TWI577756B - Color material dispersion liquid, color resin composition for color filters, color filter, and display device - Google Patents

Description

Color material dispersion, colored resin composition for color filter, color filter, and display device

The present invention relates to a color material dispersion liquid, a coloring resin composition for a color filter, a color filter, and a display device.

A thin image display device typified by a display or the like, which is a so-called flat panel display, is characterized in that it is thinner than a cathode ray tube type display and does not occupy a space in the depth direction, and has been widely marketed. Its market price is steadily increasing year by year with the evolution of production technology, and the demand is expanding, and the production volume is increasing year by year. In particular, color LCD TVs have become the mainstream of TV. In addition, an organic light-emitting display device such as an organic EL display having high visibility from self-luminous light has recently attracted attention as a next-generation image display device. In view of the performance of these image display devices, it is strongly desired to further improve image quality or power consumption, such as improvement in contrast or color reproducibility.

Color filters are used in such liquid crystal display devices or organic light emitting display devices. For example, in the case of a color liquid crystal display, a backlight is used as a light source, and the amount of light is controlled by electrically driving the liquid crystal, and the light passes through the color filter, thereby performing color expression. Therefore, color filters are indispensable for the color performance of LCD TVs and are responsible for the important role of left and right display performance. Further, in the organic light-emitting display device, a color filter is used to adjust the color of the pixel, or a color filter is used for the white light-emitting organic light-emitting device, and a color image is formed in the same manner as the liquid crystal display device.

In recent years, there has been a demand for power saving of video display devices, and in order to improve the utilization efficiency of backlights, high brightness of color filters is particularly required. Especially in mobile displays (mobile phones, smart phones, tablet PCs) has become a big issue.

Although the battery capacity has increased due to technological evolution, the mobile power storage capacity is still limited. On the other hand, there is a tendency for power consumption to increase as the screen size increases. Since it is directly related to the usable time or charging frequency of the mobile terminal, the image display device including the color filter will design the left or right mobile terminal or the performance.

Here, the color filter generally has a transparent substrate, a coloring layer formed on the transparent substrate and including a color pattern of three primary colors of red, green, and blue, and a light shielding portion formed on the transparent substrate to divide each coloring pattern.

In the method of forming such a coloring layer, a pigment dispersion method using a pigment excellent in heat resistance or light resistance as a color material is widely used. However, the use of color filters of conventional pigments has made it difficult to achieve the current higher brightness requirements.

As a means for achieving high luminance, a photosensitive resin composition for a color filter using a dye has been examined. Compared with pigments, dyes generally have a high transmittance, and can produce high-intensity color filters, but have poor heat resistance or light resistance, and chromaticity is easy to change when heated at high temperatures in the color filter manufacturing step. problem. Further, the photosensitive resin composition using a dye has a problem that foreign matter is easily precipitated in the drying step. When the foreign matter is deposited on the coating film, the contrast is remarkably deteriorated, and it is difficult to use it as a colored layer.

Patent Document 1 discloses a specific colored photosensitive resin composition containing a color material containing a specific dye and a pigment, and a specific solvent. According to Patent Document 1, it is possible to obtain high heat resistance and low coating unevenness by the colored photosensitive resin composition. Coating film.

Further, Patent Document 2 discloses a specific blue photosensitive resin composition containing an organic solvent-soluble dye having a specific structure and an organic pigment as a color material. According to Patent Document 2, a high-intensity color filter can be obtained by using the colored photosensitive resin composition.

The specific dyes described in Patent Documents 1 and 2 are used by being dissolved in a solvent, and have poor heat resistance and light resistance, and are deteriorated in stability by containing a polar solvent for dissolving the dye.

Patent Document 3 discloses a colored resin composition for a color filter, which contains a specific color material, and the color material contains a divalent or higher cation which crosslinks a plurality of dye skeletons by a crosslinking group, and a divalent or higher valence Anion. It is revealed that the coloring layer formed of the colored resin composition for a color filter containing the above color material has high contrast, and is excellent in solvent resistance and electrical reliability.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2010-211198

Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-32999

Patent Document 3: International Publication No. 2012/144521

The colored resin composition containing a specific color material described in Patent Document 3 has a problem that it is difficult to ensure viscosity stability. Further, further heat resistance of the colored layer is also required to be improved.

The present invention has been made in view of the above-described actual circumstances, and an object thereof is to provide a color material dispersion liquid which is excellent in stability over time and which can form a coating film having improved heat resistance; has excellent stability over time and can be improved in heat resistance. A colored resin composition for a color filter of a colored layer; a high-intensity color filter using the colored resin composition; and a display device having the color filter.

The color material dispersion liquid of the present invention contains a color material, a dispersant, an organic acid compound, and a solvent represented by the following general formula (I); wherein the dispersant has at least the following general formula (II) The constituent unit (a) shown is a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less; and the solvent of the above-mentioned solvent system at a temperature of 23 ° C of 0.1 (g/10 ml solvent) or less The above-mentioned amine valence of the dispersant is A (mg KOH / g), and the mass of the organic acid compound X _A (mol) contained in the above-mentioned color material dispersion is made up of the above-mentioned color material dispersion. When the ratio of the mass of the constituent unit (a) of the above dispersing agent (X) X _B (mol) is X (=X _A /X _B ), the following formulas (1) and (2) are satisfied; When the range is less than 1, the following formula (3) is further satisfied; X≦1.5 formula (1)

A×X≧40 type (2)

A×(1-X)≦42 (3)

[Chemical 1]

(In the general formula (I), the carbon atom directly bonded to the A system and N is an a-valent organic group having no π bond, and the organic group means a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain; B ^c- represents a c-valent polyacid anion containing at least tungsten; and R ⁱ to R ^v each independently represent a hydrogen atom And an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may also bond to form a ring structure; Ar ¹ represents a divalent aromatic group which may also have a substituent. Family basis; R ⁱ ~ R ^v and Ar ^{1 of the} plural number may be the same or different; a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, when e is 0 The bond does not exist; the plural e can be the same or different);

(In general formula (II), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, and R ² is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH (R ⁶ )-O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group, R ³ And R ⁴ each independently represents a chain or cyclic hydrocarbon group which may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure. R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group; x represents 1 An integer of ~18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.)

In the color material dispersion liquid of the present invention, it is preferred that the organic acid compound is selected from the group consisting of the following general formula (IV) and the following general formula (V) from the viewpoint of dispersion stability. More than one type.

(In the formulae (IV) and (V), R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group. , -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e , or -OR ^a" , a monovalent group, R Any one of ^a and R ^a' contains a carbon atom; R ^a" is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )- CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group; R ^b is an alkyl group having 1 to 18 carbon atoms, carbon number 2~ 18 alkenyl, aralkyl, aryl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e or -OR ^a monovalent group represented by ^b' ; R ^b' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group; R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO, -CO-CH=CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ^f is a monovalent group, R ^f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R ^a , R ^{a '} and R ^b are an alkyl group or an alkene The group, the aralkyl group and the aryl group may each have a substituent; s represents an integer from 1 to 18, t represents an integer from 1 to 5, and u represents an integer from 1 to 18).

In the color material dispersion liquid of the present invention, it is preferred that the color material has excellent dispersion stability, and further suppresses generation of image residue when the colored resin composition is formed, and has high development adhesiveness and superior solvent resolubility. The acid value of the dispersing agent is 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature of the dispersing agent is 30 °C or higher.

The color material dispersion of the present invention preferably further comprises a second selected from the viewpoint of being adjustable to a desired color tone. Color material and One or more types of color materials are used.

The color material dispersion liquid of the present invention is preferably the above from the viewpoint of heat resistance. Color material is Metallic lake color material.

The colored resin composition for a color filter of the present invention contains the above-described color material dispersion liquid, alkali-soluble resin, polyfunctional monomer, and initiator.

In the colored resin composition for a color filter of the present invention, the acid value of the alkali-soluble resin is preferably 80 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of improving the heat resistance of the colored layer.

In the colored resin composition for a color filter of the present invention, it is preferred that the polyfunctional monomer has a carboxyl group from the viewpoint of excellent alkali developability and heat resistance of the obtained colored layer.

A colored resin composition for a color filter of the present invention, which is composed of a counter substrate From the viewpoint of excellent adhesion and excellent development resistance, it is preferred that the alkali-soluble resin is a resin having an ethylenic double bond.

In the colored resin composition for a color filter of the present invention, the alkali-soluble resin is preferably a resin having a hydrocarbon ring from the viewpoint of dispersion stability and heat resistance.

In the colored resin composition for a color filter of the present invention, it is preferred to improve the solvent resistance by improving the curability of the colored layer, to improve water bleeding, and to increase the residual film ratio of the colored layer. The hydrocarbon ring of the above alkali-soluble resin is selected from the group consisting of cyclopentyl, cyclohexyl, Basis One or more groups of the group consisting of a substituent represented by the following formula (A), a dicyclopentyl group, a dicyclopentenyl group, an adamantyl group, and the following formula (A).

In the colored resin composition for a color filter of the present invention, it is preferred to improve the solvent resistance by improving the curability of the colored layer, to improve water bleeding, and to increase the residual film ratio of the colored layer. The above alkali-soluble resin is a compound represented by the following general formula (B).

(In the above general formula (B), X represents a group represented by the following general formula (D), and Y each independently represents a residue of a polyvalent carboxylic acid or an anhydride thereof, and R ⁱ represents a general formula (C) below. The base of the graph, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer of 1 or more.)

(In the above general formula (C), R ⁱⁱ is a hydrogen atom or a methyl group, and R ⁱⁱⁱ each independently represents a hydrogen atom or a methyl group.)

(In the above general formula (D), R ^iv each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and R ^v represents -O- or -OCH ₂ CH ₂ O-. )

In the colored resin composition for a color filter of the present invention, the initiator is preferably an oxime ester photopolymerization initiator from the viewpoint of suppressing water permeation, solvent resistance, and sensitivity.

In the colored resin composition for a color filter of the present invention, it is preferable that the content ratio of the decane coupling agent is relative to the coloring resin from the viewpoint that the coloring resin composition has excellent stability with respect to the adhesion of the substrate. The total solid content in the substance is 1% by mass or less.

The color filter of the present invention has at least a transparent substrate and is disposed on The coloring layer on the transparent substrate is characterized in that at least one layer of the colored layer has a coloring layer formed by curing the coloring resin composition of the color filter of the present invention.

The display device of the present invention is characterized by having the above-described color filter of the present invention.

According to the present invention, it is possible to provide a color material dispersion liquid which is excellent in stability over time and which can form a coating film having improved heat resistance; a coloring resin for a color filter which is excellent in stability over time and can form a coloring layer having improved heat resistance a composition; a high-intensity color filter using the colored resin composition; and a display device having the color filter.

1‧‧‧Transparent substrate

2‧‧‧Lighting Department

3‧‧‧Colored layer

10‧‧‧Color filters

20‧‧‧ opposite substrate

30‧‧‧Liquid layer

40‧‧‧Liquid crystal display device

50‧‧‧Organic protective layer

60‧‧‧Organic oxide film

71‧‧‧Transparent anode

72‧‧‧ hole injection layer

73‧‧‧ hole transport layer

74‧‧‧Lighting layer

75‧‧‧Electronic injection layer

76‧‧‧ cathode

80‧‧‧Organic emitters

100‧‧‧Organic light-emitting display device

Cations above 201‧‧‧2

Anions above 202‧‧‧2

203‧‧‧ ion bond

210‧‧‧Molecular association

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

Fig. 2 is a schematic cross-sectional view showing an example of a display device of the present invention.

Fig. 3 is a schematic cross-sectional view showing another example of the display device of the present invention.

Fig. 4 is a schematic view showing a state of molecular association of the color material represented by the general formula (I).

Fig. 5 is a plan view showing the relationship between A and X of the color material dispersion liquids of Examples 1 to 22 and Comparative Examples 1 to 16.

Hereinafter, the color material dispersion liquid, the coloring resin composition for color filters, the color filter, and the display device of the present invention will be described in order.

Still, in the present invention, the light includes electromagnetic waves of wavelengths of visible and non-visible regions, and further includes radiation, and the radiation system includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam.

In the present invention, (meth)acrylic acid means each acrylic acid and methacrylic acid; and the (meth)acrylic acid ester means each acrylate and methacrylate.

The term "organic group" as used in the present invention means a group having one or more carbon atoms.

Moreover, the solid content in the present invention means all components other than the solvent constituting the coloring resin composition, and even a liquid monomer is considered to be included in the solid content.

1. Color material dispersion

The color material dispersion liquid of the present invention contains a color material, a dispersant, an organic acid compound, and a solvent represented by the following general formula (I); wherein the dispersant has at least the following general formula (II) The constituent unit (a) shown is a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less; and the solvent of the above-mentioned solvent system at a temperature of 23 ° C of 0.1 (g/10 ml solvent) or less The above-mentioned amine valence of the dispersant is A (mg KOH / g), and the mass of the organic acid compound X _A (mol) contained in the above-mentioned color material dispersion is made up of the above-mentioned color material dispersion. When the ratio of the mass of the constituent unit (a) of the above dispersing agent (X) X _B (mol) is X (=X _A /X _B ), the following formulas (1) and (2) are satisfied; When the range is less than 1, the following formula (3) is further satisfied; X≦1.5 formula (1)

A×X≧40 type (2)

A×(1-X)≦42 (3)

[化8]

(In the general formula (I), the carbon atom directly bonded to the A system and N is an a-valent organic group having no π bond, and the organic group means a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain; B ^c- represents a c-valent polyacid anion containing at least tungsten; and R ⁱ to R ^v each independently represent a hydrogen atom And an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may also bond to form a ring structure; Ar ¹ represents a divalent aromatic group which may also have a substituent. Family basis; R ⁱ ~ R ^v and Ar ^{1 of the} plural number may be the same or different; a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, when e is 0 The bond does not exist; the plural e can be the same or different;)

(In general formula (II), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, and R ² is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH (R ⁶ )-O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group, R ³ And R ⁴ each independently represents a chain or cyclic hydrocarbon group which may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure. R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group; x represents 1 An integer of ~18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.)

Since the color material dispersion liquid of the present invention has the specific color material, the specific dispersant, the organic acid compound, and the specific solvent, the color material dispersion liquid is excellent in stability over time, and a coating film having improved heat resistance can be obtained.

The effect of the above-described effects can be exerted by the specific combination described above, and there are still unexplained parts, but the following can be inferred.

As shown in FIG. 4, the color material represented by the general formula (I) contains a divalent or higher anion 202 and a divalent or higher cation 201. Therefore, in the aggregate of the color material, the anion and the cation are not simply One molecule is ion-bonded to one molecule, and it is estimated that a molecular association body 210 in which a plurality of molecules are associated is formed via the ionic bond 203. Therefore, the apparent molecular weight of the color material represented by the general formula (I) is particularly increased as compared with the molecular weight of the conventional lake color material. The formation of the molecular association body is used to determine that the cohesive force in the solid state is further improved and the thermal motion is lowered, and the dissociation of the ion pair or the separation of the cation portion and the improvement of the heat resistance can be suppressed.

In the color material dispersion liquid of the present invention, the color material represented by the general formula (I) is an organic acid compound and a constituent unit (a) having an amine group in a side chain as a dispersing agent in a specific solvent. The block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less is dispersed. In the dispersant, the amine group of the constituent unit (a) has an affinity for the color material represented by the general formula (I), so that it can be adsorbed to the color material represented by the above general formula (I), and the estimation can be made. The color material is dispersed in a state of molecular association. By using a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less, for color The ratio of the affinity portion of the material to the affinity portion for the solvent is appropriate and the dispersibility is excellent. Further, by using the block copolymer which is present in the affinity portion of the color material as described above, it can be efficiently adsorbed to the color material having the molecular association state, and the dispersion stability is excellent.

When the amine group of the dispersant further forms a salt with the organic acid compound, it is estimated that the affinity for the specific color material can be further improved. Therefore, it is estimated that when the amine group formed by the salt is adsorbed to the color material represented by the above general formula (I), the molecular association state of the color material is stabilized, and the dispersion stability is improved. As a result, the change in viscosity with time is suppressed. Further, since the molecular association state of the color material is stabilized, even in the obtained coloring layer, the molecular association state is maintained, and the heat resistance is superior, and high luminance can be maintained even after the heating step.

As a result of intensive studies, the inventors of the present invention have obtained the following findings: the above-mentioned amine valence of the dispersing agent is A (mg KOH / g), and the organic acid compound contained in the color material dispersion is contained. When the ratio of the amount X _A (mol) to the mass of the constituent unit (a) X _B (mol) constituting the dispersing agent contained in the color material dispersion is X (=X _A /X _B ), When the dispersant is selected in such a manner that the relationship of A×X≧40 is satisfied, and the organic acid compound is present, the affinity for the color material becomes a value suitable for dispersion, so that the dispersion stability is particularly improved, and the viscosity over time is suppressed. Variety.

Further, it has been found that when X is less than 1, the dispersant is selected in such a manner that the relationship of A × (1-X) ≦ 42 is satisfied, and the organic acid compound is blended to form an amine which is not subjected to salt formation. Since the amount of the base is reduced, in the dispersion step, the molecular association state of the color material can be stably maintained, and a coating film having particularly excellent heat resistance can be formed.

In addition, it is presumed that the constituent units of the dispersant (a) are mostly not in the shape of a salt. In the case where the dispersion step is carried out, when the color material represented by the general formula (I) which forms the above-mentioned molecular association state is dispersed, the amine group of the dispersant and the general formula (I) are dispersed during the dispersion step and the firing process. The cations in the color material shown are subjected to salt exchange, and a part of the molecular association state of the color material is partially destroyed, and as a result, heat resistance is deteriorated.

Further, when X is more than 1, that is, when the organic acid compound is present in excess of the constituent unit (a), since the equilibrium is more toward the salt formation direction, the amine group which is not subjected to salt formation is further reduced, and the molecule of the color material is further reduced. The state of association is difficult to destroy. Therefore, even in the obtained coloring layer, since the molecular association state is maintained, it is excellent in heat resistance.

When X is 1.5 or less, that is, the organic acid compound is 1.5 mole equivalent or less with respect to the constituent unit (a) of the dispersant, the organic acid compound which is not formed by salt formation contributes to the molecular association state. Since it is stabilized, the dispersion stability is excellent, and since the proportion thereof is small, the organic acid compound does not precipitate. Further, it is estimated that one organic acid compound is formed into a salt with respect to one amine group of the dispersing agent, and the relationship between A and X is the same regardless of the valence of the organic acid compound.

As described above, the color material dispersion liquid of the present invention selectively uses the above-mentioned specific dispersant and organic acid compound because it satisfies the relationship of A×X≧40 and the relationship of A×(1-X)≦42. The color material dispersion has excellent stability over time, and a coating film having improved heat resistance can be obtained.

The color material dispersion liquid of the present invention contains at least the color material, the organic acid compound, and the solvent represented by the general formula (I), and is added before the effect of the present invention is not impaired, and may further contain other components as necessary.

Hereinafter, each component of the color material dispersion of the present invention will be described in detail in order.

[Color material shown in general formula (I)]

The color material dispersion liquid of the present invention contains the color material represented by the following general formula (I).

(In the general formula (I), the carbon atom directly bonded to the A system and N is an a-valent organic group having no π bond, and the organic group means a fat having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. a hydrocarbon group or an aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain; B ^c- represents a c-valent polyacid anion containing at least tungsten; and R ⁱ to R ^v each independently represent a hydrogen atom And an alkyl group which may have a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may also bond to form a ring structure; Ar ¹ represents a divalent aromatic group which may also have a substituent. Family basis; R ⁱ ~ R ^v and Ar ^{1 of the} plural number may be the same or different; a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, when e is 0 The bond does not exist; the complex e can be the same or different.)

The coloring material represented by the general formula (I) is not particularly limited, and may be appropriately selected from the compounds represented by the general formula (I) described in the specification of International Publication No. 2012/144520, and may be used alone or in combination 2 More than one kind.

Further, the color material represented by the general formula (I) may be included in the color lake material described later, but is taken up before the color material shown in the general formula (I), and in the present invention, it is regarded as For compliance The color material shown by the general formula (I).

The method for producing the color material represented by the general formula (I) is not particularly limited. It can be obtained, for example, by the production method described in the specification of International Publication No. 2012/144520.

