin composition can be designed. In particular, from the viewpoint of light absorption of i-rays (365 nm) of an exposure light source, photopolymerization of an oxime ester having a carbazolyl group which may be substituted (a group having a carbazole ring which may be substituted) is initiated. In the case of the agent (c-1), this structural property is well expressed, so it is more preferable.

At present, the market requires a high degree of shading. On the other hand, the film is BM (black matrix), and the pigment concentration is gradually increasing. Under such conditions, the oxime ester photopolymerization initiator (c-1) can effectively function.

Examples of the oxime-based compound of the oxime ester photopolymerization initiator (c-1) include compounds containing a structural moiety represented by the following general formula (22), and preferably include compounds represented by the following general formula (23) Oxime ester compounds.

In the above formula (22), R ²² represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, and an alkenoyl group having 3 to 25 carbon atoms, respectively, which may be substituted. , 3 to 8 carbon alkanoyl groups, 3 to 20 carbon alkoxycarbonyl alkyl groups, 8 to 20 carbon phenoxy carbonyl alkyl groups, 3 to 20 heteroaryloxy groups Carbonyl alkanoyl, amine alkyl carbonyl having 2 to 10 carbons, aryl fluorenyl having 7 to 20 carbons, heteroaryl fluorenyl having 1 to 20 carbons, alkoxycarbonyl having 2 to 10 carbons, or carbon Aryloxycarbonyl groups of 7 to 20.

In the above formula (23), R ^21a represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon number 1 Heteroarylalkyl of 20 to 20, alkoxycarbonylalkyl of 3 to 20 carbons, phenoxycarbonylalkyl of 8 to 20 carbons, heteroaryloxycarbonylalkyl of 1 to 20 carbons or hetero Arylsulfanyl group, amino alkyl group with 1 to 20 carbon atoms, alkyl alkyl group with 2 to 12 carbon atoms, alkenyl group with 3 to 25 carbon atoms, naphthene alkyl group with 3 to 8 carbon atoms, carbon number Aryl onium of 7 to 20, heteroaryl on carbon of 1 to 20, alkoxycarbonyl of 2 to 10 carbon, aryloxycarbonyl of 7 to 20 carbon, or cycloalkane of 6 to 20 carbon Alkyl.

R ^21b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

Moreover, R ^21a and R ^21b may form a ring together, and examples of the linking group thereof include an alkylene group having 1 to 10 carbon atoms, a polyvinyl group [-(CH = CH) _r- ], or poly Ethynyl [-(C≡C) _r- ] or a combination of these. In addition, r is an integer of 0 to 3.

R ^22a represents the same group as R ²² in the above formula (22).

Among these, from the viewpoint of sensitivity, as R ^{22 in the} above general formula (22) and R ^22a in the above general formula (23), preferably, alkyl groups of 2 to 12 carbons, carbon Heteroarylalkanoyl groups having 1 to 20 carbon atoms, and cycloalkanoyl groups having 3 to 8 carbon atoms; more preferable examples include alkyl alkanoyl groups having 2 to 10 carbon atoms; and more preferred examples include alkyl alkanoyl groups having 2 to 5 carbon atoms. .

As R ^21a in the general formula (23), from the viewpoints of solubility and sensitivity to a solvent, an alkyl group having 1 to 20 carbon atoms that can be substituted, and a carbon number that can be substituted are preferably listed. A cycloalkylalkyl group having 1 to 10 or an aryl group having 6 to 20 carbon atoms which may be substituted. More preferably, it is methyl, ethyl, propyl, cyclopentylethyl, 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl or N-ethenyl- Propyl substituted by N-ethoxyamino.

In addition, as R ^21b in the general formula (23), a carbazolyl group which may be substituted, and 9-oxysulfide, which may be substituted, are preferred. Or may be substituted phenyl sulfide. When R ^21b is contained as a carbazolyl group which may be substituted, it is more preferable for the reasons described above. An oxime ester initiator containing a carbazolyl group having a nitro group is also effective.

It is preferable that the oxime ester photopolymerization initiator (c-1) contains a carbazolyl group which may be substituted as R ^21b for the reasons described above. More preferably, it is selected from the group consisting of an aryl group having 6 to 25 carbon atoms which may be substituted, an aryl carbonyl group having 7 to 25 carbon atoms which may be substituted, and a heteroaryl group having 5 to 25 carbon atoms which may be substituted. , A heteroarylcarbonyl group having 6 to 25 carbon atoms which may be substituted, and a carbazolyl group having at least one kind of nitro group. From the viewpoint of sensitivity, particularly preferred is a carbazolyl group having at least one type selected from the group consisting of benzamyl, tolylmethyl, naphthylmethyl, thienylcarbonyl, and nitro. If the substituents that the carbazolyl group can also have are these, there is no great influence on the sensitivity of the photopolymerization initiator. Even if it has a slight effect, you can still adjust the exposure amount or adjust the photopolymerization initiator. The added amount tends to form a desired thin line.

From the viewpoint of efficiently transmitting the absorbed light energy, these groups are preferably bonded to the 3-position of the carbazole group. Similarly, the C atom in the above formula (23) is preferably bonded to the 6-position of the carbazolyl group.

The H atom bonded to the N atom of the carbazolyl group may be substituted by an arbitrary substituent. From the viewpoint of solubility in a solvent, an arbitrary substituent is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. Of alkyl.

As commercially available products of this oxime ester photopolymerization initiator (c-1), there are OXE-02 manufactured by BASF Corporation, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Qiangli Electronics Co., or ADEKA Corporation. NCI-831 and so on.

As the oxime ester photopolymerization initiator (c-1), preferred oxime ester compounds in the present invention include the compounds exemplified below, but are not limited to these compounds.

[Chemical 73]

[Chemical 75]

On the other hand, examples of the ketoxime ester compound as the oxime ester photopolymerization initiator (c-1) include compounds containing a structural moiety represented by the following general formula (24), and preferably the following general formula The oxime ester compound shown in (25).

[Chemical 76]

In the general formula (24), R ²⁴ is synonymous with R ²² in the general formula (22).

In the general formula (25), R ^23a may also represent a substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl alkyl group having 1 to 20 carbon atoms, Alkoxycarbonylalkyl with 3 to 20 carbons, phenoxycarbonylalkyl with 8 to 20 carbons, alkylsulfanyl with 2 to 20 carbons, heteroaryloxycarbonylalkane with 1 to 20 carbons Or heteroarylsulfanyl group, amino alkyl group having 1 to 20 carbon atoms, alkyl alkyl group having 2 to 12 carbon atoms, alkenyl group having 3 to 25 carbon atoms, and cycloalkyl alkyl group having 3 to 8 carbon atoms , Arylfluorenyl group with 7 to 20 carbon atoms, Heteroarylarylene group with 1 to 20 carbon atoms, Alkoxycarbonyl group with 2 to 10 carbon atoms, Aryloxycarbonyl group with 7 to 20 carbon atoms, or 6 to 20 carbon atoms Its cycloalkylalkyl.

R ^23b represents an arbitrary substituent containing an aromatic ring or a heteroaromatic ring.

Moreover, R ^23a and R ^23b may form a ring together, and examples of the linking group thereof include an alkylene group having 1 to 10 carbon atoms, a polyvinyl group [-(CH = CH) _r- ], or poly Ethynyl [-(C≡C) _r- ] or a combination of these. In addition, r is an integer of 0 to 3.

R ^24a represents an alkylfluorenyl group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkylfluorenyl group having 4 to 8 carbon atoms, and a benzamyl group having 7 to 20 carbon atoms, respectively, which may be substituted. , Heteroarylfluorenyl with 3 to 20 carbons, alkoxycarbonyl with 2 to 10 carbons, aryloxycarbonyl with 7 to 20 carbons, heteroaryl with 2 to 20 carbons, or 2 to 20 carbons Alkylaminocarbonyl.

As R ^{24 in} the general formula (24) and R ^24a in the general formula (25), preferred examples include alkyl alkanoyl groups having 2 to 12 carbon atoms, heteroaryl alkyl fluorenyl groups having 1 to 20 carbon atoms, A cycloalkanoyl group having 3 to 8 carbon atoms or an arylfluorenyl group having 7 to 20 carbon atoms.

As R ^23a in the general formula (25), an unsubstituted ethyl group, a propyl group, or a butyl group, or an ethyl group or a propyl group substituted with a methoxycarbonyl group is preferred. In addition, as R ^23b in the general formula (25), a carbazolyl group which may be substituted and a phenylthioether group which may be substituted may be mentioned. However, those containing carbazolyl as R ^23b are based on the above. The reason is better.

As the oxime ester photopolymerization initiator (c-1), preferred ketoxime ester compounds in the present invention include the compounds exemplified below, but are not limited to these compounds.

[Chem. 78]

As a commercially available product of such an oxime ester photopolymerization initiator (c-1), there is BASF OXE-01 made by the company or TR-PBG-305 made by Changzhou Qiangli Electronics Co., Ltd.

These oxime and ketoxime ester compounds are known compounds per se, for example, one of a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 or Japanese Patent Laid-Open No. 2006-36750.

The said oxime ester photopolymerization initiator (c-1) may be used individually by 1 type, and may use 2 or more types together.

<Other photopolymerization initiators>

The photopolymerization initiator (c) of the present invention contains at least the above-mentioned oxime ester photopolymerization initiator (c-1), but does not affect the product obtained by using the oxime ester photopolymerization initiator (c-1). Within the scope of the effects of the present invention, a photopolymerization initiator (c-2) other than the oxime ester photopolymerization initiator (c-1) may be used in combination. If necessary, an additive such as an accelerator or a sensitizing dye may be used.

Examples of other photopolymerization initiators (c-2) include metallocenes containing a titanocene derivative described in Japanese Patent Laid-Open No. 59-152396 and Japanese Patent Laid-Open No. 61-151197. Compounds; biimidazole derivatives described in Japanese Patent Laid-Open No. 2000-56118; halomethylation described in Japanese Patent Laid-Open No. 10-39503 Diazole derivatives, halomethyl-s-tris Derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, etc. Free radical activators or α-aminoalkylacetophenone derivatives.

Specifically, for example, as the dititanium derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl biphenyl titanium, and dicyclopentadienyl bis (2,3,4, 5,6-pentafluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2,3,5,6-tetrafluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2, 4,6-trifluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2,6-difluorophenyl-1-yl) titanium, dicyclopentadienyl bis (2,4-difluoro Phen-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-pentafluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,6-difluorophenyl-1-yl) titanium and dicyclopentyl Dienyl [2,6-di-fluoro-3- (pyrrol-1-yl) -phenyl-1-yl) titanium and the like.

Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5- Bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl)- 4,5-diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer.

In addition, as halomethylation Examples of the diazole derivatives include 2-trichloromethyl-5- (2'-benzofuranyl) -1,3,4- Diazole, 2-trichloromethyl-5- [β- (2'-benzofuranyl) vinyl] -1,3,4- Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuranyl) vinyl)]-1,3,4- Diazole and 2-trichloromethyl-5-furanyl-1,3,4- Diazole and so on.

Also, as halomethyl-s-tri Examples of the derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-tri , And 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-tri Wait.

Examples of the α-aminoalkylacetophenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2- Porinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) butane-1-one, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-diethylaminoacetophenone, 4-dimethylamine Propylbenzene, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino -3- (4-Diethylaminobenzyl) coumarin and 4- (diethylamino) chalcone.

Other examples include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, Anthraquinone derivatives such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; diphenyl ketone, Michelin, 2-methyldiphenyl ketone, 3- Diphenyl ketone derivatives such as methyl diphenyl ketone, 4-methyl diphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl ketone; 2 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylacetone, 1 -Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiobenzene Base) -2- Acetophenone derivatives such as phosphono-1-acetone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; 9-oxysulfur 2-ethyl 9-oxysulfur , 2-isopropyl 9-oxysulfur , 2-chloro9-oxysulfur 2,4-dimethyl 9-oxosulfur , 2,4-diethyl 9-oxysulfur 2,4-diisopropyl 9-oxysulfur 9-oxysulfur Derivatives; ethyl benzoate derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p-methoxyphenyl) Acridine derivatives such as acridine; 9,10-dimethylbenzophene Waiting for coffee Derivatives; Anthrone derivatives such as benzoxanthone.

These other photopolymerization initiators may be used alone or in combination of two or more.

<Accelerator>

Examples of the accelerator include 2-mercaptobenzothiazole and 2-mercaptobenzo Azole, 2-mercaptobenzimidazole and other heterocyclic mercapto compounds or aliphatic polyfunctional mercapto compounds. The accelerator may be used singly or in combination of two or more kinds.

<Sensitizing pigment>

In the photopolymerization initiator (c), a sensitizing dye combined with a wavelength of an image exposure light source may be used in combination according to the purpose of improving the sensitivity of the sensing as needed. Examples of such sensitizing dyes include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756. Pigments; coumarin pigments with heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335; Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335 3-ketocoumarin compounds described in the gazette, pyrromethene pigments described in Japanese Patent Laid-Open No. 6-19240; others, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292 Gazette, Japanese Patent Laid-Open Publication No. 45-37377, Japanese Patent Laid-Open Publication No. 48-84183, Japanese Patent Laid-Open Publication No. 52-112681, Japanese Patent Laid-Open Publication No. 58-15503, Japanese Patent Laid-Open Publication 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent A pigment having a dialkylaminobenzene skeleton as described in JP-A 5-210240 and JP-A 4-288818.

Among these sensitizing dyes, amine-containing sensitizing dyes are preferable, and compounds having an amine group and a phenyl group in the same molecule are more preferable. Particularly preferred are, for example, 4,4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4-aminodiphenyl ketone, Diphenyl ketone compounds such as 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3,4-diaminodiphenyl ketone; 2- (p- Dimethylaminophenyl) benzo Azole, 2- (p-diethylaminophenyl) benzo Azole, 2- (p-dimethylaminophenyl) benzo [4,5] benzo Azole, 2- (p-dimethylaminophenyl) benzo [6,7] benzo Azole, 2,5-bis (p-diethylaminophenyl) 1,3,4- Azole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (P-ethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diamino Ethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminobenzene) Compounds) containing p-dialkylaminophenyl and the like.

Among these, 4,4'-dialkylamino diphenyl ketone is the most preferable.

The sensitizing dye may be used alone or in combination of two or more.

[Alkali soluble resin (d)]

As the resin used in the photosensitive resin composition of the present invention, an alkali-soluble resin (d) is used. If the alkali-soluble resin (d) used in the present invention is a film obtained by coating and drying the photosensitive resin composition of the present invention containing the same, the exposed portion and the non-exposed portion are exposed to the alkali developing solution. The solubility is not particularly limited, but is preferably an alkali-soluble resin (d-1) having at least one of a carboxyl group and an ethylenically unsaturated group, and more preferably an alkali having a carboxyl group and an ethylenically unsaturated group. Soluble resin.

Specific examples include epoxy (meth) acrylate resins and acrylic copolymer resins having a carboxyl group. As a preferable one, the epoxy (meth) acrylate resin (D1-1), epoxy (meth) acrylate resin (D1-2), and acrylic acid copolymerization mentioned later are mentioned more specifically, Resin (D2-1), acrylic copolymer resin (D2-2), acrylic copolymer resin (D2-3), and acrylic copolymer resin (D2-4). These may be used singly or in combination of two or more kinds.

Among the above, an epoxy (meth) acrylate resin having a carboxyl group is particularly preferred. The reason is as follows.

