TW201606430A - Photosensitive resin composition, cured product, black matrix and image display device - Google Patents

Abstract

The present invention provides a photosensitive resin composition which is excellent in a dispersibility and capable of forming a high-definition fine line regardless of a content of color material in a photosensitive resin composition. The present invention relates to a photosensitive resin composition comprising (a) a coloring material, (b) a dispersant, (c) a photopolymerization initiator, (d) an alkali-soluble resin, (e) a solvent, wherein the dispersant (b) contains (b-1) a polyurethane dispersant having a solvophilic group and an adsorptive group, the polyurethane dispersant (b-1) contains a partial structure represented by the formula (i), and the photopolymerization 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. In particular, it is a photosensitive resin composition which is excellent in dispersibility, developability, and heat resistance and can form fine lines of high definition. The photosensitive resin composition of the present invention has a high light-shielding property, and is suitable for a photosensitive resin composition for a black matrix (Black Matrix, hereinafter sometimes referred to as "BM") which can form fine lines of high definition. Further, the present invention relates to a cured product of the photosensitive resin composition and its use.

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

As a representative production method of a color filter, a pigment dispersion method is currently known. When a color filter is produced by a pigment dispersion method, a photosensitive resin composition containing a black pigment is first applied onto a transparent substrate, dried, and further subjected to image exposure and development, and then treated at a high temperature of 200 ° C or higher. It hardens, thereby forming a BM. This color is repeated in various colors such as red, green or blue to form a color filter.

BM is generally arranged in a lattice, stripe or mosaic between pixels of red, green or blue, and has a contrast by suppressing the color mixture between the pixels. Degree or function to prevent light leakage. Therefore, high opacity is required for the BM system.

Further, since the edge portion of the pixel such as red, green, or blue formed after the formation of the BM overlaps with the BM, the BM film thickness is affected, and a step is formed in the overlapping portion. In this overlapping portion, the flatness of the pixels is impaired, unevenness of the liquid crystal lattice gap or disorder of the liquid crystal alignment occurs, and the display capability is lowered.

For this reason, in recent years, the thickness of the BM film is particularly required to be thinned, and in order to exhibit sufficient light-shielding properties when thinned, the proportion of the pigment contained in the photosensitive resin composition tends to increase.

On the other hand, in order to save energy and to extend the life of the portable battery, there is a tendency to reduce the output of the backlight, and in order to perform image display with high luminance under such conditions, the thin line of the BM belonging to the light shielding portion is performed. Chemical.

In addition, in recent years, in the market of liquid crystal displays, the miniaturization of tablet computers and the like has become mainstream, and the demand for high resolution has been increasing in large-scale televisions. For these reasons, the expectation of high-definition of BM has also changed. high. In recent years, the line width of the BM thin line has been about 10 μm from the conventional one, and has progressed to about 6 μm which is currently required.

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

As a dispersing agent for a color filter, an acrylic type, a polyurethane type, a polyethyleneimine type, a polyester type, etc. are proposed, and the structure is a random type, a block type, or a connection. Various types such as a branch type (comb shape) (for example, Patent Documents 1 to 3).

Among these, the polyurethane dispersant is a compound having a carboxyl group, a 1, 2 amino group or a thiol group by terminal addition of a urethane bond. Therefore, various forms have been developed as dispersing agents (for example, Patent Documents 4 to 9).

[Previous Technical Literature] [Patent Literature]

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

Patent Document 2: Japanese Patent No. 3095512

Patent Document 3: Japanese Patent No. 3789965

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

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

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

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

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

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

The inventors of the present invention have found that the dispersing agents described in Patent Documents 1 to 3 are not dispersible or dispersed after being dispersed depending on the type of the pigment, or are not sufficiently dispersed if not selected or the conditions are selected. Problems such as effects. Moreover, even if a high-sensitivity initiator is used in such conventional dispersants, it is impossible to form a finer fine line which is currently required.

Further, the dispersing agents described in Patent Documents 4 to 9 are insufficient to form finer fine wires under the conditions of higher opacity required at present, that is, under a condition in which the pigment content is high.

Therefore, the object of the present invention is to provide superior dispersibility and color A photosensitive resin composition which can form a high-definition fine line, and a cured product, a black matrix, and a video display device using the photosensitive resin composition.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, it has been found that a photosensitive resin composition can be used by combining a polyurethane dispersant having a specific structure with a high-sensitivity photopolymerization initiator. The medium color materials contain proportions, which can form the fine lines of high precision required by the present.

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

A photosensitive resin composition comprising a color material (a), a dispersing agent (b), a photopolymerization initiator (c), an alkali-soluble resin (d), and a solvent (e), wherein a dispersing agent ( b) is a polyurethane dispersant (b-1) having a hydrophilic solvent group and an adsorption group; the polyurethane dispersant (b-1) contains the following formula (i) Partial configuration; photopolymerization initiator (c) containing oxime ester photopolymerization initiator (c-1);

[In the formula (i), R ^a represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an extended aryl group having 6 to 20 carbon atoms, or a carbon bonded to the above-mentioned extended aryl group. The number of 7 to 20; * indicates the bond base].

2. The photosensitive resin composition according to the above-mentioned item 1, wherein the polyurethane dispersant (b-1) contains a structure containing a hydrophilic solvent group and a structure containing the above-mentioned adsorption group. The structure containing the adsorbing moiety; the structure containing the hydrophilic solvent moiety and the structure of the adsorbing moiety are by the above formula (i) Some of the structures shown are linked.

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

4. The photosensitive resin composition according to any one of the above items 1 to 3, wherein the hydrophilic solvent group contains at least one of a polyether chain and a polyester chain.

The photosensitive resin composition according to any one of the above-mentioned items, wherein the adsorption group is selected from the group consisting of a tertiary amino group, a quaternary ammonium salt group, and a nitrogen atom-containing heterocyclic group. At least one.

The photosensitive resin composition according to any one of the above aspects, wherein the adsorption group-containing partial structure has a partial structure represented by the following formula (1);

[In the 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 extended arylalkyl group or an extended aryl group which may have a substituent; * indicates a bond base].

The photosensitive resin composition according to any one of the above aspects, wherein the adsorption group-containing partial structure has at least one of the following formulas (2-1) to (2-3) structure;

[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; and R ^γ , R ^{δ ,} and R ^ε each independently represent an alkylene group which may have a substituent, a aryl group having a substituent or a group in which the above alkyl group is bonded to the above aryl group; wherein, R ^γ is an alkyl group which may have a substituent, or the above alkyl group and the above-mentioned aryl group When the base is bonded, at least a part of the methylene group constituting the alkylene group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, and a quinone bond. Substituting at least one bond in the group of ethyl thiocarbamate, thioether bond and thioester bond; further, R ^γ may also be adjacent to each other via -NH-(C=O)- group At least one of the N atoms is subjected to a urea bond together, or a guanamine bond is carried out via a carbonyl group; * is a bond group];

[In the formula (2-2), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; and R ^γ and R ^η each independently represent an alkylene group which may have a substituent, or may have a aryl group of a substituent or a group in which the above alkyl group is bonded to the above aryl group; wherein, R ^γ and R ^η are each independently an alkyl group which may have a substituent, or the above alkyl group and the above When the aryl group is bonded to the group, at least a part of the methylene group constituting the alkylene group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, and a ruthenium bond. Substituting at least one bond in the group of an amine bond, an ethyl thioglycolate bond, a thioether bond, and a thioester bond; further, R ^γ and R ^η may also be via a -NH-(C=O)- group. And carrying out a urea bond together with at least one of the adjacent N atoms, or a guanamine bond via a carbonyl group; * is a bond 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; and R ^γ′ and R ^δ each independently represent an alkylene group which may have a substituent, and may also a aryl group having a substituent or a group in which the above alkyl group is bonded to the above aryl group; wherein, R ^{γ '} is an alkyl group which may have a substituent, or an alkylene group and the above aryl group When the group is bonded, at least a part of the methylene group constituting the alkylene group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, an oxime bond, Substituting at least one bond in the group of ethyl thiocarbamate, thioether bond and thioester bond; further, R ^{γ '} may also be adjacent to each other via -NH-(C=O)- group The N atoms are bonded together by a urea bond, or a guanamine bond is carried out via a carbonyl group; R ^{ε '} represents a direct bond, an alkyl group which may have a substituent, an extended aryl group which may have a substituent, or the above extension a group in which an alkyl group is bonded to the above-mentioned aryl group; R ^ζ represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent; wherein, when R ^ζ is the above alkyl group or the above aryl group, a hydrogen atom thereof At least one of them may be substituted by a tertiary amino group or a nitrogen atom-containing heterocyclic group; * is a bonding group].

The photosensitive resin composition of any one of the above-mentioned 1st to 7th, wherein the oxime ester photopolymerization initiator (c-1) has a carbazole group which may be substituted.

The photosensitive resin composition according to any one of the above aspects, wherein the alkali-soluble resin (d) contains an alkali-soluble resin (d-1) having at least one of a carboxyl group and an ethylenically unsaturated group. .

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

The photosensitive resin composition according to the above item 10, wherein the epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin (D1-1) and an epoxy group (A) At least one of an acrylate resin (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; An epoxy group (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 .

The photosensitive resin composition according to any one of the items 1 to 11, wherein the color material (a) has an average primary particle diameter of 20 to 100 nm.

The photosensitive resin composition as described in any one of Claims 1 to 12, wherein the color material (a) contains carbon black.

The photosensitive resin composition according to the above-mentioned item 13, wherein the carbon black is contained in an amount of 40% by mass or more based on the total solid content.

A cured product obtained by curing the photosensitive resin composition according to any one of the items 1 to 14 above.

16. A black matrix comprising the cured product of item 15.

A video 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 which is excellent in dispersibility and which can form fine lines of high fineness regardless of the color material content ratio in the photosensitive resin composition. The photosensitive resin composition of the present invention is particularly high in light-shielding property and can be used as a photosensitive resin composition for a black matrix which can form fine lines of high definition.

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‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

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

The embodiments of the present invention are specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

In the present invention, the term "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and the same applies to "(meth)acrylate" and "(meth)acrylylene group". Further, "acid (anhydride)", "(anhydrous) ... acid" means both an acid and an anhydride thereof.

In the present invention, the term "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 the weight average molecular weight refer to a polystyrene-equivalent number average molecular weight (Mn) and a weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).

In the present invention, the "amine valence" is an amine valence in terms of an effective solid content, and is a value indicated by the KOH weight equivalent to 1 g of the alkali amount of the solid content of the dispersant. . Further, the measurement method will be described later. On the other hand, the "acid value" is an acid value in terms of an effective solid content, which is not particularly limited, and is calculated by neutralization titration.

Further, in the present specification, "*" may be used to indicate a bonding group.

In addition, the "polyurethane skeleton" in the present specification does not only terminate in a skeleton composed of a polyurethane, but also includes a skeleton composed of a polyurethane. Similarly, the "polyurethane dispersant" not only terminates in a dispersing agent having two or more urethane bonds, but also includes a dispersing agent having two or more urea bonds, and having an ethyl urethane. The concept of a bond and a dispersant of a urea bond.

[Photosensitive Resin Composition]

The photosensitive resin composition of the present invention contains a color material (a), a specific dispersing agent (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 mercaptan, a dispersing aid (pigment derivative), a dense adhesion promoter, a coating enhancer, and a development improver, as needed. Other compounding components such as an ultraviolet absorber, an antioxidant, and a surfactant; in general, each of the components 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 dispersing agent, and an oxime ester photopolymerization initiator (c-1) as a photopolymerization start. Agent (c).

[dispersant (b)]

The photosensitive resin composition of the present invention contains a specific polyurethane dispersant (b-1) as a dispersing agent (b).

[Polyurethane dispersant (b-1)]

The polyurethane dispersant (b-1) has a hydrophilic solvent group and an adsorption 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 which may have a substituent, an extended aryl group having 6 to 20 carbon atoms, or a carbon to which the above alkylene group and the above extended aryl group are bonded A number of 7 to 20; * indicates a bond base.

The number of carbon atoms of the alkylene group which may have a substituent in the above formula (i) is not particularly limited, and is preferably 2 or more, more preferably 3 or more, and preferably 15 or less. More preferably, it is 10 or less, and even more preferably 7 or less. When it is set to the above lower limit value, the dispersibility tends to be good, and when it is equal to or less than the above upper limit, it is possible to prevent high viscosity.

The alkyl group may be a chain or a ring, or may be a chain alkyl group and a cyclic alkyl group. From the viewpoint of dispersibility, it is preferred to have at least a cyclic portion.

Specific examples of the alkylene group include a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a octyl group, a fluorenylene group, a cyclohexylene group, a cyclohexylenemethylene group, and a stretching group. Cyclohexylmethylene groups are extended to cyclohexyl and the like. From the point of view of good dispersion, Preferably, it is a tetramethylene group, a pentamethylene group, a hexamethylene group, a cyclohexylene group, or a cyclohexylmethylene group, and more preferably a pentamethylene group, a hexamethylene group, a cyclohexylene group, or The cyclohexylmethylene group is extended to a cyclohexyl group.

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

The number of carbon atoms of the aryl group which may have a substituent in the above formula (i) is not particularly limited as long as it is in the range of 6 to 20, preferably 15 or less, more preferably 10 or less, still more preferably 8 or less. . When it is set to the above upper limit or less, it is possible to prevent a high viscosity.

Specific examples of the aryl group include the following.

Further, specific examples of the extended aryl group having a substituent include the following.

From the viewpoint of dispersibility, it is preferably represented by the formula (0-3) base.

The number of carbon atoms in the alkyl group which may have a substituent in the above formula (i) and the group in which the exoaryl group which may have a substituent is bonded is not particularly limited, and is preferably in the range of from 7 to 20. 8 or more, more preferably 9 or more, and preferably 15 or less, more preferably 14 or less, still more preferably 13 or less. When it is set to the above lower limit value, the dispersibility tends to be good, and when it is equal to or less than the above upper limit, it is possible to prevent high viscosity.

The number of the aryl groups having the above-mentioned alkyl group and the above-mentioned extended aryl group is not particularly limited as long as it is 1 or more, and is preferably 2 or more, and preferably 3 or less from the viewpoint of dispersibility. Further, the number of alkylene groups is not particularly limited as long as the number of alkylene groups is 1 or more, and is preferably 3 or less from the viewpoint of dispersibility.

Specifically, for example, one of the extended aryl groups having a substituent and one alkyl group which may have a substituent may be attached; and two of the extended aryl groups which may have a substituent may be used. It may also have a linking group of one alkyl group of a substituent.

Specific examples of the group in which the alkylene group and the above-mentioned extended aryl group are bonded to each other include the following.

Among them, from the viewpoint of dispersibility, the group represented by the above formula (0-5) is preferred.

As such alkylene, aryl, alkyl and aryl groups are attached 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, still more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples thereof include a methyl group, an ethyl group, a cyclohexyl group and the like.

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

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

Further, the polyurethane dispersant (b-1) may be connected to each other by a partial structure shown by the above formula (i). Similarly, the structure containing the adsorption group described later may be connected to each other by a partial structure represented by the above formula (i). Further, the structure containing the hydrophilic solvent group to be described later and the structure containing the adsorption group described later are connected by a partial structure represented by the above formula (i).

Thus, the polyurethane dispersant (b-1) has a partial structure represented by the above formula (i), and the structure containing the hydrophilic solvent group and the structure containing the adsorption group can be arranged on a straight line, and It is considered that the expansion of the movable region by such a partial structure tends to improve the compatibility with the solvent and the adsorption property to the pigment.

Further, the polyurethane dispersant (b-1) preferably has a main chain containing a partial structure represented by the above formula (i). Thus, by using the highly linear partial structure represented by the above formula (i) as a partial structure contained in the main chain, the solvent-containing portion can be contained. The structure and the structure containing the adsorption group are arranged on a straight line, and it is considered that the expansion of the movable region by such a partial structure tends to improve the compatibility with the solvent and the adsorption property to the pigment.

In the present specification, the main chain of the polyurethane dispersant (b-1) means a chain which is linked by two or more urethane bonds, and means the longest chain.

In a preferred embodiment, the polyurethane skeleton of the main chain has a linear structure. At this time, the main chain has a linear structure except for the bonding portion with the lyophilic solvent group, the adsorption group, and the bonding portion with the adsorption group. As described above, when the polyurethane skeleton is linear, the compatibility of the solvent-soluble solvent with the solvent or the adsorption of the adsorbing group to the pigment tends to be good. In particular, when the polyurethane skeleton is linear, the adsorption and dispersibility of the pigment by the nitrogen atom which promotes the urethane bond tend to be good.

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

(adsorption base)

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

Further, when the polyurethane dispersant (b-1) has a main chain, from the viewpoint of dispersibility, the adsorbing group is preferably selected from the main chain or bonded to the main chain and selected from the group consisting of a tertiary amine. At least one of the group of a quaternary group, a quaternary ammonium salt group, and a 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 preferred that the adsorption group-containing moiety is configured to each other, The structure containing the adsorption group portion and the structure containing the hydrophilic solvent group described later are connected by a partial structure shown by the above formula (i).

(including adsorption group part structure 1)

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

In the 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 extended arylalkyl group or an extended aryl group which may have a substituent.

* indicates the bond base.

The carbon number of the alkyl group of R ¹ is not particularly limited, but is usually 1 or more, preferably 2 or more, and is preferably 20 or less, more preferably 10 or less, still more preferably 6 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. From the viewpoint of dispersibility, it is preferably a methyl group, an ethyl group, a propyl group, a cyclopentyl group or a cyclohexyl group, more preferably a methyl group, an ethyl group or a cyclohexyl group, still more preferably a methyl group or a cyclohexyl group. .

The carbon number of the aryl group of R ¹ is not particularly limited, but is usually 6 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferred from the viewpoint of dispersibility.

The substituent which the alkyl group and the aryl group may have is not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group or a cyclohexyl group; an aryl group such as a phenyl group; and a benzyl group. Etc. 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, still more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples thereof include a methyl group, an ethyl group, a cyclohexyl group and the like.

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

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

Further, the carbon number of the alkylene group in R ² and R ³ is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 7 or less. . If it is in the above range, there is a tendency that the dispersibility is good. Specifically, for example, a methylene group, an ethylidene group, a propyl group, a butyl group, a cyclopentylmethylene group, a cyclohexylmethylene group, a cyclohexylethyl group, and a cyclohexyl group are mentioned. Base. From the viewpoint of dispersibility, a methylene group, an ethyl group, or a cyclohexylmethylene group is preferred, and an ethyl group is more preferred.

The carbon number of the extended arylalkyl group (the alkyl group and the extended aryl group) in R ² and R ³ is not particularly limited, but is usually 7 or more, preferably 8 or more, and preferably 30 or less. More preferably, it is 20 or less, and even more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a phenylmethylene group, a phenylethyl group, and a phenylphenyl group. From the viewpoint of dispersibility, a phenylmethylene group is preferred.

The carbon number of the extended aryl group in R ² and R ³ is not particularly limited, but is usually 6 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a stretching phenyl group and a stretching naphthyl group. From the viewpoint of dispersibility, a phenyl group is preferred.

The substituents which may be contained in the alkylene group, the extended alkylene group and the extended aryl group are not particularly limited, and examples thereof include a hydroxyl group; a carboxyl group; an alkyl group such as a methyl group, an ethyl group, a propyl group or a cyclohexyl group; An aryl group such as a phenyl group; an aralkyl group such as a benzyl group; 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, still more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples thereof include a methyl group, an ethyl group, a cyclohexyl group and the like.

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

Among these, from the viewpoint of suppressing steric hindrance between molecules, a hydroxyl group, a methyl group or an ethyl group is preferred.

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 each preferably independently an alkylene group.

Specific examples of the partial structure shown in the above formula (1) include the following.

Further, in the partial structure represented by the above formula (1), the entire formula (1) is an adsorption group containing a tertiary amino group. Further, by the partial structure shown in the formula (1) and the other adsorption group-containing portion structure or the hydrophilic solvent-containing portion structure, the partial structure shown in the above formula (i) can be connected to obtain the formula (1). The adsorbent group shown is disposed in the main chain of the polyurethane dispersant (b-1). At this time, the * of the above formula (1) represents a bond group between the carbonyl group of the urethane bond in the polyurethane skeleton of the main chain.

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

[Chemistry 13]

In the formula (1'), R ¹ to R ³ and * are equivalent to those 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 the aryl group of R ^A , those exemplified as R ¹ can be preferably used.

X ^- is a monovalent anion, and is not particularly limited. From the viewpoint of dispersibility, X ^{- is} preferably a halogen anion such as a chlorine anion or a methyl sulfate anion, more preferably a halogen anion, and even more preferably a chloride anion. . Formula (1 ') of the ammonium salt of 4-yl may be performed by three stages of the amine of formula (1) is obtained of this case, there is X ^- is the anion of 4 stages from the case of the agent.

Further, in the partial structure represented by the above formula (1'), the entire formula (1') is an adsorption group containing a 4-stage ammonium salt group. Further, the formula (1') can be obtained by connecting a partial structure represented by the formula (1') to a part of the structure represented by the above formula (i) in the structure of the other adsorbing group-containing moiety or the containing solvent-containing moiety. The adsorbent group shown is disposed in the main chain of the polyurethane dispersant (b-1).

Moreover, as another specific example, the partial structure shown below is mentioned. The following partial structures are all an adsorption group containing a heterocyclic group containing a nitrogen atom. The adsorbing group containing a heterocyclic group containing a nitrogen atom is considered to be the same as the tertiary amine group or the tertiary ammonium salt group because it exhibits hydrophobic bonding due to ionic bonding with a pigment and a tight binding effect. Function, showing good pigment adsorption.

Further, by the partial structure, the other adsorption group-containing partial structure or the affinity-containing medium-containing partial structure, the partial structure shown in the above formula (i) is connected, and the adsorption group shown in the partial structure can be disposed in the poly The urethane dispersant (b-1) is in the main chain.

In the above formula, * represents a bond group.

(including adsorption group part structure 2)

As another preferable example, at least one partial structure represented by the following formulas (2-1) to (2-3) is preferable. By having at least one partial structure represented by the following formulas (2-1) to (2-3), the steric hindrance of the adsorbed portion is alleviated, and the pigment can be efficiently adsorbed to the pigment by increasing the spatial freedom of the adsorbing 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 extended aryl group which may have a substituent, or a group in which the above-mentioned alkylene group is bonded to the above-mentioned extended aryl group. Wherein, when R ^γ is an alkyl group which may have a substituent, or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, at least a part of the methylene group constituting the above alkyl group may also be selected from At least one of the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, a quinone bond, a thiomethacrylate bond, a thioether bond, and a thioester bond Replaced. Further, R ^γ may be bonded to at least one of the adjacent N atoms via the —NH—(C=O)— group, or may be subjected to a guanamine bond via a carbonyl group.

* is the bonding base.

In the formula (2-2), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; and R ^γ and R ^η each independently represent an alkyl group which may have a substituent, or may have a substitution. a aryl group or a group in which the above alkyl group is bonded to the above aryl group. Wherein, when R ^γ and R ^η are each independently an alkyl group which may have a substituent or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, at least a part of the methylene group constituting the above alkyl group is also By being selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, a quinone bond, a thiocarbamate bond, a thioether bond, and a thioester bond Replaced by at least one key. Further, R ^γ and R ^η may be bonded to at least one of the adjacent N atoms via a -NH-(C=O)- group, or may be subjected to a guanamine bond via 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 extended aryl group which may have a substituent, or a group in which the above alkylene group is bonded to the above-mentioned extended aryl group. Wherein, when R ^γ' is an alkylene group which may have a substituent, or a group in which the above alkylene group is bonded to the above-mentioned extended aryl group, at least a part of the methylene group constituting the above alkylene group may also be selected At least one of the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, a quinone bond, an ethyl thioate bond, a thioether bond, and a thioester bond Replaced by the key. Further, R ^{γ '} may be bonded to an adjacent N atom via a -NH-(C=O)- group, or a guanamine bond may be carried out via a carbonyl group.

R ^{ε '} represents a direct bond, an alkyl group which may have a substituent, an extended aryl group which may have a substituent, or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group.

R ^ζ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. Wherein, when R ^ζ is an alkyl group or an aryl group, at least one of the hydrogen atoms thereof may be substituted by a tertiary amino group or a nitrogen atom-containing heterocyclic group.

* is the bonding base.

In the above formulas (2-1) to (2-3), the carbon number of the alkyl groups of R ^α , R ^β and R ^ζ is not particularly limited, but is usually 1 or more, and preferably 20 or less, more preferably 10 or less. The following, more preferably 2 or less. If it is in the above range, there is a tendency that the dispersibility is good.

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

The carbon number of the aryl group of R ^α , R ^β and R ^ζ is not particularly limited, but is usually 6 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferred from the viewpoint of dispersibility.

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

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

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

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

In the above formulas (2-1) to (2-3), the carbon number of the alkyl group of R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η which may have a substituent is not particularly The limit is usually 1 or more, preferably 2 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good.

The alkyl group may be a chain or a ring, or may be a chain alkyl group and a cyclic alkyl group. From the viewpoint of dispersibility, a chain-like alkyl group is preferred.

Specific examples thereof include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a cyclopentylenemethylene group, a cyclohexylenemethylene group, a cyclohexylenemethylene group, and a stretching ring. Hexyltrimethylene and the like. From the viewpoint of dispersibility, a methylene group, a dimethylene group or a trimethylene group is preferred, and a dimethylene group or a trimethylene group is more preferred.

The specific structure of the above formula (2-1) to (2-3) when R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η are an alkylene group which may have a substituent, For example, the following structure can be mentioned.

In the above formulas (2-1) to (2-3), R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η may further have a substituent alkyl group and may also have a substitution. The number of carbon atoms of the aryl group to be bonded is not particularly limited, but is usually 6 or more, preferably 7 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Further, the number of alkylene groups is not particularly limited as long as the number of alkylene groups is 1 or more, and is preferably 3 or less from the viewpoint of dispersibility.

Specifically, for example, one of the extended aryl groups which may have a substituent and one extended alkyl group which may have a substituent may be mentioned; or two of the extended aryl groups which may have a substituent may also be used. a group to which one alkyl group having a substituent has a substituent; a group of a pendant alkyl group which may have a substituent, which is bonded to one of the extended aryl groups which may have a substituent; and an alkylene group which may have a substituent A group which is alternately bonded to an extended aryl group which may have a substituent.

Specific examples of the group in which the alkylene group and the above-mentioned extended aryl group are bonded to each other include the following.

Among them, from the viewpoint of dispersibility, the group represented by the above formula (b3) is preferred.