<Other color materials>

The color material dispersion liquid of the present invention may further contain other color materials for the purpose of color tone control within a range that does not impair the effects of the present invention. As the other coloring material, a known pigment and a dye can be used, and one type or two or more types can be used.

From the viewpoint of obtaining a desired color tone, the preferred system further comprises a second selected from the group consisting of Color material, and One or more types of color materials are used as other color materials. As the better second Specific examples of the pigment include Pigment Violet 23 and the like. Also, as a better Specific examples of the coloring material include acid red 51, 52, 87, 92, 94, 289, 388; CI acid violet 9, 30, 102; sulfonic acid rose red G, sulfonic acid rose red B, sulfonic acid rose red 101, sulfonic acid rose 640, etc.; Japanese Patent Laid-Open No. 2010-32999, Japanese Patent Laid-Open No. 2010-211198, Japanese Patent No. 4492760, and the like. Dyes, etc.; furthermore, may be described later It is a color lake material. In the present invention, it is preferably used from the viewpoint of having both brightness and heat resistance. It is a color lake material.

In the present invention, the term "color-separating color material" means a color material which is soluble in a solvent and which is formed by salt formation and insolubilization. The lake color material can be usually obtained by mixing a color material described later with a coloring agent described later in a solvent. As the color material which is soluble in the solvent, it is preferable to use a dye having a high transmittance from the viewpoint of increasing the luminance of the color filter. The dye may be appropriately selected depending on the desired color tone, and may be an azo dye, an anthraquinone dye, or a triarylmethane dye. A dye having any one of a basic skeleton (chromophoric moiety) such as a dye, a cyanine dye, or an anthraquinone dye. Further, the dye may be a dye classified into any one of an acid dye having an anionic substituent or a basic dye having a cationic substituent.

Examples of the acid dye include CI Acid Violet 29, 31, 33, 34, 36, 36:1, 39, 41, 42, 43, 47, 51, 63, 76, 103, 118, 126, CI Acid Blue 2 , 8, 14, 25, 27, 35, 37, 40, 41, 41:1, 41:2, 43,45,46,47,49,50,51,51,53,54,55,56,57 , 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 78, 79, 80, 81, 96, 111, 124, 127, 127: 1, 129, 137, 138, 143, 145 , 150, 175, 176, 183, 198, 203, 204, 205, 208, 215, 220, 221, 225, 226, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257 , 258, 260, 261, 264, 266, 270, 271, 272, 273, 274, 277, 277: 1, 278, 280, 281, 282, 286, 287, 288, 289, 290, 291, 292, 293 , 294, 295, 298, 301, 302, 304, 305, 306, 307, 313, 316, 318, 322, 324, 327, 331, 333, 336, 339, 340, 343, 344, 350, CI Acid Green 10, 17, 25, 25: 1, 27, 36, 37, 38, 40, 41, 42, 44, 54, 59, 69, 71, 81, 84, 95, 101, 110, 117, etc. Acid dye; C I Acid Violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72, CI Acid Blue 1, 3, 5, 7, 9, 19, 22, 83, 90, 93, 100, 103,104,109, CI acid green 3,5,6,7,8,9,11,13,14,15,16,18,22,50, 50:1 triarylmethane acid dye; CI Acid red 50, 51, 52, 87, 92, 94, 289, 388, CI acid violet 9, 30, 102, sulfonic acid rose red G, sulfonic acid rose red B, sulfonic acid rose red 101, sulfonic acid rose red 640 Wait for It is an acid dye or the like. Among the acid dyes, preferred are rose red acid dyes such as CI Acid Red 50, CI Acid Red 52, CI Acid Red 289, CI Acid Violet 9, CI Acid Violet 30, and CI Acid Blue 19.

Moreover, as a commercially available basic dye, for example, CI basic violet 1, 3, 14, CI alkali low blue 1, 5, 7, 8, 11, 26, CI basic green 1, 4, etc. Methane-based basic dye; CI basic yellow 13, CI basic red 14 and other cyanine-based basic dyes; CI basic red 29 and other azo-based basic dyes; CI alkaline purple 11 etc. It is a basic dye or the like. These dyes may be used alone or in combination of two or more.

In the present invention, in view of easily obtaining a desired color tone as a colored layer, it is preferred to use one selected from the above. Acid dye and above One or more dyes which are basic dyes.

In the lake coloring material, the ion system varies depending on the type of the dye, the counter ion of the acid dye is a cation, and the counter ion of the basic dye is an anion. Therefore, the above-mentioned laking agent is appropriately selected and used in combination with the above dye. That is, in the case where the above acid dye is insolubilized, a compound which produces a cation of the dye is used as a lake forming agent; and in the case where the above basic dye is insolubilized, a compound which produces an anion of the dye is used. As a lake former.

Examples of the counter cation of the acid dye include a metal cation or an inorganic polymer in addition to the ammonium cation.

As a coloring agent which produces an ammonium cation, a 1st grade amine compound, a 2nd grade amine compound, a tertiary amine compound, etc. are mentioned, for example, and it is preferable to use 2 from a viewpoint of the outstanding heat resistance and light resistance. Amine compound or a tertiary amine compound.

Further, as the coloring agent for producing metal cations, it may be appropriately selected from metal salts having a desired metal ion.

The cation of the acid dye may be used singly or in combination of two or more.

On the other hand, examples of the inorganic anion include an anion of an oxo acid (phosphoric acid ion, sulfate ion, chromic acid ion, tungstic acid ion (WO ₄ ^2- ), molybdate ion (MoO ₄ ^2- ), etc.), or An inorganic anion or the like of a polyacid anion or the like obtained by condensing a plurality of oxyacids.

The lake color material in the present invention is preferably a lake coloring material containing a basic dye and an inorganic anion, more preferably a lake comprising a basic dye and a polyacid anion, from the viewpoint of heat resistance and light resistance. Color material.

In the present invention, a preferred combination Dye-based metal lake color material as other color materials, among which, preferred It is a metal lake color material of acid dye.

As the color lake material The acid dye is preferably a compound represented by the following general formula (VI) and having a rosin-based acid dye.

(In the general formula (VI), R ¹⁰ to R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and R ¹⁰ and R ¹² , R ¹¹ and R ¹³ may be bonded to each other to form a ring structure. ¹⁴ represents an acidic group, and X represents a halogen atom. m represents an integer of 0 to 5. The general formula (VI) has one or more acidic groups, and n is an integer of 0 or more.

The alkyl group in R ¹⁰ to R ¹³ is not particularly limited. For example, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent may, for example, be a linear or branched alkyl group having a carbon number of 1 to 8, preferably a carbon number. A linear or branched alkyl group of 1 to 5. The substituent which the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, and a hydroxyl group. The substituted alkyl group may, for example, be a benzyl group or the like, or may have a halogen atom or an acidic group. Substituent.

The aryl group in R ¹⁰ to R ¹³ is not particularly limited. For example, an aryl group having a carbon number of 6 to 20 and having a substituent may be mentioned, and among them, a phenyl group, a naphthyl group or the like is preferable. Examples of the heteroaryl group in R ¹⁰ to R ¹³ include a heteroaryl group having 5 to 20 carbon atoms which may have a substituent, and preferably a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom.

The aryl group or the heteroaryl group may have a substituent, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an acidic group, a hydroxyl group, an alkoxy group, an aminomethyl group, and a carboxylate group.

Further, R ¹⁰ to R ¹³ may be the same or different.

Specific examples of the acidic group or a salt thereof include a carboxyl group (-COOH), a carboxyl group (-COO ^- ), a carboxylate group (-COOM, wherein M represents a metal atom), and a sulfonate group (-SO ₃ ^-). a sulfonic acid group (-SO ₃ H), a sulfonate group (-SO ₃ M, wherein M represents a metal atom), and the like; wherein, preferably, a sulfonate group (-SO ₃ ^- ), a sulfonic acid group At least one of (-SO ₃ H) or a sulfonate group (-SO ₃ M). Further, examples of the metal atom M include a sodium atom and a potassium atom.

From the viewpoint of increasing the luminance, the compound represented by the general formula (VI) is preferably acid red 50, acid red 52, acid red 289, acid violet 9, acid violet 30, acid blue 19 or the like.

Further, from the viewpoint of heat resistance, in the general formula (VI), a compound having a betaine structure of m = 1 and n = 0 is preferred.

Above A metal lake coloring material which is an acid dye, which uses a metal atom as a lake former. The heat resistance of the color material is made high by using a metal atom-containing coloring agent. As such a lake-forming agent, a lake-forming agent containing a metal atom of a metal cation of two or more valences is preferable.

In the case where the other color materials are used in combination with the above-mentioned lake color materials, the blending ratio of the color materials may be appropriately adjusted in such a manner as to obtain a desired color tone. From the viewpoint of superior heat resistance and light resistance, the above-mentioned lake color material is preferably 30 to 100 parts by mass, more preferably 100 parts by mass based on the total amount of the color materials incorporating the lake color material and the other color materials. Preferably, it is 60 to 99 parts by mass, and more preferably 70 to 98 parts by mass.

[Dispersant]

In the color material dispersion liquid of the present invention, a block copolymer having at least the structural unit (a) represented by the following general formula (II) and having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less is used as a dispersing agent.

(In general formula (II), R ¹ is a hydrogen atom or a methyl group, Q is a divalent linking group, R ² is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ ) -O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - the divalent organic group, R ³ and R ⁴ respectively Independently, a chain or cyclic hydrocarbon group which may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure, and R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.

x represents an integer from 1 to 18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18. )

The amine group of the constituent unit (a) represented by the above general formula (II) is The color material shown in the above general formula (I) has an affinity, and by adsorbing the color material, the color material can be dispersed in a molecular association state. In addition, the structural unit (a) represented by the general formula (II) in the present invention is considered to be included in the above general formula (II) even when it is formed into a salt with an organic acid compound to be described later in the dispersion liquid. The constituent units shown.

Examples of the divalent linking group Q of the above general formula (II) include an alkylene group having 1 to 10 carbon atoms, an extended aryl group, a -CONH- group, a -COO- group, and an ether group having 1 to 10 carbon atoms ( -R'-OR"-: R' and R" are each independently an alkylene group) and combinations thereof. Among them, Q is preferably -COO- from the viewpoint of heat resistance of the obtained polymer or solubility in the use of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, or a relatively inexpensive material. base.

The above-mentioned divalent organic group R ² of the general formula (II) is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH(R ⁶ )-O] _x -CH(R ⁵ )-CH ( R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y . The above alkyl group having 1 to 8 carbon atoms may be any of linear or branched, such as methylene, ethyl, trimethylene, propyl, various butyl, and various pentyl groups. , a variety of extensions, a variety of extensions and so on.

R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group.

As the above R ² , from the viewpoint of dispersibility, an alkylene group having 1 to 8 carbon atoms is preferable, and among them, R ^{2 is more} preferably a methylene group, an ethyl group, a propyl group or a butyl group. More preferably, it is a methylene group and an ethyl group.

Examples of the cyclic structure in which R ³ and R ^{4 in the} above general formula (II) are bonded to each other include a nitrogen-containing heterocyclic monocyclic ring having 5 to 7 membered rings or a condensed ring in which these two are condensed. The nitrogen-containing hetero ring is preferably one which does not have aromaticity, more preferably a saturated ring.

Examples of the structural unit (a) represented by the above general formula (II) include (meth)acryloxypropyldimethylamine and (meth)acryloxyethyl dimethylamine ( A The constituent unit derived from acryloxypropyldiethylamine, (meth)acryloxyethyldiethylamine or the like is not limited thereto.

In the above dispersing agent, the constituent unit (a) represented by the general formula (II) is preferably a block portion containing three or more kinds of coloring material affinity. The block portion of the color material affinity preferably contains the constituent unit represented by the above general formula (II) from the viewpoints of excellent dispersibility and dispersion stability, suppression of viscosity change over time, and excellent heat resistance. 3~50, more preferably 6~40, and even better 10~30.

The constituent unit (a) represented by the general formula (II) may be one type or two or more constituent units.

<Other constituent units>

The block copolymer is preferably a color material affinity block portion (hereinafter sometimes referred to as an A block) having a constituent unit represented by the above general formula (II) from the viewpoint of dispersibility, and A solvent affinity block portion (hereinafter sometimes referred to as a B block) having a constituent unit (a) represented by the above general formula (II) and having a constituent unit copolymerizable with the above general formula (II). In the present invention, the arrangement of the respective blocks of the block copolymer is not particularly limited, and examples thereof include an AB block copolymer, an ABA block copolymer, and a BAB block copolymer. Among them, from the viewpoint of superior dispersibility, an AB block copolymer or an ABA block copolymer is preferred.

As a constituent unit which can be copolymerized with the above general formula (II), it is preferred from the viewpoint of improving the dispersibility and dispersion stability of the color material represented by the general formula (I) and also improving heat resistance. The constituent unit shown by the following general formula (III).

[Chemistry 13]

(In the general formula (III), R ⁷ represents a hydrogen atom or a methyl group; A represents a direct bond or a divalent linking group; and R ⁸ is an alkyl group having 1 to 18 carbon atoms; an alkylene group having 2 to 18 carbon atoms; An aralkyl group, an aryl group, a monovalent group represented by -[CH(R ⁹ )-CH(R ¹⁰ )-O] _x -R ¹¹ - or -[(CH ₂ ) _y -O] _z -R ¹¹ ; R ⁹ and R ¹⁰ are each independently a hydrogen atom or a methyl group, and R ¹¹ is a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, - a monovalent group represented by CH ₂ CHO or -CH ₂ COOR ¹² , and R ¹² is a linear, branched or cyclic alkyl group having a hydrogen atom or a carbon number of 1 to 5. x represents 1 to 18 The integer, y represents an integer from 1 to 5, z represents an integer from 1 to 18. m represents an integer from 3 to 200, and n represents an integer from 10 to 200.)

The divalent linking group A of the above general formula (III) can be the same as the Q in the above general formula (II), and the heat resistance of the obtained polymer or the use of propylene glycol monomethyl ether as a solvent can be suitably used. From the viewpoint of the solubility of acetate (PGMEA) or a relatively inexpensive material, A is preferably a -COO- group.

In R ⁸ , the alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Isobutyl, t-butyl, tert-butyl, various pentyl, various hexyl groups, various octyl groups, various fluorenyl groups, various dodecyl groups, various tetradecyl groups, various hexadecanyl groups, various octadecyl groups, rings Pentyl, cyclohexyl, cyclooctyl, cyclododeyl, Basis A group, a dicyclopentyl group, an adamantyl group, a lower alkyl group substituted adamantyl group or the like.

The alkenyl group having 2 to 18 carbon atoms may be any of a linear chain, a branched chain, and a cyclic chain. Examples of such an alkenyl group include a vinyl group, an allyl group, a propenyl group, and various butenyl groups. Various hexenyl groups, various octenyl groups, various decenensyl groups, various dodecenyl groups, various tetradecenyl groups, various hexadecenyl groups, various octadecyl groups, cyclopentenyl groups, cyclohexenyl groups, rings Octenyl and the like.

Among them, R ^{8 is} preferably a methyl group, various butyl groups, various hexyl groups, benzyl groups, cyclohexyl groups, or hydroxyethyl groups from the viewpoint of dispersibility and substrate adhesion.

Examples of the aryl group which may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The carbon number of the aryl group is preferably from 6 to 24, more preferably from 6 to 12.

Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The carbon number of the aralkyl group is preferably from 7 to 20, more preferably from 7 to 14.

Examples of the substituent of the aromatic ring such as an aryl group or an aralkyl group include an alkyl group, a nitro group, and a halogen atom, in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.

Further, the above R ¹¹ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms which may have a substituent, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO, or - A monovalent group represented by CH ₂ COOR ¹² , and R ¹² is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms.

The monovalent group represented by the above R ¹¹ may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.

The alkyl group having 1 to 18 carbon atoms and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms in the above R ¹¹ are as shown in the above R ⁸ .

In the above R ⁸ , x, y and z are the same as R ² in the above general formula (II).

In the present invention, the glass transition temperature (Tg) of the solvent affinity block portion of the block copolymer may be appropriately selected. From the viewpoint of heat resistance, the glass transition temperature (Tg) of the solvent affinity block portion is preferably 80 ° C or higher, more preferably Above 100 °C.

The glass transition temperature (Tg) of the solvent affinity block portion in the present invention can be calculated by the following formula, and the glass transition temperature of the color material affinity block portion and the block copolymer can also be calculated in the same manner.

1/Tg=Σ(Xi/Tgi)

Here, the solvent affinity block portion is a copolymerization of n monomer components from i=1 to n. Xi is the weight fraction of the i-th monomer (ΣXi=1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. Among them, the sum from i=1 to n is taken. Further, the value of the homopolymer glass transition temperature (Tgi) of each monomer can be a value of Polymer Handbook (3rd Edition) (J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).

The number of constituent units constituting the solvent affinity block portion may be appropriately adjusted depending on the range in which the amine value of the dispersant is 70 mgKOH/g or more and 160 mgKOH/g or less. In particular, the number of constituent units constituting the solvent affinity block portion is preferably from 10 to 200, more preferably 10, from the viewpoint that the solvent affinity portion and the color material affinity portion effectively act to enhance the dispersibility of the color material. ~100, more preferably 10~70.

The solvent affinity block portion may be selected so as to function as a solvent affinity portion, and the repeating unit constituting the solvent affinity block portion may be one type or two or more types of repeat units.

In the block copolymer of the dispersant of the present invention, the ratio of the unit number m of the constituent unit represented by the general formula (II) to the unit number n of the solvent affinity block portion is preferably m/n. In the range of 0.01 to 1, it is preferably in the range of 0.05 to 0.7 from the viewpoint of dispersibility and dispersion stability of the color material.

In the present invention, the dispersant is selected to have an amine price of 70 mgKOH/g. Above and 160mgKOH / g or less. When the amine value is within the above range, the viscosity stability or heat resistance is excellent, and alkali developability or solvent resolubility is also excellent. In the present invention, the amine valence of the dispersing agent is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more, from the viewpoint of dispersibility and dispersion stability. On the other hand, from the viewpoint of solvent resolubility, the amine value of the dispersing agent is preferably 120 mgKOH/g or less, more preferably 105 mgKOH/g or less.

The amine value is the number of mg of potassium hydroxide equivalent to the perchloric acid required for neutralizing the amine component contained in 1 g of the sample, and can be measured by a method defined in JIS-K7237. In the amine group formed by salting with the organic acid compound in the dispersing agent, the organic acid compound is usually dissociated, and the amine valence of the block copolymer itself as a dispersing agent can be measured.

The acid value of the dispersing agent used in the present invention is preferably 1 mgKOH/g or more from the viewpoint of the effect of suppressing the development residue. Among them, the acid value of the dispersing agent is more preferably 2 mgKOH/g or more from the viewpoint of further suppressing the effect of the development residue. Moreover, the acid value of the dispersing agent used in the present invention is preferably 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesiveness or deterioration of solvent resolubility. In particular, the acid value of the dispersing agent is preferably 16 mgKOH/g or less, and more preferably 14 mgKOH/g or less from the viewpoint of good development adhesiveness and dissolution resolubility.

Further, in the present invention, the glass transition temperature of the dispersant is preferably 30 ° C or higher from the viewpoint of improving the development adhesiveness. If the glass transition temperature of the dispersant is low, it is particularly close to the developer temperature (usually about 23 ° C), and the development adhesiveness is lowered. For this reason, it can be inferred that if the glass transition temperature is close to the developer temperature, the movement of the dispersant during development becomes large, and as a result, the development adhesiveness is deteriorated. By the glass transition temperature of 30 ° C or more, the molecular motion of the dispersant during development can be suppressed, so the suppression can be suppressed. The development of the adhesive density is reduced.

The glass transition temperature of the dispersant is preferably 32 ° C or higher, more preferably 35 ° C or higher, from the viewpoint of developing adhesion. On the other hand, from the viewpoint of ease of handling when used in a fine scale or the like, it is preferably 200 ° C or lower.

The glass transition temperature of the dispersant of the present invention can be determined by measuring by differential scanning calorimetry (DSC) according to JIS K7121.

Further, in the present invention, the dispersing agent is excellent in the viewpoint of excellent dispersion stability of the color material, suppression of development residue when the colored resin composition is formed, superior solvent resolubility, and high development-adhesiveness. The price is preferably 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature is 30 °C or more.