The alkali-soluble resin (d) is used in the present invention and contains the above-mentioned polyurethane dispersant (b-1) having a urethane skeleton, a soluble solvent group and an adsorption group, and a solvent (e). The photosensitive resin composition is well compatible, and the polyether chain and / or polyester chain of the polyurethane dispersant (b-1) and the polymer are alkali-soluble resins (d). It is a three-dimensional obstacle that prevents the color material (a) from aggregating, and maintains a good dispersion state.

In the production of a color filter, the polyether chain and / or polyester chain of the highly compatible polyurethane dispersant (b-1) and the alkali-soluble resin (d) of the polymer cross each other. Entanglement, or the adsorption group or polyurethane skeleton of the polyurethane dispersant (b-1) adsorbs to the color material (a), and if the color material (a) with high resistance is taken in, the alkali develops At or after high temperature treatment, the deformation caused by the etching or heat of the alkali developer is small.

In addition, when a color filter is produced, when a non-exposed portion is dissolved in an alkali developing solution, an alkali-soluble resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphate group, or a sulfonic acid group is used as a binder resin. In particular, when an alkali-soluble resin has a carboxyl group, it tends to be more easily dissolved in an alkali developing solution than when it has a hydroxyl group.

In addition, the phosphate group or sulfonic acid group is more acidic than the carboxyl group, but it is easy to react with a basic photopolymerization initiator, photopolymerizable monomer, dispersant, and other additives in the photosensitive resin composition. When storage stability deteriorates.

In addition, when the acidic group of the alkali-soluble resin is a carboxyl group, it does not affect the dispersion, has a weak affinity with the dispersant (b), and inhibits the erosion caused by the alkali developer during alkali development or the subsequent high-temperature treatment. The tendency to deform by heat.

When the alkali-soluble resin has an ethylenically unsaturated group, the polyether chain and / or polyester chain of the polyurethane dispersant (b-1) and the alkali are crosslinked by ultraviolet irradiation. The entanglement of the soluble resin (d) becomes stronger, and the alkali developing solution resistance and heat resistance of the ultraviolet irradiated portion tend to be very large.

When the alkali-soluble resin (d) has an ethylenically unsaturated group, the effect obtained by using a polyurethane dispersant (b-1) and an oxime ester photopolymerization initiator (c-1) in combination can be obtained. Improved even more.

Especially the connection between the substrate and the thin line pattern which are hard to reach by ultraviolet rays The sticky part or the side face of the thin line pattern that is weakened by light shielding due to the mask during ultraviolet exposure, is combined with an alkali-soluble resin having an ethylenically unsaturated group and a polyurethane dispersant (b-1 ) And the oxime ester photopolymerization initiator (c-1) tend to multiply improve the resistance and heat resistance of the alkali developing solution, and tend to form highly fine fine lines.

When an epoxy (meth) acrylate resin is used as the alkali-soluble resin having a carboxyl group and an ethylenically unsaturated group, a large amount of unsaturated groups or carboxyl groups can be added to the resin. In addition, it is possible to introduce more aromatic ring structures or alicyclic structures with a larger three-dimensional volume, and it is possible to further improve the resistance to alkali developer and heat resistance.

<Epoxy (meth) acrylate resin>

Examples of the epoxy (meth) acrylate resin having a carboxyl group include the following epoxy (meth) acrylate resin (D1-1) and / or epoxy (meth) acrylate resin (D1) -2).

<Epoxy (meth) acrylate resin (D1-1)>

The ring obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an epoxy resin to react at least one of a polybasic acid and an anhydride thereof. Oxy (meth) acrylate resin.

<Epoxy (meth) acrylate resin (D1-2)>

By adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an epoxy resin, a polyhydric alcohol and at least one of a polybasic acid and an anhydride thereof are reacted, The obtained epoxy (meth) acrylate resin.

Used as epoxy (meth) acrylate resin (D-1) and epoxy group Examples of the epoxy resin used as a raw material for the (meth) acrylate resin (D-2) include bisphenol A type epoxy resins (for example, "Epikote (registered trademark. The same applies hereinafter) 828", "828" manufactured by Mitsubishi Chemical Corporation, and " Epikote 1001 "," Epikote 1002 "," Epikote 1004 ", etc.), epoxy groups obtained by the reaction of alcoholic hydroxyl groups of bisphenol A epoxy resin with epichlorohydrin (for example," made by Nippon Kayaku Co., Ltd. " "NER-1302" (epoxy equivalent 323, softening point 76 ° C)), bisphenol F-type resin (for example, "Epikote 807", "EP-4001", "EP-4002", "EP4004, etc." manufactured by Mitsubishi Chemical Corporation "), An epoxy resin obtained by reacting an alcoholic hydroxyl group of an bisphenol F-type epoxy resin with epichlorohydrin (for example," NER-7406 "manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C) ), Bisphenol S-type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol-based novolac-type epoxy resin (for example, manufactured by Nippon Kayaku Co., Ltd. "EPPN-201", "EP-152" manufactured by Mitsubishi Chemical Corporation, "EP-154", "DEN-438" manufactured by Dow Chemical Co., Ltd.), (Neighbor, Inter, Right-) Novolac-type epoxy resin (for example, "EOCN (registered trademark. The same applies hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., triglycidyl trimer isocyanate ( For example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd., and triphenol methane epoxy resin (for example, "EPPN (registered trademark. The same applies hereinafter) -501", "EPN-502" manufactured by Nippon Kayaku Co., Ltd. , "EPPN-503", alicyclic epoxy resin ("Celloxide (registered trademark. The same applies hereinafter) 2021P", "Celloxide EHPE", manufactured by DAICEL Chemical Industries, Ltd.), and will be obtained by the reaction of dicyclopentadiene and phenol Epoxy resin (e.g., "EXA-7200" manufactured by Dainippon Ink Co., Ltd., and "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) and the following general formula (d1) ~ ( d4).

Specifically, for example, "XD-1000" manufactured by Nippon Kayakusho Co., Ltd. as an epoxy resin represented by the following general formula (d1), and by the following general formula (d2) "NC-3000" manufactured by Nippon Kayaku Co., Ltd. and "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd. of epoxy resin represented by the following general formula (d4).

In the general formula (d1), b11 represents an average value and a number from 0 to 10. R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, phenyl, naphthyl, or biphenyl. The plural R ^{11 in} one molecule may be the same as or different from each other.

In the general formula (d2), b12 represents an average value and a number from 0 to 10. R ²¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plural R ²¹ present in one molecule may be the same as or different from each other.

In the above general formula (d3), X represents the following general formula (d3-1) or (d3-2) Linker shown. Among them, the molecular structure contains one or more adamantane structures. b13 represents an integer of 2 or 3.

In the above general formulae (d3-1) and (d3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an adamantyl group, a hydrogen atom, or a carbon that may also have a substituent. An alkyl group having 1 to 12 or a phenyl group which may have a substituent. In addition, the * symbol in each formula shows the bonding site in (d3).

In the general formula (d4), p and q each independently represent an integer of 0 to 4, and R ⁴¹ and R ⁴² each independently represent an alkyl group or a halogen atom. R ⁴³ and R ⁴⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more.

Among these, an epoxy resin represented by any of the general formulae (d1) to (d4) is preferably used.

Examples of the α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group include (meth) acrylic acid, butenoic acid, o-, m-, and p-vinyl benzoic acid , (Meth) acrylic acid, α-haloalkyl, alkoxy, halogen, nitro, cyano substituted monocarboxylic acids, 2- (meth) acryloxyethyl succinic acid, 2- ( (Meth) acrylic acid oxyethyl adipic acid, 2- (meth) acrylic acid oxyethyl phthalic acid, 2- (meth) acrylic acid Oxyethylhexahydrophthalic acid, 2- (meth) acrylic acid, oxyethyl maleic acid, 2- (meth) acrylic acid, oxypropyl succinic acid, 2- (meth) acrylic acid Oxypropyl adipic acid, 2- (meth) acryloxypropyltetrahydrophthalic acid, 2- (meth) acryloxypropylphthalic acid, 2- (meth) acryloxy Propylmaleic acid, 2- (meth) acryloxybutyl succinic acid, 2- (meth) acryloxybutyl adipate, 2- (meth) acryloxybutyl Hydroxyphthalic acid, 2- (meth) acryloxybutyl phthalic acid, 2- (meth) acryloxybutyl maleic acid, ε-caprolactone, β- Monolactone monomers such as propiolactone, γ-butyrolactone, δ-valerolactone, or succinic acid added to hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate (Anhydride), phthalic acid (anhydride), maleic acid (anhydride) and other monomers of acid (anhydride), (meth) acrylic acid dimer, and the like.

Among these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.

As a method for adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, in the presence of an esterification catalyst, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid having a carboxyl group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. .

As the esterification catalyst used here, for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and tetramethylammonium chloride and tetraethyl chloride can be used. Grade 4 ammonium salts such as ammonium, dodecyltrimethylammonium chloride, etc.

Moreover, an epoxy resin, an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and an esterification catalyst may be used singly or in combination of two or more kinds.

The amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is 1 equivalent to the epoxy group of the epoxy resin, preferably in the range of 0.5 to 1.2 equivalents. A more preferable range is 0.7 to 1.1 equivalents.

If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated group introduced will be insufficient, followed by reaction with a polybasic acid and / or its anhydride Also insufficient.

Moreover, it is disadvantageous that a large amount of epoxy groups remain. On the other hand, if the amount is large, the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted substance. In any case, it is believed that the hardening characteristics tend to deteriorate.

Examples of the polybasic acid and / or its anhydride include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromelic acid, trimellitic acid, Diphenyl ketone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof Or 2 or more.

Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromelic acid, trimellitic acid or biphenyltetracarboxylic acid, or the like anhydride. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

With regard to the addition reaction of a polybasic acid and / or its anhydride, a known method can be used to add the Under the same conditions as the reaction, the reaction can be continued to obtain the target.

The addition amount of the polybasic acid and / or its anhydride component is preferably such that the carboxylic group-containing epoxy (meth) acrylate resin has an acid value in the range of 10 to 150 mgKOH / g, and more preferably 20 A degree in the range of ~ 140 mgKOH / g.

If the acid value of the carboxyl-containing epoxy (meth) acrylate resin is less than the above range, it tends to lack alkali developability, and if it exceeds the above range, it is considered that The hardening performance tends to deteriorate.

In addition, in the synthesis of the addition reaction of a polybasic acid and / or its anhydride, a polyhydric alcohol such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added as a polymorphic structure to be introduced.

Epoxy (meth) acrylate resins (D1-1) and (D1-2) are usually produced by epoxy resin and α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid with carboxyl group. The reactant of the acid ester is mixed with the polybasic acid and / or its anhydride or the reactant of the epoxy resin and the α, β-unsaturated monocarboxylic acid or the α, β-unsaturated monocarboxylic acid having a carboxyl group , Obtained by mixing a polybasic acid and / or its anhydride and a polyhydric alcohol and heating it.

In this case, the order of mixing the polybasic acid and / or its anhydride with the polyhydric alcohol is not particularly limited. By heating, any hydroxyl group present in a mixture of an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group, and a polyol , Addition reaction of polybasic acid and / or its anhydride.

If the amount of polyhydric alcohol is too small, the effect is relatively thin; if it is too large, there is a possibility of thickening or gelation. Therefore, it is more suitable for epoxy resin and α, β-unsaturated monocarboxylic acid or ester part and having carboxyl group. The reactant of α, β-unsaturated monocarboxylic acid ester is usually about 0.01 to 0.5 parts by mass, preferably about 0.02 to 0.2 times by mass.

The acid values of the epoxy (meth) acrylate resins (D1-1) and (D1-2) thus obtained are usually 10 mgKOH / g or more, and preferably 50 mgKOH / g or more. When the acid value is less than 10 mgKOH / g, the developability may be insufficient.

Moreover, if the acid value is too high, there may be a problem in the alkali resistance of the photosensitive resin composition (that is, depending on the alkaline developer, the pattern surface may be roughened or the film may be reduced). Therefore, the acid value is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less.

Gel penetration of epoxy (meth) acrylate resins (D1-1) and (D1-2) The polystyrene-equivalent weight average molecular weight (Mw) obtained by permeation chromatography (GPC) measurement is preferably 1,000 or more, and more preferably 1,500 or more. In addition, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 6,000 or less. If the weight average molecular weight (Mw) is too small, there may be a problem in sensitivity, coating film strength, or alkali resistance; if it is too large, problems in developability or resolubility may occur.

<Acrylic copolymer resin>

As the acrylic copolymer resin, for example, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-140144, and Japan Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2003-233179, Japanese Patent Laid-Open No. 2007-270147, and other polymer compounds described in various publications; Preferred examples include the following resins (D2-1) to (D2-4). Among the resins (D2-1) to (D2-4), the resins (D2-1) and (D2-3) are preferred.

(D2-1): For a copolymer of an epoxy-containing (meth) acrylate and another radical polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer The resulting resin, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as "(D2-1) resin").

(D2-2): A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as "(D2-2) resin").

(D2-3): Unsaturation of the epoxy group-containing group in the carboxyl portion of the resin (D2-2) Resin (hereinafter sometimes referred to as "(D2-3) resin").

(D2-4): (meth) acrylic resin (hereinafter sometimes referred to as "(D2-4) resin")

Moreover, the above-mentioned (D2-1) resin is also included in the concept of epoxy (meth) acrylate resin.

Each of these resins will be described below.

<(D2-1) resin>

(D2-1) As a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group in the copolymer. The resulting resin, or a resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction, more specifically, "for (meth) acrylates containing epoxy groups, 5 to 90 mol%, and 10 to 95 mol% of copolymers with other free-radically polymerizable monomers. The unsaturated monobasic acid is added to 10 to 100 mol% of epoxy groups in the copolymer. Resin, or a resin obtained by further adding polybasic acid anhydride at 10 to 100 mole% of the hydroxyl group produced by the addition reaction. "

Examples of the "epoxy-containing (meth) acrylate" constituting the (D2-1) resin include propylene oxide (meth) acrylate and 3,4-epoxybutyl (meth) acrylate. , (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, epoxypropyl ether, and the like. Among them, propylene oxide (meth) acrylate is preferred. These (meth) acrylates containing an epoxy group may be used individually by 1 type, and may use 2 or more types together.

The other radically polymerizable monomer copolymerized with the epoxy-group-containing (meth) acrylate is preferably a mono (meth) acrylate having a structure represented by the following general formula (11).

In the above general formula (11), R ⁸¹ to R ⁸⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁸⁷ and R ⁸⁸ may be connected to each other to form a ring. In the above general formula (11), the ring formed by linking R ⁸⁷ and R ⁸⁸ is preferably an aliphatic ring, which may be either saturated or unsaturated, and the number of carbons is preferably 5 to 6.

Among them, the structure represented by the above general formula (11) is preferably a structure represented by the following formula (11a), (11b), or (11c).

By introducing such a structure into an alkali-soluble resin, when the photosensitive resin composition of the present invention is used in a color filter or an image display device, its heat resistance and strength can be improved.

As the mono (meth) acrylate having the structure represented by the general formula (11), various types can be used with the structure, and particularly preferred is the one represented by the following general formula (12).

[Chemical 87]

In the general formula (12), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the general formula (11).

In the copolymer of the epoxy-containing (meth) acrylate and other radical polymerizable monomers, the repeating unit is derived from a mono (meth) acrylate having a structure represented by the general formula (11), The repeating unit derived from the "other radically polymerizable monomer" preferably contains 5 to 90 mole%, and particularly preferably contains 15 to 50 mole%.

The "other radically polymerizable monomer" other than the mono (meth) acrylate having a structure represented by the general formula (11) is not particularly limited.

