TWI519548B - Colored photosensitive resin composition, pattern forming method, method for producing color filter, color filter, and display device provided with the same - Google Patents

Description

Colored photosensitive resin composition, pattern forming method, method for producing color filter, color filter, and display device therewith

The present invention relates to a colored photosensitive resin composition, a pattern forming method, a method of producing a color filter, a color filter, and a display device including the same.

In recent years, the development of liquid crystal display devices has been carried out for use in personal computers and monitors having a small screen size, and also in television applications where the screen is large and requires high image quality.

For TV use, it is required to have higher image quality than previous monitors, ie, contrast and color purity. In order to improve the contrast, the particle size of the coloring agent (organic pigment or the like) for forming the colored photosensitive resin composition used for the color filter is required to be smaller. Further, in order to increase the color purity, the content of the color former (organic pigment) which is contained in the solid content of the colored photosensitive resin composition is required to be higher.

For the above requirements, it is necessary to make the particle diameter of the pigment finer and to require a pigment dispersion composition having higher dispersibility. In order to improve the dispersibility of the pigment, the surface of the pigment is usually modified with a derivative compound thereof, for example, on the surface of a phthalocyanine pigment, and a low molecular weight having a polar functional group which is easily adsorbed on the modified surface is used. A dispersant such as a resin is used to obtain a pigment dispersion composition containing a pigment, a surface modifier, and a dispersant while composing the dispersibility and dispersion stability of the pigment. In addition, the obtained pigment dispersion composition further contains an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and other components to form a photosensitive composition, and a color filter is obtained by photolithography or the like. .

When the pigment is made finer and the content ratio of the pigment is increased, when the image pattern is formed by photolithography, the line width sensitivity is lowered (the line width is reduced). In TV (television) use, it is particularly required to provide an inexpensive color filter, but the above-mentioned problem centered on the development step causes an increase in the exposure amount in the exposure step, that is, the necessity of increasing the exposure time. Because of this, the yield is lowered and the productivity is deteriorated, so improvement has been demanded.

In order to solve the above problems, there has been a proposal for an attempt to improve the line width sensitivity by improving the photopolymerization initiator used for the photosensitive resin composition for a color filter. For example, a three-nitrogen using a specific structure has been disclosed. a photopolymerizable composition of a compound (for example, refer to Patent Document 1), or a benzophenone type, an acetophenone type, or an oxysulfide A photoresist for a color filter which is used in combination with one or more of the compounds (for example, see Patent Document 2).

In addition, other proposals have disclosed an average double bond equivalent in an organic compound composed of a binder resin and a polymerizable compound in a coloring photosensitive resin composition, and a specific binder resin. A technique of forming a forward tapered shape by firing (see Patent Document 3).

Further, although it is not a colored photosensitive resin composition for exposure by ultraviolet light, there has been proposed a coloring resin composition which is prepared by using an allyl-containing binder resin to prepare a high sensitivity and a wide development latitude. (for example, refer to Patent Documents 4 and 5). Further, there has been proposed a method for providing a radioactive linear composition for a blue color filter having a good color reproducibility by using an N-phenyl maleimide copolymer as an adhesive resin (for example, see Patent Document 6). However, if such a technique is inferior in productivity by the ultraviolet light exposure step and the development step, sufficient productivity cannot be ensured, and therefore, the price of the color filter cannot be lowered.

In order to improve the productivity of the exposure step and the development step, a method of forming a pattern by exposure to laser light has been proposed (for example, see Patent Document 7). The laser is different from the mercury lamp which is generally used, and has a high straightness, a large output power, a focus reduction, and a feature that does not require a pattern forming mask in the exposure step. However, even in the above-described prior art, the surface of the pixel is roughened in the developing step, or the line width sensitivity of the pattern is insufficient, and the like, and the characteristics required for the coloring photosensitive resin composition are not satisfied anyway. Further, from the viewpoint of reducing the total cost of the color filter, it has been proposed that an exposure apparatus does not use a large mask (for example, refer to Patent Documents 8, 9). However, specific materials have not been shown, and proposals for materials suitable for such devices have been desired.

In particular, in the case of a blue colored photosensitive resin composition, after the post-baking due to the binder resin, the adhesive resin which is originally transparent to visible light is colored, so that it is used for the color filter. In the case of the colored pattern, there is a problem that the luminance is lowered. Therefore, there has been an urgent need for an adhesive resin which is not colored even in the case of post-application baking.

In addition, the blue colorant has a large absorption at 355 nm or 365 nm. If exposed by ultraviolet laser, the photohardening cannot be sufficiently carried out to the deep portion of the colored layer, and wrinkles may occur after post-baking (wrinkle However, there has been a desire for a blue colored photosensitive resin composition which is sufficiently hardened to a deep portion by ultraviolet laser light to have a good degree of hardening sensitivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-289611

[Patent Document 2] Japanese Patent Laid-Open No. Hei 9-80225

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-93811

[Patent Document 4] Japanese Patent Laid-Open No. 10-20496

[Patent Document 5] International Publication No. 2007/29871

[Patent Document 6] Patent No. 3362532

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2003-287614

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2008-76709

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2008-51866

An object of the present invention is to provide a colored photosensitive resin composition which is capable of forming a line width sensitivity and having excellent linearity and heat resistance of a colored pattern formed, and coloring or wrinkle generation even after post-baking. It is a suppressed color pattern and is suitable for use in ultraviolet laser exposure.

Further, another problem of the present invention is to provide a pattern forming method capable of forming a coloring pattern excellent in shape and luminance formed by using the coloring photosensitive resin composition of the present invention, and a method for producing a color filter, and A color filter having a pattern shape and a coloring pattern having a good luminance, and a display device including the color filter are provided.

The inventors of the present invention have deliberately studied the results and found that the above problems can be solved by the following methods.

<1> A colored photosensitive resin composition comprising at least: (A) a colorant, (B-1) a binder resin represented by the following formula (I) and having an acidic group in a molecule, (B) -2) a binder resin containing a structural unit represented by the following formula (II) and a structural unit having an acidic group, (C) a polymerizable compound, (D) an oxime-based photopolymerization initiator, and E) a solvent, and wherein the ratio of the (B-1) binder resin to the (B-2) binder resin on a mass basis is from 3:7 to 7:3.

In the formula (I), R ³ represents a (m+n) valent organic linking group, R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group, and A ² represents at least one selected from the group consisting of organic Pigment structure, heterocyclic structure, acidic group, group having a basic nitrogen atom, ureido group, urethane group, group having a coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxyalkyl group The epoxy group, the isocyanate group, and the partial structure of the hydroxyl group are one of the organic groups, and the n of A ² and R ⁴ may be the same or different, m is 1 to 8, and n is 2 to 9, m +n is 3 to 10, P ² is a polymer skeleton, and m 2 of P ² and R ⁵ may be the same or different;

In the formula (II), R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, and R ¹⁶ represents a hydrogen atom or a methyl group.