When the concentration of the color material is increased and the content of the dispersant is increased, the amount of the binder is relatively reduced, so that the colored resin layer is easily peeled off from the base substrate during development. When the dispersant contains a B block containing a constituent unit derived from a carboxyl group-containing monomer and has the above specific acid value and glass transition temperature, the development adhesiveness is improved. However, when the acid value is too high, it is presumed that although the developability is excellent, the polarity is too high and peeling easily occurs during development.

As the carboxyl group-containing monomer, a monomer which can be copolymerized with a monomer having a structural unit represented by the general formula (II) and contains an unsaturated double bond and a carboxyl group can be used. Examples of such a monomer include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and the like. Cinnamic acid, acrylic acid dimer, and the like. Further, an addition reactant of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. , ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Further, an acid anhydride group-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, by copolymerization or cost, solubility, glass transfer From the viewpoint of temperature and the like, (meth)acrylic acid is particularly preferred.

In the block copolymer, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is appropriately set so that the acid value of the block copolymer is within the specific acid value range, and is not particularly limited. The total mass of the total constituent units of the segment copolymer is preferably from 0.05 to 4.5% by mass, more preferably from 0.07 to 3.7% by mass.

When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is at least the above lower limit value, the effect of suppressing the development residue can be exhibited, and if it is at most the above upper limit value, deterioration of development adhesiveness or solvent redissolution can be prevented. Sexual deterioration.

In addition, the constituent unit derived from the carboxyl group-containing monomer may be one or more kinds of constituent units, and may be contained in two or more constituent units.

Moreover, the glass transition temperature of the dispersing agent used in the present invention is set to a specific value or more, and the value of the glass transition temperature (Tgi) of the monomer homopolymer is 10 ° C or more from the viewpoint of improving the developing adhesiveness. The amount of the monomer is preferably 75% by mass or more, and more preferably 85% by mass or more based on the total amount of the B block.

In the block copolymer, the ratio m/n of the unit number m of the constituent units of the A block and the unit number n of the constituent units of the B block is preferably in the range of 0.05 to 1.5. From the viewpoint of dispersibility and dispersion stability of the material, it is more preferably in the range of 0.1 to 1.0.

The weight average molecular weight Mw of the above-mentioned block copolymer is not particularly limited, and is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from the viewpoint of good dispersibility and dispersion stability of the color material. 3000~12000.

Here, the weight average molecular weight (Mw) is determined by gel permeation chromatography (GPC) in the form of a standard polystyrene equivalent.

The method for producing the above block copolymer is not particularly limited. By A block copolymer is produced by a known method, and among them, it is preferably produced by a living polymerization method. The reason for this is that it is difficult to cause chain movement or deactivation, and a copolymer having a uniform molecular weight can be produced, which can improve dispersibility and the like. Examples of the living polymerization method include a living anionic polymerization method such as a living radical polymerization method and a base transfer polymerization method, and a living cationic polymerization method. The monomers are sequentially polymerized by these methods, whereby a copolymer can be produced. For example, the block A is first produced, and the constituent unit constituting the B block is polymerized to the A block, whereby a block copolymer can be produced. Further, in the above production method, the polymerization order of the A block and the B block may be reversed. Further, the A block and the B block may be separately produced, and then the A block and the B block may be coupled.

In the color material dispersion liquid of the present invention, at least one of the polymer having the constituent unit represented by the above general formula (II) is used as a dispersing agent, and the content thereof depends on the type of the color material to be used, and further, a color filter to be described later. The concentration of the solid content in the photosensitive colored resin composition is appropriately selected.

The content of the dispersant is preferably from 3 to 45 parts by mass, more preferably from 5 to 35 parts by mass, based on 100 parts by mass of the total solid content in the color material dispersion liquid, from the viewpoint of dispersibility and dispersion stability. Proportion of proportions.

In particular, when a coating film or a colored layer having a high color material concentration is formed, the content of the dispersing agent is preferably from 3 to 25 parts by mass, more preferably, based on 100 parts by mass of the total solid content in the color material dispersion. 5 to 20 parts by mass ratio.

Further, in the present invention, the solid portion is all other than the above solvent, and includes a monomer dissolved in a solvent or the like.

[Organic acid compound]

The color material dispersion of the present invention contains an organic acid compound. Organic acidification in the present invention The compound may be a salt which can form a salt with the amine group which is used as the above-mentioned block copolymer as a dispersing agent, and can be suitably used. In the present invention, by using the organic acid compound, the dispersibility and dispersion stability of the color material are excellent, and a coating film having excellent heat resistance can be obtained, and the salt forming portion has high affinity for the alkali aqueous solution during alkali development. Therefore, it can be used as an alkali developability.

When the organic acid compound forms a salt with the amine group of the structural unit (a) represented by the above general formula (II), it has a structure represented by the general formula (II').

(In the general formula (II'), A ^- is an anion derived from an organic acid compound, and the other symbols are the same as the above general formula (II).)

In the present invention, the organic acid compound is not particularly limited as long as it is a compound having one or more carbon atoms and an acidic group. The acidic group of the organic acid compound may, for example, be a carboxyl group, a sulfonic acid group or a phosphoric acid group. From the viewpoints of dispersibility, dispersion stability, heat resistance and alkali developability, a sulfonic acid group or a phosphoric acid group is preferred. . Further, from the viewpoint of alkali developability, it is preferred to have a phosphate group.

The amount of the acidic group contained in the molecule of the organic acid compound is not particularly limited, and the acid group in one molecule is preferably from 1 to 3 from the viewpoints of dispersibility, dispersion stability, heat resistance and alkali developability. More preferably, it is 1~2. Further, the valence of the acidic group is not particularly limited, and is preferably from 1 to 3 in terms of dispersion stability, heat resistance and developability. The acid is more preferably an acid of 1 to 2 valence.

In the present invention, the organic acid compound is preferably 5,000 or less, more preferably 100 or more and 1,000 or less, still more preferably 150 or more and 500, from the viewpoint of easy salt formation with the amine group of the dispersing agent. the following.

In the present invention, the organic acid compound is preferably selected from the group consisting of the following general formula (IV) and the following general formula (V) from the viewpoint of superior dispersibility, dispersion stability, heat resistance and alkali developability. One or more of the groups.

(In the formulae (IV) and (V), R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group. , -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e , or -OR ^a" , a monovalent group, R Any one of ^a and R ^a' contains a carbon atom; R ^a" is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )- CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group; R ^b is an alkyl group having 1 to 18 carbon atoms, carbon number 2~ 18 alkenyl, aralkyl, aryl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e or -OR ^a monovalent group represented by ^b' ; R ^b' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group; R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO, -CO-CH=CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ^f is a monovalent group, R ^f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R ^a , R ^{a '} and R ^b are an alkyl group or an alkene The group, the aralkyl group, and the aryl group may each have a substituent; s represents an integer from 1 to 18, t represents an integer from 1 to 5, and u represents an integer from 1 to 18.

In the above general formula (IV), in the case where R ^a and R ^{a '} have an aromatic ring, the aromatic ring may have a suitable substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms. Wait.

The alkyl group, the aralkyl group or the aryl group having 1 to 18 carbon atoms may be the same as R ⁸ in the above dispersant.

When R ^a and/or R ^{a '} is -OR ^a" , it becomes an acidic phosphate.

Further, in the case where R ^{a "} has an aromatic ring, the aromatic ring may have an appropriate substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms.

The monovalent group represented by the above R ^e may, for example, be a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms, or a halogen such as F, Cl or Br. Atoms, etc.

The alkyl group having 1 to 18 carbon atoms in the above R ^e is represented by the above R ⁸ ; and the alkenyl group having 2 to 18 carbon atoms is represented by the above R ^a and R ^{a '} .

In R ^a , R ^{a '} and R ^a" , s is an integer from 1 to 18, t is an integer from 1 to 5, and u is an integer from 1 to 18. s is preferably an integer from 1 to 4, more preferably An integer of 1 to 2; t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

In the above general formula (V), in the case where R ^b has an aromatic ring, the aromatic ring may have an appropriate substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms.

When R ^b is -OR ^b' , it becomes an acidic sulfate. The above R ^{b '} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e Or a 1-valent group represented by -[(CH ₂ ) _t -O] _u -R ^e .

The alkyl group having 1 to 18 carbon atoms, the aralkyl group and the aryl group are represented by the above R ⁸ ; and the alkenyl group having 2 to 18 carbon atoms is represented by the above R ^a and R ^{a '} . Further, in the case where R ^{b '} has an aromatic ring, the aromatic ring may have an appropriate substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms.

The above R ^c , R ^d and R ^e are the same as described above.

In the above R ^b and R ^{b '} , s is an integer from 1 to 18, t is an integer from 1 to 5, and u is an integer from 1 to 18. Preferably, s, t, and u are the same as R ^a , R ^{a '} and R ^{a '} .

The organic acid compound represented by the above general formula (IV) is preferably a general formula (IV) from the viewpoint of improving the dispersibility of the color material and having a high contrast ratio of the obtained coloring layer and excellent heat resistance. Wherein R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, -[CH(R ^c ) -CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e , or ^a -valent group represented by -OR ^a" , R ^a and R ^a" One containing a carbon atom, and R ^a" is a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, -[CH(R ^c )-CH(R ^d ) -O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e , R ^c and R ^d are each independently a hydrogen atom or a methyl group, more preferably R ^a is a hydroxyl group, and R ^{a '} It is an aryl group which may also have a substituent.

Further, the organic acid compound represented by the general formula (V) is preferably a general formula (V) from the viewpoint of improving the dispersibility of the color material and having a high contrast ratio of the obtained coloring layer and excellent heat resistance. R ^b is methyl, ethyl, aryl or aralkyl which may also have a substituent, vinyl, allyl, -[CH(R ^c )-CH(R ^d )-O] _s - R ^e , or -[(CH ₂ ) _t -O] _u -R ^e , or a monovalent group represented by -OR ^b' , wherein R ^{b '} is a methyl group, an ethyl group, an aryl group which may have a substituent or Aralkyl, vinyl, allyl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e ,R ^c And R ^d are each independently a hydrogen atom or a methyl group, and more preferably R ^b is an aryl group which may have a substituent.

Among them, the organic acid compound represented by the above general formula (IV) and general formula (V) is improved from the viewpoint of improving the dispersibility of the color material, the contrast of the obtained coloring layer is high, and the heat resistance is excellent. Preferably, R ^a , R ^{a '} and/or R ^a" , and/or R ^b and/or R ^b' have an aromatic ring. From the viewpoint of dispersibility of the color material, R ^a , R ^{a '} and At least one of R ^{a "} or R ^b or R ^{b '} is an aryl or aralkyl group which may have a substituent, more specifically a benzyl group, a phenyl group, a tolyl group, a naphthyl group, or a biphenyl group. In the above general formula (IV), when one of R ^a and R ^{a '} has an aromatic ring, the other of R ^a and R ^{a '} may suitably use a hydrogen atom or a hydroxyl group.

Further, from the viewpoint of heat resistance, chemical resistance, and particularly alkali resistance, the organic acid compound represented by the above general formula (IV) and general formula (V) is preferably bonded directly to phosphorus. (P) or a compound of sulfur (S), preferably R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, An aryl group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group, R ^a and R ^{a '} Either contains a carbon atom. Further, R ^b is preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )-CH(R ^d )-O] _s a monovalent group represented by -R ^e and -[(CH ₂ ) _t -O] _u -R ^e .

In the present invention, the organic acid compound is preferably benzenesulfonic acid, p-toluenesulfonic acid, monobutylphosphoric acid, dibutylphosphoric acid, methylphosphoric acid, dibenzylphosphoric acid or diphenyl, in terms of dispersibility and heat resistance. Phosphoric acid, phenylphosphonic acid, etc.; among them, p-toluenesulfonic acid and phenylphosphonic acid are more preferable. Further, as the organic acid compound, a hydrate such as p-toluene phosphate monohydrate can also be used.

In the present invention, the organic acid compound may be used singly or in combination of two or more.

In the present invention, the total content of the dispersing agent and the organic acid compound is not particularly limited, and from the viewpoint of dispersibility and dispersion stability, the total content of the dispersing agent and the organic acid compound is preferably 100 parts by mass of the color material. 10 to 120 parts by mass, more preferably 20 to 100 parts by mass, still more preferably 30 to 80 parts by mass.

[Dispersant, relationship with organic acid compounds]

In the color material dispersion liquid of the present invention, by using a dispersing agent and an organic acid compound in combination as described below, the dispersibility and dispersion stability of the color material dispersion liquid are excellent, and a coating film excellent in heat resistance can be obtained. Since the salt-forming portion has high solubility in the aqueous alkali solution at the time of alkali development, it is excellent in alkali developability. In other words, the amine value of the dispersant is A (mgKOH/g), and the mass of the organic acid compound contained in the color material dispersion X _A (mol) and the color material dispersion are formed. When the ratio of the mass of the constituent unit (a) X _B (mol) of the dispersing agent contained in the above-mentioned dispersing agent is X (=X _A /X _B ), the following formulas (1) and (2) are satisfied; X is in the range of less than 1, further satisfying the following formula (3); X≦1.5 (1)

A×X≧40 type (2)

A×(1-X)≦42 (3)

The above formula (1) represents an amine group which is contained in the above dispersant, and the organic acid compound is 1.5 mol equivalent or less. When the organic acid compound is 1.5 mol equivalent or less, the ratio of the organic acid compound which is not formed by salt formation is small, the dispersion stability of the color material is excellent, and the organic acid compound does not precipitate. Still, there is no salt formation The organic acid compound has an effect of improving the heat resistance and alkali developability of the coating film. In the present invention, it is preferably X≦1.3, more preferably 0.7≦X≦1.2.

The above formula (2) represents an amine equivalent to a portion for salt formation in the amine group of the dispersing agent, assuming that the organic acid to be added and the amine group of the dispersing agent are formed by 100% salt in a ratio of 1:1. price. Further, when X is in the range of more than 1, it is estimated that the excessively-organic organic acid compound stabilizes the lake structure of the compound (I), so that heat resistance is further improved. The color material dispersion liquid satisfying the above formula (2) is suitable for dispersion because of its affinity for the color material, so that the dispersion stability is excellent.

Further, in recent years, as the color filter is made finer, the color layer of the color filter is required to be thinned. In order to reduce the thickness of the colored layer, it is necessary to increase the pigment concentration with respect to the solid content in the colored resin composition, and the developability of the dispersant is also greatly affected.

Even in the colored resin composition having a high pigment concentration, in order to achieve sufficient developability, it is preferred that the salt forming portion is large, that is, a large amount of organic acid; A × X ≧ 60, more preferably A × X ≧ 80.

From the viewpoint of resolubility to the solvent, it is preferred that the salt forming portion is small, that is, the organic acid is less; A × X ≦ 130, more preferably A × X ≦ 110.

Further, the above formula (2) indicates that when the organic acid to be added and the amine group of the dispersing agent are formed into a 100% salt by 1:1, the amine group contained in the dispersing agent corresponds to the portion for salt formation. The price of the amine. Since the color material dispersion liquid satisfying the above formula (2) has less amine groups which are not subjected to salt formation, the molecular association state of the color material is hard to be broken. Therefore, the coloring resin composition produced by using the color material dispersion liquid satisfying the above formula (2) is excellent in viscosity stability, and in the coloring layer formed by the colored resin composition, the molecular association state is maintained. Therefore, the heat resistance is excellent. In addition, when X is in the range of 1 or more, since the number of amine groups which are not salt-formed is small, it is the same as the case where X is less than 1 and the above formula (2) is satisfied. Ground, excellent heat resistance.

Further, in the present invention, the mass of the X _A- based organic acid compound is such that it does not include a counter anion or an alkali-soluble resin contained in the lake color material.

[solvent]

In the present invention, as the solvent, a solvent having a solubility in a coloring matter represented by the above general formula (I) at 23 ° C of 0.1 (g/10 ml of solvent) or less is used. By using such a solvent or a poorly soluble solvent which is substantially insoluble in the color material, the color material dispersion liquid of the present invention can disperse the color material represented by the above general formula (I) in a solvent in a molecular association state. use. In the solvent used in the present invention, the solubility of the coloring material represented by the above general formula (I) at 23 ° C is preferably from the viewpoint of obtaining a coating film having high dispersibility and heat resistance and obtaining high brightness. 0.05 (g/10 ml solvent) or less of the solvent.

Further, in the present invention, the above color material at 23 ° C and the above The solvent having a solubility of the dye of 0.1 (g/10 ml solvent) or less can be easily determined by the following evaluation method.

First, it is possible to judge whether or not the coloring material represented by the above general formula (I) is substantially insoluble in the solvent by the following method.

In a 20 mL sample vial, 0.1 g of the color material to be judged for solubility was placed, and the solvent S was placed in a 10 ml full pipette, further capped, and ultrasonically treated for 3 minutes. The obtained liquid was stored in a water bath at 23 ° C for 60 minutes. 5 ml of the supernatant was filtered through a PTFE 5 μm membrane filter, and then filtered through a 0.25 μm membrane filter to remove insoluble matter. The absorption spectrum of the obtained liquid was measured using a 1 cm tank using an ultraviolet-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation). The absorbance (abs) in the maximum absorption wavelength of each color material was obtained. At this time, if the absorbance (abs) is less than 40% of the upper limit of the measurement (on the island) In the case of UV-2500PC manufactured by Tsuzuki Seisakusho Co., Ltd., if the absorbance (abs) is less than 2), the solvent can be evaluated as a solvent in which the color material is substantially insoluble. In this case, when the absorbance (abs) is 40% or more of the upper limit of the measurement, the solubility is further determined by the following evaluation method.

First, in place of the solvent S, a good solvent (for example, an alcohol such as methanol) for determining the solubility of the color material is used, and a filtrate is prepared in the same manner to prepare a color material solution, which is then appropriately diluted to about 10,000 times to 100,000 times. The absorbance in the maximum absorption wavelength of the color material is measured. The solubility of the color material in the solvent S is calculated from the absorbance and the dilution ratio of the color material solution of the solvent S and the color material solution of the good solvent.

As a result, the solubility of the color material is 0.1 or less (g/10 ml of solvent) or less, and it is judged that the coloring material usable in the present invention is a solvent which is poorly soluble.

The solvent having a solubility of the color material of 0.1 or less (g/10 ml of the solvent) is preferably 95% by mass or more in the total solvent of the color material dispersion, from the viewpoint of improving the dispersion stability of the color material dispersion. More preferably, it is 98% by mass or more, and most preferably 100% by mass.

In the color material dispersion liquid of the present invention, it is preferably selected from the ester solvent as appropriate from the viewpoint of dispersion stability.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, ethyl methoxyacetate, and propylene glycol monomethyl ether acetate. , 3-methoxy-3-methyl-1-acetic acid butyl ester, 3-methoxyacetic acid butyl ester, butyl methoxyacetate, ethoxyethyl acetate, ethyl cyproterone acetate, two Propylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, cyclohexanol acetate, 1,6-hexanediol diacetate, diethylene glycol monoethyl ether acetate , diethylene glycol monobutyl ether acetate, and the like.

Among them, the risk to the human body is low, the volatility near the room temperature is low, but the heat is dry From the viewpoint of good dryness, propylene glycol monomethyl ether acetate (PGMEA) is preferably used. In this case, there is an advantage that a special washing step is not required in the conversion with the conventional colored resin composition using PGMEA.

The solvent to be used in the present invention is preferably propylene glycol monomethyl ether acetate in an amount of 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more in the total solvent.

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

The color material dispersion liquid of the present invention is prepared by using a solvent in a ratio of 50 to 95% by mass, preferably 60 to 85% by mass, based on the total amount of the color material dispersion liquid containing the solvent. . When the amount of the solvent is too small, the viscosity increases and the dispersibility is liable to lower. In addition, when the amount of the solvent is too small, the color material concentration is lowered, and it is difficult to achieve the target chromaticity coordinate after the coloring resin composition for a color filter is prepared.

(other ingredients)

In the color material dispersion liquid of the present invention, the dispersion auxiliary resin and other components may be further prepared as needed without impairing the effects of the present invention.