The copolymer of the epoxy-containing (meth) acrylate and the other radically polymerizable monomer as the (D2-1) resin is preferably one containing an epoxy-containing (meth) acrylate. The repeating unit is 5 to 90 mol%, and the repeating unit from other free-radically polymerizable monomers is 10 to 95 mol%. The special line includes the former 30 to 70 mol% and the latter to 70 to 30 mol%. .

(D2-1) The resin is based on the epoxy group of the copolymer of the epoxy-containing (meth) acrylate and other radical polymerizable monomers, and makes unsaturated monobasic acid (polymerizable component), Reacts with polybasic anhydride.

Here, as the "unsaturated monobasic acid" added to the epoxy group, various kinds can be used, and examples thereof include unsaturated carboxylic acids having ethylenically unsaturated double bonds. Specific examples include (meth) acrylic acid, butenoic acid, ortho-, meta-, or para-vinyl benzoic acid, α-position of haloalkyl, alkoxy, halogen atom, nitro, or cyano (Meth) acrylic acid, etc. substituted monocarboxylic acids and the like. Among these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more. By adding such ingredients, you can Polymerization is imparted to the (D2-1) resin.

These unsaturated monoacids usually add 10 to 100 mol% of the epoxy group of the above-mentioned copolymer, and preferably add 50 to 100 mol%.

In addition, as a "polyacid anhydride" which adds the hydroxyl group produced when the unsaturated monobasic acid is added to the epoxy group of a copolymer, various can be used. Examples include dibasic anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorobridged anhydride; trimellitic anhydride, pyromelic anhydride, diphenyl Triketone anhydrides such as ketone tetracarboxylic anhydride and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used singly or in combination of two or more kinds.

By adding such a component, alkali-solubility can be provided to (D2-1) resin.

These polybasic acid anhydrides usually add 10 to 100 mole% of the hydroxyl group generated by adding an unsaturated monoacid to the epoxy group of the above-mentioned copolymer, but it is preferably 30 to 80 mole%. Ear% is added.

<(D2-2) resin>

(D2-2) The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and is usually obtained by polymerizing a polymerizable monomer containing a carboxyl group.

Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, butenoic acid, itaconic acid, fumaric acid, and 2- (meth) acryloxyethyl Succinic acid, 2- (meth) acryloxyethyl adipate, 2- (meth) acryloxyethyl maleate, 2- (meth) acryloxyethylhexade Hydrophthalic acid, 2- (methyl) Acrylic acid ethyl phthalic acid, 2- (meth) acrylic acid oxypropyl succinic acid, 2- (meth) acrylic acid oxypropyl adipic acid, 2- (meth) acrylic acid oxy Propylmaleic acid, 2- (meth) acryloxypropylhydrophthalic acid, 2- (meth) acryloxypropyl phthalic acid, 2- (meth) acryloxybutyl Succinic acid, 2- (meth) acryloxybutyl adipate, 2- (meth) acryloxybutylmaleic acid, 2- (meth) acryloxybutylhydrophthalide Vinyl monomers such as acids and 2- (meth) acryloxybutylphthalic acid; ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ- Lactone monomers such as valerolactone; monomers in which succinic acid, maleic acid, phthalic acid, and anhydrides thereof are added to hydroxyalkyl (meth) acrylates Wait. These may be used alone or in combination of two or more.

Among these, (meth) acrylic acid or 2- (meth) acryloxyethyl succinic acid is preferred, and (meth) acrylic acid is more preferred.

The (D2-2) resin may be one in which another polymerizable monomer having no carboxyl group is copolymerized with the carboxyl group-containing polymerizable monomer. In this case, the other polymerizable monomer is not particularly limited, and examples thereof include those described in Japanese Patent Laid-Open No. 2009-52010. Among these polymer monomers, a copolymer resin containing benzyl (meth) acrylate is particularly preferred from the viewpoint of superior pigment dispersibility.

<(D2-3) resin>

(D2-3) The epoxy resin-containing resin added to the carboxyl portion of the (D2-2) resin and the unsaturated compound containing an epoxy group is added to the carboxyl portion of the (D2-2) resin The unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

Examples of the epoxy-containing unsaturated compound include (A Based) glycidyl acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (meth) butyric acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylpropenamide and 4-hydroxybutyl (meth) acrylate glycidyl ether containing acyclic epoxy groups Unsaturated compounds. From the viewpoints of heat resistance and dispersibility of the pigment, an unsaturated compound containing an alicyclic epoxy group described below is preferred.

Here, examples of the alicyclic epoxy group of the alicyclic epoxy group-containing unsaturated compound include 2,3-epoxycyclopentyl, 3,4-epoxycyclohexyl, and 7,8 -Epoxy (tricyclic [5.2.1.0] dec-2-yl) and the like. The ethylenically unsaturated group is preferably one derived from a (meth) acrylfluorenyl group.

<(D2-4) resin>

Examples of (D2-4) (meth) acrylic resins include (meth) acrylic resins obtained by polymerizing a compound represented by the following general formula (6) as a necessary monomer component.

In the general formula (6), R ⁷¹ and R ⁷² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

Hereinafter, the compound of general formula (6) will be described in detail.

The ether dimer represented by the general formula (6) is not particularly limited as the hydrocarbon group having 1 to 25 carbon atoms which may also have a substituent represented by R ⁷¹ and R ⁷² , and examples thereof include methyl and ethyl groups. Straight-chain or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, third butyl, third pentyl, stearyl, lauryl, and 2-ethylhexyl Aryl groups such as phenyl; cyclohexyl, third butyl cyclohexyl, dicyclopentadienyl, tricyclododecyl, iso Cycloaliphatic radicals such as alkyl, adamantyl and 2-methyl-2-adamantyl; alkyls substituted by alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl and the like. Among these, from the viewpoint of heat resistance, particularly preferred are substituents having a primary or secondary carbon atom, such as methyl, ethyl, cyclohexyl, and benzyl, which are difficult to be removed by acid or heat. . R ⁷¹ and R ⁷² may be the same substituent or different substituents.

As the ether dimer represented by the general formula (6), dimethyl-2,2 '-[oxybis (methylene)] bis-2-acrylate and diethyl-2,2 are particularly preferred. '-[Oxybis (methylene)] bis-2-acrylate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2-acrylate or dibenzyl-2 , 2 '-[oxybis (methylene)] bis-2-acrylate. These ether dimers may be used singly or in combination of two or more kinds.

When the (D2-4) resin is obtained, the proportion of the above-mentioned ether dimer in the monomer component is not particularly limited, and it is usually 2 to 60% by mass, preferably 5 to 50% by mass in the total monomer component.

(D2-4) The resin preferably has an acid group. By having an acid group, the photosensitive resin composition of the present invention obtained by using this can be used as a cross-linking reaction (hereinafter sometimes referred to as "acid-epoxy" for short) to form an ester bond by reacting an acid group with an epoxy group. Base hardening "), a photosensitive resin composition that can be hardened, or a photosensitive resin composition that can develop an unhardened portion with an alkali developing solution.

The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups contained in one molecule of the resin may be only one kind, or two or more kinds.

When introducing an acid group into the (D2-4) resin, for example, if a monomer having an acid group is used, and / or "a monomer capable of imparting an acid group after polymerization" (hereinafter also referred to as "a monomer for introducing an acid group" Monomer ") may be used as the monomer component. When using "monomer capable of imparting an acid group after polymerization" as a monomer component, it is necessary to perform a treatment for imparting an acid group after polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group, such as (meth) acrylic acid and itaconic acid; and monomers having a phenolic hydroxyl group, such as N-hydroxyphenyl maleimide diimide. ; Monomers having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride. Among these, (meth) acrylic acid is particularly preferred.

Examples of the monomer capable of imparting an acid group after the polymerization include monomers having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate; and epoxy groups having an epoxy group, such as epoxypropyl (meth) acrylate. Monomers having isocyanate groups; monomers having isocyanate groups such as 2-isocyanatoethyl (meth) acrylate and the like.

These monomers for introducing an acid group may be used singly or in combination of two or more kinds.

When the monomer component when the (D2-4) resin is obtained contains the monomer for introducing an acid group, the content ratio is usually 5 to 70% by mass, preferably 10 to 60% of the total monomer component. quality%.

The monomer component when the (D2-4) resin is obtained may contain other copolymerizable monomers in addition to the above-mentioned monomer components, if necessary.

The photosensitive resin composition of the present invention preferably contains, as the alkali-soluble resin (d), the epoxy (meth) acrylate resin (D1-1) and the epoxy (meth) acrylate resin (D1- 2), any of (D2-1) resin, (D2-2) resin, (D2-3) resin, and (D2-4) resin; more preferably epoxy resin (meth) acrylate resin ( D1-1), ring Any of oxy (meth) acrylate resins (D1-2), (D2-1) resins, and (D2-3) resins; it is particularly preferred that they contain at least epoxy (meth) acrylate resins (D1 -1) and / or epoxy (meth) acrylate resin (D1-2).

<Other alkali-soluble resins>

The photosensitive resin composition of the present invention, in addition to the epoxy (meth) acrylate resin (D1-1), epoxy (meth) acrylate resin (D1-2), (D2-1) ~ ( D2-4) In addition to the resin, one or two or more other alkali-soluble resins may be contained as the alkali-soluble resin (d).

The other alkali-soluble resin is not limited, and it may be selected from resins generally used in photosensitive resin compositions. Examples include alkali-soluble resins described in Japanese Patent Laid-Open No. 2007-271727, Japanese Patent Laid-Open No. 2007-316620, and Japanese Patent Laid-Open No. 2007-334290.

[Color material (a)]

The photosensitive resin composition of the present invention contains a color material (a). The color material (a) is a coloring material of the photosensitive resin composition of the present invention. Dyeing pigments can be used as the color material (a), but pigments are preferred from the viewpoints of heat resistance and light resistance.

Examples of the pigment include pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, or a black pigment. Examples of the structure include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinoline-based, and Series, Yin Dan Shilin series, 苝 series and other organic pigments, or various other inorganic pigments.

Specific examples of the pigments usable in the present invention are shown below with pigment numbers. Yet In addition, terms such as "C.I. Pigment Red 2" listed below refer to a color index (C.I.).

Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38 , 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1 , 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1 , 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146 , 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202 , 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250 , 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, and 276. Among them, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred; more preferably, C.I. Pigment Red 177, 209, 224, 254 is mentioned.

Examples of the blue pigment include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25 , 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 And 79. Among these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6 is preferable, and C.I. Pigment Blue 15: 6 is more preferable.

Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54 and 55. Among these, C.I. Pigment Green 7, 36, or 58 is preferable.

Examples of the yellow pigment include CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207 and 208. Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, or 185 is preferable, and C.I. Pigment Yellow 83, 138, 139, 150, or 180 is more preferable.

Examples of the orange pigment include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 and 79. Among them, C.I. Pigment Orange 38 or 71 is preferred.

Examples of the purple pigment include CI Pigment Violet 1, 1: 1,2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 and 50. Among them, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

The photosensitive resin composition of the present invention is a tree of color filters. In the case of a photosensitive resin composition for a fat black matrix, a black color material can be used as the color material (a). The black color material can be a single black color material or a mixture of red, green, and blue. These color materials can be appropriately selected from inorganic or organic pigments and dyes.

Examples of color materials that can be mixed for the preparation of black color materials include Victoria Pure Blue (42595), Aumine O (41000), Cathilon brilliant flavin (basic 13), and Rose Red 6GCP ( 45160), Rose B (45170), Saffron OK70: 100 (50240), Poppy X (42080), No. 120 / Lionol Yellow (21090), Leonor GRO (21090) Symuler fast yellow 8GF (21105), benzidine yellow 4T-564D (21095), Smler fast red 4015 (12355), Leonor red 7B4401 (15850), Fastogen blue TGR-L (74160), Leonor Blue SM (26150), Leonor Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Leonor Green 2YS (Pigment Green 36), etc. (In addition, the above The number in () means color index (CI)).

In addition, if the CI number is used to further indicate other miscible pigments, examples include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166; CI orange pigments 36, 43, 51, 55, 59, and 61; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, and 240; CI purple pigments 19, 23, 29, 30, 37, 40, and 50; CI blue pigments 15, 15: 1, 15: 4, 22, 60, and 64; CI green pigments 7; And CI brown pigments 23, 25 and 26 and so on.

Examples of the black color material that can be used alone include carbon black, ethylene black, lamp black, bone black, graphite, iron black, aniline black, cyan black, and titanium black.

When a black color material is used, among these color materials (a), carbon black is preferable from the viewpoints of light shielding rate and image characteristics. Examples of the carbon black include the following carbon blacks.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B.

Made by DEGUSSA: Printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlackFW1, ColorBlackFW2, Coo0rBlackFW2V, ColorBlackFW18, ColorBlackFW18, ColorBlackFW200, ColorBlackS160, ColorBlackS170.

Manufactured by Cabot: Monarch (registered trademark, same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, same below) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACKPEARLS480, PEARLS130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark) -8.

Made by Columbian Carbon: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000.

Carbon black can also be used by resin coating. If carbon black coated with resin is used, it has the effect of improving the adhesion to the glass substrate and the volume resistance value. As the carbon black covered with the resin, for example, carbon black described in Japanese Patent Laid-Open No. 09-71733 can be preferably used.

As the carbon black subjected to the coating treatment, the total content of Na and Ca is preferably 100 ppm or less. The reason is as follows. That is, carbon black usually contains Na, Ca, and K mixed in percentage grades with raw material oil or combustion oil (or gas) at the time of manufacture, reaction stop water or pelletized water, or furnace materials of the reaction furnace. , Mg, Al, Fe, etc. are the ash of the composition. Among them, Na and Ca generally contain hundreds of ppm or more, respectively. However, if these are present in a large amount, they may penetrate into the transparent electrode (ITO) or other electrodes and may cause the electrical short circuit.

As a method for reducing the content of ash containing such Na or Ca in carbon black, strict selection of those with very little content as raw material oil and fuel oil (or gas) and reaction stop water when producing carbon black, and extremely Reduce the amount of alkali How to increase the amount. Other methods include a method of washing carbon black produced in a furnace with water, hydrochloric acid, or the like to dissolve and remove Na or Ca.

As examples of other black pigments, titanium black, aniline black, iron oxide-based black pigments, and red, green, and blue organic pigments can be mixed and used as a black pigment.

In addition, as the pigment, barium sulfate, lead sulfate, titanium oxide, yellow lead, iron dandelion, or chromium oxide can also be used.

These various pigments may be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment may be used in combination, or a blue pigment and a purple pigment may be used in combination.

<Particle size of color material (a)>

The average primary particle diameter of the pigment belonging to the color material (a) used in the present invention is not particularly limited as long as it is a coloring layer of a color filter, which can express the desired color development. The type of pigment used varies, but it is preferably in the range of 10 to 100 nm, more preferably in the range of 10 to 70 nm, and even more preferably in the range of 20 to 60 nm. By setting the average primary particle diameter of the pigment to the above range, the color characteristics of an image display device manufactured using the photosensitive resin composition of the present invention can be made high quality. When the pigment is carbon black, the average primary particle diameter is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less. When the pigment is carbon black, the average primary particle diameter is preferably 20 nm or more, more preferably 24 nm or more, and particularly preferably 27 nm or more.

By making it below the said upper limit, there exists a tendency for the pigment intake by the polyurethane dispersant (b-1) to be favorable, and the alkali-resistant developing property and heat resistance will improve. On the other hand, by making it more than the said lower limit, there exists a tendency which can suppress the fall of a dispersibility by requiring a large amount of dispersing agent (b).