(2) The coloring photosensitive resin composition of the item (1), wherein the (D) fluorene-based photopolymerization initiator is a ketoxime-based photopolymerization initiator represented by the following formula (III):

In the formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, n is an integer from 0 to 5, and when X is present in plural, the complex X They are each independently representing a monovalent substituent and may be the same or different.

<3> The colored photosensitive resin composition according to item <1> or <2>, which is used for ultraviolet laser exposure.

(4) A coloring layer forming step of forming a colored layer by applying a colored photosensitive resin composition according to any one of the items <1> to <3> to a substrate, and coloring the coloring layer The layer is subjected to an exposure step of curing the exposed portion by ultraviolet laser exposure, and a developing step of developing and removing the uncured portion of the colored layer to form a pattern.

<5> The pattern forming method of item <4>, wherein the ultraviolet laser has an exposure wavelength in a range of 300 nm to 380 nm.

<6> The pattern forming method of item <4> or <5>, wherein the ultraviolet laser is a pulsed laser that oscillates at a frequency of 20 Hz to 2000 Hz.

<7> A method of producing a color filter, comprising the step of forming a colored pattern on a substrate according to the pattern forming method according to any one of <4> to <6>.

<8> A color filter manufactured according to the manufacturing method of the item <7>.

<9> A display device comprising the color filter of item <8>.

According to the present invention, it is possible to provide a colored photosensitive resin composition which has high line width sensitivity, excellent linearity and heat resistance of the formed coloring pattern, and can be formed to suppress color development even after post-baking. The color pattern of wrinkles, and can also be applied to ultraviolet laser exposure.

Further, by using the colored photosensitive resin composition of the present invention, it is possible to provide a pattern forming method capable of forming a colored pattern excellent in shape and brightness, a method of producing a color filter, and having a pattern shape and luminance A color filter having a good color pattern and a display device having the color filter.

[Best Embodiment of the Invention]

Hereinafter, the form of the present invention will be described in detail.

<<Coloring photosensitive resin composition》

The colored photosensitive resin composition of the present invention is characterized by comprising at least: (A) a colorant, (B-1) an adhesive resin represented by the following general formula (I) and having an acidic group in the molecule (hereinafter, , suitably referred to as "(B-1) binder resin"), (B-2) a binder resin containing a structural unit represented by the following formula (II) and a structural unit having an acidic group (hereinafter, Suitably referred to as "(B-2) binder resin"), (C) polymerizable compound, (D) oxime-based photopolymerization initiator, and (E) solvent, and wherein the (B-1) binder resin The content ratio of the (B-2) binder resin on a mass basis is from 3:7 to 7:3.

Hereinafter, each constituent component of the colored photosensitive resin composition of the present invention will be described in detail.

<(A) Colorant>

The colored photosensitive resin composition of the present invention contains at least one (A) colorant.

The content of the (A) coloring agent in the coloring photosensitive resin composition of the present invention is preferably 15% by mass to 60% by mass based on the mass fraction of the coloring photosensitive resin composition. When the content of the (A) coloring agent is less than 15% by mass, there is a possibility that the film thickness is set to be thick so as to form a desired hue, so that development is difficult or the production interval is prolonged. Happening. On the other hand, when the content of the (A) colorant is more than 60% by mass, the development time may become long and the contour shape may become an inverted edge shape.

The "solid content" of the coloring photosensitive resin composition of the present invention means a heating residue which is obtained by measuring the amount of the colored photosensitive resin composition in an amount of 1 gram in an aluminum container and drying at 160 ° C for 60 minutes. The colored photosensitive resin composition of the present invention includes all components of the colored photosensitive resin composition excluding the (E) solvent.

The content of the (A) colorant in the colored photosensitive resin composition of the present invention is more preferably 20% by mass to 50% by mass, still more preferably 25% based on the total solid content of the colored photosensitive resin composition. Mass% to 40% by mass.

(A) The colorant can be used by appropriately selecting a dye and a pigment. From the viewpoint of heat resistance and the like, a pigment is preferred.

The pigment which can be used as the (A) coloring agent can be an inorganic pigment or an organic pigment. From the viewpoint of being made into a high transmittance, it is preferred to use a particle size as small as possible. The average of the primary particle diameters is preferably from 0.01 μm to 0.1 μm, more preferably from 0.01 μm to 0.05 μm.

In the colored photosensitive resin composition of the present invention, the polymer dispersant described later is used, and even if the size of the pigment is small, the pigment dispersibility and the dispersion stability are improved. Therefore, even if the film thickness is thin, the color can be formed. A color pixel with excellent purity.

Further, in the present invention, among the pigments contained in the colored photosensitive resin composition, the proportion of the pigment having a primary particle diameter of less than 0.02 μm is preferably less than 10% in the total amount of the pigment, and the primary particle diameter is The proportion of the pigment exceeding 0.08 μm is less than 5% in the total amount of the pigment.

When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, heat resistance is good, chromaticity change can be prevented, and if the ratio of the pigment having a primary particle diameter of more than 0.08 μm is less than 5%, The comparatively good, colored photosensitive resin composition has good stability over time and can prevent foreign matter from failing.

The ratio of the pigment having a primary particle diameter of less than 0.02 μm is more preferably less than 5% from the viewpoint of heat resistance and prevention of change in chromaticity.

The proportion of the pigment having a primary particle diameter of more than 0.08 μm is preferably less than 3% from the viewpoint of improving the contrast.

The primary particle diameter of the pigment can be measured by TEM (transmission electron microscope). That is, the particle size distribution can be examined by image analysis of the TEM photograph. The particle size distribution can be grasped by measuring, for example, the total number of particles in the observation sample at 3 to 100,000 times and the number of particles of the pigment of less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder was photographed by a transmission electron microscope at 30,000 to 100,000 times, photographs were taken, and the major diameters of 1000 primary particles were measured, and the ratio of primary particles of less than 0.02 μm and more than 0.08 μm was calculated. The operation was carried out in three places by changing the parts of the pigment powder, and the results were averaged.

The inorganic pigment usable as the (A) coloring agent may, for example, be a metal compound such as a metal oxide or a metal complex salt, specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, An oxide of a metal such as zinc or bismuth, or a composite oxide of the above metal.

The aforementioned "organic pigment" is exemplified by, for example,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279; CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172 173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214; CI Pigment Orange 2, 5, 13, 16, 17:1, 31 , 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73; CI Pigment Green 7, 10, 36, 37, 58; CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, change the Cl substituent of 79 to OH, 80; CI Pigment Violet 1, 19, 23, 27, 32, 37, 42; CI Pigment Brown 25, 28, and the like.