When at least one of R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η is a group in which the above-mentioned alkylene group and the above-mentioned extended aryl group are bonded, the above formula (2-1)~ The specific structure of (2-3) is, for example, the following structure.

Among these, from the viewpoint of dispersibility, it is preferably such that (2-1-b), (2-2-b), (2-3-b), etc., R ^γ or R ^{γ '} is The alkyl group having a substituent may be bonded to a base having a substituent having an extended aryl group. In this case, from the viewpoint of dispersibility, R ^δ , R ^ε , R ^{ε '} and R ^η are preferably an alkylene group.

In the above formulas (2-1) to (2-3), the carbon number of the aryl group which may have a substituent of R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η is not particularly The limit is usually 6 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a phenylene group and a naphthyl group, and from the viewpoint of dispersibility, a phenyl group is preferred.

The specific structure of the above formula (2-1) to (2-3) when at least one of R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η is an exoaryl group, For example, the following configurations are listed.

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 Yan Fangji.

In the above formula (2-1) to (2-3), as an alkyl group, an aryl group, an alkyl group and a aryl group as R ^γ , R ^{γ '} , R ^δ , R ^ε , R ^{ε '} and R ^η The substituent which the base group may have is not particularly limited, and examples thereof include an alkyl group such as a methyl group, an ethyl group or a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; 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. More preferably, it is 1~5. The alkyl group may be linear, branched, or cyclic. Specific examples thereof include a methyl group, an ethyl group, a cyclohexyl group and the like.

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

As described above, when R ^γ , R ^{γ '} and R ^η are each independently an alkyl group which may have a substituent, or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, the above-mentioned alkylene group is formed. At least a portion 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 guanamine bond, a guanidine bond, a thiocarbamate bond, a thioether bond, and sulfur. At least one of the groups of ester bonds is replaced by at least one of the groups. Among these, from the viewpoint of dispersibility, as a preferred bond, at least a part of the methylene group constituting the above alkylene group is substituted by an urethane bond or an ester bond.

The specific structure of the above formulas (2-1) to (2-3) at this time includes, for example, the following structures.

[化22]

Particularly, from the viewpoint of dispersibility, R ^γ of the formula (2-1) is preferably a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, and constitutes a part of the methylene group of the alkyl group. It is the above formula (2-1-d') which is substituted by a urethane bond.

Further, from the viewpoint of dispersibility, R ^γ and R ^η of the above formula (2-2) are preferably an alkylene group, and at least a part of a methylene group constituting at least one alkylene group is as The above formula (2-2-d) or (2-2-d') is substituted by an ester bond.

Further, from the viewpoint of dispersibility, it is preferred that any of R ^{γ '} , R ^{δ ,} and R ^{ε ' in} the above formula (2-3) is an unsubstituted alkylene group (2-3) -a) The same. Further, it is also preferred to use R ^{γ '} of the above formula (2-3) as an alkylene group or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, and constitutes a methylene group of an alkyl group. A part is a compound of the above formula (2-3-d) or (2-3-d') which is substituted by a urethane bond, an thioglycolate bond, an ester bond or a thioether bond.

Further, as described above, R ^γ may be bonded to at least one of the adjacent N atoms via the —NH—(C=O)— group, or may be subjected to a guanamine bond via a carbonyl group.

Particularly, from the viewpoint of dispersibility, it is preferred that R ^γ of the formula (2-1) and the N atom bonded to R ^δ and R ^ε together carry out a urea bond via the -NH-(C=O)- group. Knot. The specific structure of the above formulas (2-1) and (2-2) at this time includes, for example, the following structures.

Further, as described above, R ^{γ '} may be bonded to an adjacent N atom via a -NH-(C=O)- group, or a guanamine bond may be carried out via a carbonyl group. The specific structure of the above formula (2-3) at this time includes, for example, the following structures.

Similarly, R ^η can also be bonded to an adjacent N atom via a -NH-(C=O)- group, or a guanamine linkage via a carbonyl group. The specific structure of the above formula (2-2) at this time includes, for example, the following structures.

[化25]

Further, when R ^ζ is an alkyl group or an aryl group, at least one of the hydrogen atoms may be substituted by a tertiary amino group or a nitrogen atom-containing heterocyclic group. The specific structure of the above formula (2-3) at this time includes, for example, the following structures.

In the above formulas (2-1) to (2-3), from the viewpoint of dispersibility, the following is preferable.

In the above formula (2-1), R ^{γ is} preferably a group in which the above alkylene group is bonded to the above-mentioned extended aryl group; in this case, it is preferred that at least a part of the methylene group constituting the above alkyl group is made of an amine group. The ethyl formate bond is substituted or the urea bond is bonded to the adjacent N atom via the -NH-(C=O)- group. Further, in this case, R ^δ and R ^{ε are} preferably an alkylene group. As such a specific example, the above formula (2-1-e) is shown.

[化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. Further, in this case, R ^δ and R ^{ε are} preferably an alkylene group. As such a specific example, the above formula (2-1-d) is shown below.

Further, in the above formula (2-2), R ^{γ is} preferably a group in which the above alkyl group is bonded to the above-mentioned extended aryl group; in this case, at least a part of the methylene group constituting the above alkyl group is preferably used by The urethane bond is substituted or the urea bond is carried out together with the adjacent N atom via the -NH-(C=O)- group. Further, in this case, R ^{η is} preferably an alkylene group. As such a specific example, the above formula (2-2-e) is shown below.

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

[化30]

Further, in the above formula (2-2), R ^{γ is} preferably an alkylene group. Further, in this case, R ^{η is} preferably an alkylene group; preferably at least a part of the methylene group constituting the above alkylene group is substituted by an ester bond. Specific examples of such a compound include the above formula (2-2-d').

Further, in the above formula (2-3), R ^{γ '} and R ^{δ are} preferably an alkylene group, and R ^{ε ' is} preferably a direct bond or an alkyl group; in this case, R ^{ζ is} preferably a hydrogen atom. As such a specific example, the above formula (2-3-a) is shown below.

Further, in the above formula (2-3), R ^{γ ' is} preferably a group in which the above alkylene group is bonded to the above-mentioned extended aryl group; in this case, at least a part of the methylene group constituting the above alkylene group is preferably borrowed. It is replaced by a urethane bond and/or a urethane bond. Further, in this case, R ^{δ is} preferably an alkylene group, and R ^{ε ' is} preferably a direct bond. Further, R ^{ζ is} preferably a hydrogen atom. As such a specific example, the above formula (2-3-d) is shown below.

[化33]

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

Further, R ^α , R ^β , N and R ^γ in the above formula (2-1) are an adsorption group containing a tertiary amino group. Similarly, R ^α , R ^β , N and R ^γ in the above formula (2-2) become an adsorption group containing a tertiary amino group. Further, R ^α , R ^β , N and R ^γ′ in the above formula (2-3) are an adsorption group containing a tertiary amino group. In these cases, * in the formula represents a bonding group between a carbonyl group having a urethane bond or a urea bond in the polyurethane skeleton.

Further, the partial structure shown by the above formula (i) is obtained by the partial structure shown in the above formulas (2-1) to (2-3) and the other adsorption group-containing portion structure or the hydrophilic solvent-containing portion structure. The linkage may be such that the adsorption group contained in the formulae (2-1) to (2-3) and the main chain of the polyurethane dispersant (b-1) are bonded.

Moreover, as another preferable example, it is preferable to have a partial structure shown by the following formula (2-1') - (2-3').

[化35]

In the formula (2-1'), R ^α ~ R ^ε and * are equivalent to those in the formula (2-1). The R ^A and X ^- systems are equivalent to those in the formula (1').

In the formula (2-2'), R ^α ~ R ^η and * are equivalent to those in the formula (2-2). The R ^A and X ^- systems are equivalent to those in the formula (1').

In the formula (2-3'), R ^α ~ R ^ζ and * are equivalent to those in the formula (2-3). The R ^A and X ^- systems are equivalent to those in the formula (1').

Moreover, as another specific example, the partial structure shown below is mentioned. In some of the following structures, the nitrogen atom-containing heterocyclic group becomes an adsorption group.

[化38]

In the above formula, * represents a bond group.

In contrast to the fact that a specific adsorbing group is present in the polyurethane skeleton of the main chain, it is preferred to have a pendant type in the side chain type of the polyurethane skeleton of the main chain. The nitrogen atom in the particularly preferred adsorbent group is bonded by at least one atom from the closest atom on the backbone of the backbone of the backbone. That is, it is preferably an adsorption group bonded to the main chain.

More preferably, the nitrogen atom in the specific adsorption group is separated by at least 2 atoms from the closest atom on the polyurethane skeleton of the main chain, and the specific adsorption is particularly preferred. The nitrogen atom of the base is at least 3 atoms separated by the closest atom on the backbone of the backbone.

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

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

(Content ratio containing the structure of the adsorption group)

The polyurethane dispersant (b-1) may be, for example, a structure having the above-described adsorption group-containing moiety, and may have a structure having one type of the above-mentioned adsorption group-containing moiety, or may have two or more types.

For example, all of the adsorbing groups may be made into a partial structure containing a tertiary amine group, or all of the adsorbing groups may be similarly formed into a partial structure containing a tertiary ammonium salt group, or all adsorbing groups may be made to have a nitrogen atom. Partial construction of a heterocyclic group.

From the viewpoint of dispersibility and compatibility, it is preferred that all of the adsorbing groups are a 3-stage amine group. In this case, it is possible to form a metal base having two or more kinds of tertiary amines, but by dispersibility. In view of the above, it is preferred to have one type of tertiary amino group, and more preferably have a partial structure containing a tertiary amine group selected from any one of the above formulas (1) and (2-1) to (2-3). More preferably, it has a partial structure containing a tertiary amino group represented by the formula (2-1).

On the other hand, from the viewpoint of developing solubility of the alkali developing solution, it is preferred that all of the adsorbing groups are a 4-stage ammonium salt group. Wherein, the 4-stage ammonium salt group can be prepared by subjecting the 3-stage amine group to 4-stage ammonium saltation by a 4-staged agent, but since the 4-stage ammonium group is subjected to the 4-stage ammonium saltation, there is a level 4 Since the impurities of the chemical agent tend to be formed in a large amount, from the viewpoint of suppressing the formation of impurities, the tertiary amino group portion is often left, and the tertiary amine group and the fourth-order ammonium salt group are coexistent.

Therefore, it is preferred to have both of the tertiary amine group and the tertiary ammonium salt group as the adsorption group, and more preferably selected from the combination of the above formulas (1) and (1') from the viewpoint of efficiency of production. Combination of the above formulas (2-1) and (2-1'), combinations of the above formulas (2-2) and (2-2'), and the above formulas (2-3) and (2-3') Any combination of the combinations; more preferably a combination of the above formulas (2-1) and (2-1').

In the case of having both the tertiary amine group and the tertiary ammonium salt group, the content ratio thereof is not particularly limited, and from the viewpoint of dispersibility, the partial structure containing the tertiary ammonium salt group is relative to the tertiary metal atomic group. The content ratio of the partial structure is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, and preferably 99 mol% or less, more preferably 95 mol. The ear% or less, more preferably 80% by mole or less, more preferably 60% by mole or less, particularly preferably 40% by mole or less, and most preferably 30% by mole or less.

In the same manner, the content of the structure containing the adsorbing moiety in the polyurethane dispersant (b-1) is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of dispersibility. More preferably, it is 20% by mass or more, and preferably 90% by mass. The following is more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

Further, the content ratio of the specific adsorbing group is preferably 0.001 mol or more, more preferably 0.01 mol or more, and still more preferably 0.05 mol with respect to 100 g of the polyurethane dispersant (b-1). Above the ear, it is preferably 0.8 moles or less, more preferably 0.4 moles or less, still more preferably 0.2 moles or less. Hereinafter, the ratio of this specific adsorption group to 100 g of the polyurethane dispersant (b-1) is expressed as a unit of "mole/100 g" as a specific adsorption group content.

(pro-solvent base)

The polyurethane dispersant (b-1) contains a hydrophilic solvent group. The type of the lyophilic solvent which the polyurethane dispersing agent (b-1) has is not particularly limited as long as it exhibits compatibility with a solvent. The lyophilic medium preferably contains at least one of a polyether chain and a polyester chain from the viewpoint of dispersibility. Further, in the case where 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 the key to the main chain.

The polyurethane dispersant (b-1) preferably contains a structure containing a hydrophilic solvent group containing the above-mentioned lyophilic solvent; as described above, from the viewpoint of dispersibility, it is preferred to contain a hydrophilic solvent moiety structure. The structures of the adsorbent-containing moiety and the structure containing the hydrophilic solvent-containing moiety are connected to each other by a partial structure represented by the above formula (i).

The specific partial structure of the structure containing the hydrophilic solvent moiety is not particularly limited, and is preferably a partial structure represented by the following formulas (3-1) to (3-3). In the formulae (3-1) to (3-3), R ^θ and the O atom are a hydrophilic solvent group, and other than the bond portion with the lyophilic solvent group.

[化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 extended aryl group which may have a substituent, or a group in which the above-mentioned alkylene group is bonded to the above-mentioned extended aryl group. Wherein, when R ^γ is an alkyl group which may have a substituent, or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, at least a part of the methylene group constituting the above alkyl group may also be selected from At least one of the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, a quinone bond, a thiomethacrylate bond, a thioether bond, and a thioester bond Replaced. Further, R ^γ may be urea-bonded together with an adjacent N atom via a -NH-(C=O)- group, or may be subjected to a guanamine bond via a carbonyl group.

Further, R ^γ may be bonded to the urethane bond together with an adjacent one of the O atoms via the —NH—(C=O)— group, or may be ester-bonded via a carbonyl group.

* indicates the bond 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 extended aryl group which may have a substituent, or a group in which the above alkylene group is bonded to the above-mentioned extended aryl group. Wherein, when R ^γ and R ^η are each independently an alkyl group which may have a substituent or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, at least a part of the methylene group constituting the above alkyl group is also By being selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, a quinone bond, a thiocarbamate bond, a thioether bond, and a thioester bond Replace with at least one key. Further, R ^γ and R ^η may be urea-bonded together with an adjacent N atom via a -NH-(C=O)- group, or a guanamine bond may be carried out via a carbonyl group.

Further, R ^γ may be bonded to the urethane bond together with an adjacent one of the O atoms via the —NH—(C=O)— group, or may be ester-bonded via a carbonyl group.

* indicates the bond 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 extended aryl group which may have a substituent, or a group in which the above alkylene group is bonded to the above-mentioned extended aryl group. Wherein, when R ^γ' is an alkylene group which may have a substituent, or a group in which the above alkylene group is bonded to the above-mentioned extended aryl group, at least a part of the methylene group constituting the above alkylene group may also be selected At least one of the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, a quinone bond, an ethyl thioate bond, a thioether bond, and a thioester bond Replaced by the key.

Further, R ^{γ '} may be bonded to an urethane bond together 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 extended aryl group which may have a substituent, or a group in which the above-mentioned alkylene group is bonded to the above-mentioned extended aryl group.

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

* indicates the bond base.

The number of carbon atoms of the alkylene group which may have a substituent among R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η is not particularly limited, but is usually 1 or more, preferably 2 or more, and It is preferably 20 or less, more preferably 15 or less, still more preferably 7 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, a cyclopentylenemethylene group, and a cyclohexylene group. Methylene, cyclohexyldimethylene, cyclohexyltrimethylene, etc.; from the viewpoint of dispersibility, dimethylene, trimethylene, tetramethylene, pentamethylene, Or hexamethylene, more preferably trimethylene, tetramethylene or pentamethylene.

In the above formula (3-1) to (3-3), the carbon of the above-mentioned alkyl group of R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η and the above-mentioned extended aryl group The number is not particularly limited, but is usually 6 or more, preferably 7 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. In addition, the number of the alkylene groups to be contained is not particularly limited, and is preferably 3 or less from the viewpoint of dispersibility.

Specifically, for example, one of the extended aryl groups which may have a substituent and one extended alkyl group which may have a substituent may be mentioned; or two of the extended aryl groups which may have a substituent may also be used. A group in which one alkyl group having a substituent is bonded; or a group in which two alkyl groups having a substituent are bonded via one of the extended aryl groups which may have a substituent. Specific examples of the group in which the alkylene group and the above-mentioned extended aryl group are bonded to each other include the groups represented by the above formulas (b1) to (b5).

The number of carbon atoms of the extended aryl group which may have a substituent of R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η is not particularly limited, but is usually 6 or more, and preferably 30 or less, more preferably Preferably, it is 20 or less, and more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a phenylene group and a naphthyl group, and from the viewpoint of dispersibility, a phenyl group is preferred.

Among these, from the viewpoint of dispersibility, it is preferred that R ^γ , R ^{γ '} is an alkylene group, an aryl group, or a group in which the above alkyl group is bonded to the above aryl group; ^δ , R ^ε , R ^{ε '} and R ^η are an alkylene group.

In the above formulas (3-1) to (3-3), an alkyl group which may have a substituent, such as R ^γ , R ^γ′ , R ^δ , R ^ε , R ^ε′ and R ^η , may also have a substitution. The substituent which the aryl group and the above-mentioned alkyl group and the above-mentioned extended aryl group may have are not particularly limited, and examples thereof include an alkyl group such as a methyl group, an ethyl group or a cyclohexyl group; and a phenyl group or the like. An aryl group; an aralkyl group such as a benzyl group; 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, still more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic. Specific examples thereof include a methyl group, an ethyl group, a cyclohexyl group and the like.

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

Among these, from the viewpoint 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 alkyl group which may have a substituent, or a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, the above-mentioned alkylene group is formed. At least a portion 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 guanamine bond, a guanidine bond, a thiocarbamate bond, a thioether bond, and sulfur. At least one of the groups of ester bonds is replaced by at least one of the groups.

Among these, from the viewpoint of dispersibility, as a preferred bond, a urethane bond or an ester bond may be mentioned as R ^γ , and an amine thiocarbamate bond or an amine may be mentioned as R ^γ' . Ethyl urethane bond or ester bond. Further, R ^η is preferably unsubstituted. Particularly preferably, from the viewpoint of dispersibility, R ^γ of the formula (3-1) or (3-1) is an alkylene group, or a group in which the above alkylene group is bonded to the above-mentioned extended aryl group, and is constituted. One of the methylene groups of the alkylene group is substituted by an urethane bond or an ester bond. Specific examples thereof include the following.

Further, R ^{γ '} in the above formula (3-3) is a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, and a part of the methylene group constituting the alkyl group thereof is derived from ethyl urethane. Key and / or urethane bond replacement. Specific examples thereof include the following.

Further, as described above, R ^γ and R ^η may each independently undergo a urea bond together with an adjacent N atom via a -NH-(C=O)- group, or a guanamine bond via a carbonyl group.

Among these, from the viewpoint of dispersibility, as a preferred bond, it is preferred to carry out a urea bond together with an adjacent N atom via R- ^γ through a -NH-(C=O)- group. Further, it is preferred that R ^η is not bonded to the adjacent N atom via the above bond.

Further, R ^γ and R ^γ′ may each independently be bonded to an adjacent one O atom via an —NH—(C=O)— group, or may be esterified via a carbonyl group. Bonding.

Particularly, from the viewpoint of dispersibility, R ^{γ of the} above formulas (3-1) and (3-2) is preferably an alkylene group or an extended aryl group, and is via the -NH-(C=O)- group. The urea bond is carried out together with the adjacent N atoms. Further, it is preferred to carry out urethane bonding with an adjacent one of the O atoms via the -NH-(C=O)- group, or to carry out ester bonding via a carbonyl group. Specific examples thereof include the following.

Further, in the above formula (3-3), R ^{γ '} is a group in which the above alkyl group is bonded to the above-mentioned extended aryl group, and a part of the methylene group constituting the alkyl group thereof is derived from thiocarbamate The ester bond is substituted or the urea bond is carried out together with an adjacent O atom via an -NH-(C=O)- group. Specific examples thereof can be exemplified below.

[Chem. 46]

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

Carbon atoms ^R ζ ^'in the alkyl group is not particularly limited and is usually 1 or more, preferably 2 or more, and preferably 20 or less, more preferably 10 or less, and still more preferably 6 or less. If it is in the above range, the dispersibility tends to be good.

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

The carbon number of the aryl group of R ^{ζ '} is not particularly limited, but is usually 6 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. If it is in the above range, there is a tendency that the dispersibility is good. Specific examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferred from the viewpoint of dispersibility.

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

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

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

Further, in the above R ^{ζ '} , R ^{ζ ' is} preferably a hydrogen atom from the viewpoint of dispersibility.

Examples of the polyether chain of R ^θ include those represented by the following formula (3-4). Further, 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 have a substituent. n represents an integer from 1 to 100. * indicates a bonding group with an adjacent O atom.

Further, 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 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 is preferably 50 or less, more preferably 10 or less, still more preferably 6 or less. If it is in the above range, the dispersibility tends to be good.

Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. From the viewpoint of dispersibility, a methyl group, an ethyl group, a propyl group or a butyl group is preferred, and a methyl group or an ethyl group is more preferred, and a methyl group is 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 a methyl group, an ethyl group, a propyl group or a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. Base.

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

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

Further, the carbon number of the alkylene group in R ^c is not particularly limited, but is usually 1 or more, preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, still more preferably 7 or less. If it is in the above range, there is a tendency that the dispersibility is good.

Specific examples thereof include a methylene group, an ethylidene group, a propyl group, an extended isopropyl group, a butyl group, a cyclopentylmethylene group, a cyclohexylenemethylene group, a cyclohexyl group-extended ethyl group, and Stretching cyclohexyl propyl and the like. From the viewpoint of dispersibility, it is preferably a methylene group, an ethyl group, a propyl group, an isopropyl group or a butyl group, and more preferably an ethyl group, a propyl group or a stretching group. 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 a methyl group, an ethyl group, a propyl group or a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. Base.

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

Further, the carbon number of the aryl group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group.

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

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

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

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

Further, the carbon number of the alkyl group of R ^{b '} may also vary depending on the polarity of the solvent (e) contained in the photosensitive resin composition. When the solvent (e) is a polar solvent, the number of carbon atoms 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 number of carbon atoms of the alkyl group of R ^{b '} is preferably 9 or more and 30 or less. If it is in the above range, the dispersibility tends to be good.

Specifically, when the solvent (e) is a polar solvent, it is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a decyl-1-yl group. , Decan-1-yl, undec-1-yl, or dodec-1-yl.

When the solvent (e) is a non-polar solvent, it is preferably an octyl group, a decane-1-yl group, a decane-1-yl group, an undec-1-yl group, a dodec-1-yl group, a tridecane group. 1-yl, tetradec-1-yl, pentadec-1-yl, dec-1-yl or triacon-1-yl.

Further, in the case of a polar solvent such as propylene glycol methyl ether acetate, decane-1-yl, undec-1-yl, dodec-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 a methyl group, an ethyl group, a propyl group or a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. Base. From the viewpoint of the benefit of alkali developability or the benefit of adhesion to the substrate, a hydroxyl group, a methyl group or an ethyl group is preferred.

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

Further, the carbon number of the alkyl group of R ^{c '} may also vary depending on the polarity of the solvent (e) contained in the photosensitive resin composition. When the solvent (e) is a polar solvent, the number of carbon atoms 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 nonpolar solvent, the number of carbon atoms of the alkyl group of R ^{c '} is preferably 9 or more and 26 or less. If it is in the above range, the dispersibility tends to be good.

Specifically, when the solvent (e) is a polar solvent, it is preferably a methylene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, or Extend octyl (or octamethylene).

When the solvent (e) is a non-polar solvent, it is preferably octamethylene, nonamethylene, decamethylene, undecylmethyl, dodecamethylene, thirteenmethylene, and tetradecene. A group, a fifteen methylene group, a methylene group, or a thirteen methylene group. Depending on the polarity of the solvent, it is preferred This is a combination of these.

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

In the above, the polyester chain represented by the above formula (3-5) or (3-6) is used as R ^θ , but from the viewpoint of easiness of synthesis, it is preferably represented by the above formula (3-5). By.

Further, in the case where the polyurethane dispersant (b-1) has a main chain, the formula (3-1) to (3-3) are a lyophilic group bonded to the main chain, wherein * represents A bonding group with a urethane bond or a urea bond carbonyl group in the polyurethane backbone of the main chain.

(content ratio of hydrophilic solvent base)

The polyurethane dispersing agent (b-1) may be, for example, a structure having the above-described portion containing the solvent-containing portion, and may be one having the above-described structure containing the above-mentioned containing solvent-containing portion, or two or more kinds thereof. In particular, when the structure containing the hydrophilic group having a polyether chain and the structure containing the hydrophilic group having a polyester chain are combined, the dispersion effect is further increased, which is preferable.

The mass ratio of the structure containing the hydrophilic solvent group having a polyester chain to the structure containing the hydrophilic solvent group having a polyether chain is preferably 1/99 or more, more preferably 3/97 or more, still more preferably 5/. 95 or more, and preferably 99/1 or less, more preferably 97/3 or less, still 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 formulas (3-1) to (3-3), and more preferably has a partial structure. Part of the structure shown in formula (3-1).

Similarly, the content ratio of the structure containing the hydrophilic solvent moiety in the polyurethane dispersant (b-1) is preferably 5% by mass or more, from the viewpoint of dispersibility. More preferably, it is 10 mass% or more, further preferably 20 mass% or more, more preferably 30 mass% or more, particularly preferably 40 mass% or more, most preferably 50 mass% or more, and preferably 90 mass% or less. More preferably, it is 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 lyophilic vehicle and the adsorbing group. Examples of the other functional group include an active energy ray-curable unsaturated group and the like. Specific examples thereof include an unsaturated group such as a vinyl group, an acryloyl group or a methacryl group.

In this way, it is considered that the active energy ray-curable unsaturated group tends to increase the sensitivity when the photosensitive composition is formed. On the other hand, it is considered that these functional groups react and gel at the time of dispersion. In view of the tendency of the pigment dispersion in consideration of the stability over time, it is preferred that the active energy ray-curable unsaturated group is not provided.

(The reason for the effect) <Dispersibility 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 containing a partial structure represented by the above formula (i), it is possible to arrange a hydrophilic solvent group or an adsorbing group, in particular, a structure containing an insoluble solvent group or a structure containing an adsorbing group, on a straight line, and it is considered that compatibility with a solvent can be improved. And the adsorption of the pigment as a whole. Further, the nitrogen atom in the urethane bonding site also contributes to the adsorption of the pigment, and it is considered that the pigment adsorption property is further improved by the synergistic effect with the adsorption group.

In particular, when the hydrophilic solvent group is a polyether chain and/or a polyester chain, the solvent is added to the solvent in the solvent (e) in the photosensitive resin composition, and is dispersed in the solvent. The pigment will agglomerate, which becomes a steric obstacle and has hair The tendency to prevent the function of pigment agglutination.