In addition, the average primary particle diameter of the said pigment can be calculated | required by the method which directly measures the size of a primary particle from an electron microscope photograph. Specifically, the short-axis diameter and the long-axis diameter of each primary particle were measured, and the average value was used as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle was obtained from a cuboid approximating the obtained particle diameter, and the volume average particle diameter was obtained as the average primary particle diameter. Moreover, the electron microscope system can obtain the same results regardless of whether a transmission type (TEM) or a scanning type (SEM) is used.

The photosensitive resin composition of the present invention preferably contains a pigment as the color material (a), but a dye may be used in combination as long as the effect of the present invention is not affected. Examples of the dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. .

Examples of the azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct orange 26, CI direct green 28, CI direct green 59, CI reactive yellow 2, CI reactive red 17, CI reactive red 120, CI reactive black 5, CI disperse orange 5, CI disperse red 58, CI disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, and the like.

Examples of the anthraquinone dye include CI reduction blue 4, CI acid blue 40, CI acid green 25, CI active blue 19, CI active blue 49, CI disperse red 60, CI disperse blue 56, CI disperse blue 60, and the like. .

Examples of the phthalocyanine dye include C.I. Vat Blue 5 and the like. Examples of the quinone imine-based dye include C.I. Basic Blue 3 and C.I. Basic Blue 9.

Examples of the quinoline dye include C.I. Solvent Yellow 33, C.I. Acid Yellow 3, and C.I. Disperse Yellow 64. Examples of the nitro-based dyes include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42.

[Photopolymerizable monomer]

The photosensitive resin composition of the present invention preferably contains a photopolymerizable monomer from the viewpoint of sensitivity and the like.

Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as "ethylenic monomer").

Specific examples include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a monoester of a polyhydric or unit alcohol.

In the present invention, particularly preferred is a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.

Examples of such a polyfunctional ethylenic monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound Etc. Polyvalent hydroxy compounds such as esters obtained by esterification reaction with unsaturated carboxylic acids and polycarboxylic acids.

Examples of the ester of the aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Ester, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylic acid Acrylates of aliphatic polycarboxy compounds such as esters, and methacrylates of which the acrylates of these exemplified compounds are replaced by methacrylates; the same are replaced by the iconates of the iconates and the butenes Esters of maleic acid, maleic acid esters substituted with maleic acid esters, and the like.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrocarbonate. Acrylates and methacrylates of aromatic polyhydroxy compounds such as gallic phenol triacrylate.

The ester obtained by the esterification reaction of a polyvalent carboxylic acid, an unsaturated carboxylic acid, and a polyvalent hydroxy compound is not necessarily a single substance, and representative examples thereof include acrylic acid, phthalic acid, and ethylene glycol. Condensate of alcohol, condensation of acrylic acid, maleic acid, and diethylene glycol, condensation of methacrylic acid, terephthalic acid, and pentaerythritol, and condensation of acrylic acid, adipic acid, butanediol, and glycerol Things.

In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl-containing (meth) acrylate or a polyisocyanate compound are reacted with a polyol and a hydroxyl-containing (meth) acrylate. To obtain general urethane (meth) acrylates; polyvalent epoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid-like epoxy acrylates; ethylene Acrylamides such as bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinylphthalate are useful.

In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, a compound having a caprolactone structure and two or more ethylenically unsaturated groups in the molecule (hereinafter sometimes referred to as "the caprolactone-containing structure has many Functional monomer "), because it can be compatible with the polyurethane dispersant (b-1) used in the present invention, and further improve this fraction The effect caused by the powder is useful and can be preferably used.

Examples of the polyfunctional monomer containing a caprolactone structure include trimethylolethane, bis (trimethylol) ethane, trimethylolpropane, bis (trimethylol) propane, In a polyhydric alcohol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, or trimethylolmelamine, ε-caprolactone is bonded by a ring-opening addition reaction to the ring-opening skeleton A known method for introducing a (meth) acrylfluorenyl group by reacting a (meth) acrylfluorenyl chloride with a terminal hydroxyl group or by performing an esterification reaction with (meth) acrylic acid. Multifunctional (meth) acrylate.

Such a polyfunctional monomer containing a caprolactone structure is as follows. For example, as a substance using dipentaerythritol as a polyhydric alcohol and esterifying it with acrylic acid and ε-caprolactone, there are DPCA-20 commercially available from Nippon Kayaku Co., Ltd. under the KAYARAD DPCA series, DPCA-30, DPCA-60, DPCA-120 and the like can be preferably used as the photopolymerizable monomer of the photosensitive resin composition of the present invention.

In addition, as a commercially available product of ε-caprolactone modified ginseng- (2-propenyloxyethyl) trimeric isocyanate compound, there is A-9300-1CL (in 1 mol) of Shin Nakamura Chemical Industry Co., Ltd. Among the compounds, there is 1 mol of ε-caprolactone structure), and those having ε-caprolactone structure of 0.1 to 9 mol in 1 mol compound, more preferably 1 to 3 mol, can also be compared with The photopolymerizable monomer used as the photosensitive resin composition of the present invention is preferably used.

In addition, those who use pentaerythritol as a polyhydric alcohol and esterify ε-caprolactone with terminal hydroxyl groups to further esterify acrylic acid may also preferably use photopolymerization as the photosensitive resin composition of the present invention. Sex monomer. These are those having a ε-caprolactone structure in 1 mole compound, preferably 0.1 to 20 mole, more preferably 1 to 12 mole, Extraordinary is 1 to 4 moles.

These photopolymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

[Mercaptans]

The photosensitive resin composition of the present invention preferably contains thiols in order to increase sensitivity and improve the adhesion to the substrate.

Examples of the thiols include hexanedithiophenol, decanedithiophenol, 1,4-dimethylmercaptobenzene, butanediol dithiopropionate, butanediol dithiopropionate, Ethylene glycol dithioglycolate, trimethylolpropane thioglycolate, butanediol dithiopropionate, trimethylolpropane thiosulfate, trimethylolpropane thioglycolate , Pentaerythritol thiopropionate, pentaerythritol thiopropionate, p-hydroxyethyl p-thiopropionate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate) (abbreviation PGMB), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane [trade name: Karenz (registered trademark, the same below) MT BD1, Showa Denko ( )], Butanediol trimethylolpropane ginseng (3-mercaptobutyrate), pentaerythritol (3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko Corporation), pentaerythritol Ginseng (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane ginseng (3-mercaptoisobutyrate) Acid ester), trimethylolpropane ginseng (3-mercaptobutyrate) (abbreviated TPMB), trimethylolpropane ginseng (2-mercaptoisobutyrate) (TPMIB for short) and 1,3,5-ginseng (3-mercaptobutoxyethyl) -1,3,5-tris -2,4,6 (1H, 3H, 5H) -trione (Trade name: Karenz MT NR1, manufactured by Showa Denko Corporation), etc .; these kinds can be used alone or in combination of two or more kinds.

Preferably the above-mentioned PGMB, TPMB, TPMIB, Karenz MT BD1, Multifunctional thiols such as Karenz MT PE1 and Karenz MT NR1, among which Karenz MT BD1, Karenz MT PE1, Karenz MT NR1 are more preferred, and Karenz MT PE1 is particularly preferred.

These mercaptans may be used alone or in combination of two or more.

[Solvent (e)]

The photosensitive resin composition of the present invention is generally based on an alkali-soluble resin (d), a photopolymerizable monomer, a photopolymerization initiator (c), a color material (a), a dispersant (b), and an optionally used one. Various materials are used in a state of being dissolved or dispersed in the solvent (e).

As the solvent (e) used in the present invention, an organic solvent having a boiling point (both of which are the same with respect to the boiling point under the pressure of 1013.25 [hPa]) is preferably selected in the range of 100 to 300 ° C. More preferably, it is an organic solvent having a boiling point of 120 to 280 ° C.

Examples of such an organic solvent include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether , Propylene glycol third butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether , Dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether-like glycol monoalkane Ethers; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol Glycol dialkyl ethers such as alcohol dibutyl ether and dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether Ether ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate , 2-ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, three Glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate-like glycol alkyl ether acetates; Glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diacetate, and other glycol diacetates; cyclohexanol acetate and other alkyl acetates Class; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether and dihexyl ether-like ethers; acetone, methyl Methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl Amyl ketones, methyl butyl ketones, methyl hexyl ketones, methyl nonyl ketones, and methoxymethylpentanone-like ketones Ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol Normal monovalent or polyvalent alcohols; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane-like aliphatic hydrocarbons; cyclohexane, Methylcyclohexane, methylcyclohexene and bicyclohexane-like alicyclic hydrocarbons; benzene, toluene, xylene and cumene-like aromatic hydrocarbons; amyl formate, ethyl formate, acetic acid Ethyl acetate, butyl acetate, propyl acetate Ester, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octoate , Butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate Esters, propyl 3-methoxypropionate, butyl 3-methoxypropionate and γ-butyrolactone like chain or cyclic esters; 3-methoxypropionic acid and 3-ethoxy Propanoic acid-like alkoxycarboxylic acids; chlorobutane and chloropentane-like halogenated hydrocarbons; methoxymethylpentanone-like ether ketones; acetonitrile, benzonitrile-like nitriles, etc .; Commercially available solvents include, for example, mineral spirits, Varsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28, Solvent, carbitol, ethylcarbide Alcohol, butylcarbitol, methyl cyperidine ("cyperidine" is a registered trademark, the same applies hereinafter), ethyl cyperidine, ethyl cyperidine acetate, methyl cyperidine acetate And diglyme (both trade names).

These organic solvents may be used alone or in combination of two or more.

When forming pixels or a black matrix of a color filter by photolithography, it is preferred to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.

Among the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of a good balance of coatability, surface tension, and the like, and high solubility of constituent components in the composition.

The glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, diol monoalkyl ethers are particularly preferred. among them, In terms of the solubility of the constituents in the composition, propylene glycol monomethyl ether is particularly preferred.

Moreover, glycol monoalkyl ethers have high polarity, and if the amount is too large, color materials (a) such as pigments tend to aggregate, and the storage stability of the photosensitive resin composition obtained thereafter tends to decrease. The proportion of the diol monoalkyl ethers in the solvent (e) is preferably 5 to 30% by mass, and more preferably 5 to 20% by mass.

In addition, as the solvent (e), an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as a “high-boiling-point solvent”) may be preferably used in combination. By using such a high-boiling-point solvent in combination, it is difficult to dry the photosensitive resin composition, but it has the effect of preventing the uniform dispersion state of the color material (a) in the composition from being destroyed by rapid drying. That is, it has the effect of preventing foreign matter defects caused by the precipitation and solidification of the color material (a) and the like at the tip of the slit nozzle.

From such a viewpoint of high effect, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl are particularly preferable. Ether acetate.

The content of the high-boiling point solvent in the solvent (e) is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. If the amount of the high boiling point solvent is too small, for example, the color material (a) at the front end of the slit nozzle may precipitate and solidify and cause foreign matter defects; if the amount is too high, the drying temperature of the composition will be slower, and the color will be described later The filter manufacturing steps may cause problems such as poor efficiency of the reduced-pressure drying process and pre-baked pin marks.

In addition, the high-boiling point solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a diol monoalkyl ether. In this case, a high-boiling point solvent having a boiling point of 150 ° C or higher may also be contained.

As a preferred high-boiling solvent, for example, among the above-mentioned various solvents, diethylene glycol Alcohol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, 1,6-hexanol di Acetate and glycerol triacetate.

[Other formulation ingredients of photosensitive resin composition]

In the photosensitive resin composition of the present invention, in addition to the above-mentioned components, an adhesion promoter, a coating improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent, a surfactant, and a pigment can be appropriately blended. Derivatives, polymerization accelerators, photoacid generators, crosslinking agents, plasticizers, storage stabilizers, surface protection agents, organic carboxylic acids, organic carboxylic anhydrides, development improvers, or thermal polymerization inhibitors.

<Adhesive enhancer>

In order to improve the adhesion to the substrate, the adhesion promoter may be contained in the photosensitive resin composition of the present invention. Examples of the adhesion promoter include a silane coupling agent, a phosphoric acid-based adhesion promoter, and other adhesion promoters.

As the type of the silane coupling agent, various types such as epoxy-based, (meth) acrylic-based or amine-based may be used alone, or two or more kinds may be used in combination.

Examples of preferred silane coupling agents include (meth) acrylic acid, such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane. Oxysilanes; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Epoxy silanes such as diethoxysilane and 3-glycidoxypropyltriethoxysilane; urethane silanes such as 3-uretopropyltriethoxysilane; and 3-isocyanatepropyltrisiloxane Isocyanate silanes such as ethoxysilane. Particularly preferred are silane coupling agents of epoxy silane type.

As a phosphoric acid-based adhesion promoter, (meth) acrylic acid is preferably contained Among these phosphate esters, preferred are those represented by the following general formula (g1), (g2), or (g3).

In the general formulae (g1), (g2), or (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l ′ are integers of 1 to 10, and m is 1, 2 or 3.

Examples of other tackifiers include TEGO * Add Bond LTH (manufactured by Evonik).

These phosphate-based adhesion promoters and other adhesion promoters can be used alone or in combination of two or more.

<Surfactant>

The photosensitive resin composition of the present invention may contain a surfactant in order to improve coating properties.

As the surfactant, various ones such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among them, from the viewpoint of a low possibility of adversely affecting various characteristics, it is preferable to use a nonionic surfactant, especially a fluorine-based or silicon-based surfactant, which is effective in terms of coatability.

Examples of such a surfactant include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (by BYK Chemie), KP340 (by Shin-Etsu Silicone), F-470, F-475, F-478, F-559 (by Dainippon Ink Chemical Industry Co., Ltd.), SH7PA (by Toray Silicone Co., Ltd.) ), DS-401 (made by Daikin), L-77 (made by Japan Unicar), and FC4430 (made by Sumitomo 3M).

These surfactants may be used singly or in combination of two or more kinds in any combination and ratio.

<Pigment derivative>

The photosensitive resin composition of the present invention may contain a pigment derivative in order to improve the dispersibility and storage properties. In particular, from the viewpoint of improving the dispersibility, it is preferable to use a dispersant (b) together with a pigment derivative. .

Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinoline yellow-based, isoindoline-based, and Series, anthraquinone series, indanthrene series, stilbene series, fluorenone series, diketopyrrolopyrrole series and two system. Among them, a phthalocyanine system or a quinoline yellow system is preferred.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthaloiminomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, or a sulfonylamino group, etc., directly or via An alkyl group, an aryl group, or a heterocyclic group is bonded to the pigment skeleton; a sulfonic group is preferred. Moreover, these substituents may be substituted plurally in one pigment skeleton.

Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinoline yellow, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolopyrrole Sulfonic acid derivatives and two Sulfonic acid derivatives.

These may be used alone or in combination of two or more.

[Component blending amount in the photosensitive resin composition]

The content ratio of the color material (a) of the photosensitive resin composition of the present invention is generally 1 mass% or more, preferably 5 mass% or more, and more preferably, relative to the total solid content in the photosensitive resin composition. 10% by mass or more, more preferably 20% by mass or more, 30% by mass or more, 40% by mass or more; and usually 70% by mass or less, preferably 65% by mass or less, more preferably 60% by mass or less. By setting it to be more than the above-mentioned lower limit value, there is a tendency to prevent adverse effects such as gap control when the liquid crystal cell becomes thick due to increase in film thickness in order to obtain a predetermined color density; If the value is less than or equal to the value, sufficient image formability tends to be easily obtained.

The photosensitive resin composition of the present invention can be used in various applications as described above, and the excellent image forming property caused by the photosensitive resin composition of the present invention is particularly useful when forming a black matrix for a color filter. With effect.