Among these, the pigments which are suitably used are as follows. However, the invention is not limited thereto.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36, 71; CI Pigment Red 122, 150, 171, 175, 177, 209 , 224, 242, 254, 255, 264; CI Pigment Violet 19, 23, 32, 58; CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37.

These organic pigments can be used in combination or in combination for improving color purity. Specific examples of the combination are as follows.

For example, "pigment for red layer (R)" can be used: an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment alone or at least one of these and a disazo pigment, isoporphyrin a mixture of a yellow pigment such as a pigment or a quinophthalone pigment; or at least one of an anthraquinone pigment, an anthraquinone pigment, and a diketopyrrolopyrrole pigment, and an anthraquinone pigment, an anthraquinone pigment, a condensed disazo Mixing of red pigment such as condensed disazo-based pigment or diketopyrrolopyrrole pigment. For example, CI pigment red 177 is exemplified, CI pigment red 155 and CI pigment red 224 are exemplified, and condensed disazo red pigment is CI pigment red 242, diketopyrrolopyrrole. The pigment is CI Pigment Red 254, and from the viewpoint of color reproducibility, it is preferably a mixture of CI Pigment Red 254 and CI Pigment Yellow 139 or CI Pigment Red 177.

Further, the mass ratio of the red pigment to other pigments (red pigment: other pigments) is preferably from 100:5 to 100:80. When the ratio is 100:4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity cannot be improved. Further, when it is 100:81 or more, the coloring power may be lowered. In particular, the mass ratio is most preferably in the range of 100:10 to 100:65. Further, when the red pigments are combined with each other, they can be adjusted in accordance with the chromaticity.

Further, the "green layer (G) pigment" may be a halogenated phthalocyanine pigment alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, a methine azo yellow pigment or a different pigment. Mixture of porphyrin yellow pigments. For example, such examples are preferably a mixture of C.I. Pigment Green 7, 36, 37, 58 and C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185.

The mass ratio of the green pigment to the yellow pigment is preferably from 100:5 to 100 from the viewpoint of obtaining sufficient color purity and suppressing the shift from the target hue of the NTSC (National Television System Committee): 150. The quality bit is preferably in the range of 100:30 to 100:120.

"Pigment for blue layer (B)" is available: phthalocyanine pigment alone, or two It is a blend of purple pigments. For example, a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably from 100:0 to 100:50, more preferably from 100:5 to 100:30.

When the colored photosensitive composition of the present invention is applied to a blue colored photosensitive composition, it is particularly effective because the colored layer is not colored in yellow when heated by post-baking or the like.

In the present invention, in particular, the coloring agent is an organic pigment, and it is preferred to coat the pigment with a polymer compound in the step of refining or dispersing the pigment. More preferably, a pigment coated with a polymer compound is used, and even if the fine pigmented secondary aggregate is formed, the coated pigment which is dispersed in the state of primary particles and which has improved dispersibility is dispersed. The primary particles can stably maintain the coated pigment excellent in dispersion stability.

The so-called "coated pigment" which is a suitable mode of the present invention is a pigment which is coated with a polymer compound, and if it is coated, it is considered to be a new interface of a pigment having a high surface activity by miniaturization and a polymer. The strong electrostatic action of the compound forms a strong coating layer of the polymer compound, so that a coated pigment having higher dispersion stability can be obtained. That is, even if the pigment after the coating treatment of the present invention is washed with an organic solvent capable of dissolving the polymer compound, the coated polymer compound hardly separates.

In the present invention, the "coated pigment" is a pigment particle in which a pigment particle such as an organic pigment is coated with a polymer compound having a polar group such as a hetero ring in a side chain, and a part of the surface of the pigment particle is strongly coated by the polymer compound. The effect of obtaining high dispersion stability in all or part is different from that of a general polymer dispersant which is formed by absorbing a pigment. This coating state was confirmed by measuring the free amount (free ratio) of the polymer compound by washing with an organic solvent shown below. That is, the polymer compound formed only by sorption is mostly washed by an organic solvent, and specifically, more than 65% of the polymer compound is liberated and removed, but is coated as in the present invention. In the case of the pigment on the surface, the liberation ratio is extremely small and is 30% or less.

The amount of freeness (free rate) is calculated by washing the pigment after the coating treatment with 1-methoxy-2-propanol. That is, 10 g of the pigment was put into 100 ml of 1-methoxy-2-propanol, shaken at room temperature for 3 hours using a shaker, and then the pigment was allowed to settle at a centrifugal separator at 80,000 rpm for 8 hours. The mass of the solid component of the supernatant was measured by a drying method. The liberation ratio (%) was calculated from the ratio of the mass of the solid component to the mass of the polymer compound used for the coating treatment of the pigment.

The aforementioned free amount (free rate) of a commercially available pigment can be measured by the following method. That is, the pigment is dissolved in a solvent (for example, dimethyl hydrazine, dimethylformamide, formic acid, sulfuric acid, etc.), and then separated into a polymer compound and a pigment by an organic solvent by using a difference in solubility. And calculated "the quality of the polymer compound used for the coating treatment of the pigment". Further, the pigment was washed with 1-methoxy-2-propanol, and the free amount of the obtained polymer compound was divided by the "mass of the polymer compound used for coating treatment of the pigment" to calculate the liberation ratio (%). ).

The smaller the liberation rate, the stronger the coating for the pigment, and the better the dispersibility and the dispersion stability. The preferred range of the liberation ratio is 30% or less, more preferably 20% or less, and most preferably 15% or less. The ideal is 0%.

The coating treatment is preferably carried out simultaneously with the step of refining the pigment, and specifically, by the following steps: (i) the pigment, (ii) the water-soluble inorganic salt, (iii) substantially insoluble ( Ii) a small amount of a water-soluble organic solvent, and (iv) a polymer compound, which is mechanically kneaded by a kneader or the like to obtain a mixture (referred to as a "salt milling step"); a step of stirring into a slurry by a high-speed mixer or the like; and a step of filtering the slurry, washing with water, and drying as necessary.

The salt milling described above will be more specifically described below. First, in a mixture of (i) an organic pigment and (ii) a water-soluble inorganic salt, a small amount of (iii) a water-soluble organic solvent is added as a wetting agent, and after kneading by a kneader or the like, the mixture is poured into water to A high-speed mixer or the like is stirred to form a slurry. Next, the slurry is filtered, washed with water, and dried as needed to obtain a finely divided pigment. Further, in the case of being dispersed in an oily varnish, the processed pigment before drying (referred to as "filter cake") may be referred to as a method of rinsing. Disperse the water and disperse it in an oily varnish. Further, in the case of being dispersed in a water-based varnish, the treated pigment does not need to be dried, and the filter cake can be directly dispersed in the varnish.