In addition, when the polarities of the polyether chain and the polyester chain are formed so as to match the polarity of the solvent-soluble or photosensitive resin composition, the polarity of the alkali-soluble resin (d) or the photopolymerizable monomer, the chain portion is easily used as a solvent. In the expansion, the steric obstacles become larger and there is a tendency to be well dispersed.

It is particularly preferred to have both a hydrophilic solvent group having a polyether chain and a hydrophilic solvent group having a polyester chain. It is considered that by having both of these, it is easy to adjust the polarity of the hydrophilic solvent group to match the polarity of the solvent, and the hydrophilic solvent is further expanded based on the solvent, and the steric hindrance effect is further increased, and a more dispersed state is obtained, even if it is long. The tendency to maintain a stable state after the time is still maintained.

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

<Formation of high fine lines caused by improvement in alkali development treatment resistance and heat resistance improvement>

By using a photosensitive resin composition containing a polyurethane dispersant (b-1), a high-definition color filter applied to a tablet computer or a high-definition display or the like is manufactured, especially even if a base is used. Fine or fine lines can be stably formed in the steps of development or high temperature treatment.

In order to stably form a fine fine line, it is necessary to stably form the shape of the fine line at the time of alkali development, and the heat deformation in the subsequent hardening step by a high-temperature heat treatment of 200 ° C or more is small, and the shape is stably maintained.

It is considered that the photosensitive resin composition containing the polyurethane dispersant (b-1) is resistant to alkali developer due to strong adsorption between the pigment and the dispersant. When the alkali is developed after the ultraviolet irradiation, the fine fine lines temporarily formed are prevented from penetrating into the portion where the developer adheres to the substrate even when further immersed in the alkali developing solution. It can prevent the occurrence of trapping, peeling, and deformation of the wedge shape caused by etching. In addition, when it is cured at a high temperature of 200 ° C or higher after curing, it is considered that the adsorption between the pigment and the dispersibility is not weak and the thermal deformation is small, so that the fine fine line shape can be stably maintained.

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

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

Thus, it is considered that the resistance to alkali developing solution and the resistance to high-temperature treatment can be improved by the pigment adsorption property and the solvent affinity of the polyurethane dispersant (b-1). In particular, it is effective in a photosensitive resin composition in which it is difficult to reach the deep portion of the ultraviolet light and the hardening of the deep portion is weak, and the pigment content ratio such as carbon black is high.

In particular, an oxime ester photopolymerization initiator (c-1) which has a light absorbing action and a radical action as a photopolymerization initiator (c) to be described later, and which has a high sensitivity when it is small, is polymerized. When the urethane dispersant (b-1) is used in combination, it is considered that the crosslinking of the photopolymerizable monomer or the alkali-soluble resin by ultraviolet irradiation can be promoted, and the dispersion with the polyurethane is promoted. The intertwining between the dissolving agents of the agent is further enhanced, and the alkali-resistant developability and heat resistance are improved, and the fine fine line shape is stably formed.

Especially in the case of using a resin containing a large amount of aromatic rings as an alkali soluble In the case of a resin, heat resistance and alkali resistance are also improved by the high heat resistance and high alkali resistance of the aromatic ring or the three-dimensional steric obstacle, and the fineness can be formed more stably. The tendency of thin line shapes.

In the case where an opacifier such as carbon black is used, when the average primary particle diameter is small, the polyurethane dispersant (b-1) is more likely to ingest the pigment, and the alkali developability and heat resistance are further improved. Sexuality, and there is a tendency 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 mixed with a polymer-soluble resin or a polymer. Since the photopolymerizable monomer which is crosslinked by ultraviolet rays is compatible and is more easily entangled, there is a tendency to improve resistance to an alkali developer and resistance to high temperature treatment.

Further, when the polyether chain is a long-chain alkylene oxide, it is more compatible with an alkali-soluble resin or a photopolymerizable monomer, and is easily entangled, thereby improving alkali resistance and heat resistance, and is more preferable. .

Further, the adsorbing group is preferably away from the polyurethane skeleton of the main chain. By moving the adsorbing group away from the polyurethane skeleton of the main chain, the steric hindrance of the adsorbing group upon adsorption to the pigment is reduced, and the polyurethane dispersing agent (b-1) is easy to ingest the pigment. Further, there is a tendency that the resistance to the alkali developer and the resistance to high temperature treatment increase.

[Method for Producing Polyurethane Dispersant (b-1)]

The polyurethane dispersant (b-1) can be produced, for example, using a diisocyanate compound. Further, as the adsorbing group, two hydroxyl groups, an imine group or a thiol group having a functional group reactive with an isocyanate group, and one or more compounds having an adsorbing group which does not react with the isocyanate group may be used (hereinafter sometimes referred to as For the "adsorption group introduction compound") obtain.

The above-mentioned adsorption group introduction compound is bonded to the diisocyanate compound to bond, and a linear structure of the polyurethane skeleton can be formed. Moreover, the adsorption group contained in the adsorption group introduction compound is an adsorption group for adsorbing the pigment belonging to the color material (a) in the photosensitive resin composition.

The structure in which the adsorption group is introduced into a specific adsorption group in the compound is such that the adsorption group is contained in the polyurethane skeleton, and the side chain which becomes the polyurethane skeleton forms a bond to the main The case of a pendant adsorption group of a chain polyurethane skeleton.

The urethane bond or the like in the polyurethane skeleton of the polyurethane dispersant (b-1) is adsorbed to the pigment, but further has an adsorption group adsorbed on the surface of the pigment, and When it is incorporated into a polyurethane skeleton or a side chain of a polyurethane skeleton to form a pendant adsorption group, it exhibits better pigment adsorption properties. When the adsorption group is a suspension type adsorption group, the steric hindrance at the time of pigment adsorption tends to be small, which is preferable. Details regarding these will be described later.

The lyophilic medium contained in the polyurethane dispersant (b-1) is obtained by using a compound having only one hydroxyl group, an imido group or a thiol group at one end thereof. The isocyanate group is reacted to bond to the polyurethane backbone.

The polyether chain of the preferred lyophilic group contained in the polyurethane dispersant (b-1) is a compound having two hydroxyl groups, an imido group or a thiol group at one end thereof, The two groups are reacted with an isocyanate group to bond to the polyurethane skeleton. When the other end has a group reactive with an isocyanate, it is preferred that the group is not substituted with an isocyanate group by substitution with an alkyl group or the like.

Thus, by bonding only with a diisocyanate compound at the single end, It is bonded to a polyether side chain which is formed by a side chain of a backbone chain of a main chain (hereinafter referred to as "lateral direction") to form a hydrophilic solvent group. Details regarding these will be described later.

Similarly, a preferred polyester chain contained in the lyophilic medium also reacts the two groups with an isocyanate group by using a compound having only one hydroxyl group, an imido group or a thiol group at one end thereof. It can be bonded to the polyurethane backbone. When the other end has a group reactive with an isocyanate, it is preferably substituted with an isocyanate group by substitution.

Thus, the polyester side chain of the hydrophilic solvent group can be formed by bonding only the mono-terminal to the diisocyanate compound to bond in the transverse direction from the polyurethane skeleton of the main chain. Details regarding these will be described later.

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

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

The diisocyanate compound (ba) is introduced into the compound (bb) by an adsorption group having two functional groups reactive with an isocyanate group and having one or more adsorption groups, and having an isocyanate group at only one terminal. Two compounds having a functional group and a compound (bc) containing a solvent group are bonded to each other to obtain a urethane skeleton having a linear structure of a main chain, a lyophilic group bonded to the main chain, and Adsorbent-based polyurethane dispersant (b-1).

Polyurethane dispersant (b-1) is based on a polyurethane skeleton a backbone polymer, a graft polymer having a lyophilic vehicle as a branched polymer; preferably having a backbone of a linear polyurethane backbone of the backbone polymer or bonded to the backbone Specific adsorption groups.

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

As the above diisocyanate compound (ba), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexane diisocyanate (HDI), α,α-tetramethylxylene diisocyanate (TMXDI) are preferred. ), diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI) or dicyclohexylmethane-4 a diisocyanate compound such as 4'-diisocyanate (HMDI) or a mixture of such diisocyanate compounds.

Among these, it is preferably any one of TDI, IPDI, and MDI, and more preferably TDI and/or MDI. A diisocyanate compound other than the above specific examples can also be used as the diisocyanate compound (b-a).

A compound of a plurality of diisocyanate compounds (b-a) is exemplified in the lower left side, whereby the polyurethane dispersant (b-1) can be introduced into the lower right part structure.

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

In addition to the above, a diisocyanate compound having two isocyanates may be used as a diisocyanate compound (ba) which introduces a linear polyurethane structure into a polyurethane dispersant (b-1). .

[Compound (b-b); a compound having two functional groups reactive with an isocyanate and having at least one or more adsorbing groups]

The adsorbing group contained in the polyurethane dispersing agent (b-1) is a functional group 2 having a reaction with an isocyanate group in order to form a polyurethane skeleton with the above diisocyanate compound (ba). The adsorption group was introduced into the compound (bb).

As the functional group which reacts with an isocyanate group, a hydroxyl group or an imide group is preferable. In the case of having two specific functional groups, it is preferred that one of them is a hydroxyl group and the other is an imine group, or both of them are hydroxyl groups; more preferably, both of them are hydroxyl groups.

In the case where the compound (b-b) has a basic group in addition to the functional group which reacts with the isocyanate group, the basic group is preferably such that it 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 steric hindrance group at the 2-position and/or the 6-position.

By the urethane bond and/or the 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) is introduced into the polyurethane dispersant (b-1).

Part of the structure shown in formula (1) can be introduced into the polyurethane dispersion The compound (b-b) of the agent (b-1) may be one in which both of the functional groups reactive with the isocyanate group are hydroxyl groups. The two hydroxyl groups are bonded to the two isocyanate groups of the diisocyanate compound (b-a) by urethane. Specific examples will be described later.

A part of the structure represented by the formula (2-1) can be introduced into the compound (bb) of the polyurethane dispersant (b-1), and both of the functional groups reactive with the isocyanate group are hydroxyl groups. . The two hydroxyl groups are bonded to the two isocyanate groups of the diisocyanate compound (b-a) by urethane. Specific examples will be described later.

A part of the structure represented by the formula (2-2) can be introduced into the compound (bb) of the polyurethane dispersant (b-1), and a part of the structure represented by the formula (2-2) can be mentioned. The bonding group of the N atom and the hydrogen atom are bonded to the imine group, the bonding group of the O atom, and the hydroxyl group bonded to the hydrogen atom. The imine group and the hydroxyl group are bonded to the two isocyanate groups of the diisocyanate compound (b-a) by urea bonding and urethane bonding, respectively. Specific examples will be described later.

A part of the structure represented by the formula (2-3) can be introduced into the compound (bb) of the polyurethane dispersant (b-1), and both of the functional groups reactive with the isocyanate group are hydroxyl groups. . The two hydroxyl groups are bonded to the two isocyanate groups of the diisocyanate compound (b-a) by urethane. Specific examples will be described later.

[Compound (b-b) for introducing a part of the structure shown by the formula (1)]

When the compound (bb) is a compound having a partial structure represented by the formula (1) 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 of (ba) allows the tertiary amine structure of the entire structure represented by the formula (1) to be incorporated into the polyurethane skeleton.

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

For example, the structure exemplified below can be introduced into the polyurethane dispersant (b-1) by the compound exemplified below. This corresponds to a partial configuration shown in the above formula (1). Further, it is also applicable to the synthesis of the polyurethane dispersant (b-1) if it contains a partial structure represented by the formula (1) and has a hydroxyl group at its terminal. Further, a similar urethane compound can be obtained by using a thiol group or an amine group by substituting a hydroxyl group.

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

[Compound (b-b) for introducing a part of the structure shown in (2-1) to (2-3)]

In the adsorption group introduction compound (bb), a partial structure represented by the above formula (2-1), (2-2) or (2-3) is introduced into the polyurethane dispersant (b-1). In the case of the compound, the two functional groups which are reacted with the isocyanate group of the compound (bb) and the isocyanate group of the diisocyanate compound (ba) are bonded to each other to form an adsorption group (2-1), (2). -2) or (2-3) of R ^α, R β, N, and R γ ^(R γ ^') remote from the polyurethane backbone exist.

In the adsorption group introduction compound (bb), 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-mentioned <dispersibility enhancement effect> and < alkali-resistant developer promotion and heat resistance improvement The formation of high-fine fine lines is preferred because of the reasons described.

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

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

Thus, the tertiary amine which is separated from the polyurethane structure of the linear structure of the main chain and which is bonded in the transverse direction tends to have a better adsorption function on the surface of the pigment. The tertiary amine may be partially or completely graded to form a grade 4 ammonium salt.

Examples of the fourth-order ammonium salt include R ^α , R ^β , R ^A , and N ⁺ in a partial structure represented by the formula (2-1′), (2-2′), or (2-3′). An adsorption group of R ^γ (R ^γ' ).

At this time, the adsorption group is separated from the polyurethane skeleton by bonding to the polyurethane skeleton, and as a result, the nitrogen atom of the 4-stage ammonium salt group is composed of a polyurethane skeleton. The closest atom is separated by at least 1 atom.

Specific examples of the compound in which the adsorption group is introduced into the compound (bb) and the partial structure represented by the formula (2-1) can be introduced into the polyurethane dispersant (b-1) can be exemplified as follows. However, if it contains a partial structure represented by Formula (2-1) and has two functional groups reactive with an isocyanate group at the terminal, it can also be applied to a polyurethane dispersing agent ( B-1).

Part of the structure shown in formula (2-1) is composed of at least one or more tertiary amines A compound (b-b1) having one hydroxyl group and the like is obtained. The specific reaction is as follows.

First, the hydroxyl group of the above compound (b-b1) is allowed to react with one isocyanate group of a compound containing two isocyanate groups such as toluene diisocyanate. Next, another isocyanate group is allowed to react with a secondary amine group in a compound containing one secondary amino group and at least two active 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 the compound exemplified below. This corresponds to a partial structure shown in the above formula (2-1).

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

Further, a compound having a partial structure represented by the formula (2-1) can be obtained by the following method. Specifically, a compound having at least one or more tertiary amino groups and having an ethylenically unsaturated group, and a second-order amine having a compound of two amino groups and at least two active hydroxyl groups such as diethanolamine Base to carry out the Michael.

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

[化51]

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

Further, a compound having a partial structure represented by the formula (2-1) can be obtained by the following method. For example, a compound having a 3-stage amine group and a hydroxyl group is reacted with a compound having an isocyanate group and a propylene methoxy group, and the hydroxy group and the isocyanate group are bonded to the urethane group to have a grade of 3 A method in which an unsaturated group is introduced into an amine group compound, and a secondary amine group of diethanolamine is subjected to a Michael addition. In this way, two hydroxyl groups can also be introduced.

Further, the compound having a partial structure represented by the introduction formula (2-1) has the following compounds. The structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by the compound exemplified in the lower left. This also corresponds to the partial structure shown in the above formula (2-1). Further, when a partial structure represented by the formula (2-1) is contained and two hydroxyl groups are present at the terminal, it can also be applied to the synthesis of the polyurethane dispersant (b-1).

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

Further, a compound having a partial structure represented by the formula (2-2) can be obtained by the following method. Specifically, it has a tertiary amine of dimethylaminopropylamine or the like. Among the compounds of the first-stage amine group, a compound having one hydroxyl group and an ethylenically unsaturated group, such as hydroxyethyl acrylate, is obtained by subjecting it to a Michael addition. Thereby, a compound having an imine group and a hydroxyl group obtained by the Michael addition of an ethylenically unsaturated group and a first-order amine group is obtained.

In the same manner, a compound having one hydroxyl group and a primary amino group such as monoethanolamine, and a 3-amino group and an ethylenically unsaturated group such as 2-(dimethylamino)-ethyl acrylate or the like are used. The Michael addition of the compound also gives a compound having an adsorption group of a 3-stage amine 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 the compound exemplified below. This corresponds to a partial configuration shown in the above formula (2-2). In addition, when it contains a partial structure represented by the above formula (2-2) and has one hydroxyl group and an imine group at the terminal, it can also be applied to the polyurethane dispersing agent (b-1).

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

Further, the compound having a partial structure represented by the formula (2-3) is as follows. For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by the compound exemplified below. This is equivalent to the partial structure shown in the above formula (2-3) Made.

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

Further, when a partial structure represented by the above formula (2-3) and a terminal having two hydroxyl groups are contained, it can be applied to the synthesis of the polyurethane dispersant (b-1).

For example, a compound in which two hydroxyl groups of the above compound are substituted and two primary and/or secondary amine groups are substituted may be used for the synthesis of the polyurethane dispersant (b-1). Further, a compound containing one or more specific adsorbing groups and substituting two first-order and/or second-order amine groups may be used for the synthesis of the polyurethane dispersant (b-1). Further, a compound having only one hydroxyl group (bb-1) and a part of the structure represented by the formula (2-3) which is reacted with thioglycerol can be introduced into the polyurethane dispersant (b-1- 1).

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

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

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

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

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

By using a heterocyclic compound containing a nitrogen atom as the compound (b-b), the polyurethane dispersant (b-1) can be imparted with a good pigment adsorption function. Specific examples of the structure for introducing the nitrogen atom-containing heterocyclic group when the heterocyclic ring containing a nitrogen atom is incorporated into the polyurethane skeleton, and the structure to be introduced include the following By.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by the compound exemplified below. Further, two functional groups reactive with an isocyanate group may be used as a compound which is directly bonded to a heterocyclic position at a hetero ring or a heterocyclic position bonded to a hetero ring via 1 to 10 atoms.

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

Further, when the nitrogen atom-containing heterocyclic group is isolated from at least one atom by the backbone 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 the compound exemplified below.

Further, a compound containing a ring containing a heterocyclic compound containing a nitrogen atom and two functional groups reactive with an isocyanate group at the terminal of one side chain bonded via 1 to 20 atoms may be used.

[化57]

The * adjacent to the oxygen atom means a bonding group to the carbonyl group bonded to the urethane bond in the polyurethane skeleton; the * adjacent to the nitrogen atom means that it is in the polycarbamate skeleton A bonding group between carbonyl groups of a urea bond.

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

In these cases, the heterocyclic compound containing a nitrogen atom of the compound (b-b) forms a suspended type which is separated from the at least one atom by the polyurethane skeleton. Attached to the base. The polyurethane compound (b-1-1) contains the suspension type adsorption base, and is based on the above-mentioned <dispersibility lifting effect> and the formation of high fine lines caused by the improvement of alkali-resistant developing solution and heat resistance. >The reason for the above is preferred.

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

[Method of introducing a 4-stage ammonium salt group]

As a method of introducing a 4-stage ammonium salt group into the polyurethane dispersant (b-1), for example, first, by using the formula (2-1) to (2-3) The compound of the partial structure shown is a method in which a tertiary amine group is introduced into the polyurethane dispersant (b-1), and then the tertiary amine group is subjected to a four-stage classification using any known fourth-ordering agent.

Preferred grade 4 agents are alkyl halides, aralkyl halides, dialkyl sulfates, dialkyl carbonates or epoxides. A particularly preferred leveling agent is dimethyl sulfate, benzyl chloride or styrene oxide. The tertiary amine group can be partially ammonium-salted, and all of the tertiary amine groups can be subjected to 4-stage ammonium salting.

Further, these tertiary amine groups may also form salts with any of the known organic acid compounds. Preferred organic acid compounds include organic sulfonic acid compounds such as vinyl sulfonic acid, organic phosphoric acid compounds such as dimethyl propylene methoxyethyl phosphate or phenylphosphonic acid, and the like.

[Compound (b-c); a compound having two functional groups reactive with an isocyanate group at one terminal and containing a solvent group]

The main chain of the polyurethane skeleton in the polyurethane dispersant (b-1) and the side chain of the hydrophilic solvent group bonded in the lateral direction of the side may be made only by a compound having a hydrophilic solvent group having two functional groups reactive with an isocyanate group at one end (b-c) is obtained by reacting with the above diisocyanate compound (b-a).

The two functional groups which react with the isocyanate group of the compound (bc) are preferably a hydroxyl group and/or an imide group, more preferably one is a hydroxyl group, and the other is an imine group, or both are hydroxyl groups. More preferably, both of them are hydroxyl groups.

The following is a case where the hydrophilic solvent group in the polyurethane dispersant (b-1) contains a polyether chain and/or a polyester chain, and particularly has the above formula (3-1) to (3-3). The details of the partial construction shown are detailed.

The moiety represented by the above formula (3-1), (3-2) or (3-3) can be obtained by the urethane bond or the urea bond of the compound (bc) with the diisocyanate compound (ba). The structure was introduced into a polyurethane dispersant (b-1).

a part of the structure represented by the formula (3-1) can be introduced into the compound (bc) of the polyurethane dispersant (b-1), and both of the functional groups reactive with the isocyanate group are hydroxyl groups, and The two hydroxyl groups are bonded to the two isocyanate groups of the diisocyanate compound (ba). Specific examples will be described later.

A part of the structure represented by the formula (3-2) can be introduced into the compound (bc) of the polyurethane dispersant (b-1), and the two functional groups reactive with the isocyanate group are an imido group and a hydroxyl group. The imido group is urea-bonded to the isocyanate group, and the hydroxyl group is bonded to the isocyanate group by urethane. Specific examples will be described later.

The two functional groups which react with the isocyanate group of the compound (bc) which introduces a part of the structure represented by the formula (3-3) into the polyurethane dispersant (b-1) are all hydroxyl groups, and this The two hydroxyl groups are bonded to the two isocyanate groups of the diisocyanate compound (ba). Specific examples will be described later.

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

When the compound (bc) contains a functional group reactive with an isocyanate group at both terminals, the functional group is bonded to other residual isocyanate groups in the synthesis of the polyurethane dispersant (b-1). There is a possibility of hindering the formation of the lateral side chain of the linear polyurethane skeleton in the side bond. Therefore, the compound (b-c) is preferably one which does not contain a functional group which reacts with an isocyanate group except a single terminal.

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

The alkyl group which is particularly preferably substituted with the hydrogen atom of the above hydroxyl group is an alkyl group having 1 to 50 carbon atoms. The alkyl group may be an alkyl group or a cycloalkyl group of any of the branched chains, and may be substituted for an aryl group or an aralkyl group instead of the alkyl group.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 6 carbon atoms such as a cyclopropyl group or a cyclohexyl group. The aryl group is preferably an aryl group having 6 to 10 carbon atoms such as a naphthyl 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, or a phenyl group.

The aralkyl group is preferably a 2-phenylethyl group or a benzyl group which may be substituted by a halogen, 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 a polyester chain can be suitably 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 terminal alkyl group may preferably be a linear or branched chain 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.

In the case where the polyurethane dispersant (b-1) contains a polyether side chain, it is preferred that the terminal alkyl group is an alkyl group having 1 to 4 carbon atoms from the viewpoint of easy availability from the market. More preferably, it is a methyl group. On the other hand, when the solvent (e) is a nonpolar organic solvent, the terminal alkyl group preferably has 8 or more carbon atoms.

The portion of the polyalkylene oxide chain of the polyether chain contained in the lyophilic medium (excluding the terminal alkyl group) is preferably a carbon number of 2 to 4 polyalkylene oxide. 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% from the viewpoint of substrate adhesion. More preferably, the mass% or less is more preferably no polyalkylene oxide.

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

The polyalkylene oxide portion is preferably a polypropylene oxide from the viewpoint of improving the dispersion stability over time. The polyether chain contained in the lyophilic medium of the polyurethane dispersant (b-1) preferably has an alkyl group having 1 to 10 carbon atoms as a terminal alkyl group from the viewpoint of enhancing dispersibility. And having a polyalkylene oxide having a carbon number of 2 to 4; in this case, the terminal alkyl group is more preferably a methyl group or a butyl group.

The polyester chain belonging to the lyophilic group is preferably obtained from a hydroxycarboxylic acid having 1 to 26 carbon atoms or a lactone thereof. The kind of the hydroxycarboxylic acid can be appropriately selected depending on the nature of the solvent (e) contained in the photosensitive resin composition.

When the solvent (e) is a polar organic solvent, the hydroxycarboxylic acid preferably contains at most 8 carbon atoms; and 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 lactones thereof in order to contribute to the solubility of the organic medium. Hydroxycarboxylic acid can be saturated or unsaturated And, and may be a straight chain or a branched chain.

Examples of suitable hydroxycarboxylic acids are glycolic acid, lactic acid, 5-hydroxyshikiic acid, 6-hydroxycaproic 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 by 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-t-butyl, 7- Methyl-4,4,6-trimethyl and 4,6,6-trimethyl-ε-caprolactone and mixtures thereof.

The polyester chain derived from δ-valerolactone and ε-caprolactone is particularly preferred.

The lateral side chain of the polyether chain and/or the polyester chain belonging to the hydrophilic solvent group may be composed of a single monomer or may be composed of a plurality of monomer components. Further, the polyether chain may also contain a polyester moiety, and conversely, the polyester chain may also contain a polyether moiety.

The number average molecular weight of the polyether chain and/or the polyester chain of the hydrophilic solvent group in the polyurethane dispersant (b-1) is preferably 10,000 or less, more preferably 4,000 or less, still more preferably 2,500. the following. The number average molecular weight of the polyether chain and/or the polyester chain is preferably 300 or more, more preferably 600 or more, still more preferably 800 or more. When the value is equal to or less than the above-described upper limit, the adhesion of the substrate tends to be improved. Further, the above-mentioned lower limit value or more tends to improve the dispersibility.

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

When two functional groups which react with the isocyanate group of the compound (b-a) are introduced into a single terminal of the polyether chain and/or the polyester chain, there are several methods. Thereby, the polyether chain and/or the polyester chain are bonded to the diisocyanate compound (ba) by two functional groups at one terminal to form a main chain belonging to the polyurethane skeleton, and can form a poly Ether chain and / or the side chain of the lyophilic group of the polyester chain.

In the case where the side chain of the hydrophilic solvent group in the transverse direction is a polyether chain, the compound (bc) containing the polyether chain of the solvent group preferably has two hydroxyl groups which react with the isocyanate group at one terminal, or has 1 hydroxyl group and 1 imine group. Preferably, the hydroxyl group and the imine group are at most 6 carbon atoms apart. In the case where the compound (b-c) contains two hydroxyl groups which react with an isocyanate group, these are preferably at most 17 atoms apart.

A method of introducing two hydroxyl groups into a single terminal at a single terminal reaction of an isocyanate group containing a polyether chain-containing compound (bc), and introducing a method of introducing two hydroxyl groups into the compound (bb) The same method.