When the photosensitive resin composition of the present invention is used in a black matrix, if a black color material such as carbon black or titanium black is used as the color material (a), or a plurality of color materials other than black are mixed and adjusted to black, Just fine. Among them, carbon black is particularly preferred from the viewpoint of light-shielding properties.

The effect of the photosensitive resin composition of the present invention can be effectively exhibited particularly in a field where the pigment concentration of a black pigment becomes large. As described above, in order to increase the light-shielding degree in recent years, it is necessary to increase the concentration of the black pigment. However, from the viewpoint of having a tendency to greatly produce the effects of the present invention, the content ratio of the black pigment is relative to the total solid content of the photosensitive resin composition. It is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 48% by mass or more, and particularly preferably 50% by mass or more.

In the photosensitive resin composition of the present invention, by containing a black pigment within the above range, it is possible to obtain coloring sensitivity with high light-shielding properties (optical density, OD value). Resin composition tendency. Specifically, by setting the content ratio of the black pigment to 45% by mass or more relative to the total solid content of the photosensitive resin composition, it is possible to use the photosensitive resin composition of the present invention to form a black matrix with a thickness of 1 μm. The optical density tends to be a value of 4.0 or more. This optical density is more preferably 4.2 or more.

Generally speaking, when the light-shielding property is high, it is difficult for ultraviolet rays to penetrate to the deep part of the film, and the cross-linking by photopolymerization tends to weaken especially in the close-adhesive part of the substrate and the thin wires. In the case of the photosensitive resin composition, the effect of the present invention can be remarkably confirmed even if the pigment concentration is high. The pigment concentration of the photosensitive resin composition of the present invention is particularly effective at 40 to 65% by mass based on the solid content.

Moreover, the photosensitive resin composition of the present invention is not limited to the case where the pigment concentration is high, and the effect of the present invention can be exhibited even when the pigment concentration is low. When only the pigment concentration is changed in the photosensitive resin composition, depending on the pigment concentration, thermal deformation may occur during the thermal curing treatment after development, and the line width of the fine lines may become slightly thicker or thinner. However, by adjusting photopolymerization, A thin line having a desired line width can be obtained by adjusting the amount of components such as a monomer or a photopolymerizable initiator or adjusting the exposure amount.

The content ratio of the dispersant (b) of the photosensitive resin composition of the present invention is not particularly limited, and it is usually 50% by mass or less, preferably 30% by mass or less in the total solid content of the photosensitive resin composition. It is preferably 20% by mass or less, still more preferably 15% by mass or less; and usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more.

The content of the dispersant (b) is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass based on 100 parts by mass of the color material (a). Parts by mass, preferably 80 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, particularly preferably 30 parts by mass or more under. When the content ratio of the dispersant (b) is set to the above lower limit value or more, sufficient dispersibility tends to be easily obtained. By setting the content ratio of the dispersant (b) or less to the above upper limit value, the content ratios of other components can be sufficiently ensured, It tends to be easy to obtain a desired color density, a desired sensitivity, a desired film forming property, and the like.

Moreover, the proportion of the polyurethane dispersant (b-1) in the dispersant (b) is caused by using the polyurethane dispersant (b-1) more effectively. From the viewpoint of the effect of the present invention, it is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more; It is usually 100% by mass or less.

In the photosensitive resin composition of the present invention, the content ratio of the polyurethane dispersant (b-1) is usually 2 parts by mass or more, and preferably 5 parts by mass relative to 100 parts by mass of the alkali-soluble resin (d). 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more. The amount is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less.

The content ratio of the photopolymerization initiator (c) of the photosensitive resin composition of the present invention is generally 0.1% by mass or more, and preferably 0.5% by mass or more, relative to the total solid content of the photosensitive resin composition of the present invention. , More preferably 0.7% by mass or more, even more preferably 1% by mass or more, still more preferably 3% by mass or more, particularly preferably 5% by mass or more; and usually 30% by mass or less, preferably 20% by mass or less It is more preferably 15% by mass or less, and even more preferably 10% by mass or less. By setting the content ratio of the photopolymerization initiator (c) to be above the lower limit value, sufficient sensitivity tends to be obtained; and by setting the content ratio of the photopolymerization initiator (c) or less to the above upper limit value, it is possible to suppress unexposed portions from affecting the developer. The solubility is reduced, and the tendency to develop poorly is easily prevented.

In particular, the proportion of the oxime ester photopolymerization initiator (c-1) in the photopolymerization initiator (c) is usually 10% by mass or more, preferably 50% by mass or more, and more preferably 90% by mass Above; and usually below 100% by mass. By setting the content ratio of the oxime ester photopolymerization initiator (c-1) to the above lower limit value, the polyurethane dispersant (b-1) and the alkali-soluble resin used in the present invention In the combination (d), after ultraviolet irradiation, the resistance to alkali developing solution or high-temperature treatment is good, and the formation of highly fine fine lines can be improved.

The content ratio of the photopolymerization initiator (c) is usually 100 parts by mass based on the total amount of the polyurethane dispersant (b-1), the alkali-soluble resin (d), and the photopolymerizable monomer. 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The amount is usually 100 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 40 parts by mass or less.

When the accelerator is used together with the photopolymerization initiator (c), the content ratio of the accelerator is usually 0% by mass or more, and preferably 0.02% by mass relative to the total solid content of the photosensitive resin composition of the present invention. % Or more, and usually 10% by mass or less, preferably 5% by mass or less; The accelerator is preferably 0.1 to 50% by mass, and more preferably 0.1 to 10% by mass relative to the photopolymerization initiator (c). % Used.

When a sensitizing dye is used, the content ratio of the sensitizing dye contained in the photosensitive resin composition of the present invention is usually from 0 to 20% by mass based on the total solid content of the photosensitive resin composition. It is preferably 0 to 15% by mass, and more preferably 0 to 10% by mass.

The content ratio of the alkali-soluble resin (d) of the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, with respect to the total solid content of the photosensitive resin composition of the present invention. Preferably 15% by mass or more It is preferably 20% by mass or more; and usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably 50% by mass or less. It is preferably 40% by mass or less, and most preferably 30% by mass or less.

When the content ratio of the alkali-soluble resin (d) is equal to or more than the above-mentioned lower limit value, there is a tendency that the solubility of the unexposed portion in the developing solution is suppressed from lowering, and the development of poor development is easily prevented. Furthermore, by setting it to be equal to or less than the above upper limit value, the permeability of the developer to the exposed portion tends to be kept low, and the sharpness or adhesion of the pixels tends to be easily improved.

Furthermore, as described above, the photosensitive resin composition of the present invention preferably contains the above-mentioned epoxy (meth) acrylate resin (D1-1) and epoxy (methyl) as the alkali-soluble resin (d). At least one of acrylate resins (D1-2), (D2-1) resins, (D2-2) resins, (D2-3) resins, and (D2-4) resins; more preferably, they contain epoxy groups (methyl groups) ) Acrylate resin (D1-1), epoxy (meth) acrylate resin (D1-2) resin, (D2-1) resin, (D2-3) resin; particularly preferred is epoxy resin (methyl Base) acrylate resin (D1-1) and / or epoxy (meth) acrylate resin (D1-2).

When the alkali-soluble resin (d) contains other alkali-soluble resins other than these preferred resins, the content ratio is usually 20% by mass or less, preferably 10% by mass, relative to the total of the alkali-soluble resin (d). Below, and usually 0% by mass or more.

In the photosensitive resin composition of the present invention, the amount of the alkali-soluble resin (d) is usually 20 parts by mass or more, preferably 30 parts by mass or more, and more preferably 40 parts by mass with respect to 100 parts by mass of the color material (a). It is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 80 parts by mass or less, and particularly preferably 50 parts by mass Mass parts or less. By setting the content ratio of the alkali-soluble resin (d) to the color material (a) to the above-mentioned lower limit value, From the above, there is a tendency that the solubility of the unexposed portion in the developing solution is suppressed from being lowered, and the occurrence of poor development is prevented. Furthermore, by setting the above-mentioned upper limit value or less, the desired pixel film thickness tends to be easily obtained.

The content ratio of the photopolymerizable monomer of the photosensitive resin composition of the present invention is generally 90% by mass or less, preferably 80% by mass or less, more preferably relative to the total solids content of the photosensitive resin composition of the present invention. It is 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the content of the photopolymerizable monomer is equal to or less than the above-mentioned upper limit value, there is a tendency that the permeability of the developer to the exposed portion becomes appropriate and a good image can be obtained.

The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, and preferably 5% by mass or more. When it is at least the above lower limit, there is a tendency that the light hardening by ultraviolet irradiation is improved and the alkali developability is also good.

The content of the photopolymerizable monomer is usually 2 parts by mass or more, preferably 4 based on 100 parts by mass of the total amount of the polyurethane dispersant (b-1) and the alkali-soluble resin (d). Part by mass or more, more preferably 6 parts by mass or more. The amount is usually 500 parts by mass or less, preferably 300 parts by mass or less, and more preferably 200 parts by mass or less.

By setting the amount of the polyurethane dispersant (b-1), the photopolymerizable monomer, and the photopolymerization initiator (c) to the alkali-soluble resin to the above-mentioned lower limit value or more, the photosensitive resin is used. In the solution of the composition, due to the compatibility between the polyurethane dispersant (b-1) and the alkali-soluble resin (d), the steric hindrance to the aggregation of the color material (a) is improved, so that the dispersion is dispersed. Improve the properties; or when the color filter is manufactured, the polyurethane dispersant (b-1) and the alkali-soluble resin (d) are irradiated with ultraviolet rays, so that the photopolymerization initiator (c) is used. The cross-linked ethylenically unsaturated group component further increases the cross-linking property, and improves the resistance to the alkali developer and high-temperature treatment belonging to the effect of the present invention, and easily forms a high Subtle fine line tendencies.

In addition, the amounts of the polyurethane dispersant (b-1), the photopolymerizable monomer, and the photopolymerization initiator (c) tend to deteriorate the solubility of the alkali developer, as described above. Below the upper limit, there is a tendency that the solubility of the unexposed portion of the ultraviolet ray to the alkali developing solution is increased, and the development residue on the substrate is reduced.

In the case where the thiols are used, the content ratio of the thiols is usually 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably relative to the total solid content of the photosensitive resin composition of the present invention. It is 0.5% by mass or more, and usually 10% by mass or less, and preferably 5% by mass or less. If the content of thiols is too small, the effect of improving sensitivity is insufficient; if it is too large, storage stability may be deteriorated.

When the photosensitive resin composition of the present invention contains a pigment derivative, the content ratio of the pigment derivative is usually 0.1% by mass or more with respect to the total solid content of the photosensitive resin composition of the present invention, and is usually 10% by mass. % Or less, preferably 5 mass% or less.

When a surfactant is used, its content is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, based on the total solid content in the photosensitive resin composition. It is more preferably 0.03 mass% or more, and usually 10 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, and even more preferably 0.3 mass% or less. When the content ratio of the surfactant is within the above range, the smoothness and uniformity of the coating film tend to be sufficient.

Moreover, the photosensitive resin composition of the present invention uses the above-mentioned solvent (e), and its solid content concentration is usually 5 mass% or more, preferably 10 mass% or more; and usually 50 mass% or less, preferably 30% by mass. When the content is within the above range, the coating property of the photosensitive resin composition tends to be good.

[Manufacturing method of photosensitive resin composition]

The photosensitive resin composition (hereinafter sometimes referred to as "resist") of the present invention is produced by a conventional method.

Generally, the color material (a) is preferably dispersed in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like. The color material (a) is micronized by the dispersion treatment, so that the coating characteristics of the resist are improved. In addition, when a black color material is used as the color material (a), it contributes to improving the light shielding ability.

The dispersion treatment is generally preferably performed in a system using a part or all of the color material (a), dispersant (b), solvent (e), and optionally the alkali-soluble resin (d) (hereinafter, it may be used for dispersion) The treated mixture and the composition obtained by the treatment are called "ink" or "pigment dispersion"). In this dispersing treatment, by using the polyurethane dispersant (b-1) of the present invention, it is possible to suppress the time-dependent thickening of the obtained ink and resist (excellent dispersion stability). .

In addition, when a liquid containing all components formulated in the photosensitive resin composition is subjected to a dispersion treatment, there is a possibility that the highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion processing according to a system containing the above-mentioned components.

When the color material (a) is dispersed by a sander, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm can be preferably used. The temperature of the dispersion treatment is generally in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersing time varies depending on the composition of the liquid and the size of the dispersing processing device, etc., so it should be adjusted appropriately.

The standard for dispersion is to control the gloss of the ink so that the 20-degree specular gloss of the resist [JIS Z8741 (1997)] is in the range of 100 to 200. In resist When the gloss of the agent is low, there are many cases where rough pigment (color material) particles remain due to insufficient dispersion treatment, and there is a possibility that the developability, adhesion, and resolution are insufficient. In addition, if the dispersing treatment is performed until the glossiness exceeds the above range, the pigment is broken and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

Next, the ink obtained by the above-mentioned dispersion treatment is mixed with the above-mentioned other components contained in the resist to prepare a uniform solution. In the manufacturing process of the resist, since fine impurities are often mixed in the liquid, the obtained resist is preferably subjected to a filtering treatment by a filter or the like.

[Hardened matter]

The cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The cured product obtained by curing the photosensitive resin composition of the present invention can be preferably used as a black matrix or a colored spacer.

[Black matrix]

Next, the black matrix using the photosensitive resin composition of this invention is demonstrated based on the manufacturing method.

(1) Support

As a support for forming a black matrix, the material is not particularly limited as long as it has a moderate strength. As a support body, a transparent substrate is mainly used. Examples of the material include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; thermoplastic properties such as polycarbonate, polymethyl methacrylate, and polyfluorene Resin sheet; epoxy resin, unsaturated polyester resin, poly (meth) acrylic resin Etc. thermosetting resin sheet; or various glass. Among them, glass and a heat-resistant resin are preferred from the viewpoint of heat resistance.

In addition, a transparent electrode such as ITO or IZO may be formed on the substrate surface. In addition to a transparent substrate, it may be formed on a TFT array.

For the support, in order to improve the surface properties such as adhesion, if necessary, corona discharge treatment, ozone treatment, film formation treatment of various resins such as a silane coupling agent, or a urethane resin may be performed.

The thickness of the support is usually set to a range of 0.05 to 10 mm, preferably 0.1 to 7 mm. In addition, when performing a thin film forming treatment of various resins, the film thickness is usually in the range of 0.01 to 10 μm, and preferably in the range of 0.05 to 5 μm.

(2) Black matrix

When forming the black matrix of the present invention from the photosensitive resin composition of the present invention described above, the photosensitive resin composition of the present invention is coated on a support such as a transparent substrate and dried, and then a photomask is placed on the coating film. A black matrix is formed by performing image exposure and development through the photomask, and then performing thermal curing or light curing as necessary.

(3) Formation of black matrix (3-1) Coating of photosensitive resin composition

The application of the photosensitive resin composition for a black matrix to a support such as a transparent substrate can be performed by a spin coating method, a wire rod method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. Among them, in the case of the die coating method, the amount of the coating liquid used can be greatly reduced, and the influence of fog particles and the like attached during the spin coating method is completely eliminated, and the generation of foreign matter can be suppressed, which is preferable from a comprehensive viewpoint.

If the thickness of the coating film is too thick, it may be difficult to develop the pattern and the gap adjustment in the step of the liquid crystal cell may be difficult; if it is too thin, the pigment concentration may be difficult to increase and the desired color expression may not be achieved. The thickness of the coating film is based on the thickness of the film after drying. Usually, it is preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and even more preferably in the range of 1 to 4 μm.