By using at least a part of the resin which is soluble in the organic solvent (iii) in the salt milling as the above (iv) polymer compound, it is possible to obtain a finer pigment, the surface is coated with the resin, and the pigment is agglomerated when dried. By.

Further, (iv) the polymer compound may be added at the beginning of the salt milling step, or may be added separately. Alternatively, it may be added in the dispersion step.

Any of the polymer compounds used for the coating pigment may be any one as long as it has a absorbing property for the pigment. Particularly preferred is a polymer compound having a hetero ring in a side chain. The (B-1) binder resin which will be described later in the present invention is also preferably a polymer compound which can be used for coating a pigment.

The polymer compound for coating the pigment can be used, for example, in paragraphs [0029] to [0030] of JP-A-2008-83089, and paragraphs [0044] to [0047] of JP-A-2009-62457. The person mentioned in the article.

Even in the case of using the above-described coated pigment, it is more preferred to use at least one dispersant to disperse the pigment to be used as a pigment dispersion composition. By containing a dispersing agent, the dispersibility of the pigment can be further improved.

The dispersant is used, for example, by appropriately selecting a conventional pigment dispersant or surfactant.

Specifically, a plurality of compounds can be used, and examples thereof include, for example, an organopolysiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a (meth)acrylic acid system. (Total) polymer POLYFLOW No. 75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.) Ltd.) "Cation-based surfactant"; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oxime "Non-ionic surfactant" such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (Yu Shang ( "Anionic surfactants" such as EPA); EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (all are Ciba refined ( Company (Ciba Specialty Chemicals Co., Ltd.), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (all are San Nopco Co., Ltd.) .) "polymer dispersant"; SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Various SOLSPERSE dispersants (Lubrizol Japan, Ltd.) .)); Adekapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Kasei) ADEKA Corporation) and ISONET S-20 (made by Sanyo Chemical Industries Co., Ltd.), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 161, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by BYK Chemie Corp.). Other examples include oligomers or polymers having a polar group at a molecular terminal or a side chain such as an acrylate copolymer.

The content of the dispersant in the pigment dispersion composition is preferably from 1 to 100% by mass, more preferably from 3 to 70% by mass, based on the mass of the pigment described.

The pigment derivative is one of the polymer compounds coated with the pigment, and may be added to the pigment dispersion composition as needed. A pigment derivative into which a moiety having affinity with a dispersing agent or a polar group is introduced is adsorbed on the surface of the pigment, and this is used as a absorbing point of the dispersing agent, whereby the pigment is dispersed in the photosensitive material as fine particles. The resin composition can be prevented from re-aggregating, which is effective in forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a matrix and an acidic group, a basic group, or an aromatic group is introduced as a substituent in a side chain. Specific examples of the "organic pigment" include a quinophthalone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoporphyrin pigment, and an isoindolinone pigment. , quinoline pigment, diketopyrrolopyrrole pigment, benzimidazolone pigment, and the like. Generally not called pigment naphthalene, lanthanide, trinitrogen A pale yellow aromatic polycyclic compound such as a quinolate or the like is also included in the above organic pigment. The pigment derivative can be used, for example, in JP-A-H09-49974, JP-A-H11-189732, JP-A-10-245501, JP-A-2006-265528, and JP-A-H8- It is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The content of the pigment derivative in the pigment dispersion composition is preferably from 1% by mass to 30% by mass, and more preferably from 3% by mass to 20% by mass based on the mass of the pigment. When the content is within the above range, the dispersion can be improved while the viscosity is lowered, and the dispersion stability after dispersion can be improved, and high transmittance and excellent color characteristics can be obtained, and the color filter can be produced. Forms a high contrast with good color characteristics.

The dispersion method is, for example, a method in which a pigment and a dispersant are premixed and predispersed by a homogenizer or the like, and is finely dispersed by using a bead disperser or the like using zirconium beads or the like.

When a dye is used as the (A) coloring agent in the present invention, a uniformly colored colored photosensitive resin composition can be obtained.

The dye which can be used as the (A) coloring agent is not particularly limited, and a conventional dye which has been conventionally used as a color filter can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A No. 2,592,207, and US Patent No. 4,808,501 The specification, the specification of the U.S. Patent No. 5,667,920, the specification of the U.S. Patent No. 5,059,500, the Japanese Patent Laid-Open No. Hei 5-333207, the Japanese Patent Publication No. Hei 6-35183, the Japanese Patent Laid-Open No. Hei 6-51115, and the Japanese Patent Laid-Open No. Hei 6-194428 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2002-14220, Japanese Laid-Open Patent Publication No. 2002-14221, Japanese Laid-Open Patent Publication No. 2002-14222, Japanese Laid-Open Patent Publication No. 2002-14223, Japanese Patent Application Laid-Open No. Hei No. 8-302224 8-73 The pigments disclosed in Japanese Laid-Open Patent Publication No. Hei 8- No. No. Hei.

"Chemical structure" can be used: pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, Oxonol, pyrazole triazole azo Department, pyridone azo, cyanine, thiophene Department, pyrrolopyrazole, methine azo, A dye such as a phthalocyanine, a benzopyran, or an indigo.

<(B-1) A binder resin represented by the general formula (I) and having an acidic group in the molecule>

The (B-1) binder resin used in the present invention is a polymer compound represented by the following formula (I) and having an acidic group in the molecule.

The (B-1) binder resin of the present invention has at least one acidic group in the molecule. The acidic group may be contained in the substituent A ² in the following general formula (I), or may be contained in the polymer skeleton represented by P ² , but is preferably contained in view of efficacy. In the polymer skeleton represented by P ² , it is more preferred to contain an acidic group in both of A ² and P ² .

In the above formula (I), R ³ represents a (m+n) valent organic linking group, and R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group; and A ² represents a group containing at least one selected from the group consisting of Organic pigment structure, heterocyclic structure, acidic group, group having a basic nitrogen atom, ureido group, urethane group, group having a coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxydecane a valence organic group of a partial structure of a group, an epoxy group, an isocyanate group, and a hydroxyl group; n of A ² and R ⁴ may be the same or different; m represents 1 to 8, and n represents 2 to 9, m+n can satisfy 3 to 10; P ² represents a polymer skeleton, and m of P ² and R ⁵ may be the same or different.

In the above formula (I), A ² represents a group containing at least one selected from the group consisting of an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, and having a coordination group. a monovalent organic group having a carbon atom number of 4 or more, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a partial structure of a hydroxyl group, and n of A ² may be the same or different .

That is, the aforementioned A ² represents a structure containing at least one absorbing property to a pigment such as an organic dye structure or a heterocyclic structure, or a group having an acidic group, a basic nitrogen atom, a urea group, and an amine. a carbamate group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and a functional group having an absorbing energy for a pigment One-price organic base.