Specific examples of the compound (b-b) for introducing a part of the structure represented by the formula (3-1) into the polyurethane dispersant (b-1) include the following. Further, when the partial structure represented by the formula (3-1) is contained and the terminal has two hydroxyl groups, it can be applied to the synthesis of the 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 a single terminal is reacted with an isocyanate group of a compound containing two isocyanate groups such as toluene diisocyanate. Next, another isocyanate group is reacted with a secondary amine group of a compound containing one secondary amino 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 the compound exemplified below. This corresponds to the chemical structure shown in the formula (3-1).

[化58]

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

Further, 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 a single terminal of the polyether chain-containing compound (b-c), there is also a method of subjecting diethanolamine to a Michael addition in a poly(alkylene oxide) acrylate. Specific examples thereof are as follows.

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

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

Further, in the case of having a partial structure represented by the formula (3-2), it can also be obtained by the following method.

When the two functional groups at the single terminal of the reaction of the polyether chain-containing compound (bc) with the isocyanate group are one hydroxyl group and one imine group, the same applies to the above compound (bb) and one introduction. The same method as the method of the hydroxyl group and the one imine group. Specifically, a compound having one hydroxyl group and an ethylenically unsaturated group such as hydroxyethyl acrylate and a compound having one primary amino group at the terminal of the polyalkylene oxide chain is used. The material is obtained by the addition of Michael. Thereby, an imine group obtained by the Michael addition of an ethylenically unsaturated group and an amine group, and one hydroxyl group in a hydroxy acrylate can be obtained.

In the same manner, a compound having an alkylene chain and an ethylenically unsaturated group such as a compound having one hydroxyl group and a primary amino group such as monoethanolamine or an acrylate having an ester bond to an alkylene oxide chain; The addition of the Michael can also provide a solvent-soluble portion of the alkylene oxide and a hydroxyl group and an imine group 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 the compound exemplified below. This corresponds to a partial configuration shown by the formula (3-2). Further, when a partial structure represented by the formula (3-2) and one hydroxyl group and one imine group are contained, it can also be applied to the synthesis of the polyurethane dispersant (b-1).

The * adjacent to the oxygen atom indicates a bond group to the carbonyl group of the urethane bond in the polyurethane skeleton of the main chain; the * adjacent to the nitrogen atom indicates the polyaminocarboxylic acid with the main chain A bond between the carbonyl groups of the urea bond in the ester backbone.

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

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

First, a hydroxyl group of a polyether having one hydroxyl group at the 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 thioglycerol. Thereby, a compound in which two hydroxyl groups are introduced into a single terminal of the polyether can be obtained.

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

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

A compound having a structure represented by the above formula (3-3) introduced into the polyurethane dispersant (b-1) is a compound having two hydroxyl groups at one terminal, but the above formula (3-3) A compound in which two oxygen atoms of the structure are substituted by two primary and/or secondary amine groups may also be used as a synthesis for the polyurethane dispersant (b-1). Compound (bc).

The compound (bc) used for the synthesis of the polyester chain-containing polyurethane dispersant (b-1) is preferably one end of a compound containing a polyester chain, and is contained with an isocyanate group. Two hydroxyl groups of the reaction. Preferably, the hydroxyl group is at most 17 atoms apart. The two hydroxyl groups are separated by more than 5 atoms.

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

When the terminal of the polyester chain is a hydroxyl group, one or a plurality of hydroxycarboxylic acids or a lactone thereof may be polymerized in the presence of a hydroxyl group-containing compound which is a chain-stopping compound described later.

The polyester obtained by using the hydroxyl group-containing compound of the chain-stopping compound described later is preferably 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 alkenyl group having 2 to 26 carbon atoms.

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

Further, when a compound of the formula (4) is introduced into a single terminal and a hydroxyl group and an imino group are reacted with an isocyanate group, one of the hydroxyl groups and one sub-portion of the polyether may be introduced into the single terminal. The same method as the amine method.

For example, the structure exemplified in the lower right can be introduced into the polyurethane dispersant (b-1) by the compound exemplified below. This corresponds to a partial structure shown in the above formula (3-1) or a partial structure shown in the formula (3-2). Further, when a partial structure represented by the above formula (3-1) or a partial structure represented by the formula (3-2) is contained, and a functional group such as a hydroxyl group or an imine group which reacts with an isocyanate group at the terminal is contained only Two can be applied to the polyurethane dispersant (b-1).

[化62]

The * adjacent to the oxygen atom means a bonding group to the carbonyl group of the urethane bond in the polyurethane skeleton of the main chain; the * adjacent to the nitrogen atom means a polyamine group with the main chain A bond between the carbonyl groups of the urea bond in the formate skeleton.

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

The structure corresponding to the partial structure represented by the formula (3-3) on the polyester chain may be applied to the structure corresponding to the partial structure represented by the formula (3-3) containing the polyether chain. The same construction.

For example, by the compound exemplified in the lower left, the polyurethane can be divided into The powder (b-1) is introduced into the structure exemplified in the lower right. This corresponds to the partial configuration shown in the above formula (3-3).

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

When the terminal of the polyester chain is a carboxyl group, one or a plurality of hydroxycarboxylic acids or a lactone thereof may be polymerized in the presence of a carboxyl group-containing compound which is a chain-stopping compound described later.

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

R ⁹ CO(OA-CO) _w OH (5)

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

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

When two hydroxyl groups which react with an isocyanate group are introduced at the single terminal from the compound of the above formula (5), the compound of the formula (5) is reacted with a diol such as ethylene glycol or propylene glycol to be converted into a monohydroxy compound. The obtained monohydroxy derivative is carried out in the same manner as 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 the compound exemplified below. This corresponds to a partial structure shown in the above formula (3-1) or a partial structure shown in the formula (3-2).

Further, when a partial structure represented by the above formula (3-1) or a partial structure represented by the formula (3-2) is contained, and a functional group such as a hydroxyl group or an imine group which reacts with an isocyanate group at the terminal is contained only Two can be applied to the synthesis of the polyurethane dispersant (b-1).

[化64]

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

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

The structure corresponding to the partial structure represented by the formula (3-3) on the polyester chain may be applied to the structure corresponding to the partial structure represented by the formula (3-3) containing the polyether chain. The same construction.

Further, a method of introducing a functional group reactive with an isocyanate group at the end of the polyether chain and/or the polyester chain may be carried out by other known methods. For example, there is also a polyether chain or a polyester chain having one hydroxyl group at one end, and reacting a compound having an isocyanate group and a acryloxy group, and having a polyether chain by performing urethane bonding Or a method in which an unsaturated group is introduced into a single terminal of a compound of a polyester chain, and it is subjected to a Michael addition to diethanolamine. By this method, two hydroxyl groups can also be introduced at the single end of the polyether chain or the polyester chain.

a main chain having a polyurethane skeleton, a side chain belonging to a lyophilic group bonded to a polyether chain and/or a polyester chain, and a polyaminocarboxylic acid having a specific adsorption group The ester compound (b-1-1) may be reacted with a polyfunctional acid ester and/or a polyolefin having two functional groups reactive with an isocyanate group at a single end within a range not affecting its characteristics. obtain.

When two functional groups reactive with an isocyanate group are introduced at one end of the polyacrylic acid and/or the polyolefin, the method of introducing two hydroxyl groups into the terminal of the polyether chain or the polyester chain or introducing a hydroxyl group and The same method as in the case of one imine group.

Further, in the case of synthesizing a polymer of a polyacrylate and/or a polyolefin, it can be obtained by using a polymerization initiator having two hydroxyl groups or a dihydroxy functional chain shifting agent such as thioglycerol.

By forming a reaction between a compound of a polyacrylate and/or a polyolefin having two functional groups reactive with an isocyanate group at one end and an isocyanate group of a diisocyanate compound (ba), bonding can be formed in the poly A polyacrylate and/or a polyolefin chain in the lateral direction of the side of the urethane skeleton.

[Polyurethane dispersant (b-1) may also contain any other structure]

The polyurethane dispersant (b-1), on the other hand, may also contain a structure in which a urea reaction is carried out by reacting the following compounds (bd), (be), (bf), and a urea reaction. .

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

‧ Compound (b-e): One or two or more compounds having one functional group reactive with an isocyanate group and acting as a chain stopper.

‧ Compound (b-f): One or two or more compounds which contain one isocyanate group and act as a chain stopper.

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

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

The above compound (b-d) preferably contains only two functional groups which 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, still 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 from 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 polyalkylene glycol may also be a random or block homopolymer or copolymer containing a repeating vinyloxy, propyleneoxy or butenyloxy group, including mixtures thereof.

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

[化65]

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

Further, when there are only two functional groups which react with the isocyanate group, the compound (b-d) which is introduced into the polyurethane dispersant (b-1) as the partial structure can be used.

The polyurethane skeleton in the polyurethane dispersant (b-1) preferably has a linear character in nature. However, in the case where any of the components has a polyhydric alcohol or a polyisocyanate having a functional value of more than 2 depending on the impurity type, a small amount of branched structure is introduced.

As disclosed below, the chain-stopping compound belonging to the compound (b-e) is a monofunctional compound having one functional group reactive 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 terminal of the polyurethane skeleton of the main chain of the polyurethane dispersant (b-1) to form a terminal group.

Preferred chain-stopping 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). The etheramine or the 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, whereby the polyurethane can be dispersed. The lower part of the structure is introduced into the agent (b-1).

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

Further, when only one functional group is allowed to react with the isocyanate group at the single terminal, the compound (b-e) which can introduce the above partial structure into the polyurethane dispersant (b-1) can be used.

The compound (be) is preferably a solvent-soluble base containing a polyether chain and/or a polyester chain from the viewpoint of dispersibility and dispersion stability over time; and if it has only one hydroxyl group, one A compound having a 1-stage amine group, a 2-stage amine group, or a thiol group has a chain-stopping action and can be used as a compound (be).

As the above compound (be), a compound having a polyether chain and/or a lyophilic group of a polyester chain may be substituted, and within the range which does not affect the effect of the polyurethane displacing agent (b-1), Polyacrylates or polyolefins having the same construction as this can also be used.

The monoisocyanate compound of the compound (b-f) also functions as a chain stopping compound 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 is necessary to carry out post-treatment. In this case, chain stop is preferably carried out by the compound (b-e).

[Synthesis of Polyurethane Dispersant (b-1)]

The amount of the raw material 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). % by mass of compound (ba), 1 to 24% by mass of compound (bb), 10 to 80% by mass of compound (bc), 0 to 25% by mass of compound (bd), 0 to 50% by mass of compound (be ), and 0 to 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 preferably The total mass of the raw materials of the entire polyurethane dispersant (b-1) is 35% or more.

a compound containing the polyether chain of the compound (b-c) and the compound (b-e) The compound containing a polyester chain may be individually, but preferably contains both of them. The mass ratio of the compound containing a polyether chain to the compound containing a polyester chain is preferably from 1:99 to 99:1, more preferably 3:97, based on the total mass of the compound (bc) and the compound (be). ~97:3, and even better 5:95~95:5.

The polyurethane dispersant (b-1) is a case where a polyether chain and a polyester chain are contained as a lyophilic medium, and in the formation of a tablet computer or a high-fine-line color filter BM, an alkali development process is formed in the process. It is preferable that the resistance of the liquid or the resistance at the time of high-temperature treatment becomes better. Further, in the case where the adsorbing group of the polyurethane dispersant (b-1) is a specific adsorbing group bonded to the main chain, since the specific adsorbing group is well adsorbed to the pigment, it is easy to ingest and have a developing solution. It is particularly good for pigments that are resistant to patience or high temperature treatment.

The polyurethane dispersant (b-1) can be any known in the art. Know the method to modulate. In general, the polyurethane dispersant (b-1) is in the presence of any inert solvent in an inert atmosphere at a temperature of generally from 0 to 130 ° C under substantially anhydrous conditions, and optionally In the presence of the catalyst, one or two or more kinds of the diisocyanate compound (ba) can be obtained by reacting at least one or two or more compounds (bb) and one or more compounds (bc). .

Further, one or a plurality of compounds (bd) which act as a chain extender, and any one or a plurality of compounds which act as a chain stop compound may be used together with the compound (be) and the compound (bf). Implement the reaction.

The inert environment can be carried out by any of inert gases, preferably nitrogen.

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

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

In one case, the total number of moles of the isocyanate groups in the compound (ba) may be compared with the compounds (bb), (bc) and, if necessary, the isocyanate groups of the compounds (bd) and (be). The total number of moles of the functional groups is small. At this time, any of the terminal isocyanate groups are reacted, and there is a tendency that the unreacted terminal isocyanate groups remain.

Alternatively, the total number of moles of isocyanate groups provided by the compound (ba) and the optional compound (bf) may be compared with the compounds (bb), (bc) and, if necessary, the compound (bd), (be) The total number of functional groups of the isocyanate group reacting A lot. At this time, the obtained polyurethane compound (b-1-1) tends to be a prepolymer containing a residual isocyanate group.

Thus, the prepolymer can be subjected to a chain extender such as a compound (bd) which binds to a different prepolymer chain, and/or a chain stop compound belonging to the compound (be), before being dissolved in any solvent. reaction.

Further, in the case where a prepolymer having a residual isocyanate group is present, the chain extension reaction can be carried out by water itself. Alternatively, it can be carried out by a polyol, an amino-alcohol, a first or second aliphatic, alicyclic, aromatic, or heterocyclic polyamine, especially a diamine, an anthracene or a substituted hydrazine.

As the chain extender, for example, a chain extender having two or more functional groups reactive with an isocyanate group is exemplified below, but in order to maintain a linear urethane skeleton, it is preferred to carry out the reaction with an isocyanate group. There are only two chain extenders for the functional groups of the reaction.

The chain extender to be used generally includes, for example, ethylenediamine, propylenediamine, butanediamine, hexamethylenediamine, cyclohexanediamine, and piperidine. 2-methylperazine , phenylenediamine, toluenediamine, xylene diamine, 4,4'-methylenebis(2-chloroaniline), 3,3'-dichloro-4,4'-biphenyldiamine, 2, 6-Diaminopyridine, 4,4'-diaminodiphenylmethane, methanediamine, m-xylenediamine, isophoronediamine, hydrazine, dimethylhydrazine, etc. Wait.

As a synthetic chain extender used for the polyurethane dispase (b-1) having a linear polyurethane skeleton, it is preferred to have only two functional groups reactive with an isocyanate group. A chain extender, particularly preferably hexamethylenediamine.

The chain extension reaction can be carried out at any of high temperature, low temperature and room temperature. The preferred temperature is about 5 to 95 °C.

Prepolymer method used in the preparation of polyurethane dispersant (b-1) In the case, in order to control the molecular weight of the obtained polyurethane dispersant (b-1), the amount of the chain extender and the chain stop compound can be adjusted.

The number of moles of the functional group which reacts with the isocyanate group in the chain extender is almost equal to the number of moles of the free isocyanate group in the prepolymer, and it is easy to become a high molecular weight. In order to obtain a low molecular weight polyurethane dispersant (b-1), a chain stopper can be used in combination with a chain extender in a reaction with a polyurethane prepolymer. Adjust and increase.

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 examples of the solvent include acetone, methyl ethyl ketone, dimethylformamide, dimethylacetamide, diglyme, N-methylpyrrolidone, butyl acetate, and acetic acid. Alkyl ethers of ethyl oxypropyl ester, ethyl acetate, ethylene glycol diacetate and propylene glycol diacetate, ethylene glycol acetate and propylene glycol acetate, toluene, xylene and tert-butanol, and A steric hindrance alcohol such as acetol. More preferred solvents are ethyl acetate, butyl acetate, methoxypropyl acetate and N-methylpyrrolidone.

[Physical properties of polyurethane dispersant (b-1)]

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. Further, from the viewpoint of dispersibility, it is preferably 180 mgKOH/g or less, more preferably 110 mgKOH/g or less, still 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 is easily dispersed and low. From the viewpoint of viscosity, it is preferably 50,000 The following is more preferably 40,000 or less, still more preferably 30,000 or less, and particularly preferably 20,000 or less.

Further, the hydrophilic solvent group is preferably 0.001 mol or more, more preferably 0.005 mol or more, still more preferably 0.01 mol or more, more preferably 100 mol or more per 100 g of the polyurethane dispersant (b-1). It is 0.02 mol or more; and preferably 0.5 mol or less, more preferably 0.2 mol or less, still more preferably 0.1 mol or less, and particularly preferably 0.08 mol or less. Hereinafter, the ratio of the lyophilic vehicle is expressed in units of "mole root/100 g" in terms of the content of the hydrophilic solvent group.

Here, the "mole root" of the lyophilic medium means a value obtained by dividing the amount of the raw material of the lyophilic medium by the amount of the average molecular weight thereof during the filling at the time of synthesis. Further, the "mole root" of the lyophilic medium was used, and the value corresponding to 100 g of the entire solid content of the filling amount other than the catalyst was defined as "mole root/100 g" of the hydrophilic solvent group.

<Other Embodiments>

Another embodiment of the polyurethane dispersant (b-1) of the present invention includes a non-linear chain, that is, a main chain having a bifurcated structure, that is, having at least 3 branches in the main chain. More than one branch.

In the present embodiment, as described below, the polyurethane skeleton of the main chain is close to a linear structure except that at least one of the branching structures having at least three or more branches is branched in the main chain. Since the structure of the embodiment is considered, the dispersibility in the photosensitive resin composition is considered to be good. Further, in the case of alkali development at the time of patterning or high-temperature treatment at 200 ° C or higher, it is considered that the combined oxime ester photopolymerization initiator (c-1) and the alkali-soluble resin (d) are multiplied by alkali resistance and heat resistance. Sexually promoted, thereby forming a high degree of fineness Thin line.

The main chain of the polyurethane dispersant (b-1) of the present embodiment has a branching structure other than the bonding portion between the bonding portion, the adsorption group, and the adsorption group. It is not particularly limited, and examples of the branching structure include a partial structure shown by the following general formula (ii).

In the above formula (ii), R ^e represents a trivalent alcohol compound residue, and * represents a bond group. Further, the term "alcohol compound residue" means a residue obtained by removing a hydrogen atom from the total hydroxyl group of the alcohol compound.

The carbon number of the residue of the trivalent alcohol compound in the above formula (ii) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and is preferably 100 or less, more preferably It is 50 or less, and more preferably 10 or less. When it is set to the above lower limit value, the branching structure which has a good expansion tends to be formed, and if it is equal to or less than the above upper limit value, the dispersibility tends to be good.

Specific examples of the residue of the trivalent alcohol compound include trimethylolethane, trimethylolpropane, 1,2,3-propanetriol, 1,3,5-pentanetriol, and 1,5. , 10-triol, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,3,5-trihydroxybenzene, and a mixture of 3 hydroxyl groups at the terminal An alcohol compound residue such as an alkylene oxide compound. From the viewpoint of having a well-developed branching property, trimethylolethane, trimethylolpropane, 1,2,3- are preferred. The residue of the alcohol compound of glycerol or 1,3,5-pentanetriol is more preferably an alcohol compound residue of trimethylolethane, trimethylolpropane or 1,2,3-propanetriol.

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

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

Further, the main chain of the polyurethane dispersant (b-1) of the present embodiment may contain a straight portion between the bonding portion and the adsorbing group and the bonding portion between the adsorbing group and the adsorbing group. Chain construction. As the linear structure, a partial configuration shown by the above formula (i) can be preferably employed.

In this case, the ratio of the linear structure to the branching structure included in the main chain is not particularly limited, and the branching structure is preferably 1% by mass or more, and more preferably 5% by mass or more based on the total of the linear structure and the branching structure. It is preferably 100% by mass or less, more preferably 80% by mass or less, still more preferably 60% by mass or less.

When it is set to the above lower limit value, the solvent affinity due to the polyester structure portion or the polyether structure portion tends to be improved, and the steric hindrance is reduced by setting it as the upper limit or less. The tendency to adsorb to the pigment efficiently.

Further, the specific adsorbing group of the polyurethane dispersing agent (b-1) of the present embodiment, the content ratio of the adsorbing group, the specific hydrophilic solvent group, the content ratio of the hydrophilic solvent group, and the physical properties are preferably Use the above.

Further, the method for producing the polyurethane dispersant (b-1) of the present embodiment is the same as the above-described production 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 a trifunctional or higher monomer, several branching points are formed in the main chain.

The trifunctional or higher monomer used herein may, for example, be a polyhydric alcohol, a polyamine or a polyisocyanate, preferably a polyhydric alcohol or a polyamine, and particularly preferably a polyhydric alcohol.

Since the polyurethane dispersant (b-1) of the present embodiment tends to be easily gelled, it is preferred to carry out the synthesis without causing gelation. From such a viewpoint, the number average molecular weight of the polyurethane dispersant (b-1) is preferably 40,000 or less, 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, more preferably at least 5,000 or more from the viewpoint of the dispersion effect.

The polyurethane dispersant (b-1) of the present 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]

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

The polyisocyanate compound (b-a') may contain not only the compound having three or more isocyanate groups but also the above-mentioned diisocyanate compound (b-a). In addition, when a compound containing three or more functional groups having a reaction 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, more preferably 2.2 or less. In addition, when a compound (b-d') containing three or more functional groups having a reaction with an isocyanate group is used, the average number of functional groups of the polyisocyanate compound (b-a') is particularly preferably 2.0.

Here, the average functional group number is a mixture of compounds having a different number of functional groups, and is an average value of the number of functional groups, and is calculated by the following formula.

The average number of functional groups = [{(functional number of bases) × (the number of moles of the compound having the number of functional groups thereof)} / (the total number of moles of the compound)

The compound (b-a') having an average functional group number of 2.0 is the same as the above compound (b-a).

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

The compound (bd) has two or more functional groups reactive with an isocyanate group and forms a linear polyurethane skeleton, but the compound (b-d') contains at least a reaction with an isocyanate group. By having three or more functional groups, a branched structure can be introduced into the polyurethane skeleton of the main chain.

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

a compound having three or more functional groups reactive with an isocyanate group in the compound (b-d'), and a polyurethane dispersion caused by the compound 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, ginxyl (2-aminoethyl)amine, and triethylenetetramine.

Further, by using a compound having three or four hydroxyl groups to carry out the synthesis of a polyalkylene glycol or the polymerization of a lactone, it is preferred to obtain a trivalent or tetrahydric alcohol having a number average molecular weight of 200 to 2,000. The polymer compound can also be used as the compound (b-d'). The compound (b-d') is preferably a compound having three hydroxyl groups of a low molecular weight.

Specific examples of the compound having three or more functional groups reactive with an isocyanate group in the compound (b-d') are shown in the lower left, whereby the polyurethane dispersion (b-1) can be used. Import the lower right part of the structure.

[化69]

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

Further, a compound (b-d') can also be used as a compound having three or more hydroxyl groups and/or one or two amine groups.

Further, the number average molecular weight of the compound (b-d') is preferably from 32 to 3,000, and one type of these compounds may be used, and plural numbers may be used.

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

The isocyanate group in the polyurethane dispersant (b-1) of the present embodiment is basically caused by the compound (b-a'). On the other hand, the functional group reactive with the isocyanate group is caused by the compounds (b-b), (b-c), (b-d'), and (b-e). The amount of such functional groups is preferably used in an equivalent manner as follows.

{(b-a') isocyanate number} × {(b-a') molar number} = {number of functional groups reacting with isocyanate groups in (bb)} × {(bb) molar number }+{Number of functional groups reactive with isocyanate groups in (bc)}×{Mc of (bc)}+{Number of functional groups reactive with isocyanate groups in (b-d')}×{(b -d') Molar number} + {Number of functional groups reactive with isocyanate groups in (be)} × {(be) Moire number}

Here, when the compound of (b-a') to (b-e) is a mixture, the average functional group number of the functional group of the mixture and the total number of moles of the mixture are used.

Further, a preferred structure of the polyurethane dispersant (b-1) of the present embodiment can be obtained by using the following compounds.

‧(b-a') isocyanate group number: 2

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

‧ Number of functional groups reactive with isocyanate groups in (b-c): 2

‧ Number of functional groups reactive with the isocyanate group in (b-d'): comprising a mixture of two or more, and having an average number of functional groups of at least two.

‧The functional group reacting with the isocyanate group in (b-e): 1

The branching structure of the polyurethane dispersant (b-1) of the present embodiment is preferably low. The so-called low level is represented by the following definition. First, between and In the functional group in which the cyanate group is reacted, the average functional group number of the compounds (b-b), (b-c), and (b-d') other than the compound (b-e) which acts as a chain stopper is considered. This is defined as "the average number of functional groups reactive with an isocyanate group other than the chain stopper".

"Average number of functional groups reactive with isocyanate groups other than chain stopper" = A/B

Among them, A and B are as follows.

A = {number of functional groups reactive with isocyanate groups in (bb)} × {mole of {(bb)} + {number of functional groups reactive with isocyanate groups in (bc)} × {(bc) Number of ears}+{Number of functional groups reactive with isocyanate groups in (b-d')}×{(b-d') molars}

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

The polyurethane dispersant (b-1) of the present embodiment can be a polyurethane compound having a "average number of functional groups reactive with an isocyanate group other than a chain stopper" of more than 2. In order to make the "average number of functional groups reactive with the isocyanate group other than the chain stopper" larger than 2, it is preferred to use a compound having a reaction with the isocyanate group of the compound (b-d') to have an average number of functional groups of more than 2. Therefore, the compound (b-d') may be a compound containing at least three or more functional groups having a reaction with an isocyanate group.

The functional group reactive 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.

Further, the "average number of functional groups which react with an isocyanate group other than the chain stopper" is preferably more than 2.0 and not more than 3.0. The "average number of functional groups which react with an isocyanate group other than the chain stopper" is preferably 2.6 or less, more preferably 2.4. Hereinafter, it is more preferably 2.3 or less.

The "average number of functional groups reactive with an isocyanate group other than the chain stopper" is preferably low. By making the "average number of functional groups reactive with the isocyanate group other than the chain stopper" low, it is possible to suppress 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 be deteriorated. Further, it is possible to prevent the steric obstacle from becoming large due to the entanglement of the dispersant, and it is possible to suppress the deterioration of the adsorption effect on the pigment. Thereby, the dispersibility in a solvent, the alkali-resistant developer resistance at the time of formation of a fine line, and the heat resistance at the time of high-temperature treatment are favorable, and the effect of this invention is fully exhibited.

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

<Other dispersants>

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

The other dispersing agent (b-2) is preferably a polymer dispersing agent, and more preferably a carboxyl group; a phosphate group; a sulfonic acid group; or the like; or a base; Grade 3 amine; grade 4 ammonium; pyridine, pyrimidine or pyridyl A polymer dispersant having a functional group such as a nitrogen atom-containing heterocyclic group. Among them, particularly preferred is a grade 1, 2 or 3 amine group; a grade 4 ammonium salt; pyridine, pyrimidine or pyridyl A polymer dispersant having a basic functional group such as a nitrogen atom-containing heterocyclic group.