(3-2) Drying of the coating film

The drying of the coating film after the photosensitive resin composition is applied to the support is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected in accordance with the type of the solvent component, the performance of the dryer used, and the like. The drying time is based on the type of solvent components and the performance of the dryer used. It is usually selected at a temperature of 40 ~ 200 ° C and 15 seconds ~ 5 minutes, preferably at a temperature of 50 ~ 130 ° C and 30 seconds. Choice of ~ 3 minutes.

The higher the drying temperature, the more the adhesion of the coating film to the support is increased, but if it is too high, the alkali-soluble resin is decomposed, and thermal polymerization is initiated to cause development failure. In addition, the drying step of the coating film may be a reduced-pressure drying method for drying in a reduced-pressure chamber without increasing the temperature.

(3-3) Exposure

The image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive resin composition, and irradiating a light source of ultraviolet or visible light through the mask pattern. At this time, in order to prevent the sensitivity of the photopolymerizable layer from being reduced due to oxygen, an oxygen shielding layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed.

The light source used for the image exposure is not particularly limited. As light Examples of the source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, argon ion lasers, and YAG. Laser light sources such as lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. When using a specific wavelength of light, an optical filter can also be used.

(3-4) Development

The black matrix of the present invention is formed by forming an image on a substrate by developing an organic solvent or an aqueous solution containing a surfactant and a basic compound after image exposure of a coating film of a photosensitive resin composition by the light source described above. Can be made. The aqueous solution may further contain an organic solvent, a buffering agent, a dissolving agent, a dye, or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic basic compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate and ammonium hydroxide, as well as mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or tri-methyl Organic basic compounds such as ethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline . These basic compounds may be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, dehydration, sorbitol alkyl esters, and monoglyceryl alkyl esters. Non-ionic surfactants, anionic interfaces such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates and sulfosuccinates Active agents, and amphiphilic boundaries of alkyl betaines and amino acids Surfactant.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyperidine, butyl cyperidine, phenyl cyperidine, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

The conditions for the development process are not particularly limited. Generally, the development temperature is in the range of 10 to 50 ° C, with 15 to 45 ° C being preferred, and 20 to 40 ° C being particularly preferred. The development method can be performed by any of a dip development method, a spray development method, a brush development method, and an ultrasonic development method.

(3-5) heat hardening treatment

The support after development is subjected to a thermal hardening treatment or a photohardening treatment, and preferably a thermal curing treatment. The heat curing treatment conditions at this time are selected in a range of 100 to 280 ° C, preferably in a range of 150 to 250 ° C, and selected in a range of 5 to 60 minutes.

The width of the bottom of the black matrix formed in the above manner is usually 3 to 50 μm, preferably 4 to 30 μm, especially in the case of high fine lines, it is preferably 4 to 8 μm, and the height is usually 0.5 to 5 μm, preferably It is 1 to 4 μm. The volume resistivity is 1 × 10 ¹³ Ω · cm or more, preferably 1 × 10 ¹⁴ Ω · cm or more, and the relative permittivity is 6 or less, preferably 5 or less. The optical density (OD) per 1 μm thickness is usually 3.0 or more, preferably 3.5 or more, more preferably 4.0 or more, and particularly preferably 4.2 or more.

[Formation of other color filter images]

On a support provided with a black matrix, a photosensitive resin composition containing one color material of red, green, and blue is applied and dried in the same process as in (3-1) to (3-5), and dried. Then, a mask is superimposed on the coating film, and image exposure and development are performed through the mask. If necessary, a pixel image is formed by heat curing or light curing, whereby a colored layer can be produced. This operation is performed on the photosensitive resin compositions of three colors of red, green, and blue, respectively, thereby forming a color filter image. These orders are not limited to the above.

[Coloring spacer]

In addition to the black matrix, the photosensitive resin composition of the present invention can be used as a resist for a colored spacer. When a spacer is used in a TFT type LCD, the TFT as a switching element may malfunction due to light incident on the TFT, and the colored spacer is used to prevent this; for example, Japanese Patent Laid-Open No. 8-234212 The publication discloses that the spacer is made light-shielding. The colored spacers can be formed in the same manner as the black matrix except that a mask for the colored spacers is used.

[Formation of transparent electrode]

The color filter is used to form transparent electrodes such as ITO on the image according to its original state, and is used as part of parts such as color displays and liquid crystal display devices. However, in order to improve surface smoothness and durability, it is also possible to use A top coating such as polyimide or polyimide is provided on the top. In some applications, such as a planar alignment type driving method (IPS mode), a transparent electrode may not be formed.

[Image display device]

The image display device of the present invention is not particularly limited as long as it includes a black matrix composed of the photosensitive resin composition of the present invention and displays an image or an image, and examples thereof include a liquid crystal display device and an organic EL display described later.

[Liquid crystal display device]

The liquid crystal display device of the present invention is produced by using the black matrix of the present invention, and there is no particular limitation on the formation order or formation position of the color pixels or the black matrix.

The liquid crystal display device usually forms an alignment film on a color filter. After the spacers are dispersed on the alignment film, the liquid crystal cell is bonded to the opposite substrate to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell and connected to a counter electrode. And done.

The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a quick-drying printing method are generally used, and the thickness of the alignment film is set to several tens of nm. After the hardening treatment of the alignment film is performed by thermal firing, the surface treatment is performed by ultraviolet irradiation or rubbing cloth treatment, and the surface state can be adjusted by adjusting the tilt of the liquid crystal.

As the spacer, a size that fits the gap between the substrate and the opposing substrate is used, and usually a size of 2 to 8 μm is preferred. A photoresist (PS) of a transparent resin film can also be formed on a color filter substrate by photolithography, and this can be used to replace the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferred.

The gap to be bonded to the opposite substrate varies depending on the application of the liquid crystal display device, and is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is hardened by ultraviolet (UV) irradiation and / or heating to seal the periphery of the liquid crystal cell.

The sealed liquid crystal cell is cut into panel units, and then decompressed in the vacuum chamber. After the liquid crystal injection port is immersed in the liquid crystal, the liquid crystal is injected into the liquid crystal by leaking the pressure in the chamber. Within the unit.

The degree of decompression in the liquid crystal cell is usually 1 × 10 ^-2 to 1 × 10 ^-7 Pa, and preferably 1 × 10 ^-3 to 1 × 10 ^-6 Pa. In addition, it is preferable to heat the liquid crystal cell during decompression. The heating temperature is usually 30 to 100 ° C, and more preferably 50 to 90 ° C.

The heating and maintaining during decompression is usually set in a range of 10 to 60 minutes, and then immersed in liquid crystal. The liquid crystal cell injected with liquid crystal is sealed with a liquid crystal injection port by curing a UV curing resin, thereby completing a liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and may be a conventionally known liquid crystal such as an aromatic system, an aliphatic system, or a polycyclic compound, or may be any of a liquid-crystalline liquid crystal and a thermal-crystalline liquid crystal. As the thermotropic liquid crystal, a nematic liquid crystal, a smectic liquid crystal, and a cholesteric liquid crystal are known, but any of them may be used.

[Organic EL display]

An organic EL display is shown in FIG. 1, for example. First, a pattern made of a photosensitive resin composition is produced on a transparent support substrate 10 [that is, a resin provided between a pixel 20 and an adjacent pixel 20. A black matrix (not shown)] is formed on the color filter, and the organic light-emitting body 500 is laminated on the color filter via the organic protective layer 30 and the inorganic oxide film 40 to produce an organic EL element 100.

In addition, among the pixel 20 and the resin black matrix, at least the black matrix is made by using the photosensitive resin composition of the present invention. As a method for stacking the organic light emitting body 500, for example, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on a color filter may be sequentially formed. And a method of attaching the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40 and the like.

The organic EL element 100 produced in this way can be produced according to the method described in "Organic EL Display" (Ohmsha, issued on August 20, 2004, by Jing Shi, Anda Chiba, and Hideki Hata) Organic EL display.

Moreover, the color filter of the present invention can also be applied to an organic EL display using a passive driving method or an organic EL display using an active driving method.

<Example>

Examples and comparative examples are given below to further describe the present invention, but the present invention is not limited to the following examples without exceeding the gist thereof.

<Dispersant 1>

As the dispersant 1, the polyurethane compound 1 obtained through the following (Step 1-1) to (Step 1-9) was used.

Compound A: 1-dodecanol

Compound B: ε-caprolactone

Compound C: zirconia catalyst

Compound D: toluene diisocyanate (TDI)

Compound E: Diethanolamine

Tertiary amine compound 1: 3- (diethylamino) -1,2-propanediol

Polyether compound 1: poly (propylene glycol) monobutyl ether (Mn = 1100)

(Step 1-1) Compound A (114.6 parts by mass) and compound B (912.3 parts by mass) were mixed and homogenized at 150 ° C under a nitrogen environment.

(Step 1-2) Compound C (4.0 parts by mass) was added to the mixture obtained in (Step 1-1), and reacted at 180 ° C for 20 hours.

(Step 1-3) The reaction product obtained in (Step 1-2) is cooled to room temperature to obtain waxy polyester compound 1.

(Step 1-4) Put compound D (83.46 parts by mass) into a reaction vessel under a nitrogen environment and heat to 50-60 ° C

(Step 1-5) 800 parts by mass of the polyester compound 1 obtained in (Step 1-3) was melted at 50 ° C, and the compound D heated in (Step 1-4) was heated to 50 to 60 ° C for a while. Add in 2 hours.

(Step 1-6) The mixed solution obtained in (Step 1-5) is reacted at 60 ° C. for 1 hour with stirring.

(Step 1-7) The reaction product obtained in (Step 1-6) was cooled to 20 ° C, compound E (50.37 parts by mass) was added, and the reaction was performed at 35 ° C until the residual isocyanate disappeared to obtain polyester compound 2.

(Step 1-8) Put compound D (26.68 parts by mass) in a reaction vessel under a nitrogen environment, and then, 131 parts by mass of propylene glycol methyl ether acetate in the solvent and tertiary amine compound 1 (17.12 parts by mass) 57.68 parts by mass of the above-mentioned polyester compound 2 obtained in (steps 1-7) were added, and heated to 70 ° C. with stirring.

(Step 1-9): Polyether compound 1 (17.00 parts by mass) was further added to the mixed solution obtained in (Step 1-8), and the reaction was performed at 70 ° C for 2 hours until the residual isocyanate disappeared, thereby obtaining GPC analysis. The polyurethane compound 1 having a weight average molecular weight (Mw) of 22,000 and a number average molecular weight (Mn) of 8800 was shown.

<Dispersant 2>

As the dispersant 2, the polyurethane compound 2 obtained through the following (step 2-1) to (step 2-13) was used.

Compound D: toluene diisocyanate (TDI)

Compound E: Diethanolamine

Compound F: dimethylaminopropylamine

Compound G: 2-hydroxyethyl acrylate

Compound H: 2,6-Di-tert-butyl-4-cresol

Polyether compound 1: poly (propylene glycol) monobutyl ether (Mn = 1100)

Polyester compound 1: Obtained from the above (steps 1-3).

Polyester compound 2: Obtained from the above (step 1-7).

(Step 2-1) Compound F (100 parts by mass), compound G (113.8 parts by mass), and compound H (0.29 parts by mass) were stirred at 70 ° C. for 48 hours until the Michael addition reaction was completed to obtain Level 3 amine compound 2.

(Step 2-2) In a stirred reaction container heated to 50 ° C, Compound D (25.0 parts by mass) was filled.

(Step 2-3) Polyether compound 1 (125.0 parts by mass, about 0.8 mol equivalent relative to TDI) was dropped into a funnel, maintained at a temperature between 50 and 60 ° C, and dropped to the above stirring reaction in 4 hours. Container.

(Step 2-4) The reaction product obtained in (Step 2-3) was kept at 70 ° C for 60 minutes.

(Step 2-5) The completion of the reaction is determined by titration of the residual isocyanate, and the reaction mixture is cooled to 20 ° C.

(Step 2-6) To the reaction mixture obtained in (Step 2-5), compound E (24.14 parts by mass, about 1.6 mole equivalents with respect to TDI) was added, and kept at room temperature until it was determined by infrared spectroscopic analysis. The residue of the determined isocyanate disappears.

(Step 2-7) The mixture of the product obtained in (Step 2-6) (which contains the diadduct of diethanolamine and TDI) was dissolved in diethyl ether and eluted with a silica gel column.

(Step 2-8) Wash the column that was subjected to elution in (Step 2-7) three times with diethyl ether, combine and separate the liquid, and then remove the solvent in vacuum to obtain 90 parts by mass of the polyether compound 2 Solid product.

In step (2-7) and (step 2-8) described above, the diadduct of diethanolamine and TDI is removed.

(Step 2-9) Compound D (26.68 parts by mass) was placed in a reactor under a nitrogen atmosphere.

(Step 2-10) In a reactor containing the above-mentioned compound D, methoxypropyl acetate (130.87 parts by mass), polyester compound 2 (15.23 parts by mass), and polyether compound 2 (10.68 parts by mass) were added as a solvent. ) And tertiary amine compound 2 (28.30 parts by mass).

(Step 2-11) The mixture obtained in (Step 2-10) is heated to 70 ° C with stirring.

(Step 2-12) Polyester compound 1 (26.09 parts by mass) was added to the reaction mixture of (Step 2-11), and the mixture was kept at 70 ° C for 2 hours.

(Step 2-13): It is confirmed that there is no residual isocyanate in the reaction mixture obtained in (Step 2-12), and a polyamine group having a weight average molecular weight (Mw) of 20,000 and a number average molecular weight (Mn) of 8000 by GPC analysis is obtained Formate compound 2.

<Dispersant 3>

As the dispersant 3, the polyurethane compound 3 obtained through the following (step 3-1) was used.

Compound I: benzyl chloride

(Step 3-1) Compound 200 (2.35 parts by mass, equivalent to the reactant) is added to 200 parts by mass of the reaction solution obtained in the above (step 1-9) (the content of the polyurethane compound 1 is 94.97 parts by mass). 20% of the molar number of the tertiary amine in the polyurethane compound 1 Molar number), and stirred at 70 ° C. for 20 hours, thereby obtaining a polyurethane compound 3 in which a part of the tertiary amine in the polyurethane compound 1 was partially quaternized.

<Dispersant 4>

As the dispersant 4, the polyurethane compound 4 obtained through the following (step 4-1) was used.

Compound E: Diethanolamine

(Step 4-1) In the above (Step 1-8), in addition to replacing the tertiary amine compound 1 (17.12 parts by mass, 0.12 moles), and adding the same mole number of compound E (diethanolamine, 12.62 parts by mass, Except for 0.12 mol), the rest were carried out in the same manner as in (Step 1-1) to (Step 1-9) to obtain polyurethane compound 4.

<Dispersant 5>

As the dispersant 5, the polyurethane compound 5 obtained through the following (step 5-1) was used.

Compound J: 1,6-hexanediol

(Step 5-1) In the above (Step 1-8), in addition to replacing the tertiary amine compound 1 (17.12 parts by mass, 0.12 moles), and adding the compound J (14.18 parts by mass, 0.12 moles) of the same mole number Except for), the rest are performed in the same manner as in (Step 1-1) to (Step 1-9) to obtain polyurethane compound 5.

<Dispersant 6>

As the dispersant 6, the polyurethane compound 6 obtained through the following (step 6-1) was used.

Compound K: Trimethylolpropane

(Step 6-1) In addition to the above (Step 1-8), the compound D was increased to 28.04 parts by mass, and compound K (0.52 parts by mass, 0.004 moles) was added. In the above (step 1-9), The polyether compound 1 was increased to 21.26 parts by mass, and the rest was performed in the same manner as in (Step 1-1) to (Step 1-9) to obtain a weight average molecular weight (Mw) of 23,000 and a number average molecular weight (Mn). It is 9200 polyurethane compound 6.