In the following, a part of the structure in which the absorbing energy of the pair of pigments (the above structure and functional groups) is appropriately referred to as an "adsorbing site" will be described.

The absorbing portion may be at least one type of one A ² or may contain two or more types.

Further, in the present invention, "having at least one occupant site valence organic group" may be: from the aforementioned sorption site to from 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to An organic linking group composed of 100 oxygen atoms, 1 to 400 hydrogen atoms, and 0 to 40 sulfur atoms is bonded to form a one-valent organic group. Further, in the case where the absorbing site itself constitutes a monovalent organic group, the absorbing site itself may be a monovalent organic group represented by A ² .

First, the absorbing portion constituting the aforementioned A ^{2 will} be described below.

The "organic dye structure" may, for example, be a phthalocyanine system, an insoluble azo system, an azo lake system, an anthraquinone system, a quinophthalone group, or two. Preferred examples of the dye structure of the ketone, diketopyrrolopyrrole, guanidine pyridine, fluorenone ketone ketone, indanthrone, vaginal, fluorenone, anthraquinone, and thioindigo; More preferably, phthalocyanine, azo lake, lanthanum, two A dye structure of a diketopyrrolopyrrole type; particularly preferably a pigment structure of a phthalocyanine, an anthraquinone, or a diketopyrrolopyrrole.

Further, the above "heterocyclic structure" is exemplified by, for example, thiophene, furan, , pyrrole, pyrroline, pyrrolidine, two Molar, pyrazole, pyrazoline, pyrazole, imidazole, Oxazole, thiazole, Diazole, triazole, thiadiazole, piperazine, pyridine, piperidine, two Alkane, morpholine, anthracene Pyrimidine, piperazine Trinitrogen , trithiane, isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, amber imine, phthalimide, naphthyl imine, hydantoin Hydantoin, hydrazine, quinoline, oxazole, acridine, acridone, hydrazine are preferred examples; more preferably pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazole , imidazole, triazole, pyridine, piperidine, morpholine, hydrazine Pyrimidine, piperazine Trinitrogen , isoporphyrin, isoindolinone, benzimidazolone, benzothiazole, amber imine, phthalimide, naphthyl imine, hydantoin Carbazole, acridine, acridone, hydrazine.

In addition, the "organic dye structure" or the "heterocyclic structure" may further have a substituent, and examples of the "substituent" include an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, and benzene. The carbon number of the aryl group, the hydroxyl group, the amine group, the carboxyl group, the sulfonylamino group, the N-sulfonylamino group, the ethoxy group, etc. having a carbon number of 6 to 16 such as a naphthyl group or a naphthyl group is 1 to 6 a carbon such as an alkoxy group having 1 to 20 carbon atoms, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group having a carbon number of 1 to 20 such as a methoxy group, a methoxy group or an ethoxy group. The number is a carbonate group of 2 to 7 alkoxycarbonyl group, cyano group, tertiary butyl carbonate or the like. Here, these substituents may be bonded to an organic dye structure or a heterocyclic ring via a structural unit described below or a linking group composed of the structural unit.

The above "acid group" is exemplified by a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group; more preferably a carboxylic acid group or a sulfonic acid group. A monosulfate group, a phosphoric acid group, a monophosphate group; particularly preferably a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.

Further, the "base having a basic nitrogen atom" may, for example, be an amine group (-NH ₂ ) or a substituted amino group (-NHR ⁸ , -NR ⁹ R ¹⁰ , here, R ⁸ , R ⁹ , And R ¹⁰ are each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and a mercapto group represented by the following formula (a1), The amidinyl group represented by the following formula (a2) is a preferred example.

In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

Among these, more preferred are an amine group (-NH ₂ ), a substituted amine group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ are each independently represented An alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group, and a fluorenyl group represented by the above formula (a1). In the formula (a1), R ¹¹ and R ¹² each independently represent a carbon number of 1 An alkyl group of 10, a phenyl group, a benzyl group, and a fluorenyl group represented by the above formula (a2). In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkane having a carbon number of 1 to 10. Base, phenyl, benzyl] and the like.

Particularly suitable for use are amine groups (-NH ₂ ), substituted amine groups (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ each independently represent a carbon number of 1 An alkyl group represented by the above formula (a1), wherein R ¹¹ and R ¹² each independently represent an alkane having a carbon number of 1 to 5, in the formula (a1). a phenyl group represented by the above formula (a2), wherein R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group. , benzyl] and so on.

The above "ureido group" is exemplified by, for example, -NR ¹⁵ CONR ¹⁶ R ¹⁷ (herein, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, carbon a aryl group having 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms is a preferred example; more preferably -NR ¹⁵ CONHR ¹⁷ (here, R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom, or An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms; particularly preferably -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or a carbon number) It is an alkyl group of 1 to 10, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

The above-mentioned "urethane group" may, for example, be -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each preferably a case of independently representing an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms; more preferably -NHCOOR ¹⁸ , -OCONHR ²¹ (herein, R ¹⁸ and R ²¹ are each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms); Particularly preferred are -NHCOOR ¹⁸ and -OCONHR ²¹ (herein, R ¹⁸ and R ²¹ are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aromatic group having 7 or more carbon atoms. Alkyl) and the like.

The "base having a coordinating oxygen atom" may, for example, be an ethyl acetoacetin group or a crown ether.

The above-mentioned "hydrocarbon group having 4 or more carbon atoms" is preferably an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms; more preferably; An alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like; particularly preferably an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, A dodecyl group or the like, an aryl group having 6 to 15 carbon atoms (e.g., a phenyl group, a naphthyl group, etc.), an aralkyl group having a carbon number of 7 to 15 (e.g., a benzyl group, etc.), and the like.

Examples of the above "alkoxyalkylene group" include a trimethoxyalkylene group and a triethoxyalkylene group.

In the case where the occlusion site is bonded to an organic linking group, the organic linking group preferably has from 1 to 100 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, and from 1 to 200. An organic linking group composed of a hydrogen atom and 0 to 20 sulfur atoms, and the organic linking group may be unsubstituted or further have a substituent.

Specific examples of the organic linking group include the following structural units or a combination of the structural units.

When the organic linking group has a substituent, the "substituent" may be, for example, an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, a phenyl group, a naphthyl group or the like having a carbon number of 6 a methoxy group, a methoxy group, an ethoxy group having a carbon number of 1 to 6 such as an aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylguanidino group, an ethoxylated group or the like An alkoxycarbonyl group having a carbon number of 2 to 7 such as a halogen atom having 1 to 6 carbon atoms, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; A carbonate group such as a cyano group or a tertiary butyl carbonate.

In the above, the A ^{2 is} preferably one of the sites containing at least one selected from the group consisting of an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. The price is organic.

The above A ^{2 is more} preferably a monovalent organic group represented by the following formula (4).