In addition, as another polymer dispersing agent which can be used together, for example, a urethane dispersing agent other than the polyurethane dispersing agent (b-1), an acrylic dispersing agent, and a polyethyleneimine dispersion are mentioned. Agent, polyallylamine dispersant, dispersant containing monomer and macromonomer having an amine group, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphate dispersion Agent, polyester phosphate dispersant, sorbitan fatty ester dispersant, and aliphatic modified polyester dispersant.

Specific examples of such other dispersible agents that can be used together include EFKA [registered trademark, the same applies hereinafter. EFKA CHEMICALS BV (EFKA) company. ], Disperbyk (registered trademark, the same as below. BYK Chemie Co., Ltd.), DISPARLON (registered trademark, the same as the following.), SOLSPERSE (registered trademark, the same as the following. Lubrizol company.), KP (Shin-Etsu Chemical Industry) Company system), Polyflow or Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, the same as the following. Ajinomoto Fine-techno Co., Ltd.).

More specifically, for example, EFKA-4046, -4047 (manufactured by BASF Corporation), Disperbyk-111, -161, -162, -163, -166, -167, -182, -2000, -2001 (BYK Chemie) Company system), DISPARLON DA-7301, ED-701 (made by Nanben 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 Co., Ltd.).

These polymer dispersants may be used alone or in combination with the polyurethane dispersant (b-1), or two or more kinds thereof may be used in combination.

Among these other dispersing agents, a urethane-based polymer dispersing agent other than the polyfunctional urethane dispersing agent (b-1) having a basic functional group and/or C is preferable. The olefinic polymer dispersing agent is particularly preferably an urethane-based polymer dispersing agent. Further, a polymer dispersing agent having a basic functional group and having a polyester and/or polyether bond is also preferred.

Specifically, a preferred chemical structure of the urethane-based polymer dispersant is exemplified by a polyisocyanate compound having three or more isocyanate groups such as a toluene diisocyanate trimer. a weight obtained by reacting a compound having one or two hydroxyl groups and having a lyophilic group having a number average molecular weight of 300 to 10,000 or a compound having a chain extending group, and a compound having one active hydrogen and a tertiary amino group in the same molecule A dispersion resin having an average molecular weight of 1,000 to 200,000.

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

As such a commercially available dispersing agent, there are Disperbyk-161, -162, -163, -166, -167, -182 (manufactured by BYK Chemie Co., Ltd.) or EFKA-4046, -4047 (manufactured by BASF Corporation, etc.).

In the present invention, the amine valence is a value obtained by neutralization titration of a basic amine group with an acid, and is represented by the number of mg of KOH corresponding to the acid value; specifically, it is determined by the following method. When the amine value is less than the above range, the dispersibility is lowered, and if it exceeds the above range, the developability is liable to lower.

<Method for measuring amine price>

The amine value is represented by the mass of the solvent in which the solid content of the solvent is removed from the dispersant sample, and the mass of KOH is equivalent, and can be measured by the following method.

In a 100mL beaker fine scale dispersant sample 0.5~1.5g, dissolved in 50mL acetic acid. This solution was neutralized and titrated with a 0.1 mol/L HClO ₄ (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the pH curve was titrated as the end point of the titration, and the amine price was determined by the following formula.

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

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

[Photopolymerization initiator (c)]

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

<Hydrazine ester photopolymerization initiator (c-1)>

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

That is, in the present invention, a specific polyurethane dispersant (b-1) as a dispersing agent (b) is used in a photosensitive resin composition, and an oxime ester photopolymerization initiator (c) is used. -1) When it is used as a photopolymerization initiator (c), it is easy to form the present at the time of producing a color filter, etc., by improving the resistance to the alkali developer and suppressing thermal deformation in the post-high-temperature hardening treatment. The fine lines that are required by the market.

The polyurethane dispersant (b-1) used in the present invention is obtained by ingesting a pigment at a site of an adsorbent group or a urethane skeleton as described above, in a polyester chain or a polyester chain. The portion is in good compatibility with and entangled with the resin or monomer in the photosensitive resin composition, and thereafter, the resin or monomer of the photosensitive resin composition is subjected to photopolymerization initiator (c) by ultraviolet light. In combination with the alkali developability and heat resistance of the present invention More improved. This effect is considered to be further enhanced by using the polyurethane dispersant (b-1) in combination with the oxime ester photopolymerization initiator (c-1).

In particular, the side portion of the fine line pattern which is weakened by the ultraviolet light being blocked by the mask in the adhesion portion of the substrate which is hard to reach by ultraviolet rays or the ultraviolet light exposure, by the oxime ester photopolymerization initiator (c-1) When it coexists with the polyurethane dispersant (b-1), the alkali developer resistance can be multiplied by the effect of heat resistance, and a fine line of fineness can be easily formed.

Further, the oxime ester photopolymerization initiator (c-1) has a structure for absorbing ultraviolet rays, a structure for transmitting light energy, and a structure for generating radicals in the structure, so that a small amount, that is, a high sensitivity and a reaction to heat It is stable, and a high-sensitivity photosensitive resin composition can be designed in a small amount. In particular, from the viewpoint of light absorption of i-rays (365 nm) for an exposure light source, photopolymerization initiation of an oxime ester having an optionally substituted carbazolyl group (having a group of a substituted carbazole ring) In the case of the agent (c-1), this structural property can be favorably exhibited, which is more preferable.

At present, the market requires high opacity, on the other hand, the film BM (black matrix), and the pigment concentration is gradually increased. Under such conditions, the oxime ester photopolymerization initiator (c-1) can effectively function.

The oxime compound of the oxime ester photopolymerization initiator (c-1) may, for example, be a compound having a structural moiety represented by the following general formula (22), and is preferably represented by the following general formula (23). An oxime ester compound.

In the above formula (22), R ²² represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms, and an alkenoyl group having 3 to 25 carbon atoms. , a cycloalkyl fluorenyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkyl fluorenyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl fluorenyl group having 8 to 20 carbon atoms, and a heteroaryloxy group having 3 to 20 carbon atoms. Carbonyl alkanoyl group, aminoalkylcarbonyl group having 2 to 10 carbon atoms, aryl fluorenyl group having 7 to 20 carbon atoms, heteroaryl fluorenyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, or carbon Number of 7 to 20 aryloxycarbonyl groups.

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 of 1 each independently substituted. ~20 heteroarylalkyl group, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or hetero Arylsulfanyl group, aminoalkyl group having 1 to 20 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, olefinic group having 3 to 25 carbon atoms, cycloalkylidene group having 3 to 8 carbon atoms, carbon number 7~20 aryl fluorenyl group, heterocyclic fluorenyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, or cycloalkane having 6 to 20 carbon atoms Alkyl group.

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

Further, R ^21a may form a ring together with R ^21b , and the linking group may be an alkylene group having a carbon number of 1 to 10 each having a substituent, a polyvinyl group [-(CH=CH) _r -] or a poly Ethynyl [-(C≡C) _r -] or a combination of such groups. Also, r is an integer from 0 to 3.

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

Among these, from the viewpoint of sensitivity, R ^{22 in the} above general formula (22) and R ^22a in the above general formula (23) are preferably an alkane group having 2 to 12 carbon atoms or carbon. a heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms and a cycloalkyl fluorenyl group having 3 to 8 carbon atoms; more preferably an alkyl fluorenyl group having 2 to 10 carbon atoms; more preferably an alkyl fluorenyl group having 2 to 5 carbon atoms. .

R ^21a in the above general formula (23) is preferably an alkyl group having 1 to 20 carbon atoms which may be substituted, or a carbon number which may be substituted, from the viewpoint of solubility to a solvent and sensitivity. a cycloalkylalkyl group of 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 by N-ethenyl- a propyl group substituted with an N-acetoxyamino group.

Further, as R ^21b in the above general formula (23), preferred are oxazolyl groups which may be substituted, and 9-oxosulfuric which may be substituted. A phenyl thioether group which may or may be substituted. When the carbazolyl group which may be substituted is contained as R ^21b , it is more preferable for the above reasons. Further, an oxime ester initiator containing a nitrocarbazole group is also effective.

As the oxime ester photopolymerization initiator (c-1), it is preferred to include a carbazolyl group which may be substituted as R ^21b for the above reasons. More preferably, it has an aryl group selected from carbon atoms 6 to 25 which may be substituted, and an arylcarbonyl 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. Further, a heteroarylcarbonyl group having 6 to 25 carbon atoms and a carbazolyl group having at least one group in the group of nitro groups may be substituted. From the viewpoint of sensitivity, the ligament group has at least one group selected from the group consisting of a benzamidine group, a tolylmethyl group, a naphthylmethyl group, a thienylcarbonyl group, and a nitro group. If the carbazolyl group may have a substituent for this purpose, the sensitivity of the photopolymerization initiator is not greatly affected, and even if it is slightly affected, the amount of exposure can be adjusted, or the photopolymerization initiator can be adjusted. The amount of addition is there, and there is a tendency to form a desired fine line.

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

Further, the H atom bonded to the N atom of the carbazolyl group may be any substituent The substitution is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms, from the viewpoint of solubility in a solvent. Alkyl group.

As a commercially available product of the oxime ester photopolymerization initiator (c-1), OXE-02 manufactured by BASF Corporation, TR-PBG-304 manufactured by Changzhou Strong Electronics Co., Ltd., TR-PBG-314 or ADEKA Co., Ltd. NCI-831 and so on.

As the oxime ester photopolymerization initiator (c-1), a preferred oxime ester compound in the present invention may, for example, be a compound exemplified below, but is not limited thereto.

[化73]

[化75]

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

[化76]

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

In the above 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, or a heteroarylalkyl group having 1 to 20 carbon atoms. Alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, alkylsulfanyl group having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms a heteroarylsulfanyl group, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an olefin group having 3 to 25 carbon atoms, and a cycloalkane group having 3 to 8 carbon atoms. , an aromatic fluorenyl group having 7 to 20 carbon atoms, a heteroaryl fluorenyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a carbon number of 6 to 20 a cycloalkylalkyl group.

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

Further, R ^23a may form a ring together with R ^23b , and the linking group may be an alkyl group having a carbon number of 1 to 10 each having a substituent, a polyvinyl group [-(CH=CH) _r -] or a poly Ethynyl [-(C≡C) _r -] or a combination of such groups. Also, r is an integer from 0 to 3.

R ^24a represents an alkanoyl group having 2 to 12 carbon atoms, an olefin group having 3 to 25 carbon atoms, a cycloalkane group having 4 to 8 carbon atoms, and a benzamidine group having 7 to 20 carbon atoms. , a heterocyclic fluorenyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or a carbon number of 2 to 20 An alkylaminocarbonyl group.

R ²⁴ in the above general formula (24) and R ^24a in the above general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms or a heteroarylalkyl fluorenyl group having 1 to 20 carbon atoms. A cycloalkyl fluorenyl group having 3 to 8 carbon atoms or an aromatic fluorenyl group having 7 to 20 carbon atoms.

R ^23a in the above general formula (25) is preferably an unsubstituted ethyl group, a propyl group or a butyl group, or an ethyl group or a propyl group substituted by a methoxycarbonyl group. Further, as (25) in the general formula of R ^23b, can preferably include the substituted carbazolyl, the phenyl group may be substituted with a thioether group, but contains a carbazole group R ^23b are as described above is based on Reason, so better.

As the oxime ester photopolymerization initiator (c-1), a ketone oxime ester compound which is preferable in the present invention is specifically exemplified as the compound exemplified below, but is not limited thereto.

[化78]

As a commercial 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 Power Electronics Co., Ltd.

The oxime ketone ester-based compound itself is a known compound, and is, for example, one of the compounds described in one of the series described in JP-A-2000-80068 or JP-A-2006-36750.

The above-mentioned oxime ester photopolymerization initiator (c-1) may be used alone or in combination of two or more.

<Other photopolymerization initiators>

The photopolymerization initiator (c) of the present invention contains at least the above-described oxime ester photopolymerization initiator (c-1), but does not affect the use of the oxime ester photopolymerization initiator (c-1). In the range of the effects of the present invention, other photopolymerization initiators (c-2) other than the oxime ester photopolymerization initiator (c-1) may be used in combination. Further, an additive such as an accelerator or a sensitizing dye may be used as needed.

Examples of the other photopolymerization initiator (c-2) include a metallocene containing a titanocene derivative described in JP-A-59-152396, and JP-A-61-151197. a bi-imidazole derivative described in JP-A-2000-56118, and a halomethylation described in JP-A-10-39503 Diazole derivatives, halomethyl-s-three N-aryl-α-amino acids such as derivatives and N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, etc. A radical active agent or an α-aminoalkyl acetophenone derivative or the like.

Specifically, for example, as the dititanium derivative, 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, dicyclopentadienylbis(2,6-difluorophenyl-1-yl)titanium, dicyclopentadienyldi(2,4-difluoro Benz-1-yl)titanium, bis(methylcyclopentadienyl) double (2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl-1-yl)titanium and dicyclopentane Dienyl [2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl-1-yl)titanium and the like.

Further, examples of the biimidazole derivative include 2-(2'-chlorophenyl)-4,5-diphenylimidazole 2 polymer and 2-(2'-chlorophenyl)-4,5-. Bis(3'-methoxyphenyl)imidazole 2 polymer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole 2 polymer, 2-(2'-methoxyphenyl)- 4,5-diphenylimidazole 2 polymer and (4'-methoxyphenyl)-4,5-diphenylimidazole 2 polymer.

In addition, as a halomethylation Examples of the oxadiazole 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 the like.

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

Further, examples of the α-aminoalkylacetophenone derivative include 2-methyl-1[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimylamino-1-(4- Phenylphenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylamine Propionylbenzene, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino -3-(4-diethylaminobenzimidyl)coumarin and 4-(diethylamino)chalcone.

Other examples thereof include benzoin methyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methylindole, Anthracene derivatives such as 2-ethyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole, etc.; diphenyl ketone, micactone, 2-methyldiphenyl ketone, 3- a diphenyl ketone derivative such as methyl diphenyl ketone, 4-methyl diphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone or 2-carboxydiphenyl ketone; , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1 -hydroxy-1-methylethyl-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl)one, 2-methyl-(4'-methylthiobenzene Base)-2- Acetophenone derivatives such as phenyl-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl) ketone, etc.; 9-oxosulfur 2-ethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur Derivatives; ethyl benzoic acid derivatives such as ethyl dimethylaminobenzoate, ethyl p-diethylammonium benzoate, etc.; 9-phenyl acridine, 9-(p-methoxyphenyl) Acridine derivatives such as acridine; 9,10-dimethylbenzophenone Brown Derivatives; anthrone derivatives such as benzofluorenone and the like.

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-mercaptobenzoene. a heterocyclic fluorenyl compound or an aliphatic polyfunctional fluorenyl compound such as azole or 2-mercaptobenzimidazole. The accelerator may be used singly or in combination of two or more.

<sensitized pigment>

In the photopolymerization initiator (c), a sensitizing dye which blends with the wavelength of the image exposure light source may be used in combination as needed for the purpose of improving the sensitivity. Examples of such sensitizing dyes include those described in JP-A-4-221958 and JP-A-4-219756. Japanese Patent Laid-Open No. Hei 3-239703, Japanese Patent Application Laid-Open No. Hei No. Hei 5-289335 Japanese Patent Application Laid-Open No. Hei. Japanese Patent Publication No. Sho 45-37377, Japanese Patent Laid-Open No. SHO-48-84183, Japanese Patent Laid-Open No. SHO-52-112681, Japanese Patent Laid-Open Publication No. SHO-58-15503 Japanese Patent Laid-Open No. Hei 59-56403, Japanese Patent Laid-Open No. Hei 2-69, Japanese Patent Laid-Open No. Hei 57-168088, Japanese Patent Laid-Open No. Hei 5-170761, Japanese Patent A dye having a dialkylamino-based phenyl skeleton or the like described in Japanese Laid-Open Patent Publication No. Hei-4-288818.

Among these sensitizing dyes, an amine group-containing sensitizing dye is preferred, and a compound having an amine group and a phenyl group in the same molecule is more preferred. Particularly preferred are, for example, 4,4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4-aminodiphenyl ketone, a diphenyl ketone compound such as 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone or 3,4-diaminodiphenyl ketone; 2-(pair Dimethylaminophenyl)benzo Oxazole, 2-(p-diethylaminophenyl) benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo Azole, 2,5-bis(p-diethylaminophenyl) 1,3,4- Oxazole, 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, (pair two Ethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminobenzene) A compound containing a p-dialkylaminophenyl group such as a pyrimidine or the like.

Among them, the most preferred is 4,4'-dialkylaminodiphenyl ketone.

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

[alkali soluble resin (d)]

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

Specifically, for example, an epoxy group (meth) acrylate resin having a carboxyl group and an acrylic copolymer resin can be mentioned. More specifically, an epoxy group (meth) acrylate resin (D1-1), an epoxy (meth) acrylate resin (D1-2), and an acrylic acid copolymer which will be described later are mentioned. Resin (D2-1), acrylic copolymer resin (D2-2), acrylic copolymer resin (D2-3), and acrylic copolymer resin (D2-4). These may be used alone or in combination of two or more.

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

The alkali-soluble resin (d) is a polyurethane dispersant (b-1) containing the above-described urethane skeleton and a solvate group and an adsorbing group used in the present invention, and a solvent (e) The photosensitive resin composition is well compatible, and the polyether chain and/or the polyester chain of the polyurethane dispersant (b-1) and the alkali-soluble resin of the polymer (d) It is a steric obstacle that prevents aggregation of the color material (a) and maintains a good dispersion state.

Further, in the production of the color filter, the polyether chain and/or the polyester chain of the well-miscible polyurethane dispersant (b-1) is mixed with the alkali-soluble resin (d) of the polymer. The adsorption or the polyurethane skeleton of the entangled or polyurethane emulsifier (b-1) is adsorbed to the color material (a), and the color material (a) with high tolerance is ingested. At the time of high temperature treatment at or after the time, the deformation due to the etching or heat of the alkali developing solution is small.

Further, in the production of a color filter, when the non-exposed portion is dissolved in the alkali developing solution, an alkali-soluble resin having an acidic functional group such as a hydroxyl group, a carboxyl group, a phosphoric acid group or a sulfonic acid group is used as the binder resin. In particular, when the alkali-soluble resin has a carboxyl group, it tends to be more soluble in the alkali developer than in the case of having a hydroxyl group.

Further, the phosphate group or the sulfonic acid group has a higher acidity than the carboxyl group, but is easily reacted with a photopolymerization initiator, a photopolymerizable monomer, a dispersant, and other additives having a basicity in the photosensitive resin composition. The situation in which the stability is deteriorated.

Further, when the acidic group of the alkali-soluble resin is a carboxyl group, it does not affect the dispersion, and has a weak affinity with the dispersing agent (b), and suppresses the etching by the alkali developing solution during alkali development, or the subsequent high-temperature treatment. The tendency of deformation caused by heat.

Further, in the case where the alkali-soluble resin has an ethylenically unsaturated group, crosslinking is carried out by ultraviolet irradiation, and the polyether chain and/or the polyester chain and the base of the above-mentioned polyurethane dispersant (b-1) are mixed. The entanglement of the soluble resin (d) is further enhanced, and the alkali developer resistance and heat resistance of the ultraviolet ray irradiation portion tend to be extremely large.

Further, in the case where the alkali-soluble resin (d) has an ethylenically unsaturated group, the effect of using the polyurethane dispersant (b-1) and the oxime ester photopolymerization initiator (c-1) can be obtained. More improved.

Especially in the connection between the substrate and the fine line pattern that is difficult to reach by ultraviolet rays. The side portion of the fine line pattern which is weakened by the ultraviolet light being blocked by the mask during the ultraviolet exposure, by using an alkali-soluble resin having an ethylenically unsaturated group and a polyurethane dispersant (b-1) And the oxime ester photopolymerization initiator (c-1) tends to multiply the alkali developer resistance and heat resistance, and tends to form fine lines.

Further, when an epoxy group (meth) acrylate resin is used as the alkali-soluble resin having a carboxyl group and an ethylenically unsaturated group, an unsaturated group or a carboxyl group can be added to the resin in a large amount. Further, the aromatic ring structure can be introduced in a large amount or the alicyclic structure having a large solid volume can be introduced, and the alkali-resistant developing liquid property and heat resistance can be further improved.

<Epoxy (meth) acrylate resin>

Examples of the epoxy group-containing (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)>

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

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

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

As the epoxy (meth) acrylate resin (D-1) and epoxy group For the epoxy resin of the raw material of the (meth) acrylate resin (D-2), for example, a bisphenol A type epoxy resin (for example, "Epikote (registered trademark. The same applies hereinafter) 828" manufactured by Mitsubishi Chemical Corporation, " Epikote 1001", "Epikote 1002", "Epikote 1004", etc.), an epoxy group obtained by the reaction of an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example, manufactured 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 the reaction of an alcoholic hydroxyl group of a 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 epoxy propyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), and phenol novolak 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), (oight, inter, and -) A novolac type epoxy resin (for example, "EOCN (registered trademark. The same as below) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., and triepoxypropyl trimeric isocyanate ( For example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd., and a trisphenol-based epoxy resin (for example, "EPPN (registered trademark. The same applies below)-501" and "EPN-502" manufactured by Nippon Kayaku Co., Ltd. "EPPN-503", alicyclic epoxy resin ("Celloxide (registered trademark: the same below) 2021P", "Celloxide EHPE") manufactured by DAICEL Chemical Industry Co., Ltd., which is obtained by the reaction of dicyclopentadiene with phenol. Epoxy resin which is epoxidized by phenol resin (for example, "EXA-7200" manufactured by Dainippon Ink Co., Ltd., "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) and the following general formula (d1)~( D4) The epoxy resin shown.

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

In the above general formula (d1), b11 represents an average value and represents a number of 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, a phenyl group, a naphthyl group or a biphenyl group. Further, the plural R ¹¹ present in one molecule may be the same or different from each other.

In the above general formula (d2), b12 represents an average value and represents a number of 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. Further, the plural R ²¹ present in one molecule may be the same or different from each other.

In the above general formula (d3), X represents the following general formula (d3-1) or (d3-2) The linker shown. Among them, one or more adamantane structures are contained in the molecular structure. B13 represents an integer of 2 or 3.

In the above general formulas (d3-1) and (d3-2), R ³¹ to R ³⁴ and R ³⁵ to R ³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon which may have a substituent. An alkyl group having 1 to 12 alkyl groups or a phenyl group which may have a substituent. Further, the * mark in each formula indicates the bonding portion in (d3).

In the above 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 one of the general formulas (d1) to (d4) is preferably used.

Examples of the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid. a monocarboxylic acid such as an α-haloalkyl group of an (meth)acrylic acid, an alkoxy group, a halogen, a nitro group, a cyano substituent, or the like, 2-(meth)acryloxyethyl succinic acid, 2-( Methyl) propylene methoxyethyl adipate, 2-(methyl) propylene methoxyethyl phthalic acid, 2-(methyl) propylene hydride Oxyethylhexahydrophthalic acid, 2-(methyl)propenyloxyethyl maleate, 2-(methyl)propenyloxypropyl succinic acid, 2-(methyl)acrylic acid Oxypropyl adipic acid, 2-(methyl) propylene methoxy propyl tetrahydro decanoic acid, 2-(methyl) propylene methoxy propyl decanoic acid, 2-(methyl) propylene fluorenyloxy Propyl maleic acid, 2-(methyl) propylene decyloxybutyl succinic acid, 2-(methyl) propylene methoxy butyl adipate, 2-(methyl) propylene oxy butyl Hydrogen hydrazine, 2-(methyl) propylene oxy butyl phthalic acid, 2-(methyl) propylene oxy butyl maleic acid, ε-caprolactone added to acrylic acid, β- a lactone monomer such as propyl lactone, γ-butyrolactone or δ-valerolactone, or succinic acid added to hydroxyalkyl (meth) acrylate or pentaerythritol tri (meth) acrylate A monomer (acid anhydride) such as (anhydride), citric acid (anhydride) or maleic acid (anhydride), and a (meth)acrylic acid dimer.

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

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

As the esterification catalyst used herein, a tertiary amine such as triethylamine, trimethylamine, benzyldimethylamine or benzyldiethylamine, and tetramethylammonium chloride or tetraethylchlorinated can be used. A grade 4 ammonium salt such as ammonium or dodecyltrimethylammonium chloride.

Further, the epoxy resin, the α,β-unsaturated monocarboxylic acid, or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two or more.

The α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is used in an amount of from 1 to 1.2 equivalents per 1 equivalent of the epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.

If the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group is used in a small amount, the amount of the unsaturated group introduced is insufficient, and then the reaction with the polybasic acid and/or its anhydride is carried out. Not enough.

Further, it is also disadvantageous in the case where a large amount of epoxy groups remain. On the other hand, when the amount used is large, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains in the form of an unreacted product. It is considered that there is a tendency for the hardening characteristics to deteriorate in either case.

Examples of the polybasic acid and/or its anhydride include, but are selected from the group consisting of maleic acid, succinic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, hexahydrophthalic acid, pyrogal acid, and trimellitic acid. One of diphenyl ketone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrofurfuric acid, chlorohatchanoic acid, methyltetrahydrofurfuric acid, biphenyltetracarboxylic acid, and the like Or two or more.

Preferred are maleic acid, succinic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, hexahydrophthalic acid, pyrogalic acid, trimellitic acid or biphenyltetracarboxylic acid, or the like. anhydride. Particularly preferred is tetrahydrofurfuric acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

With respect to the addition reaction of the polybasic acid and/or its anhydride, a known method can be used, in addition to the α,β-unsaturated monocarboxylic acid of the epoxy resin or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group. Under the same conditions of the reaction, the reaction can be continued to obtain a target.

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

When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is less than the above range, there is a tendency to lack alkali developability, and if it exceeds the above range, it is determined There is a tendency for the hardening property to deteriorate.

Further, in the case of addition reaction of a polybasic acid and/or an anhydride thereof, a polyhydric alcohol such as trimethylolpropane, pentaerythritol or dipentaerythritol may be added as a structure into which a multi-tiller structure is introduced.

The epoxy (meth) acrylate resins (D1-1) and (D1-2) are usually derived from an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid having a carboxyl group. The reactant of the acid ester, after mixing the polybasic acid and/or its anhydride, or in the reaction of the epoxy resin with the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group After mixing a polybasic acid and/or its anhydride and a polyhydric alcohol, it is obtained by heating.