The dispersing auxiliary resin may, for example, be an alkali-soluble resin exemplified as a colored resin composition for a color filter to be described later. The color materials are hardly contacted with each other by the steric hindrance of the alkali-soluble resin, and there is a case where the dispersion is stabilized or the effect of the dispersion is reduced by the effect of the dispersion stabilization. The alkali-soluble resin is preferably a resin having a hydrocarbon ring from the viewpoint of dispersion stability and heat resistance, and is preferably used from the viewpoint of stabilizing the molecular association state of the color material and improving heat resistance. A resin with a high acid value.

Further, examples of the other component include a surfactant, an antifoaming agent, an anti-shrinking agent, an antioxidant, an anti-aggregating agent, and an ultraviolet absorber for improving wettability.

The color material dispersion liquid of the present invention is used as a preliminary preparation for preparing a colored resin composition for a color filter to be described later. In other words, the color material dispersion liquid is a ratio of (a color component in the composition)/(a solid content other than the color material component in the composition) prepared in the pre-stage of preparing the colored resin composition described later ( A color material dispersion with a higher mass ratio). Specifically, the ratio (mass ratio) of the (color component in the composition) / (solid content other than the color component in the composition) is usually 1.0 or more. For example, by mixing the color material dispersion with at least the photosensitive binder component, a colored resin composition having excellent dispersibility can be prepared.

[Manufacturing method of color material dispersion]

In the present invention, the method for producing a color material dispersion liquid is not particularly limited as long as the color material shown in the above formula (I) is dispersed in a solvent by a dispersant to obtain a color material dispersion liquid, for example: 1) The dispersant is previously mixed and stirred in a solvent to prepare a dispersant solution, and then the organic acid compound is mixed to form a salt of the amine group and the organic acid compound which the dispersant has. Mixing the color material represented by the general formula (I) with other components as needed, and dispersing it by using a known mixer or disperser; (2) mixing and stirring the dispersant in a solvent to prepare a dispersant solution, Next, the color material and the organic acid compound represented by the general formula (I), and other components as necessary, are mixed by a known agitator or a disperser; (3) the dispersant is mixed and stirred in a solvent to prepare a dispersion. The agent solution is then mixed with a color material represented by the general formula (I) and optionally other components, and a method of adding an organic acid compound by using a known mixer or disperser to form a dispersion.

In the present invention, from the viewpoint of dispersion stability of the color material, the method of the above (1) is preferred.

As the dispersing machine for performing the dispersion treatment, a double roll or a triple roll can be cited. Ball mills such as ball mills, ball mills, vibrating ball mills, paint blenders, continuous disc bead mills, continuous loop bead mills, etc. As a preferred dispersion condition of the bead mill, the bead diameter to be used is preferably from 0.03 to 2.00 mm, more preferably from 0.10 to 1.0 mm.

Specifically, the dispersion is carried out by a 2 mm zirconia bead having a relatively large bead diameter, and the dispersion is carried out by using a relatively small 0.1 mm zirconia bead having a bead diameter. Further, after dispersion, it is preferably filtered by a membrane filter of 0.5 to 0.1 μm.

2. Colored resin composition for color filter

The colored resin composition for a color filter of the present invention is characterized by comprising the above-described color material dispersion liquid, alkali-soluble resin, polyfunctional monomer, and initiator.

Since the colored resin composition for a color filter of the present invention contains the above-described color material dispersion liquid of the present invention, it has excellent stability over time, and can form a coloring layer having improved heat resistance, and is excellent in alkali developability.

The colored resin composition for a color filter of the present invention contains at least a color material, a dispersant, an organic acid compound, an alkali-soluble resin, a polyfunctional monomer, a starter, and a solvent represented by the general formula (I); It may be further provided without further impairing the effects of the present invention, and may further contain other components as needed.

Hereinafter, each component of the colored resin composition for a color filter of the present invention will be described in detail. However, the color material, the dispersant, the organic acid compound, and the solvent can be used as the color material of the present invention. Since the dispersion is the same, the description thereof is omitted here.

[alkali soluble resin]

The alkali-soluble resin in the present invention usually has a carboxyl group and has a bond as a binder. The action of the resin may be appropriately selected and used on the premise that the developer used for pattern formation is particularly soluble in the alkali developer. Further, the alkali-soluble resin may be included in the organic acid compound, but the alkali-soluble resin in the present invention is considered to be different from the organic acid compound.

The acid value of the alkali-soluble resin in the present invention is not particularly limited. From the viewpoint of improving the stability over time of dispersion stability and the like and improving the heat resistance of the coloring layer obtained from the resin composition, it is preferable to use an acid value of 80 mgKOH/g or more and 300 mgKOH/g or less as the alkali-soluble resin. Resin. The acid-based acid group having an acid value of 80 mg KOH/g or more is relatively large, and the interaction between the molecular association of the color material represented by the above general formula (I) and the amine group of the dispersant is stabilized. It is judged that the stability over time of dispersion stability and the like can be improved, and the heat resistance of the coloring layer obtained from the resin composition can be improved.

Further, the acid value in the present invention means the mass (mg) of KOH required for neutralizing 1 g of the solid fraction, and the value obtained by potentiometric titration according to JIS K 0070.

Since the alkali-soluble resin having an acid value of 80 mgKOH/g or more is a resin having a relatively large amount of acidic groups, it is easy to have an anion existing in the vicinity of the surface of the molecular association body of the color material represented by the above general formula (I). The basic group interacts, and as a result, it is estimated that the alkali-soluble resin is easily adsorbed on the surface of the above-mentioned molecular complex. Since the acid-soluble valence of the alkali-soluble resin is relatively high, it is difficult to dissociate even when heated under high temperature, and the decomposition of the color material can be further suppressed, and the decrease in brightness can be suppressed, and the heat resistance can be particularly improved. Further, by using an alkali-soluble resin having an acid value of 80 mgKOH/g or more, the acidic group contributes to the adhesion to the substrate even if a conventional decane coupling agent for improving the adhesion to the substrate is not used. , still improve the adhesion between the substrate and the substrate.

Preferred alkali-soluble resins in the present invention, specifically, An acrylic copolymer having a carboxyl group, an epoxy (meth)acrylate resin having a carboxyl group, or the like. Among these, a photopolymerizable functional group having a carboxyl group in a side chain and an ethylenically unsaturated group in a side chain is particularly preferable. This is because the film strength of the cured film formed by the photopolymerizable functional group is improved. Further, these acrylic copolymers and epoxy acrylate resins may be used in combination of two or more kinds.

The acrylic copolymer having a constituent unit having a carboxyl group is obtained by, for example, (co)polymerizing a carboxyl group-containing ethylenically unsaturated monomer and, if necessary, another monomer copolymerizable by a known method. ) Polymer.

Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, and itaconic acid. , butenoic acid, cinnamic acid, acrylic acid dimer, and the like. Further, an addition reactant of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride or decanoic anhydride or cyclohexane dicarboxylic anhydride may be used. , ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Further, an anhydride-containing monomer such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Among them, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, glass transition temperature and the like.

The alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer. By having a hydrocarbon ring belonging to a large group among the alkali-soluble resins, shrinkage at the time of curing can be suppressed, the peeling from the substrate can be alleviated, and the substrate adhesion can be improved. Moreover, the inventors of the present invention have found that by using an alkali-soluble resin having a hydrocarbon ring, the solvent resistance of the obtained colored layer can be suppressed, and in particular, swelling of the colored layer can be suppressed. Although the effect has not yet been elucidated, it is presumed that the molecular action in the colored layer is suppressed by the inclusion of a large hydrocarbon ring in the colored layer, and as a result, the strength of the coating film is increased to suppress the swelling caused by the solvent.

Examples of such a hydrocarbon ring include a cyclic aliphatic hydrocarbon ring which may have a substituent, an aromatic ring which may have a substituent, and combinations thereof; and the hydrocarbon ring may have a carbonyl group, a carboxyl group, an oxycarbonyl group, or a hydrazine group; a substituent such as an amine group. Among them, when the aliphatic ring is contained, the heat resistance or the adhesion of the colored layer can be improved, and the brightness of the resulting colored layer can be improved.

Specific examples of the hydrocarbon ring include cyclopropane, cyclobutane, cyclopentane, cyclohexane, and descending. An aliphatic hydrocarbon ring of an alkane, a tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), an adamantane or the like; an aromatic ring such as benzene, naphthalene, anthracene, phenanthrene or anthracene; biphenyl, triple a chain polycyclic ring such as benzene, diphenylmethane, triphenylmethane or hydrazine; or a cardo structure represented by the following chemical formula (A).

As the hydrocarbon ring, when the aliphatic ring is contained, it is particularly preferable from the viewpoint of improving the heat resistance or adhesion of the colored layer and simultaneously increasing the brightness of the obtained colored layer.

Moreover, in the case of containing the cardo structure represented by the above chemical formula (A), it is preferable from the viewpoint of improving the hardenability of the colored layer and improving the solvent resistance (NMP swelling inhibition).

In the alkali-soluble resin used in the present invention, it is preferred to have a carboxyl group from the viewpoint of easily adjusting the respective constituent unit amounts and increasing the constituent unit amount of the hydrocarbon ring to easily improve the function of the constituent unit. In addition to the unit, an acrylic copolymer having the above constituent unit having a hydrocarbon ring is additionally used.

The constituent unit having a carboxyl group and the above-mentioned acrylic copolymer having a hydrocarbon ring can be used as the above-mentioned "copolymerizable other monomer" by using an ethylenically unsaturated monomer having a hydrocarbon ring. Modulated by the body.

Examples of the ethylenically unsaturated monomer having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and (meth)acrylic acid. Ester, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and the like.

The alkali-soluble resin of the present invention preferably has an ethylenic double bond from the viewpoint of improving the development resistance of the cured film and improving the heat shrinkage of the cured film and being excellent in adhesion to the substrate. In the case of having an ethylenic double bond, in the hardening step of the resin composition at the time of production of the color filter, the alkali-soluble resins or the alkali-soluble resin and the polyfunctional monomer may form a cross-linking bond. As a result, it is estimated that the film strength of the cured film of the colored layer can be improved, and the heat shrinkage of the cured film can be suppressed to be excellent in adhesion to the substrate. By selecting an alkali-soluble resin having an ethylenic double bond and using the coloring layer formed of the colored resin composition for a color filter of the present invention, the decane will be described later even with respect to the total solid content of the colored resin composition. When the coupling agent is used in an amount of 1 part by mass or less, the substrate adhesion is still excellent.

The method of introducing an ethylenic double bond into the alkali-soluble resin may be appropriately selected by a conventionally known method. For example, a compound having an epoxy group and an ethylenic double bond in a component, such as a carboxyl group having an epoxy group and an ethylenic double bond, may be added to the side chain to introduce an ethylenic double bond. Or a method in which a compound having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenic double bond is added to the molecule, and a vinyl double bond is introduced into the side chain.

The alkali-soluble resin of the present invention may further contain other constituent units such as a constituent unit having an ester group such as methyl (meth)acrylate or ethyl (meth)acrylate. The constituent unit having an ester group functions not only as an alkali-soluble component for suppressing the coloring resin composition for a color filter, but also as a solvent to improve solubility and even It functions as a component of solvent resolubility.

The alkali-soluble resin in the present invention preferably has an acrylic copolymer having a carboxyl group and a constituent unit having a hydrocarbon ring; more preferably, it has a constituent unit having a carboxyl group, a constituent unit having a hydrocarbon ring, and An acrylic copolymer of a constituent unit of an ethylenic double bond.

As the alkali-soluble resin of the present invention, an epoxy group-containing (meth) acrylate resin (hereinafter referred to as cardo resin) having a carboxyl group structure as described above can be preferably used.

The correct mechanism of the carboxyl group-containing epoxy (meth) acrylate resin (hereinafter referred to as cardo resin) containing the cardo structure has not been elucidated, but since the tibia lattice contains a π-conjugated system, it is considered to be highly sensitive to free radicals. . By combining an oxime ester photopolymerization initiator described later with a cardo resin, the required properties such as solvent resistance, water bleeding, and sensitivity can be further improved.

The cardo resin is preferably a polymerizable compound represented by the following general formula (B) described in JP-A-2007-119720, and a ruthenium skeleton described in JP-A-2006-308698. A reaction product (polycondensate) of an epoxy group (meth) acrylate with a polybasic acid or the like.

(In the above general formula (B), X represents a group represented by the following general formula (D), and Y each independently represents a residue of a polyvalent carboxylic acid or an anhydride thereof, and R ⁱ represents a general formula (C) below. The base of the graph, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer of 1 or more.)

(In the above general formula (C), R ⁱⁱ represents a hydrogen atom or a methyl group, and R ⁱⁱⁱ each independently represents a hydrogen atom or a methyl group.)

(In the above general formula (D), R ^iv each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and R ^v represents -O- or -OCH ₂ CH ₂ O-. )

The cardo resin used in the present invention can be obtained by, for example, epoxidizing a bismuth bisphenol compound to form an epoxy compound of a bisphenol compound, and reacting the (meth)acrylic acid to form an epoxy group (methyl). An acrylate obtained by reacting the epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.

The bisphenol compound preferably has the above formula (D), and R ^v is -O-, and this -O- is -OH.

Examples of the quinone bisphenol compound include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and 9,9-bis(4-hydroxyl). 3-methoxyphenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-fluorophenyl)anthracene 9,9-bis(4-hydroxy-3-chlorophenyl)indole, 9,9-bis(4-hydroxy-3-bromophenyl)anthracene, 9,9-bis(4-hydroxy-3,5 a bisphenol compound such as -dichlorophenyl)anthracene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene, and the like Things.

Examples of the polyvalent carboxylic acid and an acid anhydride used in the reaction of the epoxy group (meth) acrylate resin having an anthracene skeleton include maleic acid, succinic acid, itaconic acid, citric acid, and tetrahydroanthracene. a dicarboxylic acid such as acid, hexahydrophthalic acid, methyltetrahydrofurfuric acid, methyl endomethylenetetrahydrofurfuric acid, chlorohydrin, methyltetrahydrofurfuric acid, glutaric acid or the like; or an acid anhydride thereof; Biphenyltetracarboxylic acid, diphenylketonetetracarboxylic acid, biphenyl ether tetracarboxylic acid, biphenyl fluorene tetracarboxylic acid, 4-(1,2-dicarboxyethyl)-1,2,3,4 a tetracarboxylic acid such as tetrahydronaphthalene-1,2-dicarboxylic acid, butanetetracarboxylic acid or pyromic acid or an acid dianhydride thereof; a tricarboxylic acid such as trimellitic acid or an anhydride thereof or the like Such as acid anhydride and the like. These may be used alone or in combination of two or more.

The cardo resin used in the present invention is preferably a ring having an anthracene skeleton which is an addition product of an anthracene epoxy (meth) acrylate derivative and a dicarboxylic anhydride and/or a tetracarboxylic dianhydride. An oxy (meth) acrylate adduct.

The commercially available product name of the cardo resin which can be used in the present invention includes INR-16M (manufactured by Nagase ChemteX Co., Ltd.) and trade name V259ME (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

The epoxy group (meth) acrylate resin having a carboxyl group may be used alone or in combination of two or more.

The alkali-soluble resin to be used in the coloring resin composition may be used singly or in combination of two or more kinds, and the content thereof is not particularly limited, and the coloring resin composition for a color filter is used. The total amount of the solid content, the alkali-soluble resin is preferably in the range of 5 to 60% by mass, more preferably 10 to 40% by mass. If the content of the alkali-soluble resin is less than the above lower limit, sufficient alkali developability may not be obtained. Further, if the content of the alkali-soluble resin is more than the above upper limit, film roughness or pattern defect may occur during development. The situation. Further, in the present invention, the solid portion means the above dissolution The owner other than the agent also includes liquid polyfunctional monomers and the like.

The alkali-soluble resin can be used as an alkali-soluble resin having desired properties by appropriately adjusting the amount of each constituent unit.

The amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5 to 50% by mass, more preferably 10 to 40% by mass based on the total amount of the monomers.

When the ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by mass, the solubility of the obtained coating film to the alkali developing solution is lowered, and pattern formation becomes difficult. In addition, when the ratio of the carboxyl group-containing ethylenically unsaturated monomer exceeds 50% by mass, when the image is developed by an alkali developer, the formed pattern tends to fall off from the substrate or the film on the pattern surface tends to be rough.

Further, in the acrylic copolymer having a carboxyl group and a constituent unit having a hydrocarbon ring as an alkali-soluble resin, the amount of the carboxyl group-containing ethylenically unsaturated monomer is relatively small. The total amount of the body is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. Further, in the acrylic copolymer, the amount of the hydrocarbon-containing ring-containing ethylenically unsaturated monomer is preferably from 30 to 80% by mass, and more preferably from 40 to 75% by mass based on the total amount of the monomers.

Further, in the acrylic copolymer having a carboxyl group, a constituent unit having a hydrocarbon ring, and a constituent unit having an ethylenic double bond, which is an alkali-soluble resin, the ethyl group having no carboxyl group is preferably used. A saturated monomer is added to a compound having an epoxy group and an ethylenic double bond in a molecule, and when an ethylenic double bond is introduced, a carboxyl group-containing ethylenically unsaturated monomer is charged in a total amount relative to the monomer. The amount is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. In the acrylic copolymer, the amount of the hydrocarbon-containing ring-containing ethylenically unsaturated monomer is preferably from 30 to 80% by mass, more preferably from 40 to 75% by mass, based on the total amount of the monomers. Moreover, in the acrylic copolymer, both The compound having an epoxy group and an ethylenic double bond is preferably 10 to 95% by mass, more preferably 15 to 90% by mass based on the amount of the carboxyl group-containing ethylenically unsaturated monomer.

When the acrylic copolymer has a constituent unit having a carboxyl group and a hydrocarbon ring, the constituent unit is considered to be contained in a constituent unit having a carboxyl group and a constituent unit having a hydrocarbon ring.

In the alkali-soluble resin of the present invention, the constituent unit having a carboxyl group, the constituent unit having a hydrocarbon ring, and other constituent units other than the constituent unit having an ethylenic double bond are preferably 0 to 30 in the total constituent unit. The mass %, more preferably 0 to 20 mass%.

The alkali-soluble resin is selected from the viewpoints of developability (solubility) of the aqueous alkali solution used for the developer and the heat resistance of the colored layer. The acid value is preferably 80 mgKOH/g or more and 300 mgKOH/g. The following. Among them, it is preferably 90 mgKOH/g or more and 280 mgKOH/g or less, more preferably 100 mgKOH/g or more and 250 mgKOH/g or less. The alkali-soluble resin having an acid value of 100 mgKOH/g or more is preferable from the viewpoint of improving brightness, heat resistance and adhesion. Further, when the color material represented by the general formula (I) and the metal lake color material of the acid dye are used in combination, it is preferred to use a base having an acid value of 90 mgKOH/g or more from the viewpoint of improving heat resistance. Soluble resin.

The alkali-soluble resin having an acid value of not less than the above lower limit is likely to interact with the basic group of an anion existing in the vicinity of the surface of the molecular association body of the color material represented by the above general formula (I). The alkali-soluble resin is easily adsorbed on the surface of the above-mentioned molecular association body. Since the acid-soluble valence of the alkali-soluble resin is relatively high, it is difficult to dissociate even when heated under high temperature, and the decomposition of the color material can be further suppressed, and the decrease in brightness can be suppressed, and the heat resistance can be particularly improved.

In the case where the side chain of the alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated bond equivalent is preferably in the range of from 100 to 2,000, particularly preferably The range of 140~1500. When the ethylenically unsaturated bond equivalent is 2,000 or less, development resistance or adhesion is excellent. In addition, when the ratio is 100 or more, the ratio of the constituent unit having the carboxyl group or the other constituent unit having the constituent unit of the hydrocarbon ring can be relatively increased, so that the developability or heat resistance is excellent.

Here, the ethylenically unsaturated bond equivalent is a weight average molecular weight per one mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (4).

(In the formula (4), W represents the mass (g) of the alkali-soluble resin, and M represents the molar number (mol) of the ethylenic double bond contained in the alkali-soluble resin W (g).)

The ethylenically unsaturated bond equivalent can be calculated, for example, according to the test method of the iodine value described in JIS K 0070:1992.