In the above formula (4), B ¹ represents the sorption site (that is, selected from the group consisting of an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a urethane group). a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R ²⁴ represents a single bond or (a+1) valence The organic linking group; a is an integer representing 1 to 10, and a of B ¹ may be the same or different.

The absorbing portion represented by the above B ^{1 is the same} as the absorbing portion constituting A ² of the above formula (1), and preferred examples are also the same.

Among them, a site selected from the group consisting of an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable.

R ²⁴ represents a single bond or an (a+1)-valent organic linking group, and a represents 1 to 10; preferably a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3. .

The (a+1)-valent organic linking group is exemplified by: 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 a group of sulfur atoms, and may be unsubstituted or further substituted.

The (a+1)-valent organic linking group may be exemplified by the following structural unit or a group in which the structural unit is combined (may also form a ring structure).

R ^{24 is} preferably a single bond, or from 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms. The (a+1)-valent organic linking group; more preferably a single bond, or from 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 (a+1)-valent organic linking group composed of a hydrogen atom and 0 to 7 sulfur atoms; particularly preferably a single bond, or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to (a+1)-valent organic linking group composed of 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.

In the above, when the (a+1)-valent organic linking group has a substituent, the "substituent" may, for example, be an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, or a phenyl group. The naphthyl group having a carbon number of 6 to 16 such as a naphthyl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylguanamine group, an ethoxy group or the like has a carbon number of 1 to 6 The number of carbon atoms such as an alkoxy group having 1 to 6 carbon atoms, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group having a carbon number of 1 to 6 such as an oxy group, a methoxy group or an ethoxy group; It is a carbonate group of 2 to 7 alkoxycarbonyl group, a cyano group, a tertiary butyl carbonate or the like.

In the above formula (I), R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group. n of R ⁴ may be the same or different. Further, m of R ⁵ may be the same or different.

The divalent organic linking group is exemplified by 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group is constituted and may be unsubstituted or further have a substituent.

Specific examples of the above-mentioned divalent organic linking group include the following structural units or a group composed of the structural units.

R ⁴ and R ^{5 are} preferably a single bond, or from 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 a divalent organic linking group composed of a sulfur atom; more preferably a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms a divalent organic linking group composed of an atom and 0 to 7 sulfur atoms; particularly preferably a single bond, or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms a divalent organic linking group composed of 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms.

In the above, when the divalent organic linking group has a substituent, the "substituent" may, for example, be an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, a phenyl group, a naphthyl group or the like. a carbon number of from 1 to 6 such as an aryl group having 6 to 16 carbon atoms, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylguanidino group, an ethoxylated group or the like, The alkoxy group having a carbon number of 1 to 6 such as an oxy group or an ethoxy group, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group has a carbon number of 2 to 7 A carbonate group such as an alkoxycarbonyl group, a cyano group or a tertiary butyl carbonate.

In the above formula (I), R ³ represents a (m+n)valent organic linking group. m+n is achievable from 3 to 10.

The (m+n)-valent organic linking group represented by the above R ³ may be exemplified by 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100. A hydrogen atom, and a group of 0 to 20 sulfur atoms, and may be unsubstituted or further have a substituent.

Specific examples of the (m+n)-valent organic linking group include the following structural units or a group in which the structural units are combined (may also form a ring structure).

The (m+n) valence organic linking group preferably has from 1 to 60 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 40 oxygen atoms, from 1 to 120 hydrogen atoms, and from 0 to 10 a group consisting of sulfur atoms; more preferably 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 a group consisting of a sulfur atom; particularly preferably 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms The basis of the atom.

In the above, when the (m+n)-valent organic linking group has a substituent, the "substituent" may, for example, be an alkyl group having a carbon number of 1 to 20 such as a methyl group or an ethyl group, or a phenyl group. The naphthyl group having a carbon number of 6 to 16 such as a naphthyl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylguanamine group, an ethoxy group or the like has a carbon number of 1 to 6 The number of carbon atoms such as an alkoxy group having 1 to 6 carbon atoms, a halogen atom such as chlorine or bromine, a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group having a carbon number of 1 to 6 such as an oxy group, a methoxy group or an ethoxy group; It is a carbonate group of 2 to 7 alkoxycarbonyl group, a cyano group, a tertiary butyl carbonate or the like.

Specific examples of the (m+n)-valent organic linking group represented by the above R ³ [specific examples (1) to (17)] are shown below. However, the invention is not limited to these.

In the above specific examples, the optimum (m+n) valence organic linking group is the following group from the viewpoints of availability of raw materials, easiness of synthesis, and solubility to various solvents.

In the above formula (I), m represents 1 to 8. m is preferably from 1 to 5, more preferably from 1 to 4, particularly preferably from 1 to 3.

Further, in the above formula (I), n represents 2 to 9. n is preferably from 2 to 8, more preferably from 2 to 7, and particularly preferably from 3 to 6.

Further, P ² in the general formula (I) represents a polymer skeleton, and may be selected from a conventional polymer or the like depending on the purpose and the like. m of P ² may be the same or different.

Among the polymers, the polymer skeleton is preferably a polymer or copolymer selected from a vinyl monomer, an ester polymer, an ether polymer, an urethane polymer, or a amide amine. a polymer, an epoxy polymer, a polyoxymethylene polymer, and a modified or copolymer thereof [for example, a copolymer comprising a polyether/polyurethane, a polyether/derived from a vinyl monomer At least one selected from the group consisting of a copolymer of a polymer (any of a random copolymer, a block copolymer, and a graft copolymer); more preferably selected from the group consisting of vinyl monomers At least one of a group consisting of a substance or a copolymer, an ester polymer, an ether polymer, a urethane polymer, and a modified or copolymer thereof; particularly preferably a vinyl monomer Polymer or copolymer.

Further, it is preferred that the polymer is soluble in an organic solvent. When the affinity with the organic solvent is low, for example, when it is used as a pigment dispersant, the affinity with the dispersion medium may be weak, so that a sufficient absorbing layer required for dispersion stabilization cannot be secured.

In the present invention, it is preferred to have at least one acidic group in the polymer skeleton represented by P ² .

The method of introducing an acidic group into the polymer skeleton is not particularly limited, and a method of introducing a vinyl monomer having an acidic group and introducing an acidic group by using a crosslinkable side chain may be employed. However, as will be described later, from the viewpoint of easy control of the amount of introduction of the acidic group and the viewpoint of the synthesis cost, it is preferred that the polymer skeleton is composed of a structural unit derived from a vinyl monomer having an acidic group. The mode of the acidic base.

Here, the "acid group" is the same as the "acid group" which has been exemplified in the description of A ² above, and is preferably a carboxyl group.