At this time, the order of mixing the polybasic acid and/or its anhydride with the polyol is not particularly limited. By heating, any reactant of the epoxy resin and the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and any hydroxyl group present in the mixture with the polyol The polyacid and/or its anhydride are subjected to an addition reaction.

If the amount of the polyol is too small, the effect is thin; if too much, there is a possibility of thickening or gelation, so the epoxy resin and the α,β-unsaturated monocarboxylic acid or the ester moiety and the carboxyl group are The reactant of the 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 value of the epoxy group (meth) acrylate resins (D1-1) and (D1-2) thus obtained is usually 10 mgKOH/g or more, preferably 50 mgKOH/g or more. When the acid value is less than 10 mgKOH/g, the developability may be insufficient.

Further, when the acid value is too high, there is a problem that the alkali resistance of the photosensitive resin composition occurs (that is, depending on the alkaline developing solution, the surface of the pattern is roughened or the film is reduced), so the acid value is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

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

<Acrylic copolymer resin>

As the acrylic copolymer resin, for example, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, Japanese Patent Laid-Open No. Hei 11-140144, and Japan Various polymer compounds described in each of the publications of JP-A-H07-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2007-270147; The following may be listed as the resin of (D2-1) to (D2-4). Among them, among the resins of (D2-1) to (D2-4), the resins of (D2-1) and (D2-3) are preferred.

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

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

(D2-3): Desaturation of an epoxy group in the carboxyl group of the above (D2-2) resin Resin added as a compound (hereinafter referred to as "(D2-3) resin").

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

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

Hereinafter, each of these resins will be described.

<(D2-1) Resin>

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

Examples of the "epoxy group-containing (meth) acrylate" constituting the (D2-1) resin include, for example, glycidyl (meth)acrylate and 3,4-epoxybutyl (meth)acrylate. And (3,4-epoxycyclohexyl)methyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl ether, and the like. Among them, preferred is glycidyl (meth)acrylate. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The other radical polymerizable monomer which is 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 general formula ^{(11), R 81 ~ R} 88 each independently represent a hydrogen atom, or an alkyl group having a carbon number of 1 to 3, R ⁸⁷ and R ⁸⁸ may also 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, and may be either saturated or unsaturated, and the carbon number is preferably from 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 the alkali-soluble resin, when the photosensitive resin composition of the present invention is used in a color filter or a video display device, heat resistance and strength can be improved.

As the mono(meth)acrylate having the structure represented by the above general formula (11), various structures can be used as long as it has such a structure, and it is particularly preferable to be as shown in the following general formula (12).

[化87]

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

In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono(meth) acrylate having the structure represented by the above general formula (11), In the repeating unit derived from "other radical polymerizable monomer", it is preferably contained in an amount of from 5 to 90 mol%, particularly preferably from 15 to 50 mol%.

In addition, the "other radical polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the above general formula (11) is not particularly limited.

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

In the resin (D2-1), the epoxy group of the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer is an unsaturated monobasic acid (polymerizable component), Reacts with polybasic anhydrides.

Here, as the "unsaturated monobasic acid" to be added to the epoxy group, various types may be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond. Specific examples thereof include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, α-position haloalkyl, alkoxy group, halogen atom, nitro group or cyano group. A monocarboxylic acid or the like which is substituted with (meth)acrylic acid or the like. Among them, (meth)acrylic acid is preferred. These may be used alone or in combination of two or more. By adding such ingredients, The (D2-1) resin was imparted with polymerizability.

These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the above copolymer, and preferably 50 to 100 mol%.

Further, as the "polybasic acid anhydride" which is added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, various types can be used. Examples thereof include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, decanoic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloro-hydro anhydride; trimellitic anhydride, pyrogallic anhydride, and diphenyl An anhydride of a trivalent or higher acid such as a ketone tetracarboxylic anhydride or a biphenyltetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

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

These polybasic acid anhydrides are usually added in an amount of 10 to 100 mol% of a hydroxyl group produced by adding an unsaturated monobasic acid to the epoxy group of the above copolymer, but preferably 30 to 80 mol. Ear % is added.

<(D2-2) Resin>

(D2-2) The linear alkali-soluble resin having 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 carboxyl group-containing polymerizable monomer.

Examples of the carboxyl group-containing polymerizable monomer include (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, and 2-(methyl)acryloxyethyloxy group. Succinic acid, 2-(methyl) propylene methoxyethyl adipate, 2-(methyl) propylene oxiranyl ethyl maleate, 2-(methyl) propylene methoxyethyl hexa Hydrogen phthalic acid, 2-(methyl) Propylene methoxyethyl phthalate, 2-(methyl) propylene methoxy propyl succinic acid, 2-(methyl) propylene methoxy propyl adipic acid, 2-(methyl) propylene decyloxy Propyl maleic acid, 2-(methyl)propenyloxypropyl hydroquinone, 2-(methyl)propenyloxypropyl niobate, 2-(methyl)propenyloxybutyrate Succinic acid, 2-(methyl)propenyloxybutyl adipate, 2-(methyl)propenyloxybutyl maleate, 2-(methyl)propenyloxybutyl hydroquinone a vinyl monomer such as an acid or 2-(meth)acryloxybutyl phthalic acid; ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ- added to acrylic acid a monomer of a lactone such as valerolactone; a monomer of an acid or anhydride such as succinic acid, maleic acid, and citric acid, and the like; Wait. These may be used alone or in combination of two or more.

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

Further, the (D2-2) resin may be one obtained by copolymerizing another polymerizable monomer having no carboxyl group in the carboxyl group-containing polymerizable monomer. In this case, the other polymerizable monomer is not particularly limited, and those described in JP-A-2009-52010 can be cited. Further, 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) an epoxy group added as a carboxyl group of the (D2-2) resin in a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the above (D2-2) resin The ethylenically unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

As the epoxy group-containing unsaturated compound, for example, (A Glycidyl acrylate, allyl epoxidized propyl ether, epoxypropyl-α-ethyl acrylate, crotonyl epoxidized propyl ether, (meth) epoxidized propyl propyl ether, N-(3,5-dimethyl-4-epoxypropyl)benzyl acrylamide and 4-hydroxybutyl (meth) acrylate epoxy propyl ether and the like containing an acyclic epoxy group Unsaturated compound. From the viewpoint of heat resistance and dispersibility of the pigment, an alicyclic epoxy group-containing unsaturated compound described below is preferred.

Here, examples of the alicyclic epoxy group containing an alicyclic epoxy group-containing unsaturated compound include 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, and 7,8. - an epoxy group (tricyclo[5.2.1.0]non-2-yl) and the like. Further, as the ethylenically unsaturated group, those derived from a (meth) acrylonitrile group are preferred.

<(D2-4) Resin>

The (meth)acrylic resin obtained by polymerizing a monomer component which is a compound represented by the following general formula (6) as a (D2-4) (meth)acrylic resin is mentioned.

In the above 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 the general formula (6) will be described in detail.

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

As the ether dimer represented by the general formula (6), particularly preferred is dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2 '-[Oxobis(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 alone or in combination of two or more.

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

The (D2-4) resin preferably has an acid group. By using the acid group, the photosensitive resin composition of the present invention obtained by the use of the present invention can be used as a crosslinking reaction by forming an ester bond by reacting an acid group with an epoxy group (hereinafter sometimes referred to simply as "acid-epoxy" A photosensitive resin composition which can be cured by a base hardening or a photosensitive resin composition which can develop the unhardened part by 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 acid anhydride group. These acid groups contained in one molecule of the resin may be one type or two or more types.

When an acid group is introduced into the (D2-4) resin, for example, a monomer having an acid group and/or a "monomer capable of imparting an acid group after polymerization" (hereinafter also referred to as "introduction of an acid group" is used. The monomer ") may be used as a monomer component. In addition, when "a monomer which can provide an acid group after a polymerization" is used as a monomer component, it is necessary to carry out the process for providing an acid group after the polymerization.

Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid; and a monomer having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide. a monomer 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 a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or an epoxy group such as a glycidyl (meth)acrylate. a monomer having a radical; a monomer having an isocyanate group 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.

When the monomer component in the case of obtaining the (D2-4) resin is a monomer containing the above-mentioned acid group, the content ratio is usually 5 to 70% by mass, preferably 10 to 60% in the total monomer component. quality%.

The monomer component in the case of obtaining the (D2-4) resin may contain other copolymerizable monomers in addition to the above monomer components.

The photosensitive resin composition of the present invention preferably contains the above epoxy group (meth) acrylate resin (D1-1) and epoxy (meth) acrylate resin (D1) as the alkali-soluble resin (d). 2), (D2-1) resin, (D2-2) resin, (D2-3) resin, and (D2-4) resin; more preferably an epoxy (meth) acrylate resin ( D1-1), ring Any one of an oxy (meth) acrylate resin (D1-2), a (D2-1) resin, and a (D2-3) resin; particularly preferably an epoxy (meth) acrylate resin (D1) -1) and/or epoxy (meth) acrylate resin (D1-2).

<Other alkali soluble resins>

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

The other alkali-soluble resin is not limited, and may be a resin which is usually selected from the group consisting of photosensitive resin compositions. An alkali-soluble resin described in, for example, Japanese Laid-Open Patent Publication No. 2007-316620, Japanese Patent Laid-Open No. Hei. No. 2007-316290, and the like.

[color material (a)]

The photosensitive resin composition of the present invention contains a color material (a). The color material (a) is a coloring agent for the photosensitive resin composition of the present invention. As the color material (a), a dye can be used, but from the viewpoints of heat resistance, light resistance, and the like, a pigment is preferable.

Examples of the pigment include pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, or a black pigment. Further, examples of the structure include an azo system, a phthalocyanine system, a quinophthalone type, a benzimidazolone type, an isoporphyrin type, and Organic pigments such as linden, indanthrene, and lanthanide, or various other inorganic pigments.

Specific examples of the pigment usable in the present invention are shown below by the dye number. Yet Further, the terms "C.I. Pigment Red 2" listed below refer to the 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, preferred are C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254; more preferably C.I. Pigment Red 177, 209, 224, 254.

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 preferred, and C.I. Pigment Blue 15:6 is more preferred.

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

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, and 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, 170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196 199, 200, 202, 203, 204, 205, 206, 207, and 208. Among them, preferred are C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185; more preferably C.I. Pigment Yellow 83, 138, 139, 150 or 180.

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 violet 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 preferable, and C.I. Pigment Violet 23 is more preferable.

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

Examples of the color material which can be used in combination for modulating a black color material include Victoria Pure Blue (42595), Goldamine O (41000), Cathilon flavin (Basic 13), Rose Red 6GCP ( 45160), Rose Red B (45170), Safranin OK70: 100 (50240), Epilepsy X (42080), No. 120 / Lionol Yellow (21090), Leonor Yellow GRO (21090) ,Symuler fast yellow 8GF (21105), benzidine yellow 4T-564D (21095), Smeller 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. The number in ( ) means the color index (CI)).

Further, if other pigments which can be used in combination are further indicated by the CI number, for example, 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 violet pigments 19, 23, 29, 30, 37, 40 and 50; CI blue pigments 15, 15: 1, 15: 4, 22, 60 and 64; CI green pigment 7; And CI brown pigments 23, 25 and 26, etc.

Further, examples of the black color material that can be used alone include carbon black, B fast black, lamp black, bone black, graphite, iron black, nigrosine, cyanine black, and titanium black.

When a black color material is used, among these color materials (a), carbon black is preferred from the viewpoint of light blocking ratio and image characteristics. Examples of the carbon black include carbon black as follows.

Mitsubishi Chemical Corporation manufactures: 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, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW 1, Color Black FW 2, Coo Tr Black FW 2 V, Color Black FW 18, Color Black FW 18, Color Black FW 200, Color Black S 160, Color Black S 170.

Cabot company: Monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the 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 those covered by resin. When carbon black coated with a resin is used, there is an effect of improving the adhesion and volume resistance of the glass substrate. For example, carbon black or the like described in JP-A-H09-71733 is preferably used as the carbon black coated with the resin.

The carbon black to be subjected to the coating treatment preferably has a total content of Na and Ca of 100 ppm or less. The reason is as follows. That is, the carbon black usually contains Na, Ca, and K mixed by the raw material oil or the combustion oil (or gas) at the time of manufacture, the reaction stop water or the granulated water, or the furnace material of the reaction furnace. , Mg, Al or Fe, etc. are ash components. In particular, Na and Ca are each contained in a range of several hundred ppm or more. However, if there are many such cases, they may penetrate into a transparent electrode (ITO) or other electrodes, which may cause electrical short-circuiting.

As a method of reducing the content of the ash content of the Na or Ca in the carbon black, it is possible to strictly select the raw material oil, the fuel oil (or gas) and the reaction stop water in the case of producing carbon black, and the like. Reduce the adjustment of the structure of the alkali substance The method of adding amount. As another method, a method in which carbon black produced by a furnace is washed with water, hydrochloric acid or the like to dissolve or remove Na or Ca is exemplified.

As an example of other black pigments, titanium black, aniline black, iron oxide black pigment, and organic pigments of three colors of red, green, and blue may be mixed and used as a black pigment.

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

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

<Particle size of color material (a)>

The average primary particle diameter of the pigment of the color material (a) used in the present invention is not particularly limited as long as it is a coloring layer of the color filter, and is not particularly limited. The type of the pigment to be used varies, but is preferably in the range of 10 to 100 nm, more preferably in the range of 10 to 70 nm, still 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 the image display device produced by using the photosensitive resin composition of the present invention can be made high. Further, the average primary particle diameter when the pigment is carbon black is preferably 100 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less, and particularly preferably 50 nm or less. Further, 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.

When it is set to the above upper limit value, the pigment obtained by the polyurethane dispersant (b-1) tends to have a good intake, and the alkali-resistant developability and heat resistance tend to be improved. On the other hand, when it is set to the above lower limit value, it is possible to suppress a decrease in dispersibility due to a large amount of the dispersant (b).

Further, the average primary particle diameter of the above pigment can be obtained by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average value thereof is used as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle was determined by approximating the rectangular body having the obtained particle diameter, and the volume average particle diameter was determined to obtain the average primary particle diameter. Furthermore, the electron microscope can obtain the same result regardless of whether it uses a penetrating type (TEM) or a scanning type (SEM).

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 within a range that does not impair the effects of the present invention. Examples of the dye that can be used together include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone dye, a quinoline dye, a nitro dye, a carbonyl dye, a methine dye, and the like. .

Examples of the azo dye 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 Dispersion Blue 165, CI alkaline blue 41, CI alkaline red 18, CI mordant red (mordant red) 7, CI mordant yellow 5, CI mord black 7 and so on.

Examples of the lanthanoid dyes include CI reduced blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI dispersed red 60, CI dispersed blue 56, CI dispersed blue 60, and the like. .

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

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 dye include C.I. Acid Yellow 1, C.I. Acid Orange 3, and C.I. Disperse Yellow 42 and the like.

[Photopolymerizable monomer]

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

The photopolymerizable monomer used in the present invention may be a compound having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as "ethylenic monomer").

Specific examples thereof include (meth)acrylic acid, alkyl (meth)acrylate, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, and a monoester of a polyvalent or monohydric alcohol.

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

Examples of such a polyfunctional ethylenic monomer include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; esters of an aromatic polyhydroxy compound with an unsaturated carboxylic acid; aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds; An ester obtained by an esterification reaction between a polyvalent hydroxy compound and an unsaturated carboxylic acid or a polyvalent carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the 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 glycerin acrylic acid An acrylate of an aliphatic polycarboxy compound such as an ester, and a methacrylate in which an acrylate of the above-exemplified compounds is replaced with a methacrylate; an imiconate which is also replaced by an itaconate, replaced with butene The butenoate of the acid ester is replaced by a maleic acid ester of maleic acid ester or the like.

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

The ester obtained by the esterification reaction of a polyvalent carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, and specific examples thereof include acrylic acid, citric acid, and ethylene. a condensate of an alcohol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensation of acrylic acid, adipic acid, butanediol, and glycerin Things and so on.

Other, as the polyfunctional ethylenic monomer used in the present invention, for example, reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate And the like of ethyl methacrylate (meth) acrylate; polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid addition reaction like epoxy acrylate; ethylene A acrylamide such as bisacrylamide or the like; an allyl ester such as diallyl phthalate; a vinyl group-containing compound such as divinyl phthalate or the like is useful.

In addition, the polyfunctional ethylenic monomer used in the present invention is, for example, a compound having a caprolactone structure and two or more ethylenically unsaturated groups in the molecule (hereinafter sometimes referred to as "caprolactone-containing structure" The functional monomer ") is well compatible with the polyurethane dispersant (b-1) used in the present invention, and further enhances the aliquot The effect of the powder is useful and can be preferably used.

Examples of the polyfunctional monomer having a caprolactone structure include trimethylolethane, bis(trimethylol)ethane, trimethylolpropane, and bis(trimethylol)propane. In a polyol such as pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin or trimethylol melamine, ε-caprolactone is bonded to the ring-opening skeleton by a ring-opening addition reaction, and is opened to the ring skeleton. A known method in which a terminal hydroxyl group is reacted with a (meth) acrylonitrile-based chloride or a (meth)acrylic acid group is subjected to an esterification reaction with (meth)acrylic acid, and a synthetic ε-caprolactone-containing structure can be synthesized. Polyfunctional (meth) acrylate.

Such a polyfunctional monomer having a caprolactone structure is as follows. For example, as a polyol which uses dipentaerythritol as a polyhydric alcohol and esterified with ε-caprolactone, it is a DPCA-20 which is marketed by the Nippon Kayaku Co., Ltd. according to the KAYARAD DPCA series. As the photopolymerizable monomer which is a photosensitive resin composition of the present invention, DPCA-30, DPCA-60, DPCA-120 and the like can be preferably used.

In addition, as a commercial product of ε-caprolactone modified ginseng-(2-propenyl methoxyethyl) trimeric isocyanate compound, there is A-9300-1CL of New Nakamura Chemical Industry Co., Ltd. (in 1 mol) The compound has a structure of 1 mol of ε-caprolactone, and has a structure of 0.1 to 9 mol, more preferably 1 to 3 mol, in the 1 mol compound. A photopolymerizable monomer which is a photosensitive resin composition of the present invention is preferably used.

Further, by using pentaerythritol as a polyol, esterifying it with ε-caprolactone, and further esterifying the acrylic acid at the terminal hydroxyl group, it is also preferred to use photopolymerization as the photosensitive resin composition of the present invention. Sexual monomer. These are those in which the ε-caprolactone structure is preferably 0.1 to 20 moles, more preferably 1 to 12 moles, in the 1 molar compound. Very good for 1 to 4 moles.

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

[thiol]

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

Examples of the type of the mercaptan include hexane dithiol, decane dithiol, 1,4-dimethylnonylbenzene, butanediol dithiopropionate, butanediol dithioglycolate, and the like. Ethylene glycol dithioglycolate, trimethylolpropane thioglycolate, butanediol dithiopropionate, trimethylolpropane thiopropionate, trimethylolpropane thioglycolate , pentaerythritol thiopropionate, pentaerythritol thioglycolate, hydroxyethyl thiopropionate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) (abbreviation) PGMB), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy)butane [trade name: Karenz (registered trademark, the same below) MT BD1, Showa Denko ( Co., Ltd.], butanediol trimethylolpropane ginseng (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko Co., Ltd.), pentaerythritol Ginseng (3-mercaptobutyrate), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane ginseng (3-mercaptoisobutylate) Acid ester), trimethylolpropane ginseng (3-mercaptobutyrate) (abbreviation TPMB), trimethylolpropane ginseng (2-mercaptoisobutyrate) (TPMIB for short) and 1,3,5-gin(3-mercaptobutoxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.), etc.; these may be used alone or in combination of two or more.

Preferably, the above PGMB, TPMB, TPMIB, Karenz MT BD1 A polyfunctional thiol such as Karenz MT PE1, Karenz MT NR1 or the like, more preferably Karenz MT BD1, Karenz MT PE1, Karenz MT NR1, and particularly preferably Karenz MT PE1.

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

[solvent (e)]

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

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

As such an organic solvent, the following are mentioned, for example.

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 tert-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 Ether ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene Alcohol dibutyl ether and dipropylene glycol dimethyl ether like glycol dialkyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl Ethyl 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 Ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate-like glycol alkyl ether acetate; a glycol diacetate such as diol diacetate, 1,3-butylene glycol diacetate or 1,6-hexanol diacetate; an alkyl acetate such as cyclohexanol acetate a class of ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether and dihexyl ether; acetone, Ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl Ethyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl decyl ketone and methoxy methyl pentanone Ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol and benzyl alcohol Monovalent or polyvalent alcohols; n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene and dodecane-like aliphatic hydrocarbons; cyclohexane, Methylcyclohexane, methylcyclohexene and cyclohexane-like alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, xylene and cumene; amyl formate, ethyl formate, acetic acid Ethyl ester, butyl acetate, acrylic acid Ester, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate , butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ester, 3-methoxypropionic acid propyl ester, butyl 3-methoxypropionate and γ-butyrolactone-like chain or cyclic esters; 3-methoxypropionic acid and 3-ethoxyl Propionic acid like alkoxycarboxylic acids; chlorobutane and chloropentane-like halogenated hydrocarbons; methoxymethyl pentanone-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, ethyl carbene Alcohol, butyl carbitol, methyl acesulfame ("Cerma" is a registered trademark, the same below), ethyl cyproterone, ethyl cyproterone acetate, methyl cyproterone acetate And diglyme (all are trade names) and the like.

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

When a pixel or a black matrix of a color filter is formed by photolithography, it is preferred to select a range of a boiling point of 100 to 200 ° C as an organic solvent. More preferred is a boiling point of 120 to 170 ° C.

Among the above organic solvents, a glycol alkyl ether acetate is preferred because the balance between coatability and surface tension is good, and the solubility of constituent components in the composition is high.

Further, the glycol alkyl ether acetates may be used singly or in combination with other organic solvents. As the organic solvent to be used in combination, a glycol monoalkyl ether is particularly preferred. among them, From the viewpoint of solubility of the constituent components in the composition, propylene glycol monomethyl ether is particularly preferred.

In addition, the diol monoalkyl ether has a high polarity, and if the amount of the diol is too large, the color material (a) such as a pigment tends to aggregate, and the storage stability of the photosensitive resin composition obtained thereafter increases, and the storage stability tends to decrease. The proportion of the diol monoalkyl ether in the solvent (e) is preferably from 5 to 30% by mass, more preferably from 5 to 20% by mass.

Further, as the solvent (e), an organic solvent having a boiling point of 150 ° C or higher (hereinafter sometimes referred to as "high boiling point solvent") may preferably be used in combination. When such a high boiling point solvent is used in combination, the photosensitive resin composition is difficult to dry, but has an 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 an effect of preventing, for example, the occurrence of foreign matter defects caused by precipitation of the color material (a) or the like at the tip end of the slit nozzle.

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

The content ratio of the high boiling point solvent in the solvent (e) is preferably from 3 to 50% by mass, more preferably from 5 to 40% by mass, even more preferably from 5 to 30% by mass. When the amount of the high-boiling solvent is too small, for example, the coloring material (a) at the tip end of the slit nozzle may be precipitated and solidified to cause foreign matter defects; if too large, the drying temperature of the composition may be slow, and color will be described later. In the filter manufacturing step, there are problems such as poor efficiency in causing the vacuum drying process and pre-baked pin marks.

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

As a preferable high boiling point solvent, for example, among the above various solvents, diethyl 2 can be cited. Alcohol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol Acetate and triacetin, etc.

[Other compounding ingredients of photosensitive resin composition]

In the photosensitive resin composition of the present invention, in addition to the above components, a tackifier, a coating enhancer, a development improver, an ultraviolet absorber, an antioxidant, a decane coupling agent, a surfactant, and a pigment may be appropriately formulated. A derivative, a polymerization accelerator, a photoacid generator, a crosslinking agent, a plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, an organic carboxylic anhydride, a development improver, or a thermal polymerization inhibitor.

<Adhesive Lifting Agent>

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

As the type of the decane coupling agent, one type of the epoxy group, the (meth)acrylic type, or the amine group may be used alone or two or more types may be used in combination.

Preferred examples of the decane coupling agent include (meth)acryl oxime such as 3-methacryloxypropylmethyldimethoxydecane and 3-methylpropoxypropyltrimethoxydecane. Oxydecanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyl Epoxy decanes such as diethoxy decane and 3-glycidoxypropyl triethoxy decane; urea decanes such as 3-ureidotriethoxy decane; and 3-isocyanate propyl trisole An isocyanate decane such as ethoxy decane. Particularly preferred are decane coupling agents for epoxy decanes.

As the phosphate-based dense adhesion promoter, it is preferred to contain (meth) propylene oxime The phosphates of the group are preferably those represented by the following general formula (g1), (g2) or (g3).

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

Other examples of the adhesion promoter include TEGO*Add Bond LTH (manufactured by Evonik Co., Ltd.).

These phosphoric acid-based adhesion promoters and other adhesion promoters may 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 coatability.

As the surfactant, various types such as an anionic system, a cationic system, a nonionic system, and an amphoteric surfactant can be used. Among them, from the viewpoint of a low possibility of adversely affecting various characteristics, it is preferred to use a nonionic surfactant, and particularly a fluorine- or lanthanide-based surfactant has an effect on coatability.

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

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

<Pigment Derivative>

The photosensitive resin composition of the present invention may contain a pigment derivative in order to enhance dispersibility and preservability, and in particular, from the viewpoint of improving dispersibility, it is preferred to use a dispersant (b) in combination with a pigment derivative. .

Examples of the pigment derivative include an azo type, a phthalocyanine type, a quinophthalone type, a benzimidazolone type, a quinoline yellow type, an isoporphyrin type, and the like. Department, lanthanide, indanthrene, lanthanide, anthrone, diketopyrrolopyrrole and 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 sulfonylamino group and a 4-stage salt thereof, a quinone imine methyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group or a decylamino group, etc., directly or via An alkyl group, an aryl group or a heterocyclic group or the like bonded to a pigment skeleton; preferably a sulfonic acid group. Further, these substituents may be subjected to plural substitution in one pigment skeleton.

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

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

[Component Composition in Photosensitive Resin Composition]

The content ratio of the color material (a) of the photosensitive resin composition of the present invention is usually 1% by mass or more, preferably 5% by mass or more, more preferably 5% by mass or more based on the total solid content of the photosensitive resin composition. 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 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. When the value is equal to or higher than the lower limit value, it is possible to prevent the adverse effect such as the gap control during the liquid crystal cell formation due to the increase in the film thickness in order to obtain a predetermined color density, and the upper limit is also set. Below the value, there is a tendency to easily obtain sufficient image formation properties.