Further, the ethylenically unsaturated bond equivalent can be obtained by setting the W in the formula (1) to the total mass (g) of the monomer and the compound constituting the alkali-soluble resin, and setting M to the following formula. (5) The molar number (mol) of the ethylenic double bond in the calculated alkali-soluble resin, and the amount of the mixture in the synthesis of the alkali-soluble resin is simply calculated.

(other resin)

The colored resin composition of the present invention may further contain other resins insofar as the effects of the present invention are not impaired. Specific examples of the other resin include polycarbonate resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, and phenol. Resin, An alkyd resin, an epoxy resin, a polyurethane resin, a polyester resin, a maleic acid resin, a polyamide resin, a polyimide resin, or the like; wherein, from the viewpoint of heat resistance, The polyamine resin or the polyimine resin is preferably a polyamine resin having a cyclic structure or a polyimide resin having a cyclic structure. These resins may be those having an alkali solubility or those having no alkali solubility. Further, these resins may be used alone or in combination of two or more.

The weight average molecular weight of the alkali-soluble resin is not particularly limited. Among them, it is preferably in the range of 1,000 to 500,000, more preferably in the range of 3,000 to 200,000. When it is less than 1,000, the function of the binder after hardening is remarkably lowered. When it exceeds 500,000, when patterning is performed by an alkali developer, pattern formation becomes difficult.

The alkali-soluble resin to be used in the colored resin composition for a color filter of the present invention may be used singly or in combination of two or more kinds thereof; the content thereof is based on the mass of the color material 100 contained in the colored resin composition. The portion is usually in the range of 10 to 1000 parts by mass, preferably 20 to 500 parts by mass. When the content of the alkali-soluble resin is too small, sufficient alkali developability may not be obtained. Further, when the content of the alkali-soluble resin is too large, the ratio of the color material is relatively low, and a sufficient coloring concentration may not be obtained.

[Polyfunctional monomer]

The polyfunctional monomer to be used in the coloring resin composition for a color filter of the present invention is not particularly limited as long as it can be polymerized by a starting agent to be described later, and usually has two or more kinds of ethylenicity. The compound having an unsaturated double bond is particularly preferably a polyfunctional (meth) acrylate having two or more acryl fluorenyl groups or methacryl fluorenyl groups, more preferably a trifunctional or higher polyfunctional (meth) acrylate.

In the polyfunctional (meth) acrylate, examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri(meth)acrylate and trimethylolethane tris(methyl). Acrylate, tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl modified dipentaerythritol tri(meth)acrylate, succinic anhydride modified pentaerythritol IV (meth) acrylate, tris(meth) acrylate, propylene (propylene oxy oxy) isomeric cyanurate, stilbene (methacryloxyethyl) isomeric cyanurate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, bis(trimethylolpropane)tetraacrylate, alkyl modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxy five (Meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, carboxylic acid modified dipentaerythritol Acrylate, succinic anhydride modified dipentaerythritol penta (methyl) propyl Ester, urethane tri (meth) acrylate, an ester tri (meth) acrylate, urethane hexa (meth) acrylate ester hexa (meth) acrylate.

In the present invention, the polyfunctional monomer preferably has three (trifunctional or higher) or more polymerizable double bonds from the viewpoint of enhancing photocurability (high sensitivity); for example, a polyvalent amount of three or more may be appropriately cited. Poly(meth)acrylates of alcohols. Further, in the present invention, the polyfunctional monomer preferably has a carboxyl group from the viewpoint of improving alkali developability. Examples of the polyfunctional monomer having a carboxyl group include a polycarboxylic acid modified product of a poly(meth)acrylate of the above polyol.

Specific examples of the poly(meth)acrylates of the polyhydric alcohols include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

Further, examples of the carboxylic acid modified product of the poly(meth)acrylate of the polyhydric alcohol include a succinic acid modified product of pentaerythritol tri(meth)acrylate and a succinic acid modified product of dipentaerythritol penta (meth)acrylate. Wait.

These polyfunctional monomers may be used alone or in combination of two or more. For example, a polyfunctional monomer having a carboxyl group may be used in combination with a polyfunctional monomer having no carboxyl group. From the viewpoint of improving heat resistance and adhesion, a succinic acid modified product of a pentaerythritol tri(meth)acrylate having a carboxyl group and a succinic acid modified product of dipentaerythritol penta (meth) acrylate are preferable.

Commercially available products such as a succinic acid modified product containing dipentaerythritol penta (meth) acrylate may be suitably used as such a polyfunctional monomer, and may be exemplified by trade names M-520D and TO-2371 (East Asia Synthesis). (share) company system) and so on.

The content of the above polyfunctional monomer used in the colored resin composition for a color filter of the present invention is not particularly limited, and the content of the polyfunctional monomer is preferably 5 based on the total amount of the solid content of the colored resin composition. ~60% by mass, more preferably 10 to 40% by mass. When the content of the polyfunctional monomer is less than the above range, the photocuring is not sufficiently performed, and the exposed portion is eluted. Further, when the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered.

[starting agent]

The initiator used in the coloring resin composition for a color filter of the present invention is not particularly limited, and one or two or more kinds of the various initiators known in the art can be used in combination.

Examples of the initiator include aromatic ketones, benzoin ethers, and halomethyl groups. Diazole compound, α-amino ketone, biimidazole, N,N-dimethylaminodiphenyl ketone, halomethyl-S-three Compound, 9-oxosulfur Wait. Specific examples of the initiator include diphenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, and 4-methoxy-4'-dimethylaminodiphenyl ketone. Aromatic ketones; benzoin ethers such as benzoin methyl ether; benzoin such as ethyl benzoin; 2-(o-chlorophenyl)-4,5-phenylimidazole dimer Ethylene imidazole; 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4- Halomethyl group such as oxadiazole Diazole compound; 2-(4-butoxy-naphthalen-1-yl)-4,6-bis-trichloromethyl-S-three Halomethyl-S-three Compound; 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2- Phenanthroline, 1,2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzamidine benzoic acid, benzamidine benzoic acid methyl ester, 4-benzylidene-4' -methyldiphenylsulfide, benzylmethylketal, dimethylaminobenzoate, p-dimethylamino benzoic acid isoamyl ester, 2-n-butoxyethyl-4-dimethyl Amino benzoate, 2-chloro-9-oxo 2,4-diethyl-9-oxosulfur 2,4-dimethyl-9-oxosulfur Isopropyl-9-oxosulfur , 4-benzylidene-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4- Phenyl)phenyl]-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzylidene)phosphine oxide, 2- Methyl-1-[4-(methylthio)phenyl]-2-(4- Polinyl)-1-propanone and the like.

Among them, 2-methyl-1-[4-(methylthio)phenyl]-2- is preferably used. Lolinylpropan-1-one, 2-mercapto-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone, 4,4'-bis(diethylamino)diphenyl ketone, diethyl-9-oxosulfur . From the viewpoint of adjusting sensitivity, inhibiting water bleeding, and improving development resistance, a more preferable combination such as 2-methyl-1-[4-(methylthio)phenyl]-2- 啉-ylpropan-1-one-like α-aminoacetophenone-based initiator and, for example, diethyl-9-oxosulfur 9-oxygen sulfur Is the initiator.

α-Aminoacetophenone-based initiator and 9-oxosulfur The content of the initiator is preferably from 5 to 15% by mass based on the total amount of the solid content of the colored resin composition. If the starting dose is 15% by mass or less, the sublimate in the manufacturing process is reduced, which is preferable. When the amount of the initiator is 5% by mass or more, development resistance such as water bleeding is improved.

In the present invention, from the viewpoint of high water permeation inhibiting effect, it is preferred that the initiator contains an oxime ester photoinitiator. Further, the term "water infiltration" refers to a phenomenon in which, after aging with pure water, a trace such as water infiltration occurs. Since such water permeation disappears after prebaking, there is no problem as a product, but when the appearance of the patterned surface is examined after development, it is detected as an unevenness abnormality, and there is a possibility that the normal product and the abnormal product cannot be distinguished. The problem has occurred. Therefore, if the inspection sensitivity of the inspection apparatus is lowered at the time of visual inspection, the result is that the yield of the final color filter article is lowered, causing a problem.

The oxime ester-based photoinitiator preferably has an aromatic ring, and more preferably has a fragrance, from the viewpoint of reducing contamination by a colored resin composition for a color filter due to decomposition products or contamination of a device. The condensed ring of the ring; more preferably, it has a condensed ring containing a benzene ring and a hetero ring.

As the oxime ester photoinitiator, 1,2-octanedione-1-[4-(phenylthio)-, 2-(o-benzylidene fluorenyl)], 1-(o-ethylindenyl) can be used. 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone, Japanese Patent Laid-Open No. 2000-80068, JP-A-2001-233842 The oxime ester photoinitiator described in the above-mentioned Japanese Patent Publication No. 2010-527339, No. 2010-527338, and JP-A-2013-041153 is appropriately selected. As a commercially available product, IRGACURE OXE-01, IRGACURE OXE-02, IRGACURE OXE-03 (above, BASF), ADEKA OPT-N-1919, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-831 (above) ADEKA company), TR-PBG-304, TR-PBG-326, TR-PBG-345, TR-PBG-3057 (above State Strong Electronic New Materials Co., Ltd.).

The oxime ester-based photoinitiator used in the present invention is preferably produced by the use of solvent resistance, development resistance, suppression effect of pattern defects, and water permeation suppression effect. An aryl radical, especially an oxime ester photoinitiator which produces a phenyl radical, more preferably an oxime ester photoinitiator which produces an alkyl radical, in particular a methyl radical. This reasoning is that the radical movement of the alkyl radical is easily activated compared to the aryl radical. As the oxime ester photoinitiator which produces an alkyl radical, 1-(o-ethylindenyl) 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indole is exemplified. Zyridin-3-yl]-ethanone (trade name: IRGACURE OXE-02, manufactured by BASF), (2,4,6-trimethylphenyl)[8-[[(ethylideneoxy)imino) ][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]oxazol-5-yl] -Methyl ketone (trade name: IRGACURE OXE-03, manufactured by BASF), 1-(o-ethyl fluorenyl) 1-[9-ethyl-6-(1,3-dioxolan, 4-(2- Methoxyphenoxy)-9H-indazol-3-yl]-ethanone (trade name: ADEKA OPT-N-1919, manufactured by ADEKA), o-acetyl hydrazine (9-ethyl-6-nitrate) -9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl)]-methanone (trade name: ADEKA ARKLS NCI-831, ADEKA company, 1-(o-ethylindenyl) 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzimidyl)-9H-indazol-3-yl] 1-acetone (trade name: TR-PBG-304, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1-(o-ethenylhydrazine) 3-cyclopentyl-1-[2-(2-pyrimidinylthio) )-9H-carbazol-3-yl]-1-propane (trade name: TR-PBG-314, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), 1- (oight) Ethyl hydrazide) 2-cyclohexyl-1-[2-(2-pyrimidinyloxy)-9H-indazol-3-yl]-ethanone (trade name: TR-PBG-326, Changzhou Power Electronics) Manufactured by Material Co., Ltd., 1-(o-ethylindenyl) 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-indazol-3-yl]-ethanone (trade name: TR -PBG-331, manufactured by Changzhou Power Electronic Materials Co., Ltd.), 1-(o-ethylidene) 肟) 1-[4-[3-[1-[(Ethyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)sulfide ]]-2-methylbenzylidene]-9H-carbazol-9-yl]phenyl]-1-octanone (trade name: EXTA-9, manufactured by UNION CHEMICAL).

Further, from the viewpoint of enhancing the sensitivity, it is preferred to use a photoinitiator having a tertiary amine structure in combination with an oxime ester photoinitiator. The reason is that a photoinitiator having a tertiary amine structure has a tertiary amine structure belonging to an oxygen quencher in the molecule, so that a radical generated by the initiator is difficult to be deactivated by oxygen. Can increase the sensitivity. A commercially available product of the above-mentioned photoinitiator having a tertiary amine structure may, for example, be 2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one (for example, IRGACURE 907, manufactured by BASF Corporation), 2-benzyl-2-(dimethylamino)-1-(4- Polinylphenyl)-1-butanone (for example, IRGACURE 369, manufactured by BASF Corporation), 4,4'-bis(diethylamino)diphenyl ketone (for example, HICURE ABP, manufactured by Kawaguchi Pharmaceutical Co., Ltd.), and the like.

In the present invention, the initiator is preferably an oxime ester photoinitiator, and more preferably an alkyl radical oxime ester compound.

When an alkyl radical oxime ester compound and an α-aminoalkylphenone-based initiator are combined, a coating film having an excellent water permeation inhibiting effect can be obtained, and the sensitivity can be easily adjusted.

Further, when an alkyl radical oxime ester compound or an aryl radical oxime ester compound is used in combination, a coating film which is particularly excellent in solvent resistance and water permeation suppression can be obtained with a small initial dose, and sensitivity Adjustment is also easy.

The amount of the alkyl radical oxime ester compound is preferably from 2 to 7% by mass based on the total amount of the solid content of the colored resin composition. If the starting dose is less than 7% by mass, since the pattern is not too thick for the mask opening, it is preferable. When the starting dose is 2% by mass or more, the solvent resistance becomes good.

The content of the initiator used in the colored resin composition of the present invention is not particularly limited, and is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass based on the total amount of the solid content of the colored resin composition. %, particularly preferably 3 to 20% by mass. If the content is less than the above range, a sufficient polymerization reaction cannot be produced, so that the hardness of the colored layer may not be sufficient. On the other hand, if it is more than the above range, the solid content of the colored resin composition is The content of the color material or the like is relatively small, and there is a case where a sufficient coloring density cannot be obtained.

<arbitrarily added ingredients>

In the colored resin composition of the present invention, various additives may be contained as needed within the range not impairing the object of the present invention. Examples of the additive include an antioxidant, a polymerization stopper, a chain shifting agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a decane coupling agent, an ultraviolet absorber, a dense adhesion promoter, and the like.

(decane coupling agent)

In the present invention, a decane coupling agent may be used in order to improve the adhesion to the substrate. In the present invention, the decane coupling agent is a compound having one or more groups selected from the group consisting of a decyl group and an alkoxy group.

The decane coupling agent is usually used in an amount of 2% by mass or more based on the total solid content of the colored resin composition from the viewpoint of adhesion. On the other hand, the inventors of the present invention have found that when a decane coupling agent is used in combination with the coloring matter represented by the above general formula (I), the decane coupling agent changes over time. Therefore, from the viewpoint of obtaining a pattern-like colored layer as designed, even if the adhesion to the substrate after storage for a long period of time is not lowered and the sensitivity change is suppressed, it is preferable to form a solid layer with respect to the colored resin composition. Part, the decane coupling agent is set It is 1% by mass or less; more preferably, it is 0.5% by mass or less based on the total solid content of the colored resin composition; more preferably, it is substantially not contained.

Specific examples of the decane coupling agent include vinyl decane such as vinyl gin (β-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl trimethoxy decane; γ-methyl propylene; a (meth)acrylic acid decane such as methoxypropyltrimethoxydecane or 3-methylpropenyloxypropyltrimethoxydecane; β-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, β-(3,4-epoxycyclohexyl)methyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β-(3, Epoxy decane such as 4-epoxycyclohexyl)methyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-β (amino group B) Γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyl Amino decane such as trimethoxy decane, N-phenyl-γ-aminopropyltriethoxy decane; γ-mercaptopropyl A decane coupling agent such as a thiodecane such as methoxy decane or γ-mercaptopropyltriethoxy decane; and among them, 3-methyl propylene is preferred from the viewpoint of adhesion to a substrate. Methoxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methyl Acryloxypropyltriethoxydecane.

(Antioxidants)

The colored resin composition of the present invention preferably contains an antioxidant from the viewpoint of heat resistance and light resistance. The antioxidant can be appropriately selected from those well-known by those skilled in the art. Specific examples of the antioxidant include hindered phenol-based antioxidants and amine-based antioxidants. A phosphorus-based antioxidant, a sulfur-based antioxidant, an antimony-based antioxidant, or the like is preferably a hindered phenol-based antioxidant from the viewpoint of heat resistance and light resistance.

The hindered phenol-based antioxidant is, for example, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF Corporation), 1, 3,5-gin(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate (trade name: IRGANOX 3114, manufactured by BASF Corporation), 2,4,6-gin (4-hydroxy-3) ,5-di-t-butylbenzyl) 1,3,5-trimethylbenzene (trade name: IRGANOX 1330, manufactured by BASF Corporation), 2,2'-methylenebis(6-tert-butyl-4- Methylphenol) (trade name: Sumilizer MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: IRGANOX 1081, manufactured by BASF Corporation) 3,5-di-tert-butyl-4-hydroxybenzylsulfonate (trade name: IRGAMOD 195, manufactured by BASF Corporation). Among them, from the viewpoint of heat resistance and light resistance, pentaerythritol 肆 [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, BASF) is preferred. Company system).

When the antioxidant is used, the amount thereof is not particularly limited as long as it does not impair the effects of the present invention. The amount of the antioxidant is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 to 4.0 parts by mass, per 100 parts by mass of the total solid content in the colored resin composition. When it is more than the above lower limit, heat resistance and light resistance are excellent. On the other hand, when it is at most the above upper limit value, the colored resin composition of the present invention can be used as a highly sensitive photosensitive resin composition.

Further, examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether. Polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and the like. Further, a fluorine-based surfactant may also be used.

Further, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and trimethyl phenol. Examples of the antifoaming agent and the leveling agent include a quinone-based, fluorine-based, and acrylic-based compound.

(chain moving agent)

As the chain shifting agent, for example, a monofunctional thiol compound or a polyfunctional thiol compound is preferable, and among them, a polyfunctional thiol compound is more preferable.

Examples of the monofunctional thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoene. Oxazole, 2-mercaptomethylbenzimidazole, 2-mercaptomethylbenzo Oxazole, 2-mercaptomethylbenzothiazole and the like. Among them, the monofunctional thiol compound is preferably 2-mercaptomethylbenzothiazole from the viewpoint of chain-shifting the radical generated by the photopolymerization initiator and improving the hardenability.

The polyfunctional thiol compound is not particularly limited, and various compounds can be used. The polyfunctional thiol compound may, for example, be 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, 1,8-octane Mercaptan, 1,2-cyclohexanedithiol, decanedithiol, ethylene glycol dithioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol dithioglycolate , 1,4-butanediol dithioglycolate, 1,4-butanediol bis(3-mercaptopropionate), trimethylolpropane thioglycolate, trimethylolpropane (3-mercaptopropionate), pentaerythritol thioglycolate, pentaerythritol ruthenium (3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), various other polyols and thioglycolic acid, An ester of a thiol-containing carboxylic acid such as mercaptopropionic acid.

Further, examples of the polyfunctional thiol compound include trisylpropionate (2-hydroxyethyl)trimeric isocyanate, 1,4-dimethylnonylbenzene, and 2,4,6-trimethyl-s-trid. , 2-(N,N-dibutylamino)-4,6-dimercapto-s-three Wait. Further, examples of the polyfunctional thiol compound include 2,5-hexanedithiol, 2,9-nonanedithiol, 1,4-bis(1-mercaptoethyl)benzene, and di(1-decylethyl) phthalate. ), bis(2-mercaptopropyl phthalate), bis(3-mercaptobutyl phthalate), bis(3-mercaptoisobutyl phthalate), etc. based on the alpha and/or beta positions relative to the thiol a polyfunctional thiol compound having a substituent of a carbon atom; ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), Butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolpropane ginseng (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptobutyrate) , dipentaerythritol tert-(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate) ), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane ginseng (2-mercaptopropionate), pentaerythritol bismuth (2-mercaptopropionate) Acid ester), dipentaerythritol tert-(2-mercaptopropionate), ethylene glycol bis(3-mercaptoisobutyrate), propylene glycol bis(3-mercaptoisobutyrate), diethylene glycol bis (3-巯Isobutyrate), butanediol bis(3-mercaptoisobutyrate), octanediol bis(3-mercaptoisobutyrate), trimethylolpropane ginseng (3-mercaptoisobutyrate) , pentaerythritol bismuth (3-mercaptoisobutyrate), dipentaerythritol ter (3-mercaptoisobutyrate), ethylene glycol bis(2-mercaptoisobutyrate), propylene glycol bis(2-mercaptoisobutyrate) , diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolpropane Reference (2-mercaptoisobutyrate), pentaerythritol bismuth (2-mercaptoisobutyrate), dipentaerythritol tert-(2-mercaptoisobutyrate), ethylene glycol bis(4-mercaptovalerate), propylene glycol Bis(4-mercaptoisovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate) , trimethylolpropane ginseng (4-mercapto valerate), pentaerythritol bismuth (4-mercapto valerate), dipentaerythritol tert-(mercapto valerate), ethylene glycol bis(3-mercaptovalerate) ), propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), propylene glycol bis(3-mercaptovalerate), octanediol bis(3-mercapto pentane) Ester), trimethylolpropane reference (3-mercaptovalerate), pentaerythritol tetrakis (3-mercapto-valerate), dipentaerythritol land (3-mercaptovalerate) and the like.