The "vinyl monomer" is not particularly limited, and is preferably, for example, a (meth) acrylate, a crotonate, a vinyl ester, a maleic acid diester, or a fumaric acid. Esters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimide, (meth) propylene Nitrile, vinyl monomer having an acidic group, and the like.

Hereinafter, preferred examples of such vinyl monomers will be described.

Examples of the "(meth) acrylates" include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. N-butyl acrylate, isobutyl (meth)acrylate, butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclomethacrylate Ester, tert-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trioctyl (meth)acrylate, dodecyl (meth)acrylate, (methyl) ) octadecyl acrylate, ethoxylated ethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-chloroethyl (meth)acrylate, ( Glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (methyl) Vinyl olefinate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxy (meth) acrylate Ethyl ester, propargyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, Triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monomethyl ether (meth)acrylate, poly(methyl)acrylate Alcohol monoethyl ether ester, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, Dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate, (methyl) Dicyclopentyl acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, (meth)acrylic acid-γ-butyrolactone, and the like.

Examples of the "crotonate" include butyl crotonate and hexyl crotonate.

Examples of the "vinyl esters" include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, methoxyvinyl acetate, and vinyl benzoate.

Examples of the "maleic acid diester" include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the "fumaric acid diester" include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the "iconic acid diester" include dimethyl isonate, diethyl itaconate, and dibutyl itaconate.

Examples of the "(meth)acrylamides" include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl. (Meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N- Cyclohexyl (meth) acrylamide, N-(2-methoxyethyl)(meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl Base (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl ( Methyl) acrylamide, (meth) propylene decyl morpholine, diacetone acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, vinyl (meth) acrylamide N,N-diallyl (meth) acrylamide, N-allyl (meth) acrylamide, and the like.

Examples of the "styrene" include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, and hydroxystyrene. , methoxystyrene, butoxystyrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, deprotected by acidic substances ( For example, hydroxystyrene, methyl benzoate, and α-methylstyrene which are protected by a tertiary butyloxycarbonyl group (t-Boc: t-butoxycarbonyl).

Examples of the "vinyl ethers" include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, and butyl vinyl. Ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

Examples of the "vinyl ketone" include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

Examples of the "olefin" include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

Examples of the "m-butylene imine" are: maleimide, butyl maleimide, cyclohexyl maleimide, phenyl-butylene Amines, etc.

It is also possible to use (meth)acrylonitrile, a vinyl group which is substituted heterocyclic group (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N - vinylacetamide, N-vinylimidazole, vinyl caprolactone, and the like.

In addition to the above compounds, a vinyl monomer having a functional group such as a urethane group, a ureido group, a sulfonylamino group, a phenol group or a quinone group can also be used. These monomers having a urethane group or a ureido group can be suitably synthesized, for example, by an addition reaction of an isocyanate group with a hydroxyl group or an amine group. Specifically, an addition reaction of a monomer containing an isocyanate group with a compound containing one hydroxyl group or a compound containing one primary or secondary amine group, or a monomer having a hydroxyl group or containing a primary or secondary amine The monomer is appropriately synthesized by an addition reaction with a monoisocyanate or the like.

Next, a vinyl monomer having an acidic group used for introducing an acidic group into the polymer skeleton P ² will be described.

Examples of the above-mentioned "vinyl monomer having an acidic group" include a vinyl monomer having a carboxyl group or a vinyl monomer having a sulfonic acid group.

The "vinyl monomer having a carboxyl group" is exemplified by (meth)acrylic acid, vinylbenzoic acid, maleic acid (maleic acid), monoalkyl maleate, fumaric acid. (Fumaric acid), itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Further, it is also possible to use a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride or cyclohexane dicarboxylic anhydride. A reactant, ω-carboxy-polycaprolactone mono(meth)acrylate, or the like. Further, a monomer containing an anhydride such as maleic anhydride, itaconic anhydride or citraconic anhydride may be used as the carboxyl precursor. Further, among these, (meth)acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

In addition, the "vinyl monomer having a sulfonic acid group" is exemplified by 2-propenylamine-2-methylpropane sulfonic acid; and the "vinyl monomer having a phosphate group" is exemplified by phosphoric acid (2). - propylene methoxyethyl ester), mono(1-methyl-2-propenyloxyethyl phosphate), and the like.

Further, the "vinyl monomer having an acidic group" may be a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group.

In the case where the polymer skeleton P ² contains a structural unit derived from a vinyl monomer having an acidic group, the content of the structural unit derived from the vinyl monomer having an acidic group in the polymer skeleton is preferably 3 mol. The ear is from 0% to 40% by mole, more preferably from 5% to 20% by mole.

In the polymer compound represented by the above formula (I), it is preferable to satisfy all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below.

R ³ : The aforementioned specific examples (1), (2), (10), (11), (16), or (17).

R ⁴ : a single bond, or a structural unit of the following or a combination of the structural unit, "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 a divalent organic linking group composed of up to 30 hydrogen atoms and 0 to 5 sulfur atoms (may also have a substituent, and the "substituent" is, for example, a carbon such as a methyl group or an ethyl group. An alkyl group having a carbon number of from 1 to 20, a phenyl group, a naphthyl group or the like having 6 to 16 carbon atoms, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group, an acetamidine group a halogen atom having a carbon number of 1 to 6 such as a methoxy group, a methoxy group or an ethoxy group having 1 to 6 carbon atoms, a halogen atom such as chlorine or bromine, a methoxycarbonyl group or an ethoxy group. Examples of the carbonyl group, the cyclohexyloxycarbonyl group and the like have a carbon number of 2 to 7 such as an alkoxycarbonyl group, a cyano group or a carbonate group such as a butyl cyanocarbonate.

R ⁵ : a single bond, an ethyl group, a propyl group, a group (a), or a group (b) below.

Further, in the following group, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : a copolymer of a vinyl monomer having a carboxyl group and another vinyl monomer; a polymer or copolymer of a vinyl monomer having no acidic group; an ester polymer, an ether polymer, and an amine selected from the group consisting of A urethane-based polymer and such a modified substance, and may also contain at least one acidic group.

m: 1 to 3.

n: 3 to 6.

The content of the acidic group in the (B-1) binder resin of the present invention can be appropriately determined depending on the acid value of the (B-1) binder resin. The acid value of the (B-1) binder resin is preferably from 30 to 200 (mgKOH/g), more preferably from 40 to 160 (mgKOH/g), particularly preferably from 50 to 120 (mgKOH/g). When the acid value is less than 30 (mgKOH/g), the alkali developability of the colored photosensitive resin composition may be insufficient. When the acid value is more than 200 (mgKOH/g), a pigment is used. When the coloring agent (A) is used, there is a concern that the dispersibility and dispersion stability of the pigment may be adversely affected.