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

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

The effect by the photosensitive resin composition of the present invention can be effectively exhibited particularly in the field of increasing the pigment concentration of the black pigment. As described above, in recent years, in order to increase the opacity, it is necessary to increase the black pigment concentration. 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, still 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 in the above range, coloring sensitivity which is high in light-shielding property (optical density, OD value) can be obtained. The tendency of the resin composition. Specifically, when the content ratio of the black pigment is 45 mass% or more based on the total solid content of the photosensitive resin composition, when the photosensitive resin composition of the present invention is used to form a black matrix having 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.

In general, in the case where the light-shielding property is high, it is difficult for the ultraviolet rays to penetrate to the deep portion of the film, and there is a tendency that the crosslinking by the photopolymerization is weakened particularly in the dense portion of the substrate and the fine line, but the present invention is used. In the case of the photosensitive resin composition, the effect of the present invention can be remarkably confirmed even when the pigment concentration is high. The pigment concentration of the photosensitive resin composition of the present invention is particularly effective in a solid content of 40 to 65 mass%.

Further, the photosensitive resin composition of the present invention is not limited to a case where the pigment concentration is high, and the effect of the present invention can be exhibited even at a low level. When only the pigment concentration is changed in the photosensitive resin composition, the pigment concentration may be thermally deformed during the heat curing treatment after development, and the line width of the fine line may be slightly thicker or thinner, but by adjusting the photopolymerization. The amount of the component such as a monomer or a photopolymerizable initiator or the amount of exposure can be adjusted to obtain a thin line having a desired line width.

The content ratio of the dispersing agent (b) of the photosensitive resin composition of the present invention is not particularly limited, and is usually 50% by mass or less, preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. It is preferably 20% by mass or less, 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, still more preferably 8% by mass or more.

In addition, the content ratio of the dispersing agent (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% by mass based on 100 parts by mass of the color material (a). The amount is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. under. When the content ratio of the dispersing agent (b) is at least the above lower limit value, it is easy to obtain sufficient dispersibility, and by setting it as the upper limit or less, it is possible to sufficiently ensure the content ratio of other components. There is a tendency to easily obtain a desired color density, a desired sensitivity, a desired film forming property, and the like.

Further, the ratio of the polyurethane dispersant (b-1) occupied in the dispersing agent (b) is more effectively obtained by using the polyurethane dispersant (b-1). From the viewpoint of the effects of the present invention, it is preferably 50% by mass or more, more preferably 60% by mass or more, still 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 of the polyurethane dispersant (b-1) is usually 2 parts by mass or more, preferably 5 parts by mass based on 100 parts by mass of the alkali-soluble resin (d). The amount is more than 10 parts by mass, 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. In general, it is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 100 parts by mass or less, still 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 usually 0.1% by mass or more, preferably 0.5% by mass or more based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.7% by mass or more, 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. More preferably, it is 15 mass% or less, and still more preferably 10 mass% or less. When the content ratio of the photopolymerization initiator (c) is at least the above lower limit value, sufficient sensitivity may be obtained. Further, by setting it as the upper limit or less, it is possible to suppress the unexposed portion to the developer. The solubility is lowered, and the development failure tends to be 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. The above; and usually 100% by mass or less. When the content ratio of the oxime ester photopolymerization initiator (c-1) is at least the above lower limit, the polyurethane dispersant (b-1) and the alkali-soluble resin used in the present invention are used. In the combination of (d), after the ultraviolet irradiation, the resistance to the alkali developer or the high-temperature treatment is good, and the formation of fine lines of fineness can be improved.

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

In the case where an accelerator is used together with the photopolymerization initiator (c), the content ratio of the accelerator is usually 0% by mass or more, preferably 0.02% by mass based on 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; and the accelerator may be preferably 0.1 to 50% by mass, more preferably 0.1 to 10% by mass based on the photopolymerization initiator (c). The percentage of % is used.

In addition, when the sensitizing dye is used, the content ratio of the sensitizing dye contained in the photosensitive resin composition of the present invention is usually 0 to 20% by mass in the total solid content of the photosensitive resin composition. It is preferably 0 to 15% by mass, 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, based on the total solid content of the photosensitive resin composition of the present invention. Good for 15% by mass or more, and even 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 at least the above lower limit value, the solubility of the unexposed portion in the developer is suppressed from being lowered, and the development failure is easily prevented. In addition, the permeability of the developer to the exposed portion tends to be low, and the sharpness or adhesion of the pixel tends to be improved.

In addition, as the alkali-soluble resin (d), the photosensitive resin composition of the present invention preferably contains the above epoxy (meth) acrylate resin (D1-1) and epoxy group (methyl). At least one of an acrylate resin (D1-2), a (D2-1) resin, a (D2-2) resin, a (D2-3) resin, and a (D2-4) resin; more preferably an epoxy group (methyl group) ) acrylate resin (D1-1), epoxy (meth) acrylate resin (D1-2) resin, (D2-1) resin, (D2-3) resin; particularly preferably contains epoxy group (A) Acrylate resin (D1-1) and/or epoxy (meth) acrylate resin (D1-2).

When the alkali-soluble resin (d) is an alkali-soluble resin other than the above-mentioned preferable resin, the content ratio thereof is usually 20% by mass or less, preferably 10% by mass based on the total of the alkali-soluble resin (d). Hereinafter, it is 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% based on 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 or less. Below the mass. By setting the content ratio of the alkali-soluble resin (d) to the color material (a) to the above lower limit value, In addition, it is possible to suppress the decrease in the solubility of the unexposed portion in the developer, and it is possible to prevent the development failure from being induced. Further, when the thickness is not more than the above upper limit, the desired pixel thickness tends to be easily obtained.

The content ratio of the photopolymerizable monomer of the photosensitive resin composition of the present invention is usually 90% by mass or less, preferably 80% by mass or less, more preferably the total solid 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 not more than the above upper limit value, the permeability of the developer to the exposed portion is appropriate, and a good image tends to be obtained.

The lower limit of the content of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more. When it is at least the above lower limit, there is a tendency that the photocuring by ultraviolet irradiation is improved and the alkali developability is also good.

In addition, the content ratio 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). More than or equal to the mass part, more preferably 6 parts by mass or more. Further, it is usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less.

The amount of the polyurethane dispersant (b-1), the photopolymerizable monomer, and the photopolymerization initiator (c) relative to the alkali-soluble resin is at least the above lower limit value, and the photosensitive resin is used. In the solution of the composition, the steric hindrance of the agglomeration of the color material (a) due to the compatibility of the polyurethane dispersant (b-1) and the alkali-soluble resin (d) is dispersed Orientation; or in the production of a color filter, the polyurethane dispersant (b-1) and the alkali-soluble resin (d) are irradiated with ultraviolet light to have a photopolymerization initiator (c) The component of the crosslinked ethylenically unsaturated group further increases the crosslinkability, and the resistance to the alkali developer and the high temperature treatment which are the effects of the present invention is improved, and the formation is high. The tendency of subtle thin lines.

In addition, the amount of the polyurethane dispersant (b-1), the photopolymerizable monomer, and the photopolymerization initiator (c) which tends to deteriorate the solubility of the alkali developer is as described above. Below the upper limit, there is a tendency to improve the solubility of the unexposed portion of the ultraviolet light to the alkali developer and to reduce the development residue on the substrate.

In addition, when the thiol is used, the content of the thiol is usually 0.1% by mass or more, preferably 0.3% by mass or more, and more preferably 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, preferably 5% by mass or less. If the content of the mercaptan is too small, the effect of improving the sensitivity is insufficient; if it is too large, the storage stability is 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, and usually 10% by mass based on the total solid content of the photosensitive resin composition of the present invention. % or less, preferably 5% by mass or less.

In addition, when the surfactant is used, the content of the surfactant 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 of the photosensitive resin composition. It is more preferably 0.03 mass% or more, and is usually 10 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, still 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.

In the photosensitive resin composition of the present invention, the solvent (e) is used, and the solid content concentration thereof is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, and more preferably 30% by mass way to adjust the liquid. When it is in 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 of the present invention (hereinafter sometimes referred to as "resist") is produced by a usual method.

Usually, the color material (a) is preferably subjected to dispersion treatment using a paint conditioner, a sander, a ball mill, a roll mill, a stone grinder, a jet mill, a homogenizer or the like in advance. The color material (a) is microparticulated by the dispersion treatment, so that the coating properties of the resist are improved. Moreover, when a black color material is used as the color material (a), it contributes to the improvement of the light-shielding ability.

The dispersion treatment is usually preferably carried out in accordance with a system in which a part or all of the color material (a), the dispersing agent (b), the solvent (e), and optionally the alkali-soluble resin (d) are used in combination (hereinafter, it is sometimes used for dispersion). The treated mixture and the composition obtained by the treatment are referred to as "ink" or "pigment dispersion"). In the dispersion 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 the resist (excellent dispersion stability), so that it is preferred. .

In addition, when the liquid containing all the components blended in the photosensitive resin composition is subjected to dispersion treatment, the components having high reactivity may be modified due to heat generated during the dispersion treatment. Therefore, it is preferred to carry out a dispersion treatment in accordance with a system containing the above 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 dispersion treatment conditions are usually from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time is different depending on the composition of the liquid and the size of the dispersion processing apparatus, etc., and is appropriately adjusted.

The standard of dispersion is to control the gloss of the ink in such a manner that the 20 degree specular gloss of the resist [JIS Z8741 (1997)] becomes in the range of 100 to 200. In the resist When the glossiness of the agent is low, the dispersion treatment is insufficient and the coarse pigment (color material) particles remain, and there are cases where the developability, the adhesion, the resolution, and the like are insufficient. Further, when the dispersion treatment is carried out until the gloss exceeds the above range, the pigment is broken and a large number of ultrafine particles are generated, which tends to impair the dispersion stability.

Next, the ink obtained by the above dispersion treatment is mixed with the above-mentioned other components contained in the resist to prepare a uniform solution. In the step of producing the resist, since fine impurities are mixed in the liquid, the obtained resist is preferably subjected to filtration treatment by a filter or the like.

[hardened material]

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, a black matrix using the photosensitive resin composition of the present invention will be described based on the production method.

(1) Support

The material for forming the black matrix is not particularly limited as long as it has moderate strength. As the support, a transparent substrate is mainly used. Examples of the material include a polyester resin such as polyethylene terephthalate; a polyolefin resin such as polypropylene or polyethylene; and thermoplasticity such as polycarbonate, polymethyl methacrylate or polyfluorene. Resin sheet; epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin A thermosetting resin sheet or the like; or various glasses or the like. Among them, from the viewpoint of heat resistance, glass or a heat resistant resin is preferred.

Further, a case where a transparent electrode such as ITO or IZO is formed on the surface of the substrate may be used. In addition to the transparent substrate, it may be formed on the TFT array.

In order to improve the surface physical properties such as adhesion, the support may be subjected to a film forming treatment of various resins such as a corona discharge treatment, an ozone treatment, a decane coupling agent, or a urethane resin.

The thickness of the support is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Further, when the film formation treatment of various resins is carried out, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black matrix

When the black matrix of the present invention is formed by the photosensitive resin composition of the present invention, the photosensitive resin composition of the present invention is applied onto a support such as a transparent substrate and dried, and then a photomask is placed on the coating film. The image is exposed and developed through the mask, and then thermally hardened or photohardened as needed to form a black matrix.

(3) Formation of black matrix (3-1) Coating of photosensitive resin composition

The coating of the photosensitive resin composition for a black matrix on a support such as a transparent substrate can be carried out by a spin coating method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In addition, in the case of the die-coating method, the amount of the coating liquid to be used can be greatly reduced, and the influence of the mist or the like adhered by the spin coating method is not obtained at all, and the occurrence of foreign matter can be suppressed, and it is preferable from the viewpoint of the overall viewpoint.

If the thickness of the coating film is too thick, pattern development is difficult, and the gap adjustment in the liquid crystal cell step is difficult. If it is too thin, the pigment concentration is difficult to increase and the desired color expression cannot be performed. The thickness of the coating film is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and still more preferably in the range of 1 to 4 μm, in terms of the film thickness after drying.

(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 carried out 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 above solvent component, the performance of the dryer to be used, and the like. The drying time is usually in the range of 40 to 200 ° C, 15 seconds to 5 minutes, preferably in the range of 50 to 130 ° C, 30 seconds. ~3 minutes range selection.

When the drying temperature is higher, the adhesion of the coating film to the support is increased. However, if the drying temperature is too high, the alkali-soluble resin is decomposed to cause thermal polymerization to cause development failure. Further, the drying step of the coating film may be a vacuum drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) exposure

The image exposure is performed on the coating film of the photosensitive resin composition, and the negative mask pattern is superimposed, and the light source of the ultraviolet ray or the visible ray is irradiated through the mask pattern. In this case, in order to prevent the sensitivity of the photopolymerizable layer due to oxygen from being lowered, 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 above image exposure is not particularly limited. As light Examples of the source include a lamp source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, and a fluorescent lamp, and an argon ion laser, YAG. Laser sources such as lasers, excimer lasers, nitrogen lasers, cadmium-cadmium lasers, and semiconductor lasers. An optical filter can also be utilized when illuminating a specific wavelength of light.

(3-4) Development

In the black matrix of the present invention, after the image of the photosensitive resin composition is image-exposed by the light source, an image is formed on the substrate by using an organic solvent or an aqueous solution containing a surfactant and a basic compound. Can be made. The aqueous solution may further contain an organic solvent, a buffer, a distorer, a dye or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium metasilicate, and sodium phosphate. Inorganic basic compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and mono- or di-ethanolamine, mono- or di-trimethylamine, single or two or three Organic basic compounds such as ethylamine, mono or diisopropylamine, n-butylamine, mono- or di-isopropanolamine, ethyleneimine, ethylenediimide, tetramethylammonium hydroxide (TMAH) and choline . These basic compounds may also be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ester dehydration, sorbitol alkyl esters, and monoglyceryl alkyl esters. Anionic interfaces such as nonionic surfactants, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, and sulfosuccinates Active agents, as well as the amphoteric boundaries of alkylbetaines and amino acids Surfactant.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyproterone, butyl cyanidin, phenyl cyanidin, propylene glycol, and diacetone alcohol. The organic solvent may be used singly or in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, preferably 15 to 45 ° C, particularly preferably 20 to 40 ° C. The developing method can be carried out by any one of a dipping development method, a spray development method, a brush development method, or an ultrasonic development method.

(3-5) Thermal hardening treatment

The developed support is subjected to a heat hardening treatment or a photohardening treatment, preferably a heat hardening treatment. The thermal hardening treatment conditions at this time are selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the 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, particularly preferably 4 to 8 μm in the case of high thin wires, and usually 0.5 to 5 μm in height, preferably It is 1~4μm. Further, 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. Further, 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]

A photosensitive resin composition containing a color material of one of red, green, and blue is applied to a support having a black matrix and dried in the same manner as in the above (3-1) to (3-5). Thereafter, a mask is superposed on the coating film, and image exposure and development are performed through the mask. A colored image can be formed by forming a pixel image by heat hardening or photohardening as needed. This operation is performed on the photosensitive resin compositions of the three colors of red, green, and blue, respectively, whereby a color filter image can be formed. The order of these is not limited to the above.

[Coloring spacer]

In addition to the black matrix, the photosensitive resin composition of the present invention may be used as a resist for a coloring spacer. When a spacer is used for a TFT type LCD, there is a case where a TFT as a switching element malfunctions due to light incident on the TFT, and a coloring spacer is used to prevent this; for example, Japanese Patent Laid-Open No. Hei 8-234212 The publication discloses that the spacer is made to have a light blocking property. The coloring spacer can be formed in the same manner as the black matrix described above except that a mask for the coloring spacer is used.

[Formation of Transparent Electrode]

The color filter is formed as a transparent electrode such as ITO on the image according to its original state, and is used as a part of a color display or a liquid crystal display device. However, in order to improve surface smoothness and durability, the image may be used as needed. A top coat of polyamine or polyimine or the like is provided thereon. Further, in some applications such as a planar alignment type driving method (IPS mode), there is a case where a transparent electrode is not formed.

[Image display device]

The image display device of the present invention is not particularly limited as long as it has a black matrix composed of the photosensitive resin composition of the present invention and displays an image or a map, and examples thereof include a liquid crystal display device and an organic EL display, which will be 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 described above, and the order in which the color pixels or the black matrix are formed or the formation position is not particularly limited.

A liquid crystal display device usually forms an alignment film on a color filter, and after dispersing a spacer on the alignment film, bonding the counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and wiring the counter electrode And finished.

As the alignment film, a resin film such as polyimide or the like is preferable. For the formation of the alignment film, a gravure printing method and/or a quick-drying printing method are usually employed, and the thickness of the alignment film is set to several tens of nm. After the hardening treatment of the alignment film by thermal baking, the surface treatment is carried out by treatment with ultraviolet rays or a rubbing cloth, and the surface state is adjusted so that the liquid crystal is tilted.

As the spacer, the size of the gap between the counter substrate and the counter substrate is used, and it is usually preferably 2 to 8 μm. The light spacer (PS) of the transparent resin film may also be formed on the color filter substrate by photolithography, and this may be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap to be bonded to the counter substrate differs 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 by a sealing material such as epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and/or heating to seal the periphery of the liquid crystal cell.

The liquid crystal cell sealed in the periphery is cut into a panel unit, and then decompressed in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal by leaking pressure in the chamber. Within the unit.

The degree of pressure reduction in the liquid crystal cell is usually from 1 × 10 ^-2 to 1 × 10 ^-7 Pa, preferably from 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Further, when the pressure is reduced, the liquid crystal cell is preferably heated, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C.

The heating at the time of pressure reduction is usually set to a range of 10 to 60 minutes, and thereafter immersed in a liquid crystal. The liquid crystal cell in which the liquid crystal is injected is sealed by sealing the liquid crystal injection port by hardening the UV hardening resin, thereby completing the liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and may be any known liquid crystal such as an aromatic type, an aliphatic type or a polycyclic compound, or may be a liquid crystal liquid or a thermal liquid crystal. A nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, or the like is known to the thermal liquid crystal, but any of them may be used.

[Organic EL Display]

In the organic EL display, for example, as shown in FIG. 1, first, a pattern formed of a photosensitive resin composition is formed on the transparent supporting substrate 10 (that is, a resin provided between the pixel 20 and the adjacent pixel 20). A color filter formed of a black matrix (not shown) is formed on the color filter by laminating the organic light-emitting body 500 via the organic protective layer 30 and the inorganic oxide film 40 to form the organic EL element 100.

Further, in the pixel 20 and the resin black matrix, at least the black matrix is produced by using the photosensitive resin composition of the present invention. As a method of laminating the organic light-emitting body 500, for example, a method of sequentially forming the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light-emitting layer 53, the electron injection layer 54, and the cathode 55 on the color filter may be mentioned. And a method of bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40, and the like.

The organic EL device 100 produced in this manner can be produced by, for example, the method described in "Organic EL Display" (Ohmsha, issued on August 20, 2004, at the time of Jing Shi, Anda Chiba, and Takada Kazuo). Organic EL display.

Furthermore, the color filter of the present invention can also be applied to an organic EL display of a passive driving type or an organic EL display of an active driving type.

<Example>

The present invention will be specifically described below by way of examples and comparative examples, but the present invention is not limited to the following examples without departing from the spirit thereof.

<Dispersant 1>

The polyurethane compound 1 obtained through the following (Step 1-1) to (Step 1-9) was used as the dispersing agent 1.

Compound A: 1-dodecanol

Compound B: ε-caprolactone

Compound C: zirconia catalyst

Compound D: Toluene diisocyanate (TDI)

Compound E: Diethanolamine

Grade 3 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 atmosphere.

(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 reactant obtained in (Step 1-2) was cooled to room temperature to obtain a waxy polyester compound 1.

(Step 1-4) Compound D (83.46 parts by mass) was placed in a reaction vessel under nitrogen atmosphere and heated to 50-60 ° C

(Step 1-5) 800 parts by mass of the polyester compound 1 obtained in (Step 1-3) is melted at 50 ° C, and is heated in the compound D heated at 50 to 60 ° C in (Step 1-4) Add for 2 hours.

(Step 1-6) The mixed liquid obtained in (Step 1-5) was reacted at 60 ° C for 1 hour with stirring.

(Step 1-7) The reactant obtained in (Step 1-6) was cooled to 20 ° C, and Compound E (50.37 parts by mass) was added and reacted at 35 ° C until the residual isocyanate disappeared to obtain Polyester Compound 2.

(Step 1-8) Compound D (26.68 parts by mass) was placed in a reaction vessel under a nitrogen atmosphere, followed by a solvent of propylene glycol methyl ether acetate 131 parts by mass, and a tertiary amine compound 1 (17.12 mass) (Part 1), 57.68 parts by mass of the above polyester compound 2 obtained in (Step 1-7), and heated to 70 ° C with stirring.

(Step 1-9): Further, a polyether compound 1 (17.00 parts by mass) was further added to the mixed liquid obtained in (Step 1-8), and the reaction was carried out at 70 ° C for 2 hours until the residual isocyanate disappeared, thereby obtaining a GPC-based analysis. A polyurethane compound 1 having a weight average molecular weight (Mw) of 22,000 and a number average molecular weight (Mn) of 8,800 was shown.

<Dispersant 2>

The polyurethane compound 2 obtained through the following (Step 2-1) to (Step 2-13) was used as the dispersing agent 2.

Compound D: Toluene diisocyanate (TDI)

Compound E: Diethanolamine

Compound F: dimethylaminopropylamine

Compound G: 2-hydroxyethyl acrylate

Compound H: 2,6-di-t-butyl-4-cresol

Polyether compound 1: poly(propylene glycol) monobutyl ether (Mn=1100)

Polyester Compound 1: Obtained from the above (Step 1-3).

Polyester Compound 2: obtained by 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 completion of the Michael addition reaction. Grade 3 amino compound 2.

(Step 2-2) Compound D (25.0 parts by mass) was charged in a stirred reaction vessel heated to 50 °C.

(Step 2-3) Polyether compound 1 (125.0 parts by mass, relative to TDI of about 0.8 mole equivalent) was dropped and filled into a funnel, maintained at a temperature between 50 and 60 ° C, and dropped to the above stirring reaction for 4 hours. In the container.

(Step 2-4) The reactant obtained in (Step 2-3) was kept at 70 ° C for 60 minutes.

(Step 2-5) The completion of the reaction was determined by titration of residual isocyanate, and the reaction mixture was cooled to 20 °C.

(Step 2-6) In the reaction mixture obtained in (Step 2-5), Compound E (24.14 parts by mass, about 1.6 mole equivalents relative to TDI) is added and kept at room temperature until analyzed by infrared spectrometry. The determined isocyanate residue 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 by a silica gel chromatography column.

(Step 2-8) The column to be eluted (Step 2-7) is washed three times with diethyl ether, and the liquid separation is carried out, and then the solvent is removed in a vacuum to obtain 90 parts by mass of the polyether compound 2 Solid product.

The diadduct of diethanolamine and TDI is removed in the above (steps 2-7) and (steps 2-8).

(Step 2-9) Compound D (26.68 parts by mass) was placed in a reactor under a nitrogen atmosphere.

(Step 2-10) In the 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 the tertiary amino compound 2 (28.30 parts by mass).

(Step 2-11) The mixture obtained in (Step 2-10) was 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 kept at 70 ° C for 2 hours.

(Step 2-13): It was confirmed that the reaction mixture obtained in (Step 2-12) had no residual isocyanate, 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 was obtained. Formate compound 2.

<Dispersant 3>

The polyurethane compound 3 obtained through the following (step 3-1) was used as the dispersing agent 3.

Compound I: benzyl chloride

(Step 3-1) Compound I (2.35 parts by mass, equivalent to the reactant) is added to 200 parts by mass of the reaction liquid 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 The amount of the molar number was stirred at 70 ° C for 20 hours, whereby a polyurethane compound 3 in which one of the tertiary amines in the polyurethane compound 1 was 4-staged was obtained.

<Dispersant 4>

The polyurethane compound 4 obtained through the following (Step 4-1) was used as the dispersing agent 4.

Compound E: Diethanolamine

(Step 4-1) In the above (Step 1-8), except for the substitution of the tertiary amine compound 1 (17.12 parts by mass, 0.12 moles), the same molar number of the compound E (diethanolamine, 12.62 parts by mass, Other than 0.12 moles, the same procedure as in (Step 1-1) to (Step 1-9) was carried out to obtain a polyurethane compound 4.

<Dispersant 5>

The polyurethane compound 5 obtained through the following (step 5-1) was used as the dispersing agent 5.

Compound J: 1,6-hexanediol

(Step 5-1) In the above (Step 1-8), except for the substitution of the tertiary amine compound 1 (17.12 parts by mass, 0.12 moles), the same molar number of the compound J (14.18 parts by mass, 0.12 moles) was added. Except for the other steps (Step 1-1) to (Step 1-9), the polyurethane compound 5 was obtained.

<Dispersant 6>

The polyurethane compound 6 obtained through the following (Step 6-1) was used as the dispersing agent 6.

Compound K: Trimethylolpropane

(Step 6-1) In addition to the above (Step 1-8), Compound D is increased to 28.04 parts by mass, and Compound K (0.52 parts by mass, 0.004 moles) is added, in the above (Step 1-9), The polyether compound 1 was increased to 21.26 parts by mass, and the same procedure as in (Step 1-1) to (Step 1-9) was carried out to obtain a weight average molecular weight (Mw) of 23,000 and a number average molecular weight (Mn). It is a polyurethane compound 6 of 9,200.

The constituent elements of the dispersing agents 1 to 6 are shown in Table 1.

<Carbon black ink 1>

The pigment, the dispersant, the dispersing aid, and the solvent were formulated according to the following composition, and the carbon black ink 1 was prepared in the following manner.

First, the solid content of the pigment, the dispersant, and the dispersing aid is formulated in the following manner.

‧Pigment SB350 (carbon black manufactured by DEGUSSA): 100 parts by mass

‧ Dispersant Dispersant 1: 20 parts by mass (solid content conversion)

‧ Dispersing aid (pigment derivative) S12000 (manufactured by Lubrizol, phthalocyanine pigment derivative having an acidic group): 2 parts by mass

‧Solvent Propylene glycol monomethyl ether acetate: 226.6 parts by mass

The above components were thoroughly stirred and mixed.

Then, dispersion treatment was carried out for 6 hours in a range of 25 to 45 ° C by a paint conditioner to obtain a dispersion. As the beads, zirconia beads having a diameter of 0.5 mm were used, and 60 parts by mass of the dispersion and 180 parts by mass of the beads were added. After the completion of the dispersion, the beads were separated from the dispersion by a filter to prepare a carbon black ink 1 having a solid content of 35% by mass.