The components of the dispersants 1 to 6 are shown in Table 1.

<Carbon Black Ink 1>

A pigment, a dispersing agent, a dispersing aid, and a solvent are prepared in the following composition, and the carbon black ink 1 is prepared in the following method.

First, the solid content of a pigment, a dispersing agent, and a dispersing assistant is prepared as follows.

‧Pigment SB350 (carbon black manufactured by DEGUSSA): 100 parts by mass

‧Dispersant 1: 20 parts by mass (equivalent to solid content)

‧Dispersion aid (pigment derivative) S12000 (Lubrizol company, acidic phthalocyanine pigment derivative): 2 parts by mass

‧ Solvent Propylene glycol monomethyl ether acetate: 226.6 parts by mass

The above-mentioned components are sufficiently stirred and mixed.

Next, a dispersion conditioner was used for 6 hours in the range of 25-45 degreeC, and the dispersion liquid was obtained. As the bead ball, zirconia beads having a diameter of 0.5 mm were used, and 60 parts by mass of a dispersion liquid and 180 parts by mass of the bead ball were added. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a carbon black ink 1 having a solid content of 35% by mass.

<Preparation of carbon black ink 2 ~ 14>

The type of the dispersant and pigment of the carbon black ink 1 was changed to the dispersant and pigment described in Table 2. Stirring and mixing were performed in the same manner as the carbon black ink 1, and the dispersion treatment was performed with a paint conditioner to prepare a solid content of 35. Mass% carbon black ink 2 ~ 14.

The details of each component in Table 2 are as follows.

‧SB350: Carbon black pigment made by DEGUSSA, average primary particle size: 31nm

‧MA77: Carbon black pigment made by Mitsubishi Chemical Corporation, average primary particle size: 23nm

‧Disperbyk-161: Dispersant manufactured by BYK Chemie, a high molecular weight dispersant with a structure in which a polyurethane frame formed by a toluene diisocyanate polymer is connected by a backbone linking group. Has a basic functional group.

‧Disperbyk-167: a dispersant manufactured by BYK Chemie, a medium to low molecular weight dispersant with a structure in which a polyurethane frame formed by a toluene diisocyanate polymer is connected by a backbone linking group. Has a basic functional group.

‧Ajisper PB-821: Ajinomoto Fine, a dispersant manufactured by Techno, with Polyethyleneimine or polyethylene / polyamine backbone basic graft polymers.

‧Flowlen KDG-2400: Dispersant manufactured by Kyoeisha Chemical Co., a polyacrylic acid graft polymer with basic functional group.

‧HIPLAAD ED-701: Dispersant manufactured by Nanben Chemical Co., Ltd., a basic graft polymer with polyethyleneimine or polyethylene / polyamine skeleton.

‧Disperbyk-2000: Dispersant manufactured by BYK Chemie, grade 4 ammonium salt of grade 3 amine modified acrylic block copolymer.

‧Disperbyk-2001: Dispersant manufactured by BYK Chemie, a grade 3 amine acid modified acrylic block copolymer.

<Alkali soluble resin (1): epoxy (meth) acrylate resin (D1-2)>

50 g of the epoxy compound (epoxy equivalent 264) having the above structure, 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of p-methoxyphenol were placed in the installation. In a thermometer, a stirrer, and a flask with a cooling tube, the reaction was performed at 90 ° C. with stirring until the acid value became 5 mgKOH / g or less. The reaction required 12 hours to obtain an epoxy acrylate solution (1).

25 parts by mass of the epoxy acrylate solution (1), 0.76 parts by mass of trimethylolpropane (TMP), 3.3 parts by mass of biphenyltetracarboxylic acid anhydride (BPDA), and tetrahydrophthalic anhydride (THPA) 3.5 parts by mass was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 105 ° C. with stirring to perform a reaction.

After the resin solution became transparent, it was diluted with butyl methoxyacetate and adjusted so that the solid content became 50% by mass to obtain an acid value of 115 mgKOH / g and a weight average molecular weight in terms of polystyrene measured by GPC ( Mw) 2600 alkali-soluble resin (1).

<Alkali soluble resin (2): epoxy (meth) acrylate resin (D1-2)>

In the same manner as in the production of the alkali-soluble resin (1), an epoxy compound (epoxy equivalent 264), acrylic acid, butyl methoxyacetate, triphenylphosphine, and p-methoxyphenol were reacted to obtain a ring. Oxyacrylate solution (2).

25 parts by mass of the epoxy acrylate solution (2), 0.37 parts by mass of trimethylolpropane (TMP), 4.76 parts by mass of biphenyltetracarboxylic acid anhydride (BPDA), and tetrahydrophthalic anhydride (THPA) 1.02 parts by mass was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was gradually raised to 105 ° C. with stirring to perform a reaction.

After the resin solution became transparent, it was diluted with butyl methoxyacetate and adjusted so that the solid content became 50% by mass, to obtain an acid value of 100 mgKOH / g and a weight average molecular weight in terms of polystyrene measured by GPC ( Mw) 10,000 alkali-soluble resin (2).

<Alkali soluble resin (3): epoxy (meth) acrylate resin (D1-1)>

300 parts by mass of "XD1000" (dicyclopentadiene‧phenol polymer polyglycidyl ether, epoxy equivalent 252) made by Nippon Kayaku Co., Ltd., 104 parts by mass of methacrylic acid, and p-methoxyphenol 0.2 parts by mass, 5 parts by mass of triphenylphosphine, and 255 parts by mass of propylene glycol monomethyl ether acetate were filled in a reaction vessel and stirred at 100 ° C. until the acid value became 3.0 mg-KOH / g. Next, 145 parts by mass of tetrahydrophthalic anhydride was added, and the temperature was adjusted to 120 ° C. The reaction was performed for 4 hours to obtain an alkali-soluble resin (3) having a solid content of 50% by mass, an acid value of 106 mg-KOH / g, and a polystyrene-equivalent weight average molecular weight (Mw) of 1,580 as measured by GPC.

<Photopolymerization initiator (1)> (Dione body)

Ethylcarbazole (5 g, 25.61 mmol) and o-naphthyl chloride (5.13 g, 26.89 mmol) were dissolved in 30 ml of dichloromethane, cooled to 2 ° C in an ice-water bath and stirred, and AlCl ₃ (3.41 g, 25.61 was added) mmol). After stirring for 3 hours at room temperature, 15 ml of a methylene chloride solution of crotonyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, and AlCl ₃ (4.1 g, 30.73 mmol) was added, followed by stirring for 1 hour and 30 minutes. The reaction solution was placed in 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

(Oxime body)

The diketone body (3.00 g, 7.19 mmol), NH ₂ OH‧HCl (1.09 g, 15.81 mmol) and sodium acetate (1.23 g, 15.08 mmol) were mixed into 30 ml of isopropanol and refluxed for 3 hours. After completion of the reaction, the reaction solution was concentrated, 30 ml of ethyl acetate was added to the obtained residue, and the mixture was washed with 30 ml of a saturated sodium bicarbonate aqueous solution and 30 ml of a saturated saline solution, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 1.82 g of a solid. This was purified by column chromatography to obtain 2.22 g of oxime as a pale yellow solid.

(Oxime ester)

The oxime body (2.22 g, 4.77 mmol) and acetamidine chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane and cooled with ice. Triethylamine (1.77 g, 17.5 mmol) was dropped and reacted directly for 1 hour. After confirming that the starting material disappeared by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of a saturated sodium bicarbonate aqueous solution, twice with 5 ml of a saturated saline solution, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator ( 1). The chemical shift of ¹ H-NMR of the photopolymerization initiator (1) is shown below.

¹ H-NMR (CDCl ₃ ): σ1.17 (d, 3H), 1.48 (t, 3H), 1.53 (s, 3H), 1.81 (s, 3H), 2.16 (s, 3H), 2.30 (s, 3H), 3.17-3.32 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7.45-7.59 (m, 5H), 7.65 (dd, 1H), 7.95 (m, 2H) , 8.04 (m, 2H), 8.14 (dd, 1H), 8.42 (d, 1H), 8.64 (d, 1H)

The structure of the photopolymerization initiator (1) is as follows.

<Example 1> (Preparation of resist 1 (photosensitive resin composition 1))

Using the carbon black ink 1 previously prepared, each component described in Table 3 was prepared so as to have the ratio shown in Table 3, and it was dissolved by stirring with a stirrer to prepare a resist 1 having a solid content concentration of 15% by mass.

The details of each component in Table 3 are as follows.

‧PM21: a methacryl group-containing phosphate ester (manufactured by Nippon Kayaku Co., Ltd., KAYAMER (registered trademark) PM21, adhesion promoter).

‧SH6040: epoxy silane coupling agent (manufactured by Toray Co., Ltd., SH6040, adhesion promoter)

‧F-559: Surfactant (manufactured by Dainippon Ink Chemical Industry Co., Ltd., F559)

<Examples 2 to 7, Comparative Examples 1 to 9> (Preparation of resist 2-16 (photosensitive resin composition 2-16))

Using the carbon black inks shown in Tables 4, 5 and 6, the type of each component of the resist 1 was changed to each of the components described in Tables 4, 5 and 6, and these were performed so as to have the ratios shown in Table 3. In the same manner as in the resist 1, the mixture was stirred by a stir bar to dissolve it, and the resists 2 to 16 having a solid content concentration of 15% by mass were prepared. Among them, the total solid content concentration of IRG907 and DETX-S in resist 15 is in the same manner as the solid content concentration of photopolymerization initiator (1) in resist 1 with a mass of 4: 1. Ratios are mixed.

The details of each component in Tables 5 and 6 are as follows.

‧IRG907: IRGACURE907, manufactured by Chiba Speciality Chemicals, 2-methyl-1- [4- (methylthio) phenyl] -2- Phenylpropane-1-one.

‧DETX-S: KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd., 2,4-dimethyl 9-sulfur . The solid content of the resist 15 was 1.6% by mass.

‧Photopolymerization initiator (2): OXE02, manufactured by BASF. Has the following chemical structure.

(Evaluation of ink) (1) Evaluation of the viscosity of carbon black ink

The viscosity of the prepared carbon black inks 1 to 14 was measured with a viscometer (manufactured by Toki Sangyo, RE105L). The viscosity of any carbon black ink is in the range of 10 ~ 20mPa‧s. The ink viscosity immediately after the carbon black ink was prepared (immediately after dispersing) and after standing at room temperature for one week was measured and classified according to the following criteria. The results are shown in Table 7.

：: Even after the ink was dispersed, the ink was hardly thickened even after being left at room temperature for one week.

○: After dispersing the ink, it was left to stand at room temperature for 1 week, although the viscosity was increased, it was stable within 20 mPa · s.

△: After the ink is dispersed, it is left to stand at room temperature for 1 week to continuously increase the viscosity, exceeding 20 mPa‧s.

×: The viscosity increased significantly after the ink was dispersed, and it exceeded 20 mPa‧s within 3 days.

(Evaluation of resist) (1) Evaluation of the viscosity of a resist (photosensitive resin composition)

The viscosity of the prepared resists 1 to 15 was measured by a viscometer (manufactured by Toki Sangyo, RE105L). The viscosity of any resist is in the range of 2 ~ 5mPa‧s. The viscosity of the resist immediately after the preparation of the resist and after standing at room temperature for one month was measured, and classified according to the following criteria. The results are shown in Table 7.

：: After the resist was prepared, even if left at room temperature for one month, there was almost no thickening.

○: After the resist was prepared, it was left to stand at room temperature for 1 month, although the viscosity was increased, the degree of increase was within 0.5 mPa‧s.

△: After the resist was prepared, it was left to stand at room temperature for 1 month to increase the viscosity, and the degree of increase was over 0.5 mPa‧s.

×: After the resist was prepared, it was thickened after being left at room temperature for one week, and the thickening degree exceeded 0.5 mPa‧s.

Since the viscosity of the resist is greatly affected during coating, it is compared with ink The evaluation is carried out on the strict standards as described above.

(2) Production of Black Matrix (BM)

The prepared resists 1 to 16 were applied to a glass substrate by a spin coater, dried under reduced pressure, and then dried on a hot plate at 100 ° C. for 150 seconds. Next, the obtained dried coating film was subjected to pattern exposure by a high-pressure mercury lamp at 30 mJ through an exposure mask having openings having a pattern width of 6 μm and 5 μm, and then prepared with ultrapure water at room temperature (23 ° C) The KOH aqueous solution of 0.04 mass% was spray-developed as an alkali developing solution, and after removing the unexposed part, it was spray-washed with ultrapure water. Then, post-baking was performed in a furnace at 230 ° C. for 30 minutes to produce a BM having a film thickness of about 1 μm.

(3) Evaluation of optical density (OD value) and film thickness of BM

The BM film thickness produced in (2) was measured by a step measurement device Alpha-Step-500 (KLA-Tencor), and the OD value was measured by a penetration concentration measurement device GretagMacbeth D200-II (manufactured by GretagMacbeth). In this way, an OD value (unit OD value) per 1 μm was obtained. The unit viscosity OD of the results of the evaluation of the resist viscosity was 4.2 / μm.

(4) 6μm fine line evaluation (after development)

Using an exposure mask having a plurality of 6 μm openings (openings with a width of 6 μm), the development time was set to the following conditions, and coating, exposure, and development were performed in the same process as in (2) to produce BM fine lines. Hereinafter, a BM thin line produced using an exposure mask having a 6 μm opening will be simply referred to as “6 μm thin line”.

If the alkali development time is too short, the dissolution of the alkali-soluble resin may occur And the pigment remains and the substrate is contaminated obviously; on the other hand, if it is too long, the BM thin line is gradually eroded by the alkaline developer and peeled off. In addition, the shortest dissolution time (the shortest time for which patterning on a substrate can be confirmed) indicates the ease of alkali development of the photosensitive resin composition.

In the BM thin line evaluation, not only the shortest dissolution time, but also the BM line width when developing several times (for example, 1.5 times, 2 times, etc.) the shortest dissolution time may be evaluated. The magnification becomes larger, the line width becomes gradually narrower, or the alkali developing solution penetrates to the portion where the substrate and the BM thin line are closely adhered, and the sag portion appears, and it is easy to peel off. Moreover, as the multiple becomes smaller, the residue tends to remain.

Generally, when patterning is confirmed, the BM line width tends to become thick due to the influence of refracted light from the exposure mask. Therefore, in order to evaluate the target line width, the development time of 1.5 times the minimum dissolution time is Develop the right spot. Also, the shortest dissolution time varies depending on the composition of the photosensitive resin composition. However, if the value of the multiple of the shortest dissolution time is the same, the same degree of development is achieved.

The minimum dissolution time of the resist (photosensitive resin composition) 1 to 16 is 40 to 60 seconds, respectively. Therefore, several samples are made based on the development time of 60 times to 90 seconds, which is 1.5 times of the individual, and the following evaluations are performed.

(4-1) Evaluation of 6μm fine line

The sample prepared in (4) above was measured for line width at three places with an optical microscope. Further, the average value was obtained. The results are shown in Table 7.

(4-2) Evaluation of linearity of 6 μm thin line

The thin threads are etched unevenly by the alkaline developer or subsequent shower pressure. Therefore, its linearity may deteriorate. By observing with an optical microscope, the linearity of a 6 μm thin line was observed at three places on the substrate, and the classification was performed in the following manner. The results are shown in Table 7.

：: The linearity of all the 6 μm fine lines is very good.

(Circle): The part which started to be eroded by the alkali developing solution was seen, but linear deterioration was not remarkable.