In the present invention, among the above polyfunctional thiol compounds, decyl pentaerythritol (3-mercaptobutyrate) is preferred.

The product is exemplified by pentaerythritol strontium (3-mercaptobutyrate) (PTMP; "Karenz MT (trademark) PE1" manufactured by Showa Denko Co., Ltd.).

<Preparation ratio of each component in the colored resin composition>

The total content of the color material and other color materials represented by the general formula (I) is preferably from 3 to 65% by mass, more preferably from 4 to 55% by mass, based on the total amount of the solid content of the colored resin composition. The ratio is adjusted. When it is more than the above lower limit value, the colored layer has a sufficient color density when the colored resin composition is applied to a predetermined film thickness (usually 1.0 to 5.0 μm). Moreover, when it is at most the above upper limit value, dispersibility and dispersion stability are excellent, and a coloring layer having sufficient hardness or adhesion to a substrate can be obtained. Further, in the present invention, the solid content is an owner other than the above solvent, and includes a liquid polyfunctional monomer or the like.

In addition, the content of the dispersing agent is not particularly limited as long as the coloring material represented by the general formula (I) can be uniformly dispersed. For example, the total amount of the solid content of the colored resin composition can be used. 40% by mass. Further, the total amount of the solid content of the colored resin composition is preferably 5 to 35% by mass, particularly preferably 5 to 25% by mass. When it is more than the above lower limit value, the color material shown by the general formula (I) is excellent in dispersibility and dispersion stability, and the viscosity stability over time is excellent. Moreover, when it is below the said upper limit, the brightness of a colored layer can be favorable.

The total content of the alkali-soluble resin, the polyfunctional monomer, and the starter is preferably from 10 to 92% by mass, more preferably from 10 to 92% by mass based on the total amount of the solid content of the colored resin composition. The ratio is 15~87% by mass. When it is at least the above lower limit value, a coloring layer having sufficient hardness or adhesion to the substrate can be obtained. Moreover, if it is less than the above upper limit, the occurrence of minute wrinkles due to heat shrinkage is also suppressed.

Further, the content of the solvent can be appropriately set within a range in which the coloring layer can be formed with high precision. The total amount of the above colored resin composition containing the solvent is usually in the range of 55 to 95% by mass, and more preferably in the range of 65 to 88% by mass. When the content of the above solvent is within the above range, it is possible to obtain a coating property superior.

<Method for Producing Colored Resin Composition for Color Filter>

The method for producing a colored resin composition for a color filter of the present invention is a mixture containing the above-described color material dispersion liquid of the present invention, an alkali-soluble resin, a polyfunctional monomer, a starter, a solvent, and the like. The component may be added, and the color material may be uniformly dispersed in a solvent by a dispersing agent, and may be prepared by mixing using a known mixing means.

Examples of the method for preparing the resin composition include (1) mixing the alkali-soluble resin, the polyfunctional monomer, the initiator, and various additives to be used as needed in the color material dispersion of the present invention. (2) a method of simultaneously adding a coloring material, a dispersing agent, an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives as required in a solvent, and mixing them in a solvent; (3) a method of adding and mixing a dispersing agent, an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives to be used as needed, and then adding a coloring material and dispersing it in a solvent; (4) in a solvent, A coloring material, a dispersing agent, and an alkali-soluble resin are added to prepare a dispersion liquid, and an alkali-soluble resin, a polyfunctional monomer, an initiator, and various additives to be used as needed are added and mixed in the dispersion. .

Among these methods, from the viewpoint of effectively preventing aggregation of the color material and uniformly dispersing it In other words, the method of the above (4) is preferred.

3. Color filter

The color filter of the present invention includes at least a transparent substrate and a colored layer provided on the transparent substrate, and at least one of the colored layers has a colored layer formed by curing the colored resin composition of the present invention.

The color filter of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding portion 2, and a coloring layer 3.

(colored layer)

At least one of the coloring layers used in the color filter of the present invention is a coloring layer formed by curing the coloring resin composition of the color filter of the present invention.

The colored layer is usually formed on the opening of the light-shielding portion on the transparent substrate to be described later, and is usually composed of three or more colored patterns.

In addition, the arrangement of the colored layer is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangular type, or a four-pixel arrangement type. Further, the width, area, and the like of the colored layer can be arbitrarily set.

The thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration or viscosity of the colored resin composition, and the like, and is usually preferably in the range of 1 to 5 μm.

For example, when the colored resin composition is a photosensitive resin composition, the colored layer can be formed by the following method.

First, the coloring resin composition for a color filter of the present invention is coated by a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. A wet coating film is formed on a transparent substrate to be described later.

Then, the wet coating film is dried by a hot plate or an oven, and then exposed to a mask of a predetermined pattern, and an alkali-soluble resin, a polyfunctional monomer, or the like is photopolymerized to form a photosensitive coating film. Examples of the light source used for the exposure include ultraviolet rays such as a low pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the thickness of the light source or coating film to be used and the like.

Further, after the exposure, in order to promote the polymerization reaction, heat treatment may be performed. The heating conditions are appropriately selected depending on the blending ratio of each component in the colored resin composition to be used, the thickness of the coating film, and the like.

Next, development processing is carried out using a developing solution to dissolve and remove the unexposed portion, thereby forming a coating film in a desired pattern. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. In the alkaline solution, a surfactant or the like may be added in an appropriate amount. Further, the development method can employ a general method.

After the development treatment, the developer is usually washed and the cured coating film of the colored resin composition is dried to form a colored layer. Further, after the development treatment, heat treatment may be performed in order to sufficiently cure the coating film. The heating conditions are not particularly limited and may be appropriately selected depending on the use of the coating film.

(lighting part)

The light-shielding portion of the color filter of the present invention is formed into a pattern on a transparent substrate to be described later, and can be used as a light-shielding portion in a general color filter.

The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include a black pigment dispersed or dissolved in a binder resin, or a metal film such as chromium or chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a two-layer layer of a Cr film; or a CrO _x film (x is an arbitrary number) or a CrN _y film which further reduces the reflectance. (y is an arbitrary number) and three layers of the Cr film are laminated.

When the light-shielding portion is formed by dispersing or dissolving the black color material in the binder resin, the method of forming the light-shielding portion may be a method of patterning the light-shielding portion, and is not particularly limited. For example, a photolithography method using a colored resin composition for a light-shielding portion, a printing method, an inkjet method, or the like is exemplified.

The patterned light-shielding portion can be formed, for example, in the same manner as the formation of the colored layer described above.

The film thickness of the light-shielding portion is about 0.2 to 0.4 μm in the case of a metal thin film, and is about 0.5 to 2 μm when the black color material is dispersed or dissolved in the binder resin.

The chromaticity of the color layer of the color filter can be appropriately adjusted in accordance with a light source or the like, and is not particularly limited. For example, in the case of a blue colored layer, when the chromaticity (x, y) under the C light source is preferable, x is preferable. It is in the range of 0.12 to 0.27 and y is in the range of 0.04 to 0.18.

(transparent substrate)

The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples thereof include a flexible transparent rigid material such as quartz glass, an alkali-free glass, or a synthetic quartz plate, or a flexible transparent material such as a transparent resin film, an optical resin plate, or a flexible glass.

The thickness of the transparent substrate is not particularly limited, and for the use of the color filter of the present invention, for example, about 100 μm to 1 mm can be used.

Further, the color filter of the present invention may be, for example, a protective layer or a transparent electrode layer, an alignment film, an alignment protrusion, a columnar spacer, or the like in addition to the transparent substrate, the light shielding portion, and the coloring layer.

4. Display device

The display device of the present invention is characterized by having the above-described color filter of the present invention. In the present invention, the configuration of the display device is not particularly limited, and may be appropriately selected from known display devices, and examples thereof include a liquid crystal display device and an organic light-emitting display device.

[Liquid Crystal Display Device]

The liquid crystal display device is characterized by comprising the color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.

The liquid crystal display device of the present invention will be described with reference to the drawings. 2 is a schematic view showing an example of a liquid crystal display device. As shown in FIG. 2, the liquid crystal display device 40 includes a color filter 10, an opposite substrate 20 having a TFT array substrate, and a liquid crystal layer 30 formed between the color filter 10 and the counter substrate 20.

Further, the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and can be generally configured as a liquid crystal display device used for a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method used in a general liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.

Further, as the counter substrate, the driving side of the liquid crystal display device according to the present invention can be used. Select the appropriate use.

In addition, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and a mixture thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method of forming the liquid crystal layer, a method generally used as a method for producing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

[Organic light-emitting display device]

The organic light-emitting display device is characterized by comprising the above-described color filter of the present invention and an organic light-emitting body.

Such an organic light-emitting display device will be described with reference to the drawings. 3 is a schematic cross-sectional view showing an example of an organic light emitting display device. As shown in FIG. 3, the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light-emitting body 80.

As a method of laminating the organic light-emitting body 80, for example, a method of sequentially forming the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 on the color filter may be mentioned. Or a method of bonding the organic light-emitting body 80 formed on another substrate to the inorganic oxide film 60 or the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light-emitting layer 74, the electron injection layer 75, and the cathode 76 in the organic light-emitting body 80, and other configurations can be suitably used. The organic light-emitting display device 100 thus fabricated can also be applied to, for example, a passively driven organic EL display or an active driving organic EL display.

Further, the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and can be generally configured as an organic light-emitting display device used for a color filter.

[Examples]

Hereinafter, the embodiments will be specifically described with reference to the present invention. The invention is not limited to the description.

Further, the weight average molecular weight Mw of the basic copolymer in the present invention is determined by GPC (gel permeation chromatography) in terms of a standard polystyrene conversion value. For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, N-methylpyrrolidone with 0.01 mol/liter lithium bromide was added as the elution solvent, and the calibration curve was set to Mw377400 and 210500 using the polystyrene standard. , 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (above is Easi PS-2 series made by Polymer Laboratories) and Mw1090000 (made by Tosoh Co., Ltd.), with TSK-GEL ALPHA-M×2 (Tosoh Co., Ltd.) was carried out as a measuring column. Further, the macromonomer or the graft copolymer which is a raw material of the basic copolymer is also subjected to the above conditions.

Further, the acid value (mgKOH/g) is a value obtained by a potentiometric titration method in accordance with JIS K 0070.

(Synthesis Example 1: Synthesis of Intermediate 1)

The production of 1-iodonaphthalene 15.2g (60mmol) and Mitsui Chemicals Co., Ltd. Alkyldiamine (NBDA) (CAS No. 56602-77-8) 4.63 g (30 mmol), sodium butoxide sodium 8.07 g (84 mmol), 2-dicyclohexylphosphino-2', 6'-di, manufactured by Aldrich 0.09 g (0.2 mmol) of methoxybiphenyl and 0.021 g (0.1 mmol) of palladium acetate produced by Wako Pure Chemical Industries Co., Ltd. were dispersed in 30 mL of xylene, and reacted at 130-135 ° C for 48 hours. After completion of the reaction, the mixture was cooled to room temperature and added with water for extraction. Then, the mixture was dried over magnesium sulfate and concentrated to give 8.5 g (yield: 70%) of Intermediate 1 of the formula (1) below.

The obtained compound was confirmed to be the target compound by the following analysis.

‧MS(ESI)(m/z):407(M+H)

‧ Elemental analysis values: CHN measured values (85.47%, 8.02%, 6.72%); theoretical values (85.26%, 8.11%, 6.63%)

(Synthesis Example 2: Synthesis of Intermediate 2)

8.46 g (20.8 mmol) of Intermediate 1, Tokyo Chemical Industry Co., Ltd. 4,4'-bis(dimethylamino)diphenyl ketone 13.5 g (41.6 mmol), toluene 60 mL, and 45-50 ° C Stir. 6.38 g (51.5 mmol) of phosphonium chloride was prepared by the Wako Pure Chemical Industries, and refluxed for 2 hours and cooled. After the reaction was completed, toluene was decanted. To the resinous precipitate, 40 mL of chloroform, 40 mL of water, and concentrated hydrochloric acid were added to dissolve, and a chloroform layer was separated. The chloroform layer was washed with water, dried over magnesium sulfate and concentrated. 65 mL of ethyl acetate was added to the concentrate and refluxed. After cooling, the precipitate was filtered to obtain 15.9 g (yield: 70%) of the intermediate 2 (BB7-Nb-dimer) represented by the following chemical formula (2).

The obtained compound was confirmed to be the target compound by the following analysis.

‧MS(ESI)(m/z): 511(+), 2 price

‧ Elemental analysis values: CHN measured values (78.13%, 7.48%, 7.78%); theoretical values (78.06%, 7.75%, 7.69%)

(Synthesis Example 3: Synthesis of color material A)

5.00 g (4.58 mmol) of the intermediate 2 was added to 300 ml of water, and dissolved at 90 ° C to prepare an intermediate 2 solution. Then, 10.4 g (3.05 mmol) of phosphotungstic acid ‧n hydrate H ₃ [PW ₁₂ O ₄₀ ]‧nH ₂ O (n=30) manufactured by Nippon Chemical Industry Co., Ltd. was placed in 100 mL of water, and stirred at 90 ° C to prepare An aqueous solution of phosphotungstic acid. The aqueous solution of phosphotungstic acid was mixed at 90 ° C in the previous intermediate 2 solution, and the resulting precipitate was collected by filtration and washed with water. The obtained cake was dried to obtain 13.25 g (yield 98%) of a color material A represented by the following chemical formula (3).

The obtained compound was confirmed to be the target compound by the following analysis. (Morby W/Mo=100/0)

‧MS(ESI)(m/z): 510(+), 2 price

‧ Elemental analysis values: CHN measured values (41.55%, 5.34%, 4.32%); theoretical values (41.66%, 5.17%, 4.11%)

Further, it was confirmed by ³¹ P-NMR that the polyacid structure of the phosphotungstic acid remained after the coloring material A.

(Synthesis Example 4: Synthesis of Block Copolymer I)

The 500-ml four-necked flask was dried under reduced pressure and then replaced with Ar (argon). Under a stream of Ar, 100 g of dehydrated THF, 1.6 g of methyltrimethyldecyl dimethyl ketene acetal, and 1 M acetonitrile solution of tetrabutylammonium-3-chlorobenzoate (TBACB) were added, and 1,5 ml, 3,5-trimethylbenzene 0.2 g. Using a dropping funnel, 40 g of methyl methacrylate was dropped over 45 minutes. Since the reaction was heated, the temperature was kept below 40 ° C by ice cooling. After 1 hour, 10 g of dimethylaminoethyl methacrylate was dropped over 15 minutes. After reacting for 1 hour, 5 g of methanol was added to stop the reaction. The solvent is removed under reduced pressure to obtain Block copolymer I. The weight average molecular weight Mw determined by GPC measurement (NMP LiBr 10 mM) was 7.600, and the amine value was 70 mgKOH/g.

The obtained block copolymer I was dissolved in PGMEA to prepare a 60 wt% solution.

(Synthesis Example 5: Synthesis of Block Copolymer II)

In the same manner as in Synthesis Example 4 except that 37 g of methyl methacrylate and 13 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer II was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 90 mgKOH/g.

(Synthesis Example 6: Synthesis of Block Copolymer III)

In the same manner as in Synthesis Example 4 except that 35 g of methyl methacrylate and 15 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer III was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 105 mgKOH/g.

(Synthesis Example 7: Synthesis of Block Copolymer IV)

In the same manner as in Synthesis Example 4 except that 33 g of methyl methacrylate and 17 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer IV was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 120 mgKOH/g.

(Synthesis Example 8: Synthesis of Block Copolymer V)

In the same manner as in Synthesis Example 4 except that 30 g of methyl methacrylate and 20 g of dimethylaminoethyl methacrylate were changed in Synthesis Example 4, Block copolymer V. The weight average molecular weight Mw was 7.600, and the amine value was 140 mgKOH/g.

(Synthesis Example 9: Synthesis of Block Copolymer VI)

In the same manner as in Synthesis Example 4 except that 27.5 g of methyl methacrylate and 22.5 g of dimethylaminoethyl methacrylate were changed to Synthesis Example 4, a block copolymer VI was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 160 mgKOH/g.

(Comparative Synthesis Example 1: Synthesis of Block Copolymer VII)

In the same manner as in Synthesis Example 4 except that 41.5 g of methyl methacrylate and 8.5 g of dimethylaminoethyl methacrylate were changed, the block copolymer VII was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 60 mgKOH/g.

(Comparative Synthesis Example 2: Synthesis of Block Copolymer VIII)

In the same manner as in Synthesis Example 4 except that 26 g of methyl methacrylate and 24 g of dimethylaminoethyl methacrylate were changed to the synthesis example 4, the block copolymer VIII was obtained. The weight average molecular weight Mw was 7.600, and the amine value was 170 mgKOH/g.

The obtained block copolymer VIII was dissolved in PGMEA to prepare a 60 wt% solution.

(Comparative Synthesis Example 3: Synthesis of Graft Copolymer I) (1) Synthesis of giant monomer-I

80.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was added to a reactor equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated while stirring under a nitrogen stream. Temperature 90 ° C. 50.0 parts by mass of methyl methacrylate, 30.0 parts by mass of n-butyl methacrylate, 20.0 parts by mass of benzyl methacrylate, 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and α,α'-azo were dropped over 1.5 hours. A mixed solution of 1.0 part by mass of diisobutyronitrile (abbreviated as AIBN) was further reacted for 3 hours. Then, the nitrogen gas flow was stopped, and the reaction solution was cooled to 80 ° C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko Co., Ltd.), 0.125 g of dibutyltin dilaurate, 0.125 parts by mass of p-methoxyphenol, and PGMEA were added. 10 parts by mass and stirred for 3 hours, thereby obtaining a 49.5% solution of macromonomer I. The GPC measurement result of the obtained macromonomer I was 4010, the weight average molecular weight (Mn) was 1910, and the molecular weight distribution (Mw/Mn) was 2.10.

(2) Synthesis of graft copolymer I

80.0 parts by mass of PGMEA was placed in a reactor equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to a temperature of 85 ° C while stirring under a nitrogen stream. 75.76 parts by mass of the macromonomer I solution of the above (1) (49.5 parts by mass of the solid content), 12.5 parts by mass of dimethylaminoethyl methacrylate (DMMA), and n-dodecyl alcohol 1.24 were added dropwise over 1.5 hours. A mixed solution of a mass fraction, PGMEA 20.0 parts by mass, and AIBN 0.5 parts by mass, and after heating and stirring for 3 hours, a mixture of 0.10 parts by mass of AIBN and 10.0 parts by mass of PGMEA was dropped over 10 minutes, and further aged at the same temperature for 1 hour. This gave a 25.4% solution of graft copolymer I. As a result of GPC measurement of the obtained graft copolymer I, the weight average molecular weight (Mw) was 11,480, and the number average molecular weight (Mn) was 4,650. The distribution (Mw/Mn) was 2.47. Further, the amine value was 89 mgKOH/g.

(Production Example 1: Synthesis of alkali-soluble resin A)

150 parts by mass of PGMEA was placed in a polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), and PERBUTYL O (Nippon Oil Co., Ltd.) were added. 6 parts by mass of a chain shifting agent (n-dodecylmercaptan), 2 parts by mass, continuously dripped for 1.5 hours. Thereafter, the reaction was continued at 100 ° C, and after completion of the dropwise addition of the above-mentioned main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization.

Next, 14 parts by mass of glycidyl methacrylate (GMA) was added as an epoxy group-containing compound while blowing air, and the temperature was raised to 110 ° C, and 0.8 parts by mass of triethylamine was added thereto, and the mixture was added at 110 ° C. After reacting for 15 hours, an alkali-soluble resin A solution (weight average molecular weight (Mw) 9,000, acid value: 90 mgKOH/g, solid content: 40% by mass) was obtained.