<Modulation of carbon black ink 2~14>

The dispersant and the pigment of the carbon black ink 1 were changed to the dispersant and the pigment described in Table 2, and the mixture was stirred and mixed in the same manner as the carbon black ink 1, and dispersed by a paint conditioner to prepare a solid portion 35. Mass% of carbon black ink 2~14.

The details of the ingredients 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: a dispersant made by BYK Chemie Co., Ltd. having a high molecular weight dispersant having a structure in which a polyurethane skeleton formed of a toluene diisocyanate polymer is linked by a backbone linking group. Has a basic functional group.

‧Disperbyk-167: a dispersant made by BYK Chemie Co., Ltd., having a medium-low molecular weight dispersant having a structure in which a polyurethane skeleton formed of a toluene diisocyanate polymer is linked by a backbone linking group. Has a basic functional group.

‧Ajisper PB-821: Ajinomoto Fine, a dispersant made by Techno, with Alkaline graft polymer of polyethyleneimine or polyethylene/polyamine backbone.

‧Flowlen KDG-2400: a dispersant made by Kyoritsu Chemical Co., Ltd., a polyacrylic graft polymer having a basic functional group.

‧ HIPLAAD ED-701: a dispersant made by Nanben Chemical Co., Ltd., an alkaline graft polymer with a polyethyleneimine or a polyethylene/polyamine backbone.

‧Disperbyk-2000: a dispersant made by BYK Chemie, a grade 4 amine ammonium salt modified acrylic block copolymer.

‧Disperbyk-2001: Dispersant made 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 therein. In a flask of a thermometer, a stirrer, and a cooling tube, the reaction was carried out at 90 ° C under stirring until the acid value became 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution (1).

25 parts by mass of the above 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 mixture was slowly heated to 105 ° C under stirring to carry out a reaction.

After the resin solution became transparent, it was diluted with methoxybutyl butyl acrylate and adjusted so that the solid content was 50% by mass to obtain an acid value of 115 mg KOH/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)>

The epoxy compound (epoxy equivalent 264), acrylic acid, butyl methoxyacetate, triphenylphosphine, and p-methoxyphenol are reacted in the same manner as in the production of the alkali-soluble resin (1) to obtain a ring. Oxy acrylate solution (2).

25 parts by mass of the above 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 mixture was slowly heated to 105 ° C under stirring to carry out a reaction.

After the resin solution was made transparent, it was diluted with butyl methoxyacetate, and the solid content was adjusted to 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) 10000 alkali-soluble resin (2).

<Alkali-soluble resin (3): epoxy (meth) acrylate resin (D1-1)>

300 parts by mass of "XD1000" (polyepoxypropyl ether of dicyclopentadiene phenol polymer, epoxy equivalent 252), 104 parts by mass of methacrylic acid, p-methoxyphenol, manufactured by Nippon Kayaku Co., Ltd. 0.2 parts by mass, 5 parts by mass of triphenylphosphine, and 255 parts by mass of propylene glycol monomethyl ether acetate were placed in a reaction vessel and stirred at 100 ° C until the acid value became 3.0 mg-KOH/g. Then add 145 parts by mass of tetrahydrophthalic anhydride to 120 ° C After reacting for 4 hours, 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 was obtained.

<Photopolymerization initiator (1)> (dione)

Ethyl oxazole (5 g, 25.61 mmol) and o-naphthoquinone chloride (5.13 g, 26.89 mmol) were dissolved in 30 ml of dichloromethane, cooled to 2 ° C with ice-water bath and stirred, and AlCl ₃ (3.41 g, 25.61) was added. Mm). After stirring at room temperature for 3 hours, crotonic acyl chloride (2.81g, 26.89mmol) in 15ml of methylene chloride in the reaction solution was added AlCl ₃ (4.1g, 30.73mmol), stirred for 1 hour 30 minutes. The reaction solution was placed in 200 ml of ice water, and dichloromethane (200 ml) was added and the organic layer was separated. The organic layer which was collected was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a white solid (10 g).

(肟体)

A diketone (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 to 30 ml of isopropyl alcohol and refluxed for 3 hours. After the completion of the reaction, the reaction mixture was concentrated, and ethyl acetate (30 ml) was added, and the mixture was washed with 30 ml of saturated aqueous sodium hydrogen carbonate and 30 ml of saturated aqueous sodium chloride, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure toield. This was purified by column chromatography to give 2.22 g of a pale yellow solid.

(肟 ester)

The oxime (2.22 g, 4.77 mmol) and acetonitrile (1.34 g, 17.0 mmol) were added to dichloromethane (20 ml) and ice-cooled, and triethylamine (1.77 g, 17.5 mmol) was dropped and reacted for 1 hour. After confirming the disappearance of the starting material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of a saturated aqueous sodium hydrogen carbonate solution, and then washed twice with 5 ml of saturated brine, 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 give 0.79 g of a pale yellow solid. 1). The chemical shift of ¹ H-NMR of the photopolymerization initiator (1) is shown below.

¹ H-NMR (CDCl ₃ ): σ 1.17 (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))

Each of the components described in Table 3 was prepared by using the previously prepared carbon black ink 1 in the proportions shown in Table 3, and the mixture was stirred and dissolved by a stirrer to prepare a resist 1 having a solid content concentration of 15% by mass.

The details of the ingredients in Table 3 are as follows.

‧PM21: Phosphate containing methacryl oxime (KAYAMER (registered trademark) PM21, made by Nippon Kayaku Co., Ltd., dense adhesion promoter).

‧SH6040: Epoxy decane coupling agent (made by Toray Co., Ltd., SH6040, dense adhesion promoter)

‧F-559: Surfactant (made by Dainippon Ink Chemical Industry Co., Ltd., F559)

<Examples 2 to 7, Comparative Examples 1 to 9> (Preparation of resist 2 to 16 (photosensitive resin composition 2 to 16))

Using the carbon black inks shown in Tables 4, 5, and 6, the types of the respective components of the resist 1 were changed to the components described in Tables 4, 5, and 6, and the ratios shown in Table 3 were used. In the same manner as in the resist 1, the mixture was stirred and dissolved by a stirrer, and the resists 2 to 16 having a solid content concentration of 15% by mass were prepared. The total solid concentration of the IRG 907 and the DETX-S of the resist 15 is 4:1 in the same manner as the solid content concentration of the photopolymerization initiator (1) in the resist 1. The ratio is mixed.

The details of the components in Tables 5 and 6 are as follows.

‧IRG907: IRGACURE907, manufactured by Chiba Speciality Chemicals, 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-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 contained 1.6% by mass.

‧Photopolymerization initiator (2): OXE02, manufactured by BASF Corporation. It has the following chemical structure.

(evaluation of ink) (1) Viscosity evaluation of carbon black ink

The viscosity of the prepared carbon black inks 1 to 14 was measured by a viscometer (RE105L, manufactured by Toki Sangyo Co., Ltd.). The viscosity of any carbon black ink is in the range of 10-20 mPa ‧ s. The viscosity of the ink immediately after preparation of the carbon black ink (just after dispersion) and after standing at room temperature for one week was determined by the following criteria. The results are shown in Table 7.

◎: After the ink was dispersed, it was almost tack-free even after being left at room temperature for one week.

○: After the ink was dispersed, it was thickened at room temperature for one week, but it was stable within 20 mPa·s.

△: After the ink was dispersed, it was allowed to stand at room temperature for 1 week to continue to increase in viscosity, exceeding 20 mPa·s.

×: The viscosity was greatly increased immediately after the ink was dispersed, and exceeded 20 mPa·s within 3 days.

(evaluation of resist) (1) Viscosity evaluation of resist (photosensitive resin composition)

The viscosity of the prepared resists 1 to 15 was measured by a viscosity meter (manufactured by Toki Sangyo Co., Ltd., RE105L). The viscosity of any resist is in the range of 2 to 5 mPa ‧ s. The viscosity of the resist immediately after the resist was prepared and allowed to stand 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, it was almost tack-free even after being left at room temperature for one month.

○: After the resist was prepared, it was thickened at room temperature for one month, but the degree of viscosity was within 0.5 mPa·s.

△: After the resist was prepared, it was allowed to stick at room temperature for 1 month, and the viscosity increased to more than 0.5 mPa·s.

X: After the resist was prepared, it was thickened at room temperature for one week, and the viscosity increased to more than 0.5 mPa·s.

The viscosity of the resist is significantly different from that of the ink due to the large influence on the coating. The above-mentioned strict benchmark implementation evaluation.

(2) Production of black matrix (BM)

The prepared resists 1 to 16 were applied onto a glass substrate by a spin coater, dried under reduced pressure, and dried at 100 ° C for 150 seconds on a hot plate. Next, the obtained dried coating film was subjected to pattern exposure by an exposure mask having an opening portion having a pattern width of 6 μm and 5 μm by a high-pressure mercury lamp at 30 mJ, and then prepared at room temperature (23 ° C) using ultrapure water. The KOH aqueous solution of 0.04% by mass was spray-developed as an alkali developing solution, and the unexposed portion was removed, and then spray-washed with ultrapure water. Subsequently, post-baking was performed in a furnace at 230 ° C for 30 minutes to prepare 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-difference measuring apparatus Alpha-Step-500 (KLA-Tencor Co., Ltd.), and the OD value was measured by a penetration concentration measuring apparatus GretagMacbeth D200-II (manufactured by GretagMacbeth Co., Ltd.). Thereby, the OD value (unit OD value) per 1 μm was obtained. The results of the evaluation of the resist viscosity were ◎ and the unit OD values of both were 4.2/μm.

(4) 6 μm thin line evaluation (after development)

Using a plurality of exposure masks having openings of 6 μm (openings of 6 μm in width), the development time was set to the following conditions, and coating, exposure, and development were carried out in the same process as in (2) to prepare BM thin wires. Hereinafter, the BM thin line produced by using the exposure mask having an opening of 6 μm is simply referred to as “6 μm thin line”.

If the alkali development time is too short, there is a dissolution residue of the alkali-soluble resin. In the case where the pigment remains and the substrate contamination is obvious, on the other hand, if it is too long, the BM fine line is gradually etched by the alkali developing solution and peeled off. In addition, the shortest dissolution time (the shortest time for patterning on the substrate can be confirmed) indicates the ease of alkali development of the photosensitive resin composition.

When the BM thin line evaluation is performed, not only the shortest dissolution time but also the case where the BM line width at the time of development is several times (for example, 1.5 times, twice, etc.) of the shortest dissolution time is evaluated, but with respect to the shortest dissolution time The multiple is increased, the line width is gradually tapered, or the alkali developing solution penetrates to the portion where the substrate and the BM fine line are adhered to each other, and the depressed portion appears and is easily peeled off. Further, as the multiple becomes smaller, the residue tends to remain.

In general, when patterning is confirmed, the BM line width tends to become thick due to the influence of the 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 appropriate point. Moreover, the shortest dissolution time differs depending on the composition of the photosensitive resin composition, but the same development degree is obtained when the value of the multiple of the shortest dissolution time is the same.

The shortest dissolution time of the resist (photosensitive resin composition) 1 to 16 was 40 to 60 seconds, respectively, and several samples were prepared according to the development time between 1.5 and 60 seconds of the individual 1.5 times, and the following evaluations were performed.

(4-1) Evaluation of 6μm thin line

The sample prepared in the above (4) was measured for line width at three places by an optical microscope. Then find the average value. The results are shown in Table 7.

(4-2) Linearity evaluation of 6μm thin line

The fine thread is unevenly etched by the alkali developer, or the subsequent washing of the shower, Therefore, there is a case where the linearity deteriorates. The linearity of the 6 μm thin line was observed at three places on the substrate by observation under an optical microscope, and classified in the following manner. The results are shown in Table 7.

◎: The linearity of all 6 μm thin wires is very good.

○: The portion which was initially etched by the alkali developing solution was observed, but the linearity deterioration was not remarkable.

△: The linearity is deteriorated as a whole, and some defects and the like are also observed.

×: The overall linearity is very poor and there are many defects.

(4-3) Pattern embedding of 6μm thin lines

This cross section in which one of the prepared 6 μm thin wires was cut out at 3 o'clock was observed by SEM photograph. From the cross-sectional observation, it was observed whether or not the adhesive surface of the substrate and the 6 μm fine line pattern was etched by the alkali developing solution, and was trapped, and evaluated according to the following classification. The results are shown in Table 7.

(interpolation evaluation)

A: No damage was observed at the 3 points observed.

B: The mixture has a point which is completely untrapped and is good, and a point where no adhesion is observed but the adhesion surface is observed to be etched.

C: At the 3 points observed, it was observed that the adhesive surface began to be etched although there was no insertion.

D: The point where the mixture was not entangled but the viscous surface began to be etched and the point where the entanglement was apparent was observed.

E: Insertion was clearly observed at the 3 points observed.

F: There are points where the insertion is clearly seen and the point of large insertion.

G: A large intrusion occurred at the 3 points observed.

(5) 6 μm thin line evaluation (after heat treatment)

The BM thin wire subjected to the development treatment is further coated with a photosensitive resin composition of red, green, and blue, and then heat-treated at a high temperature to be cured. Therefore, the 6 μm thin wire was heat-treated at 230 ° C for 30 minutes. In the heat treatment, the flow of the photosensitive resin composition which is not sufficiently cured, or the detachment of the residual solvent, etc., may cause thermal deformation of the fine lines and thickening of the line width.

The line width of the 6 μm fine line after the heat treatment was measured at three places. Then find the average value. Further, from the difference between the line width after development and the line width after heat treatment, the line width was increased and the following evaluation criteria were set. The results are shown in Table 7.

(line width evaluation (average value))

○: Within the range of 5.6 to 6.5 μm.

×: Outside the range of 5.6 to 6.5 μm.

(Increase line width evaluation)

A: All three points observed were 0.1 μm or less.

B: The three points observed were mixed in an amount of 0.1 μm or less, and more than 0.1 μm and 0.3 μm or less.

C: All three points observed exceeded 0.1 μm and 0.3 μm or less.

D: The three points observed were mixed in excess of 0.1 μm and 0.3 μm or less, and more than 0.3 μm and 0.4 μm or less.

E: All three points observed exceeded 0.3 μm and 0.4 μm or less.

F: The three points observed were mixed in excess of 0.3 μm and 0.4 μm or less, and more than 0.4 μm.

G: All three points observed exceeded 0.4 μm.

In addition, the 6 μm thin wire after heat treatment was evaluated for line width and increase. A part of the line width sample was cut out at 3 points and subjected to SEM observation. The profile of the thin line is trapezoidal. The bottom angle of both ends of the lower bottom corresponding to the contact surface of the thin line and the substrate is 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: All three points observed are 73 degrees or more.

B: A point where the mixture has a point of 73 degrees or more and a degree of 63 degrees or more and less than 73 degrees.

C: All three points observed were 63 degrees or more and less than 73 degrees.

D: A point where 63 degrees or more and less than 73 degrees are mixed, and a point of 59 degrees or more and less than 63 degrees is mixed.

E: All three points observed were 59 degrees or more and less than 63 degrees.

F: The mixture has a point of 59 degrees or more and less than 63 degrees, and a point of less than 59 degrees.

G: All three points observed were less than 59 degrees.

As shown in Table 7, the 6 μm thin wires after development of Examples 1 to 7 were all very linear, and were completely free of traps. On the other hand, in the 6 μm thin wires after the development of Comparative Examples 1 to 9, the linearity was deteriorated, and the pinching was observed in the joint portion with the substrate.

Further, in the 6 μm thin wires after the heat treatment of Examples 1 to 7, the line width was maintained in the range of 5.6 μm to 6.5 μm, and the 6 μm thin wires were favorably formed. The line width is suppressed to 0.3 μm or less, and the taper angle is also 63 degrees or more, so that it is a good thin line.

On the other hand, Comparative Examples 1 to 9 were all 6 μm thin wires after heat treatment, and had a line width of more than 0.3 μm, a taper angle of less than 63 degrees, a line width of more than 6.5 μm, and a 6 μm thin wire of 5.6 to 6.5 μm could not be formed. In particular, Comparative Example 9 using an initiator other than the oxime ester photopolymerization initiator was deteriorated after development and after heat treatment.

(6) 5 μm thin line evaluation (after development and after heat treatment)

Further, the BM thin line (5 μm thin line) produced by using the exposure mask having an opening of 5 μm was also evaluated in 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 the range of 4.6 to 5.5 μm.

×: outside the range of 4.6 to 5.5 μm.

As shown in Table 8, containing dispersant 1, and oxime ester photopolymerization initiator The 5 μm thin wire after development of Example 1 of the photosensitive resin composition is more susceptible to alkali developing solution or heat treatment because it is thinner than the 6 μm thin wire, and the linear deterioration is somewhat observed, or the line width is slightly thicker. 0.1 μm, the taper angle was slightly reduced by 5 degrees, but a fine line of 5 μm of 4.6 to 5.5 μm was well formed.

Further, 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, whereby the affinity between the lyophilic medium adsorbed to the dispersant of the pigment and the alkali-soluble resin is effectively When it is compatible, as a result, in the same manner as in the case of a 6 μm thin wire, a 5 μm thin wire having good linearity and good trapping can be formed.

The polyurethane dispersant used in the resist of the present embodiment, because of the combination with the alkali-soluble resin, allows the dissolving agent of the dispersing agent to be well compatible with the alkali-soluble resin to form a good steric barrier. Both viscosity and OD are good and dispersion is also good.

Further, in the examples, an oxime ester photopolymerization initiator having an ultraviolet absorbing portion, an energy transmitting portion, and a radical generating portion in one molecule is used, whereby even in the vicinity of the dense surface of the substrate which is difficult to reach by ultraviolet rays, An alkali-soluble resin or the like can be efficiently polymerized. Therefore, it is considered that the entanglement of the solvent-soluble portion of the alkali-soluble resin and the polyurethane dispersant becomes stronger, and when the curing by ultraviolet irradiation is performed, the aggregation of the pigment is also suppressed, and the dispersion state can be maintained. The alkali-resistant developability and heat resistance derived from the pigment are uniformly expressed in the fine line, and the linearity is good, and the trapping and the etching by the alkali developing solution are less.

Further, it is considered that all of the adsorbing groups of the dispersing agents used in Examples 1, 2, and 3 are suspended, so that the adsorption force with the pigment is increased and the amount of free dispersion is reduced. Therefore, it is considered that the free dispersing agent acts as a lubricant during the heat treatment, and it is possible to prevent the taper angle from decreasing and the line width from increasing.

On the other hand, it is considered that the photosensitive resin composition of Comparative Example 9 is used together with an IRG907 initiator which mainly has a radical generating moiety, and a DETXS initiator which mainly has an ultraviolet absorbing site to generate a radical, but two kinds are used. The photopolymerization initiator has a poor radical generation efficiency, and it is difficult to carry out polymerization in a portion where ultraviolet rays are hard to reach, such as in the vicinity of the dense surface of the substrate, and thermal deformation occurs during heat treatment.

Further, Comparative Examples 1 and 5 using a dispersing agent 5 having no adsorbing group, and Comparative Examples 4, 5 and 6 using a dispersing agent which is a graft polymer other than the polyurethane skeleton, were used between the pigments and the pigments. The adsorption force is weak, and the dispersibility of the pigment in the resist is insufficient.

Therefore, it is considered that when the color filter is produced, the bond between the pigment and the dispersant is weakened during the heat treatment, and aggregation of the pigment occurs, and the alkali-resistant developability and heat resistance from the pigment are not sufficiently expressed, and thermal deformation occurs.

Further, Comparative Examples 2 and 3 using a commercially available dispersant having a urethane bond are a skeleton which is connected by a plurality of polymers of toluene diisocyanate having three or more isocyanates, The dispersing agent composed of a plurality of hydrophilic solvents or adsorbing groups reduces the coating effect on the pigment, and also causes steric hindrance to the adsorbing group, so that the adsorption performance to the pigment is low. Further, it is considered that the amount of the hydrophilic solvent group or the amount of the adsorbing group is smaller than that of the polyurethane dispersing agent used in the examples, and the compatibility between the solvent-soluble medium and the alkali-soluble resin is insufficient, and pigment aggregation occurs, and the pigment is derived from the pigment. The alkali-resistant developability and heat resistance cannot be sufficiently expressed.

Further, in Comparative Examples 7 and 8 in which an acrylic AB block type dispersant was used, since the adsorption group was concentrated on one of the dispersing agents, the pigment adsorbing groups were sterically hindered from each other and could not be sufficiently adsorbed to the pigment to cause a free dispersing amount. increase. Therefore, it can be considered that the substrate and the substrate are not sufficiently obtained to be densely adhered via the dispersant. Force, alkali development resistance is lowered and it is difficult to obtain patterning.

The present invention has been described in detail with reference to the specific embodiments thereof. In addition, the present application is hereby incorporated by reference in its entirety in its entirety in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire content

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‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Claims (17)

A photosensitive resin composition containing a color material (a), a dispersing agent (b), a photopolymerization initiator (c), an alkali-soluble resin (d), and a solvent (e), wherein the dispersing agent (b) A polyurethane dispersant (b-1) having an affinic solvent group and an adsorbing group; the polyurethane dispersant (b-1) containing a partial structure represented by the following formula (i) The photopolymerization initiator (c) contains an oxime ester photopolymerization initiator (c-1); [In the formula (i), R ^a represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an extended aryl group having 6 to 20 carbon atoms, or a carbon bonded to the above-mentioned extended aryl group. The number of 7 to 20; * indicates the bond base]. The photosensitive resin composition of the first aspect of the invention, wherein the polyurethane dispersant (b-1) contains a structure containing a hydrophilic solvent group containing the lyophilic solvent, and contains the adsorption The base-containing adsorption moiety structure; the affinity-containing moiety structure and the adsorption group-containing moiety structure are linked by a partial structure represented by the above formula (i). The photosensitive resin composition according to claim 1 or 2, wherein the polyurethane dispersant (b-1) has a main chain, and the main chain contains the formula (i) Partial construction. The photosensitive resin composition according to any one of claims 1 to 3, wherein the hydrophilic solvent group contains at least one of a polyether chain and a polyester chain. The photosensitive resin composition according to any one of claims 1 to 4, wherein the adsorption group is selected from the group consisting of a tertiary amino group, a 4- toly ammonium group, and a nitrogen atom-containing heterocyclic group. At least one of them. The photosensitive resin composition according to any one of claims 2 to 5, wherein the adsorption group-containing partial structure has a partial structure represented by the following formula (1); [In the 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 extended arylalkyl group or an extended aryl group which may have a substituent; * indicates a bond base]. The photosensitive resin composition according to any one of the items (2) to (2-3), wherein the adsorption group-containing partial structure has at least one of the following formulas (2-1) to (2-3). Partial construction [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; and R ^γ , R ^{δ ,} and R ^ε each independently represent an alkylene group which may have a substituent, a aryl group having a substituent or a group in which the above alkyl group is bonded to the above aryl group; wherein, R ^γ is an alkyl group which may have a substituent, or the above alkyl group and the above-mentioned aryl group When the base is bonded, at least a part of the methylene group constituting the alkylene group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, and a quinone bond. Substituting at least one bond in the group of ethyl thiocarbamate, thioether bond and thioester bond; further, R ^γ may also be adjacent to each other via -NH-(C=O)- group At least one of the N atoms is bonded together by a urea bond, or a guanamine bond is carried out via a carbonyl group; * represents a bond group; [In the formula (2-2), R ^α and R ^β each independently represent an alkyl group or an aryl group which may have a substituent; and R ^γ and R ^η each independently represent an alkylene group which may have a substituent, or may have a aryl group of a substituent or a group in which the above alkyl group is bonded to the above aryl group; wherein, R ^γ and R ^η are each independently an alkyl group which may have a substituent, or the above alkyl group and the above When the aryl group is bonded to the group, at least a part of the methylene group constituting the alkylene group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, and a ruthenium bond. Substituting at least one bond in the group of an amine bond, an ethyl thioglycolate bond, a thioether bond, and a thioester bond; further, R ^γ and R ^η may also be via a -NH-(C=O)- group. And carrying out a urea bond together with at least one of the adjacent N atoms, or a guanamine bond via a carbonyl group; * is represented as a bond 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; and R ^γ′ and R ^δ each independently represent an alkylene group which may have a substituent, and may also a aryl group having a substituent or a group in which the above alkyl group is bonded to the above aryl group; wherein, R ^{γ '} is an alkyl group which may have a substituent, or an alkylene group and the above aryl group When the group is bonded, at least a part of the methylene group constituting the alkylene group may also be selected from the group consisting of an ester bond, an ether bond, a urethane bond, a urea bond, a guanamine bond, an oxime bond, Substituting at least one bond in the group of ethyl thiocarbamate, thioether bond and thioester bond; further, R ^{γ '} may also be adjacent to each other via -NH-(C=O)- group The N atoms are bonded together by a urea bond, or a guanamine bond is carried out via a carbonyl group; R ^{ε '} represents a direct bond, an alkyl group which may have a substituent, an extended aryl group which may have a substituent, or the above extension a group in which an alkyl group is bonded to the above-mentioned extended aryl group; R ^ζ represents a hydrogen atom, an alkyl group which may also have a substituent or an aryl group which may 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 amino group or a nitrogen atom-containing heterocyclic group; * represents a bonding group]. The photosensitive resin composition according to any one of claims 1 to 7, wherein the oxime ester photopolymerization initiator (c-1) has an oxazolyl group which may be substituted. The photosensitive resin composition of any one of Claims 1 to 8, wherein the alkali-soluble resin (d) contains an alkali-soluble resin (d-1) having at least one of a carboxyl group and an ethylenically unsaturated group. ). The photosensitive resin composition of claim 9, wherein the alkali-soluble resin (d-1) is an epoxy (meth) acrylate resin. The photosensitive resin composition of claim 10, wherein the epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin (D1-1) and an epoxy group (hereinafter). At least one of a methyl acrylate resin (D1-2); (1) an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is added thereto An epoxy group, an epoxy (meth) acrylate resin (D1-1) obtained by reacting at least one of a polybasic acid and an anhydride thereof, and (2) an α,β-unsaturated monocarboxylic acid or An epoxy (meth) acrylate resin obtained by adding an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polyol with at least one of a polybasic acid and an anhydride thereof (D1-2). The photosensitive resin composition according to any one of claims 1 to 11, wherein the color material (a) has an average primary particle diameter of 20 to 100 nm. The photosensitive resin composition according to any one of claims 1 to 12, wherein the color material (a) contains carbon black. The photosensitive resin composition of claim 13, wherein the carbon black is contained in an amount of 40% by mass or more based on the total solid content. A cured product obtained by hardening a photosensitive resin composition according to any one of claims 1 to 14. A black matrix containing a cured product of claim 15 of the patent application. An image display device having a black matrix of claim 16 of the patent application.