Δ: Deterioration of linearity was seen in the whole, and some defects were also seen.

×: The overall linearity is very poor and there are many defects.

(4-3) Pattern insertion of 6μm fine lines

A section of the 6 μm thin line was cut out at three points, and the cross section was observed with a SEM photograph. By cross-sectional observation, it was observed whether the bonding surface between the substrate and the 6 μm thin line pattern was etched by the alkaline developer to be entrapped, and evaluated according to the following classification. The results are shown in Table 7.

(Insertion evaluation)

A: None of the three points observed were trapped and were good.

B: There are mixed no-sags and good points, and no-sags are observed, but the points where the dense surface begins to be eroded are mixed.

C: At all three points observed, it was observed that although there was no intrusion, the dense adhesive surface began to be eroded.

D: There are mixed points where no sticking is observed, but the cohesive surface begins to be eroded, and points where there is obvious sticking.

E: Insertion was clearly seen at all three points observed.

F: There is a point where an indentation is clearly seen and a point where a large intrusion is observed.

G: Significant intrusion occurred at all three points observed.

(5) 6μm fine line evaluation (after heat treatment)

The thin line of BM that has undergone the development process is further coated with red, green, and blue photosensitive resin compositions. Therefore, it is necessary to perform heat treatment at a high temperature to harden it. Therefore, the 6 μm fine wire was heat-treated at 230 ° C. for 30 minutes. Due to the heat treatment, the thin wires may be thermally deformed and the line width may become thick due to the flow of the photosensitive resin composition that is not sufficiently hardened or the detachment of the residual solvent.

The line width of the 6 μm thin wire after the heat treatment was measured at three places. Further, the average value was obtained. In addition, from the difference between the line width after the development and the line width after the heat treatment, the increase of the line width was determined and the following evaluation criteria were set. The results are shown in Table 7.

(Line width evaluation (average value))

：: Within a range of 5.6 to 6.5 μm.

×: Outside the range of 5.6 to 6.5 μm.

(Increase line width evaluation)

A: The three points observed are all 0.1 μm or less.

B: The observed three points are a mixture of 0.1 μm or less and a range exceeding 0.1 μm and 0.3 μm or less.

C: All three points observed exceeded 0.1 μm to 0.3 μm.

D: The observed three points are a mixture of more than 0.1 μm and 0.3 μm and more than 0.3 μm and 0.4 μm.

E: All three points observed exceed 0.3 μm and 0.4 μm or less.

F: The observed three points are a mixture of more than 0.3 μm and 0.4 μm or less, and more than 0.4 μm.

G: All three points observed exceeded 0.4 μm.

The 6μm fine wire after heat treatment was evaluated for line width and increase. A part of the line-width sample was cut out at three points and observed by SEM. The cross section of the thin line is trapezoidal. The bottom angles corresponding to both ends of the lower bottom of the contact surface between the thin line and the substrate are referred to as a taper angle. This cone angle was evaluated according to the following criteria. The results are shown in Table 7.

(Cone angle evaluation)

A: The three points observed are all 73 degrees or more.

B: A point of 73 degrees or more and a point of 63 degrees or more and less than 73 degrees are mixed.

C: The three points observed are all 63 degrees or more and less than 73 degrees.

D: A point of 63 degrees or more and less than 73 degrees and a point of 59 degrees or more and less than 63 degrees are mixed.

E: The three points observed are all 59 degrees or more and less than 63 degrees.

F: A point of 59 degrees or more and less than 63 degrees and a point of less than 59 degrees are mixed.

G: The three points observed are all below 59 degrees.

As shown in Table 7, the 6 μm fine lines after development in Examples 1 to 7 all had very good linearity and no sags at all. On the other hand, in the 6 μm thin lines of Comparative Examples 1 to 9 after development, linearity was deteriorated, and sags were seen in the adhesion portion between the substrate and the substrate.

In addition, the 6 μm fine wires after the heat treatment in Examples 1 to 7 all maintained a line width within a range of 5.6 μm to 6.5 μm, and 6 μm fine wires could be formed satisfactorily. Increasing the line width is suppressed to 0.3 μm or less, and the taper angle is also 63 degrees or more, so it becomes a good thin line.

On the other hand, Comparative Examples 1 to 9 were all 6 μm thin wires after heat treatment, which increased the line width to exceed 0.3 μm, the taper angle was also less than 63 degrees, and the line width exceeded 6.5 μm, and it was impossible to form 6 μm thin lines of 5.6 to 6.5 μm. In particular, Comparative Example 9 using an initiator other than the oxime ester photopolymerization initiator deteriorated after development and after heat treatment.

(6) 5 μm fine line evaluation (after development and after heat treatment)

Furthermore, the BM thin line (5 μm thin line) produced using an exposure mask having a 5 μm opening was also evaluated by the same evaluation method and evaluation classification as the 6 μm thin line. The results are shown in Table 8.

(Line width evaluation (average value))

：: Within a range of 4.6 to 5.5 μm.

×: Outside the range of 4.6 to 5.5 μm.

As shown in Table 8, the photopolymerization initiator containing dispersant 1 and oxime ester In the photosensitive resin composition of Example 1, the 5 μm thin line after development was thinner than the 6 μm thin line, so it was more susceptible to the influence of alkali developing solution or heat treatment. Some signs of linearity reduction were seen, or the line width was slightly thickened. 0.1 μm, the taper angle is slightly reduced by 5 degrees, but 5 μm fine lines of 4.6 to 5.5 μm can be formed well.

In addition, it is considered that in Example 6, since the primary particle diameter of the pigment is as small as 23 nm and the surface area is large, the dispersant is easily adsorbed to the pigment, and the affinity between the hydrophilic media group of the dispersant adsorbed on the pigment and the alkali-soluble resin is effectively reduced. As a result, similar to the case of the 6 μm fine line, a 5 μm fine line with good linearity and good interstitial can be formed.

The polyurethane dispersant used in the resist of this embodiment, due to the combination with the alkali-soluble resin, makes the dissolving agent's affinity vehicle group and the alkali-soluble resin well compatible and forms a good three-dimensional obstacle. Both viscosity and OD are good and dispersibility is good.

In the examples, an oxime ester photopolymerization initiator having an ultraviolet absorption site, an energy transmission site, and a free radical generating site within one molecule was used, and thus, even in the vicinity of the adhesive surface of the substrate, where ultraviolet rays are difficult to reach, The alkali-soluble resin and the like can be effectively polymerized. Therefore, it is considered that the entanglement of the alkali-soluble resin and the hydrophilic solvent portion of the polyurethane dispersant becomes stronger, and during curing by ultraviolet irradiation, the aggregation of the pigment is suppressed, and a good dispersion state can be maintained. The alkali-resistant developing property and heat resistance from the pigment are uniformly expressed in the thin line, the linearity is good, and the entrapment and the erosion caused by the alkali developing solution are reduced.

In addition, it can be considered that the dispersing agent used in Examples 1, 2, and 3 has a pendant adsorption group, so the adsorption force with the pigment is improved, and the amount of free dispersing agent is reduced. Accordingly, it is considered that during the heat treatment, the free dispersant functions as a lubricant, and it is possible to prevent a decrease in the taper angle and an increase in the line width.

On the other hand, it is considered that the photosensitive resin composition of Comparative Example 9 is based on the combination of an IRG907 initiator mainly having a radical generating portion and a DETXS initiator mainly having an ultraviolet absorption site. The photopolymerization initiator has poor radical generation efficiency, and particularly, it is difficult to polymerize the parts that are hard to reach by ultraviolet rays, such as near the substrate adhesion surface, and thermal deformation occurs during heat treatment.

In addition, Comparative Example 1 using a dispersant 5 having no adsorption group, and Comparative Examples 4, 5 and 6 using a dispersant which is a graft polymer other than polyurethane skeleton, are between pigments. The adsorption force is weak, and the dispersibility of the pigment in the resist is insufficient.

Therefore, it is considered that during the manufacture of a color filter, the bond between the pigment and the dispersant becomes weaker during heat treatment, aggregation of the pigment occurs, the alkali-resistant developing property and heat resistance from the pigment are not sufficiently expressed, and thermal deformation occurs.

In addition, Comparative Examples 2 and 3 using a commercially available dispersant having a urethane bond were formed by a plurality of bone chains connected by a bone chain linking group by a polymer of toluene diisocyanate having three or more isocyanates. A dispersant composed of several solvent-soluble or adsorbent groups reduces the coating effect on the pigment, and also creates a three-dimensional obstacle to the adsorbent group, so the pigment's adsorption performance is low. In addition, it can be considered that the amount of the soluble vehicle group or the adsorption group is less than that of the polyurethane dispersant used in the examples, the compatibility between the soluble vehicle group and the alkali-soluble resin is insufficient, and pigment agglomeration occurs. The alkali developability and heat resistance cannot be fully expressed.

Further, in Comparative Examples 7 and 8 using an acrylic AB block dispersant, it is considered that since the adsorption groups are concentrated on one of the dispersants, the pigment adsorbing groups are sterically hindered from each other, and the pigments cannot be sufficiently adsorbed to disperse the free dispersing amount. increase. Therefore, it is considered that the substrate adhesion via the dispersant cannot be sufficiently obtained between the pigment and the substrate. Strength, alkali development resistance is reduced, and patterning is difficult to obtain.

Although the present invention has been described in detail using specific aspects, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. Furthermore, this application is based on the Japanese patent application (Japanese Patent Application No. 2014-143279) filed on July 11, 2014, and the entirety thereof is incorporated herein by reference.

Claims (14)

A photosensitive resin composition containing a color material (a), a dispersant (b), a photopolymerization initiator (c), an alkali-soluble resin (d) and a solvent (e), wherein the dispersant (b) It contains a polycarbamate dispersant (b-1) with a solvent affinity group and an adsorption group; the polyurethane dispersant (b-1) contains: a part represented by the following formula (i) The structure, the structure containing the affinity group containing the above affinity group, and the structure containing the adsorption group containing the adsorption group; the structure containing the affinity group containing the adsorption group and the structure containing the adsorption group are given by the above formula (i) The part of the structure shown is connected; the part of the structure containing the adsorption group is selected from the part of the structure including the following formula (1), the part of the structure shown in the following formula (2-1), the following formula (2-2) Partial structure shown, and at least one partial structure in the group of partial structures shown in formula (2-3) below; photopolymerization initiator (c) is a photopolymerization initiator containing oxime ester (c-1) );

[In formula (i), R ^a represents an alkylene group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon through which the alkylene group and the aryl group are connected The base of the number 7 ~ 20; * indicates the bonding base];

[In formula (1), R ¹ represents an alkyl group or an aryl group that may have a substituent, and R ² and R ³ each independently represent an alkylene group, an aryl alkylene group, or an aryl group that may also have a substituent; * Indicates bonding base];

[In formula (2-1), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^γ , R ^δ and R ^ε independently represent an alkylene group which may also have a substituent, An aryl group which may have a substituent, or a group in which the above alkyl group extends from the above aryl group; where R ^γ is an alkyl group which may also have a substituent, or the above alkyl group and the above aryl group When the group is connected via a group, at least a part of the methylene group constituting the above alkylene group can also be selected from the group consisting of an ester bond, an ether bond, an urethane bond, a urea bond, an amide bond, and an amide imide bond. , At least one bond in the group of thiocarbamate bond, thioether bond and thioester bond; in addition, R ^γ can also be connected to the adjacent through the -NH- (C = O)-group At least any one of the N atoms together performs urea bonding, or amide bonding via a carbonyl group; * indicates a bonding group;]

[In formula (2-2), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^γ and R ^η independently represent an alkylene group which may also have a substituent, and may also have The aryl aryl group of the substituent, or the group through which the above-mentioned alkylene group and the above-mentioned aryl group are connected; wherein, R ^γ and R ^η are each independently an optionally extended alkylene group, or the above-mentioned alkylene group and the above When the aryl aryl group is connected through a group, at least a part of the methylene group constituting the above alkylene group can also be At least one bond in the group of amine bond, thiocarbamate bond, thioether bond and thioester bond is substituted; in addition, R ^γ and R ^η may also be substituted by -NH- (C = O)-group Urea bonding with at least one adjacent N atom or amide bonding via a carbonyl group; * indicates a bonding group;]

[In formula (2-3), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; R ^{γ ′} and R ^δ each independently represent an alkylene group which may also have a substituent, or Aryl group having a substituent, or a group in which the above alkyl group and the above aryl group are connected; wherein, R ^{γ ′} is an alkyl group which may also have a substituent, or the above alkyl group and the above aryl group When the group is connected, at least a part of the above-mentioned alkylene-containing methylene group can also be selected from the group consisting of an ester bond, an ether bond, an urethane bond, a urea bond, an amide bond, an amide imide bond, At least one bond in the group of ethyl thiocarbamate bond, thioether bond and thioester bond is substituted; in addition, R ^{γ '} can also be connected to the adjacent via the -NH- (C = O)-group The N atoms of the urea bond together, or the amide bond via the carbonyl group; R ^{ε '} represents a direct bond, an alkylene group that may also have a substituent, an aryl group that may also have a substituent, or the above extension A group in which an alkyl group is connected to the above arylene group; R ^ζ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may also have a substituent; wherein, when R ^ζ is an alkyl group or an aryl group, At least one of its hydrogen atoms may also be substituted by a tertiary amine group or a heterocyclic group containing a nitrogen atom; * represents a bonding group]. The photosensitive resin composition according to item 1 of the patent application, wherein the above-mentioned polyurethane dispersant (b-1) has a main chain, and the main chain contains a partial structure represented by the above formula (i) . The photosensitive resin composition as claimed in item 1 or 2 of the patent application, wherein the solvent-soluble group contains at least one of a polyether chain and a polyester chain. The photosensitive resin composition as claimed in item 1 or 2 of the patent application, wherein the above-mentioned adsorption group is at least one selected from the group consisting of a tertiary amine group, a tertiary ammonium salt group and a nitrogen-containing heterocyclic group . The photosensitive resin composition according to item 1 or 2 of the patent application, wherein the oxime ester photopolymerization initiator (c-1) has a carbazolyl group which may be substituted. The photosensitive resin composition according to claim 1 or 2, wherein the alkali-soluble resin (d) is an alkali-soluble resin (d-1) having at least one of a carboxyl group and an ethylenically unsaturated group. For example, in the photosensitive resin composition of claim 6, the alkali-soluble resin (d-1) is an epoxy (meth) acrylate resin. The photosensitive resin composition as claimed in item 7 of the patent application, wherein the epoxy (meth) acrylate resin is the following epoxy (meth) acrylate resin (D1-1) and epoxy ( At least one of meth) acrylate resins (D1-2); (1) Adding α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having carboxyl group to epoxy resin, Furthermore, an epoxy (meth) acrylate resin (D1-1) obtained by reacting at least one of a polybasic acid and its anhydride; (2) α, β-unsaturated monocarboxylic acid or α having a carboxyl group , β-unsaturated monocarboxylic acid ester is added to epoxy resin, and then reacted with polyhydric alcohol, polyhydric acid and at least one of its anhydride obtained epoxy (meth) acrylate resin (D1-2 ). For example, the photosensitive resin composition according to item 1 or 2 of the patent application, wherein the average primary particle diameter of the color material (a) is 20 to 100 nm. The photosensitive resin composition as claimed in item 1 or 2 of the patent application, wherein the color material (a) contains carbon black. The photosensitive resin composition according to item 10 of the patent application scope contains 40% by mass or more of the carbon black relative to the total solid content. A hardened product obtained by hardening the photosensitive resin composition according to any one of patent application items 1 to 11. A black matrix containing the hardened product of the patent application item 12. An image display device is provided with the black matrix of the patent application item 13.