Further, the above weight average molecular weight was measured by using Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. Further, the method for measuring the acid value is measured in accordance with JIS K 0070. The following alkali-soluble resins B to E were also subjected to the same method to measure a weight average molecular weight and an acid value.

(Production Example 2: Synthesis of alkali-soluble resin B)

In the same manner as in Production Example 1, except that the methacrylic acid (MAA) was 26.5 parts by mass and the cyclohexyl methacrylate (CHMA) was 59.5 parts by mass, the alkali-soluble resin was obtained. PPGMEA solution of B (solid content 40% by mass). The alkali-soluble resin B has a weight average molecular weight of 9,000 and an acid value of 120 mg KOH / g.

(Production Example 3: Synthesis of alkali-soluble resin C)

In the same manner as in Production Example 1, except that the methacrylic acid (MAA) was 29.5 parts by mass and the cyclohexyl methacrylate (CHMA) was 56.5 parts by mass, the alkali-soluble resin was obtained. PPGMEA solution of C (solid content 40% by mass). The alkali-soluble resin C had a weight average molecular weight of 9,000 and an acid value of 140 mgKOH/g.

(Production Example 4: Synthesis of alkali-soluble resin D)

In the same manner as in Production Example 1, except that the methacrylic acid (MAA) was 18.5 parts by mass and the cyclohexyl methacrylate (CHMA) was 67.5 parts by mass, the alkali-soluble resin was obtained. DPGMEA solution (solid content 40% by mass). The alkali-soluble resin D had a weight average molecular weight of 9,000 and an acid value of 70 mgKOH/g.

(Production Example 5: Synthesis of alkali-soluble resin E)

129 parts by mass of PGMEA was placed in a polymerization tank, and after heating to 100 ° C in a nitrogen atmosphere, 5.8 parts by mass of methacrylic acid (MAA), 20.4 parts by mass of methyl methacrylate (MMA), and glycidyl methacrylate were added. (BzMA) 59.8 parts by mass and 6 parts by mass of PERBUTYL O (manufactured by Nippon Oil Co., Ltd.) and 2 parts by mass of a chain shifting agent (n-dodecylmercaptan) were continuously dropped over 1.5 hours. Thereafter, the reaction was continued at 100 ° C, and after completion of the dropwise addition of the above-mentioned main chain-forming mixture for 2 hours, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor, and polymerization was stopped to obtain an alkali-soluble resin E solution (weight-flat The average molecular weight (Mw) was 9,000, the acid value was 70 mgKOH/g, and the solid content was 40% by mass.

(Preparation Example 1: Preparation of Photosensitive Adhesive Component CR-1)

To 31.4 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Production Example 1, 18.8 parts by mass of dipentaerythritol hexaacrylate (DPHA) (ARONIX M402 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added. 5.9 parts by mass of IRGACURE 907 (manufactured by BASF), 2.0 parts by mass of KAYACURE-DETX-S (manufactured by Nippon Kasei Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 41.2 parts by mass of PGMEA were obtained as a starter. The adhesive component CR-1.

(Preparation Example 2 to 3: Modulation of photosensitive adhesive component CR-2 to CR-3)

In the preparation example 1, except for the alkali-soluble resin A solution (solid content: 40% by mass), the alkali-soluble resin B-C solution (solid content: 40% by mass) of Production Examples 2 to 3 was used, and the other examples were prepared. 1 In the same manner, photosensitive adhesive components CR-2 to CR-3 were obtained.

(Preparation Example 4: Modulation of photosensitive adhesive component CR-4)

To 31.4 parts by mass of the alkali-soluble resin B solution (solid content: 40% by mass) obtained in Production Example 2, 18.8 parts by mass of a polybasic acid-modified acrylic oligomer (ARONIX M520 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added. 5.9 parts by mass of IRGACURE 907 (manufactured by BASF), 2.0 parts by mass of KAYACURE-DETX-S (manufactured by Nippon Kasei Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 41.2 parts by mass of PGMEA were obtained as a starter. The adhesive component CR-4.

(Preparation Example 5: Modulation of photosensitive adhesive component CR-5)

In the same manner as in Preparation Example 1, except that the alkali-soluble resin A solution (solid content: 40% by mass) was used instead of the alkali-soluble resin A solution (solid content: 40% by mass) of the production example 1 was used. The photosensitive adhesive component CR-5 was obtained.

(Example 1: Preparation of color material dispersion A-1)

65.2 parts by mass of PGMEA, 14.6 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass), and 6.8 parts by mass of a block copolymer (solid content: 60% by mass) of Synthesis Example 4 were stirred and stirred in a 225 mL mayon bottle. . To this was added 0.48 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.6 molar equivalent to the tertiary amine group of the block copolymer), and the mixture was stirred at room temperature for 30 minutes.

1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion A-1 was obtained.

(Examples 2 to 19: color material dispersions A-2 to A-3, B-1 to B-6, C-1 to C-2, D-1 to D-4, E-1 to E-2 , modulation of F-1~F-2)

In the first embodiment, the total mass of the block copolymer and the total mass of the organic acid compound were fixed, and the type of the block copolymer and the blending ratio with the phenylphosphonic acid were changed as shown in Table 1. In the same manner as in Example 1, the color material dispersions A-2 to A-3, B-1 to B-6, C-1 to C-2, D-1 to D-4, and E-1 to E were obtained. -2, F-1~F-2.

(Comparative Examples 1 to 15: color material dispersions A-4, B-7 to B-8, C-3 to C-4, D-5 to D-7, Modulation of E-3~E-4, F-3~F-5, G, H)

In the first embodiment, the total mass of the block copolymer and the total mass of the organic acid compound were fixed, and the type of the block copolymer and the blending ratio with the phenylphosphonic acid were changed as shown in Table 1. In the same manner as in Example 1, the color material dispersions A-4, B-7~B-8, C-3~C-4, D-5~D-7, E-3~E-4, F were obtained. -3~F-5, G, H.

(Comparative Example 16: Modulation of Color Material Dispersion I)

65.3 parts by mass of PGMEA, 14.3 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass), Disperbyk LPN6919 (acrylic dispersant made by BYK Chemie Co., Ltd., 60 parts by mass of solid content) (amine) in a 225 mL mayon bottle The price was 120 mgKOH/g, and the solid content was 60% by mass) of 6.3 parts by mass and stirred. 0.77 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added thereto (0.6 molar equivalent to the amine group of LPN6919), and the mixture was stirred at room temperature for 30 minutes.

1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion I was obtained.

(Comparative Example 17: Modulation of Color Material Dispersion J)

To 225 mL of a cannabis bottle, 57.6 parts by mass of PGMEA and 14.6 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass) were added, and the graft copolymer I of Comparative Synthesis Example 4 was compared (amine price: 89 mgKOH/g, solid content: 25.4) Mass%) 13.7 parts by mass and stirred. Ethyl oxyethyl methacrylate was added thereto (trade name: P-2M, Gongrong Shehua 1.07 parts by mass (0.6 molar equivalents relative to the amine group of the graft copolymer I), and stirred at room temperature for 30 minutes.

1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion J was obtained.

<Evaluation of dispersion stability of color material dispersion>

The color material dispersion liquids of the examples and the comparative examples were each stored at room temperature (25 ° C), and the viscosity was measured after one day of preparation and one month after storage. The viscosity was measured at 25.0 ± 1.0 ° C using a vibrating viscometer (VM-200T2 manufactured by SEKONIC), and the value was 30 seconds after the start of the measurement.

The viscosity after 1 day of dispersion was compared with the viscosity after 1 month of storage. The viscosity was changed to 10% or less, and the viscosity was changed to 10%. The results are shown in Table 1. When the viscosity change is within 10%, the dispersion stability is excellent, and the evaluation is a practical range.

(Example 20: Modulation of colored resin composition)

30.5 parts by mass of the color material dispersion liquid A-1 of Example 1, 26.9 parts by mass of the photosensitive adhesive component CR-1 of Preparation Example 1, 0.01 parts by mass of the surfactant MEGAFAC R08MH (manufactured by DIC), and 42.5 parts by mass of PGMEA The colored resin composition of Example 20 was obtained.

(Examples 21 to 38: Preparation of Colored Resin Composition)

In the same manner as in Example 20, except that the color material dispersion liquid A-1 was replaced with the color material dispersion liquid described in Table 2 below, the coloring resin compositions of Examples 21 to 38 were obtained. Things.

(Examples 39 to 42: Preparation of Colored Resin Composition)

In the example 20, the color material dispersion liquid D-1 was used instead of the color material dispersion liquid A-1, and the photosensitive adhesive agent component CR-1 was used instead of the photosensitive adhesive component CR-2 to CR-5. The rest was carried out in the same manner as in Example 20 to give the colored resin compositions of Examples 39 to 42.

(Comparative Examples 18 to 34: Preparation of Colored Resin Composition)

In the same manner as in Example 20 except that the color material dispersion liquid and the photosensitive binder component were changed to the combination of the following Table 2, the colored resin compositions of Comparative Examples 18 to 34 were obtained.

<Evaluation of Viscosity Stability of Colored Resin Composition>

The colored resin compositions of the examples and the comparative examples were measured by the same method as the evaluation of the dispersion stability of the color material dispersion.

Comparing the viscosity after 1 day of preparation and the viscosity after 1 month of storage, the viscosity is changed to 3% or less, and the viscosity is changed to more than 3% and within 5%, B is set, and more than 5% is set. C. The results are shown in Table 2. If the viscosity change is within 5%, the stability is excellent, and the evaluation is a practical range.

<heat resistance evaluation>

Each of the colored resin compositions of the examples and the comparative examples was applied onto a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm using a spin coater. Thereafter, the film was dried by heating on a hot plate at 80 ° C for 3 minutes. A cured film (blue colored film) was obtained by irradiating ultraviolet rays of 60 mJ/cm ² with an ultrahigh pressure mercury lamp without using a photomask. The film thickness (T; μm) of the cured film was adjusted so that the chromaticity after post-baking was y=0.090. The chromaticity (L ₀ , a ₀ , b ₀ ) of the colored film was measured, and thereafter, the glass plate on which the colored film was formed was post-baked in a dust-free oven at 230 ° C for 25 minutes, and the color of the obtained colored film was measured again. Degree (L ₁ , a ₁ , b ₁ ).

In addition, the chromaticity of the colored film was measured using the "microscopic spectroscopic measuring device OSP-SP200" manufactured by Olympus Co., Ltd.

The chromaticity change of the color film before and after baking was evaluated by the following formula. The results are shown in Table 2.

△Eab={(L ₁ -L ₀ ) ² +(a ₁ -a ₀ ) ² +(b ₁ -b ₀ ) ² } ^1/2

When ΔEab is 3 or less, A is set, ΔEab is more than 3 and 5 or less is B, ΔEab is more than 5 and 6 or less is C, and ΔEab is more than 6 is D. When ΔEab is 5 or less, heat resistance is excellent, and it is evaluated as a practical range.

<Evaluation of development time>

The colored resin compositions of the comparative examples in which the viscosity stability was evaluated as B in the examples and the comparative examples were each applied to a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm using a spin coater. . The film thickness was adjusted to 2.5 μm. Thereafter, the film was dried by heating on a hot plate at 80 ° C for 3 minutes, and then irradiated with ultraviolet rays of 60 mJ/cm ² through a mask pattern using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development using a 0.05 mass% potassium hydroxide aqueous solution as an alkali developing solution, and the time until the mask pattern was completely formed was measured. The results are shown in Table 2.

<Evaluation of solvent resolubility>

Only the glass rods in which the number of the colored resin compositions evaluated were prepared were immersed in the colored resin composition of the comparative example in which the viscosity stability was evaluated as B in the examples and the comparative examples, and were adhered to each other. It was dried for 30 minutes in an environment of a temperature of 23 ° C and a humidity of 70%. Thereafter, the front end of the glass rod to which the colored resin composition was attached was immersed in PGMEA and stirred for 15 seconds. When the colored resin composition adhering to the glass rod within 1 minute after the stirring was all dissolved, it was set to A, and if it was not completely dissolved, the peeling sheet remained as B. The results are shown in Table 2.

[Results integration]

It is understood that the color material dispersion liquid of Examples 1 to 19 having the general formula (I), the dispersant, and the organic acid compound, and the dispersant and the organic acid compound satisfy the above formulas (1) to (3) Even after the storage for 1 month, the viscosity change is still within 10%, and the dispersion stability is excellent.

Moreover, it is understood that the colored resin compositions of Examples 20 to 42 prepared by using the color material dispersion liquids of Examples 1 to 19 are excellent in dispersion stability, and can form a coating film having improved heat resistance.

Further, it is understood that X is a colored resin composition of Examples 21, 22, 25-28, 30, 32-34, 36, and 38 of 0.9 or more; Examples 39 and 40 using an alkali-soluble resin having a high acid value; Further, the colored resin composition of Example 41 using a polyfunctional monomer having a carboxyl group has particularly excellent heat resistance.

The results of the examples and comparative examples will be described with reference to Fig. 5 . Fig. 5 is a plan view showing the relationship between A and X of the color material dispersion liquids of Examples 1 to 22 and Comparative Examples 1 to 15. Further, in Fig. 5, graphs showing A × X = 40, A × (1-X) = 42, A = 160, A = 70, and X = 1.5 are shown. In Fig. 5, a region satisfying A × X ≧ 40, A × (1-X) ≦ 42, A ≦ 160, A ≧ 70, and X ≦ 1.5 is referred to as region I; A × X ≧ 40, A × will be satisfied. The area of (1-X)>42 and A≦160 is set to area II; the area satisfying A×X<40, A×(1-X)≦42 and A≧70 is set as area III; A region where X<40, A×(1-X)>42, A≦160, and A≧70 is set as the region IV.

In the region I, the color material dispersion liquids of Examples 1 to 19 were included. The color material dispersion of Comparative Examples 3, 5, 7, 8, 10, 12 and 13 was included in the area II. The color material dispersion of Comparative Example 1 was included in the region III. Also, Region IV includes Comparative Examples 2, 4, and 6. 9 and 11 color material dispersion.

As shown in the results of the above Table 1, the color material dispersion liquids of the examples and the comparative examples included in the regions I and II were excellent in dispersion stability. In particular, comparison of the color material dispersion liquids of Examples 1, Comparative Examples 3, 5, 7, 10, and 12 with the color material dispersion liquids of Comparative Examples 1, 2, 4, 6, 9, and 11 shows that at A × When X=40 is a boundary line and A×X≧40 (Formula 2) is satisfied, the dispersion stability of the color material dispersion liquid is excellent.

On the other hand, as shown in the results of Table 2, it was found that the coloring film formed of the colored resin compositions of Examples 20 to 42 and Comparative Example 18 contained in the color material dispersion liquids included in the regions I and III was used. The heat resistance was evaluated as A or B, and the heat resistance was excellent. In particular, from the results of Examples 23, 29, 31, 35 and 37 of Examples 4, 10, 12, 16 and 18 using the point at A × (1-X) = 42, it is known that at A × ( 1-X)=42 is a boundary line and satisfies A×(1-X)≦42 (Formula 3), and the heat resistance of the colored film is excellent.

(Examples 43 to 61: Preparation of color material dispersion)

In the same manner as in Examples 1 to 19, except that the molar amount of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of PPA, each of Examples 1 to 19 was obtained. The color material dispersions of Examples 43 to 61 (in the order of K-1~K-3, L-1~L-6, M-1~M-2, N-1~N-4, O-1~) O-2, P-1~P-2).

(Comparative Examples 35 to 47: Preparation of Color Material Dispersion)

In Comparative Examples 1 to 13, except that each of the molar amounts of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of PPA, the same procedure as in Comparative Examples 1 to 13 was carried out. The color material dispersions of Comparative Examples 35 to 47 (in the order of K-4, L-7~L-8, M-3~M-4, N-5~N-7, O-3~O-4, P-3~P-4).

With respect to the color material dispersion liquids of Examples 43 to 61 and Comparative Examples 35 to 47, the dispersion stability of the color material dispersion liquid was evaluated in the same manner as the dispersion stability evaluation of the above color material dispersion liquid. The results are shown in Table 3.

(Examples 62 to 80: Preparation of Colored Resin Composition)

In the same manner as in Example 20 except that the color material dispersion liquid and the photosensitive binder component were changed to the combination of the following Table 4, the colored resin compositions of Examples 62 to 80 were obtained.

(Comparative Examples 48 to 60: Preparation of Colored Resin Composition)

In the same manner as in Example 20 except that the color material dispersion liquid and the photosensitive binder component were changed to the combination of the following Table 4, the colored resin compositions of Comparative Examples 48 to 60 were obtained.

The colored resin compositions of Examples 62 to 80 and Comparative Examples 48 to 60 were the same as the evaluation of the viscosity stability, the evaluation of the heat resistance, the evaluation of the development time, and the evaluation of the solvent resolubility of the colored resin composition, respectively. Method, evaluation. The results are shown in Table 4.

[Results integration]

It is understood that the color material dispersion liquid of the examples 43 to 61 of the above formulas (1) to (3) is obtained by the color material, the dispersant, and the organic acid compound represented by the general formula (I), and the dispersant and the organic acid compound satisfy the above formulas (1) to (3). Even after the storage for 1 month, the viscosity change is still within 10%, and the dispersion stability is excellent.

Further, it was found that the colored resin compositions of Examples 62 to 80 prepared by using the color material dispersion liquids of Examples 43 to 61 were excellent in dispersion stability and formed a coating film having improved heat resistance.

From the comparison of Table 2 and Table 4, the colored resin compositions of Examples 20 to 42 and Comparative Examples 18 to 30 which are phenylphosphonic acids belonging to the divalent organic acid compound were used; and in addition to the use of the monovalent organic acid compound The colored resin compositions of Examples 62 to 80 and Comparative Examples 48 to 60, which correspond to the above-mentioned colored resin composition, other than p-toluenesulfonic acid, were evaluated for viscosity stability, heat resistance evaluation, and development of the colored resin composition. Both the evaluation of the time and the evaluation of the solvent resolubility gave the same results as the corresponding colored resin composition. From this, it is understood that the formula (1) to the formula (3) are satisfied regardless of the valence of the organic acid compound. As a result, it is presumed that the block copolymer has a constituent unit (a) represented by the general formula (II) and an organic acid compound which is formed by salt formation in a one-to-one manner regardless of the valence of the organic acid compound.

(Synthesis Example 10: Synthesis of Block Copolymer IX)

In the same manner as in Synthesis Example 4 except that 36.5 g of methyl methacrylate and 13.5 g of dimethylaminoethyl methacrylate were changed, the block copolymer IX was obtained. The weight average molecular weight Mw is 7,600, and the amine price is 95 mg KOH / g.

(Synthesis Example 11: Synthesis of Block Copolymer X)

To a 500 mL round bottom four-neck separation flask equipped with a cooling tube, an addition funnel, a nitrogen gas inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added, and nitrogen substitution was sufficiently performed. After cooling the reaction flask to -60 ° C, 4.9 parts by mass of butyllithium (15 mass% hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 part by mass of methyl isobutyrate were injected using a syringe. 2.2 parts by mass of 1-ethoxyethyl methacrylate (EEMA) of the B block, 29.1 parts by mass of 2-(trimethyldecyloxy)ethyl methacrylate (TMSMA), methacrylic acid 12.8 parts by mass of 2-ethylhexyl ester (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA). Use the addition funnel to drip for 60 minutes. After 30 minutes, the A block was dropped with 26.7 parts by mass of a monomeric dimethylaminoethyl methacrylate (DMMA) over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to prepare a 30% by mass solid solution. 32.5 parts by mass of water was added, and the temperature was raised to 100 ° C for 7 hours. The constituent unit derived from EEMA was deprotected to form a constituent unit derived from methacrylic acid (MAA), and the constituent unit derived from TMSMA was deprotected to prepare a methyl group. The constituent unit of 2-hydroxyethyl acrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, and purified by filtration and vacuum drying to obtain a block copolymer X (acid value: 8 mg KOH / g, Tg 38 ° C). The block copolymer X thus obtained was confirmed by GPC (gel permeation chromatography), and the weight average molecular weight Mw was 7730. The amine value was also 95 mgKOH/g.

(Synthesis Examples 12 to 15: Synthesis of Block Copolymers XI to XIV)

In the synthesis example 11, the block copolymers XI to XIV were obtained in the same manner as in the synthesis example 11 except that the monomer ratio was changed as shown in Table 5.

The abbreviations in the table are as follows.

PME-200: methoxypolyethylene glycol monomethacrylate (trade name: PME-200, manufactured by Nippon Oil Co., Ltd., BLEMMER-PME-200, ethoxylated repeat number = 4)

(Preparation Example 6: Modulation of photosensitive adhesive component CR-6)

36.9 parts by mass of dibasic pentaerythritol hexaacrylate (DPHA) (ARONIX M402 (manufactured by Toagosei Co., Ltd.)), which is a polyfunctional monomer, was added to 36.9 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) obtained in Production Example 1, 1.8 parts by mass of IRGACURE 907 (manufactured by BASF), 0.6 parts by mass of KAYACURE-DETX-S (manufactured by Nippon Kasei Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 37.9 parts by mass of PGMEA were obtained as a starter. The adhesive component CR-6.

(Preparation Example 7 to 12: Modulation of Photosensitive Adhesive Component CR-7~12)

In the same manner as in Preparation Example 6, except that the type of the initiator and the amount of the preparation were changed to the combinations described in the columns of Examples 96 to 101 of Table 8, the photosensitive adhesive component CR was obtained. -7~12.

Further, the abbreviations of the initiators in Table 8 are as follows.

IRG907: IRGACURE 907 (made by BASF)

DETX: KAYACURE-DETX-S (made by Nippon Kasei Co., Ltd.)

OXE01: IRGACURE OXE01 (made by BASF)

OXE02: IRGACURE OXE02 (manufactured by BASF)

NCI930: ADEKA ARKLS NCI-930 (made by ADEKA, oxime-based photoinitiator)

PBG304: TR-PBG-304 (made by Changzhou Power Electronic New Material Co., Ltd., oxime ester photoinitiator)

(Preparation Examples 13 to 19: Modulation of Photosensitive Adhesive Components CR-13 to 19)

In addition to replacing the alkali-soluble resin A solution (solid content 40% by mass), it was changed to an alkali-soluble resin F solution (carboxy-containing epoxy (meth) acrylate resin containing cardo structure, model number INR-16M Nagase ChemteX (share) In the same manner as in Preparation Examples 6 to 12, the photosensitive adhesive components CR-13 to 19 were obtained, except that the amount of the solid content was adjusted to 54.5%.

(Preparation Example 20 to 26: Modulation of Photosensitive Adhesive Component CR-20~26)

In place of the alkali-soluble resin A solution (solid content: 40% by mass), the solution was changed to an alkali-soluble resin G solution (a propylene glycol monomethyl ether acetate solution having an anhydride polycondensate of an epoxy acrylate having an anthracene skeleton, trade name V259ME, In the same manner as in the preparation examples 6 to 12, a photosensitive adhesive component was obtained, except that the amount of the solid portion was adjusted to be the same by the amount of the solid portion, which was 55.8 mass%). CR-20~26.

(Preparation Example 27: Modulation of photosensitive adhesive component CR-27)

To 26.4 parts by mass of the alkali-soluble resin G solution (solid content: 55.8 mass%), 22.1 parts by mass of pentaerythritol tetraacrylate (PETA) (ARONIX M305 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added, and IRGACURE as a starter was added. 1.2 parts by mass of OXE01 (manufactured by BASF), 1.2 parts by mass of IRGACURE OXE02 (manufactured by BASF Pharmaceutical Co., Ltd.), 0.8 parts by mass of antioxidant IRGANOX 1010 (manufactured by BASF), and 37.9 parts by mass of PGMEA. To the photosensitive adhesive component CR-27.

(Preparation Example 28: Modulation of photosensitive adhesive component CR-28)

To 26.4 parts by mass of the alkali-soluble resin G solution (solid content: 55.8 mass%), 22.1 parts by mass of a polybasic acid-modified acrylic oligomer (ARONIX M520 (manufactured by Toagosei Co., Ltd.)) as a polyfunctional monomer was added as a starter. 1.2 parts by mass of IRGACURE OXE01 (manufactured by BASF), 1.2 parts by mass of IRGACURE OXE02 (manufactured by BASF), 0.8 parts by mass of an antioxidant IRGANOX 1010 (manufactured by BASF), and 37.9 parts by mass of PGMEA, a photosensitive binder component CR-28 was obtained.

(Example 81: Modulation of color material dispersion Q)

63.3 parts by mass of PGMEA, 13.0 parts by mass of an alkali-soluble resin E solution (solid content: 40% by mass), and a block copolymer IX solution of Synthesis Example 10 (amine price 95 mgKOH/g, solid content 45) were added to a 225 mL mayon bottle. Mass%) 10.0 parts by mass and stirred. To this was added 0.72 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) (0.6 molar equivalent to the tertiary amine group of the block copolymer), and the mixture was stirred at room temperature for 30 minutes.

1 part by mass of the color material A of the synthesis example 3 and 100 parts by mass of zirconia beads having a particle diameter of 2.0 mm were shaken by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 1 hour as a preliminary pulverization, and then changed to a particle diameter of 0.1 mm. 200 parts of zirconia beads were dispersed by a coating shaker for 4 hours to form a solid dispersion, and a color material dispersion liquid Q was obtained.

(Examples 82 to 87: Preparation of color material dispersion)

In Example 81, except for the substituted block copolymer IX solution, it was changed to The coloring material dispersions R to W of Examples 82 to 87 were obtained in the same manner as in Example 81 except for the block copolymer X to XIV solutions of Synthesis Examples 11 to 15.

With respect to the color material dispersion liquids of Examples 81 to 87, the dispersion stability of the color material dispersion liquid was evaluated in the same manner as the dispersion stability evaluation of the above color material dispersion liquid. The results are shown in Table 6.

(Example 88: Preparation of colored resin composition)

27.4 parts by mass of the color material dispersion liquid of Example 81, 23.5 parts by mass of the photosensitive adhesive component CR-1 of Preparation Example 1, and pentacene tetradecanoate (3-mercaptobutyrate) (PTMP; "Karenz MT" by Showa Denko Co., Ltd. (Trademark) PE1") 0.47 parts by mass, surfactant MEGAFAC R08MH (manufactured by DIC) 0.01 parts by mass, and PGMEA 48.6 parts by mass, the colored resin composition of Example 88 was obtained.

(Examples 89 to 94: Preparation of Colored Resin Composition)

In the same manner as in Example 88 except that the color material dispersion liquid Q was changed to the color material dispersion liquid R to W, the colored resin compositions of Examples 89 to 94 were obtained.

The colored resin compositions of Examples 88 to 94 were evaluated in the same manner as the evaluation of the viscosity stability of the colored resin composition, the evaluation of heat resistance, the evaluation of development time, and the evaluation of solvent resolubility. The results are shown in Table 7.

(Examples 95 to 117: Preparation of Colored Resin Composition)

In Example 88, the coloring of Examples 95 to 117 was carried out in the same manner as in Example 88 except that the photosensitive adhesive component CR-1 was replaced with the photosensitive adhesive component CR-6 to 28, respectively. Resin composition.

(Example 118: Preparation of colored resin composition)

27.4 parts by mass of the color material dispersion R of Example 82, 23.5 parts by mass of the photosensitive adhesive component CR-6 of Preparation Example 6, and quinone tetradecanoate (3-mercaptobutyrate) (PTMP; "Karenz MT, manufactured by Showa Denko" (Trademark) PE1") 0.47 parts by mass, surfactant MEGAFAC R08MH (manufactured by DIC) 0.01 parts by mass, and PGMEA 48.6 parts by mass, the colored resin composition of Example 118 was obtained.

(Examples 119 to 140: Preparation of Colored Resin Composition)

In the same manner as in Example 118 except that the photosensitive adhesive component CR-6 was replaced by the photosensitive adhesive component CR-6, the coloring of Examples 119 to 140 was obtained. Resin composition.

(Examples 141 to 150: Preparation of Colored Resin Composition)

In the same manner as in Example 118 except that the color material dispersion liquid and the photosensitive binder component shown in the table were changed, the colored resin compositions of Examples 141 to 150 were obtained.

<Solvent resistance: NMP swelling test>

The colored resin composition of the example was applied to a glass substrate having a thickness of 0.7 mm and 100 mm × 100 mm by a spin coater and a film thickness of about 2.5 μm after baking (NH TECHNO GLASS, Ltd., "NA35"). Thereafter, the film was dried by heating on a hot plate at 80 ° C for 3 minutes. The ultraviolet rays of 40 mJ/cm ^{2 were} irradiated with an ultrahigh pressure mercury lamp without using a photomask, and post-baking was performed for 30 minutes in a dust-free furnace at 220 ° C to obtain a cured film (blue colored film).

The film thickness of the obtained cured film was measured and referred to as T1. Thereafter, the film was immersed in 25° C-methylpyrrolidone for 60 minutes, and the film thickness immediately after the extraction was measured to obtain T2. Calculate T2/T1×100 (%), set the case of less than 103% to AA, 103% or more and less than 105%, and set it to A, 105% or more and less than 110%. When it is more than % and less than 115%, it is set to C, and 115% or more is set to D. The results are shown in Tables 8 to 10. If the above evaluation criteria are AA, A, B or C, it is practical, but if the evaluation result is B and further A, the effect is further superior.

<Development residue evaluation>

Each of the colored resin compositions of the examples was applied onto a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm by a spin coater, and then dried at 80 ° C using a hot plate. 3 minutes, thereby forming a coloring layer having a thickness of 3.0 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The unexposed portion (50 mm × 50 mm) of the glass substrate after the formation of the colored layer was visually observed, and then thoroughly wiped with a lens cleaning cloth (trade name: TORAYSEE MK cleaning cloth, manufactured by Toray Industries, Inc.) containing ethanol to visually observe the lens. The degree of coloring of the cleaning cloth. The results are shown in Tables 8 to 10.

(Development residue evaluation standard)

A: The development residue was not visually confirmed, and the lens cleaning cloth was completely free from coloration.

B: The development residue was not visually observed, and it was confirmed that the lens cleaning cloth was slightly colored.

C: A slight development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

D: The development residue was visually confirmed, and the color of the lens cleaning cloth was confirmed.

If it is the above evaluation criteria A, B or C, it is practical, but if the evaluation result is B and further A, the effect is more excellent. The results are shown in Tables 8 to 10.

<Water Infiltration Evaluation>

Each of the colored resin compositions of the examples was applied onto a glass substrate (manufactured by NH TECHNO GLASS, "NA35") having a thickness of 0.7 mm and 100 mm × 100 mm by a spin coater, and then dried at 80 ° C using a hot plate. 3 minutes, thereby forming a coloring layer having a thickness of 3.0 μm. Thereafter, ultraviolet rays of 40 mJ/cm ^{2 were} completely irradiated with an ultrahigh pressure mercury lamp without passing through a photomask. Next, the mixture was rotated and developed with 0.05 wt% of potassium hydroxide (KOH) as a developing solution, and the solution was liquid-contacted with the developing solution for 60 seconds, and then washed with pure water to carry out development treatment, and the washed substrate was rotated for 10 seconds to be centrifuged. Immediately after the water was removed, the contact angle of the pure water was measured as described below, and the water bleeding was evaluated.

The contact angle of pure water was measured on the surface of the colored layer immediately after the water was removed by centrifugation, and a droplet of 1.0 μL of pure water was dropped, and the static contact angle after the dropping for 10 seconds was measured by the θ/2 method. The measurement apparatus was measured using a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Tables 8 to 10.

(evaluation benchmark)

A: The contact angle is 80 degrees or more

B: The contact angle is 65 degrees or more and less than 80 degrees.

C: contact angle of 50 degrees or more and less than 65 degrees

D: The contact angle is less than 50 degrees

If the water infiltration evaluation standard is A or B, it is available for practical use; but if the evaluation result is A, the effect is more superior.

<Development and adhesion evaluation>

Each of the photosensitive colored resin compositions obtained in the examples and the comparative examples was applied to a glass substrate having a thickness of 0.7 mm and 100 mm × 100 mm using a spin coater (NH TECHNO GLASS, "NA35"). After the above, drying was performed at 60 ° C for 3 minutes using a hot plate, thereby forming a coloring layer having a thickness of 2.5 μm. The colored layer was irradiated with ultraviolet rays of 60 mJ/cm ² using an ultrahigh pressure mercury lamp through a mask having a mask opening width of 2 to 80 μm. The glass plate on which the colored layer was formed was subjected to shower development using a 0.05% by mass aqueous potassium hydroxide solution as an alkali developing solution for 60 seconds. The developed substrate was observed with an optical microscope to observe the presence or absence of a colored layer with respect to the opening line width of the mask. The results are shown in Tables 8 to 10.

(Development adhesion evaluation standard)

A: A colored layer was observed in a portion of the mask opening line width of less than 10 μm.

B: A colored layer was observed in a portion of the mask opening line width of 10 μm or more and less than 20 μm.

C: A colored layer was observed in a portion of the mask opening line having a width of 20 μm or more and less than 50 μm.

D: A colored layer was observed in a portion of the mask opening line width of 50 μm or more and less than 80 μm.

E: No colored layer was observed in a portion of the mask opening line width of 80 μm or less.

When the evaluation criteria are A, B or C, it is practical. However, when the evaluation result is B and further A, the photosensitive colored resin composition for a color filter is suitable for higher definition.

[Results integration]

It is understood that a colored resin composition having a dispersant having an acid value of 1 mgKOH/g or more and 18 mgKOH/g or less and a glass transition temperature of 30 ° C or more is used, and development residue, substrate adhesion, and development adhesion are particularly excellent.

It is understood that the colored resin composition using the alkali-soluble resin represented by the general formula (B) is more excellent in suppressing swelling and solvent resistance by NMP.

Moreover, it is understood that the examples using the oxime ester-based initiator are superior in solvent resistance (NMP swelling inhibition) and further suppress the occurrence of water bleeding.

Claims (16)

A color material dispersion liquid comprising a color material, a dispersant, an organic acid compound, and a solvent represented by the following general formula (I); wherein the dispersant has at least the following general formula (II); a constituent unit (a), a block copolymer having an amine value of 70 mgKOH/g or more and 160 mgKOH/g or less; and the solvent is a solvent having a solubility of the color material at 23 ° C of 0.1 (g/10 ml solvent) or less; The amine value of the dispersant is A (mgKOH/g), and the mass X _A (mol) of the organic acid compound contained in the color material dispersion is contained in the color material dispersion. When the ratio of the mass of the constituent unit (a) X _B (mol) of the dispersing agent is X (=X _A /X _B ), the following formulas (1) and (2) are satisfied; when X is less than In the range of 1 , the following formula (3) is further satisfied; X ≦ 1.5 (1) A × X ≧ 40 (2) A × (1-X) ≦ 42 (3) (In general formula (I), the carbon atom to which A is directly bonded to N does not have a π-bonded a-valent organic group, and the organic group represents an aliphatic group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N. The hydrocarbon group or the aromatic group having the aliphatic hydrocarbon group may further contain O, S, and N in the carbon chain; B ^c- represents a c-valent polyacid anion containing at least tungsten; and R ⁱ to R ^v each independently represent a hydrogen atom; Further, it may have an alkyl group having a substituent or an aryl group which may have a substituent, and R ⁱⁱ and R ⁱⁱⁱ , R ^iv and R ^v may be bonded to form a ring structure; and Ar ¹ represents a divalent aromatic group which may have a substituent. The plural R ⁱ ~ R ^v and Ar ¹ may be the same or different, respectively; a and c represent an integer of 2 or more, b and d represent an integer of 1 or more; e is 0 or 1, and when e is 0 The knot does not exist; the plural e can be the same or different;) (In general formula (II), R ¹ is a hydrogen atom or a methyl group, Q is a direct bond or a divalent linking group, and R ² is an alkylene group having 1 to 8 carbon atoms, -[CH(R ⁵ )-CH (R ⁶ )-O] _x -CH(R ⁵ )-CH(R ⁶ )- or -[(CH ₂ ) _y -O] _z -(CH ₂ ) _y - a divalent organic group, R ³ And R ⁴ each independently represents a chain or cyclic hydrocarbon group which may be substituted, or R ³ and R ⁴ are bonded to each other to form a cyclic structure; R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group; x represents 1 An integer of ~18, y represents an integer from 1 to 5, and z represents an integer from 1 to 18.) The color material dispersion liquid according to claim 1, wherein the organic acid compound is one or more selected from the group consisting of the following general formula (IV) and the following general formula (V); (In the formulae (IV) and (V), R ^a and R ^{a '} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group or an aryl group. , -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e , or -OR ^a" , a monovalent group, R Any one of ^a and R ^a' contains a carbon atom; R ^a" is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )- CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group; R ^b is an alkyl group having 1 to 18 carbon atoms, carbon number 2~ 18 alkenyl, aralkyl, aryl, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , -[(CH ₂ ) _t -O] _u -R ^e or -OR ^a monovalent group represented by ^b' ; R ^b' is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -[CH(R ^c )-CH(R ^d )-O] _s -R ^e , or -[(CH ₂ ) _t -O] _u -R ^e represents a monovalent group; R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, -CHO, -CH ₂ CHO, -CO-CH=CH ₂ , -CO-C (CH ₃ ) = CH ₂ or -CH ₂ COOR ^f is a monovalent group, R ^f is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; and R ^a , R ^{a '} and R ^b are an alkyl group or an alkene The group, the aralkyl group and the aryl group may each have a substituent; s represents an integer from 1 to 18, t represents an integer from 1 to 5, and u represents an integer from 1 to 18). The color material dispersion liquid according to claim 1, wherein the acid value of the dispersing agent is 1 mgKOH/g or more and 18 mgKOH/g or less, and the glass transition temperature of the dispersing agent is 30 °C or higher. The color material dispersion of claim 1, wherein the composition further comprises two selected from the group consisting of Color material and One or more types of color materials are used. The color material dispersion of claim 4, wherein the above Color material is A dyed metal lake color material. A colored resin composition for a color filter, comprising the color material dispersion liquid according to any one of claims 1 to 5, an alkali-soluble resin, a polyfunctional monomer, and a starter. The colored resin composition for a color filter according to claim 6, wherein the alkali-soluble resin has an acid value of 80 mgKOH/g or more and 300 mgKOH/g or less. A colored resin composition for a color filter according to claim 6, wherein the polyfunctional monomer has a carboxyl group. The colored resin composition for a color filter according to claim 6, wherein the alkali-soluble resin is a resin having an ethylenic double bond. The colored resin composition for a color filter according to claim 6, wherein the alkali-soluble resin is a resin having a hydrocarbon ring. The coloring resin composition for a color filter according to claim 6, wherein the hydrocarbon-soluble resin of the alkali-soluble resin is selected from the group consisting of a cyclopentyl group and a cyclohexyl group. Basis One or more groups consisting of a group consisting of a dicyclopentyl group, a dicyclopentenyl group, an adamantyl group, and a substituent represented by the following chemical formula (A); The colored resin composition for a color filter according to claim 6, wherein the alkali-soluble resin is a compound represented by the following general formula (B); (In the above general formula (B), X represents a group represented by the following general formula (D), and Y each independently represents a residue of a polyvalent carboxylic acid or an anhydride thereof, and R ⁱ represents a general formula (C) below. The base of the graph, j is an integer from 0 to 4, k is an integer from 0 to 3, and n is an integer greater than 1; (In the above general formula (C), R ⁱⁱ is a hydrogen atom or a methyl group, and R ⁱⁱⁱ each independently represents a hydrogen atom or a methyl group;) (In the above general formula (D), R ^iv each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen atom, and R ^v represents -O- or -OCH ₂ CH ₂ O-) . The coloring resin composition for a color filter according to claim 6, wherein the above-mentioned initiator is an oxime ester photopolymerization initiator. The coloring resin composition for a color filter of claim 6, wherein the content ratio of the decane coupling agent is 1% by mass or less based on the total solid content in the colored resin composition. A color filter comprising at least one of a transparent substrate and a coloring layer provided on the transparent substrate; wherein at least one of the colored layers has a color filter of claim 6 a colored layer formed by hardening of the object. A display device characterized by having a color filter of claim 15.