(B-1) The molecular weight of the binder resin is preferably from 3,000 to 100,000, more preferably from 5,000 to 80,000, particularly preferably from 7,000 to 60,000, based on the weight average molecular weight. When the weight average molecular weight is within the above range, the effects of a plurality of the absorbing sites introduced at the end of the polymer can be sufficiently exhibited, and the adsorption property on the solid surface, the formation of the micetes, and the interface activity are excellent. Performance.

Hereinafter, an exemplified compound relating to the (B-1) binder resin of the present invention will be listed, but the present invention is not limited thereto, and any structure may be adopted as long as it is contained in the formula (I).

In the above-mentioned (B-1) binder compound, the content ratio of the structural unit having a carboxylate in the polymer skeleton to the structural unit having a carboxyl group (p ¹ : p ² ), in mass conversion, It is preferably in the range of 95:5 to 80:20.

Among the above-exemplified compounds, a content ratio of a structural unit having a carboxylate in a polymer skeleton and a structural unit having a carboxyl group in a structure represented by the above B-1-22, particularly preferably The conversion is 90:10, and the molecular weight is 20,000, and the acid value is 82.

The (B-1) binder resin represented by the above formula (I) can be synthesized by, for example, the method disclosed in JP-A-2006-278118.

In the colored photosensitive resin composition of the present invention, the content of the (B-1) binder resin is preferably in the range of 5% by mass to 70% by mass based on the solid content of the colored photosensitive resin composition. More preferably, it is in the range of 10% by mass to 50% by mass.

<(B-2) A binder resin containing a structural unit represented by the general formula (II) and a structural unit having an acidic group>

The colored photosensitive resin composition of the present invention comprises (B-2) an adhesive resin containing a structural unit represented by the following general formula (II) and a structural unit having an acidic group.

[Structural unit represented by the general formula (II)]

In the formula (II), R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, and R ¹⁶ represents a hydrogen atom or a methyl group.

R ¹¹ to R ¹⁵ in the formula (II) are preferably each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 5 to 14 carbon atoms. More preferably, it is a hydrogen atom, a bromine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 7 carbon atoms or an aryl group having 5 to 10 carbon atoms.

The alkyl group may have a substituent, and the substituent may be a straight chain, a branch, or a ring, and examples thereof include a methyl group, a n-propyl group, an isopropyl group, a tertiary butyl group and the like, and preferably a carbon number. It is an alkyl group of 1 to 7. Further, the aryl group may have a substituent, and the substituent may, for example, be an alkyl group having 1 to 7 carbon atoms or an aryl group having 5 to 14 carbon atoms, and preferably a phenyl group, a furyl group or a naphthyl group.

Among these, as the general formula (II), it is preferred that R ¹¹ to R ¹⁵ are each independently a hydrogen atom, a methyl group, a phenyl group or a halogen atom, and R ¹⁶ is a hydrogen atom or a methyl group.

(B-2) The binder resin may contain a plurality of structural units represented by the above formula (II).

In the (B-2) binder resin, the structural unit represented by the above formula (II) is preferably contained in the molecule in an amount of 20 mol% or more and 90 mol% or less, more preferably 50 mol%. The above 80 mol% or less, and more preferably 60 mol% or more and 80 mol% or less. In the binder resin, when the total amount of each of the above structural units is within the above range, the development latitude is good, the film reduction at the time of development after exposure is small, and the surface of the obtained cured film is smooth. Sex becomes good.

[Structural unit having an acidic group]

Further, the (B-2) binder resin contains a structural unit having an acidic group in the molecule.

The structural unit having an acidic group is a structural unit derived from an unsaturated monomer having a carboxyl group. Examples of the "carboxy group-containing unsaturated monomer" include "unsaturated monocarboxylic acids" such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid (maleic acid), An unsaturated dicarboxylic acid such as maleic anhydride, fumaric acid (fumaric acid), itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride or mesaconic acid or an anhydride thereof; a trivalent or higher unsaturated polycarboxylic acid or an anhydride thereof; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxy group One of the divalent or higher polycarboxylic acids such as ethyl]ester [(meth) propylene decyloxyalkyl] ester; poly(meth)acrylic acid ω-carboxycaprolactone and the like having a carboxyl group at both ends One of the polymers of the hydroxyl group (meth) acrylate or the like.

Among the carboxyl group-containing unsaturated monomers, mono(2-propenyloxyethyl) succinate and mono(2-propenyloxyethyl) phthalate have been respectively M- The trade names of 5300 and M-5400 (made by Toagosei Co., Ltd.) are sold on the market.

The above-mentioned carboxyl group-containing unsaturated monomer may be contained in the resin alone or in combination of two or more.

Among these, preferred structural units having an acidic group are derived from a carboxylic acid, a chalcogen analog of a carboxylic acid, a carboxy azide acid [RC(=NNH ₂ )OH], a carboxyimidic acid [RC (=NH)OH], sulfonic acid [RS(O) ₂ OH], sulfinic acid [RS(O)OH], sulfenamide [RSOH], selenate [RSe(O) ₂ OH], selenite [ Structural units of RSe(O)OH], selenoic acid [RSeOH], phosphoric acid and its acid-related compounds, citric acid, and boric acid analogs; particularly preferred are structural units derived from acrylic acid, methacrylic acid, and phosphoric acid.

The content of the structural unit having an acidic group in the (B-2) binder resin is preferably 5 mol% or more and 50 mol% or less, more preferably 10 mol% or more and 30 mol% or less. When it is in this range, surface smoothness and heat resistance at the time of development are favorable.

(B-2) The binder resin may further contain other structural units in addition to the above respective structural units. The other structural unit is a structural unit derived from an unsaturated monomer described below.

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene , o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl ring "Aromatic vinyl compound" such as oxypropyl ether or p-vinylbenzyloxypropyl ether; "oxime" such as hydrazine or 1-methyl hydrazine; methyl (meth) acrylate, (a) Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, dibutyl (meth) acrylate Ester, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2-hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, (methyl) Cyclohexyl acrylate Phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxydiglycol (meth)acrylate, (methyl) ) methoxy triethylene glycol acrylate, methoxypropylene glycol (meth) acrylate, methoxy dipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo(methyl) acrylate [5.2.1.0 ^2,6 ] decane-8-yl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol mono(meth)acrylate, etc. Esters; 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-aminopropyl (meth)acrylate, 2-(meth)acrylate "unsaturated carboxylic acid aminoalkyl esters" such as dimethylaminopropyl propyl ester, 3-aminopropyl (meth) acrylate or 3-dimethylaminopropyl (meth) acrylate; "Unsaturated carboxylic acid glycidyl ester" such as methyl acrylate propylene acrylate; "unsaturated carboxylic acid oxetane alkyl ester" such as (meth)acrylic acid oxetane ester; "Carboxylic acid, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. "Ester esters";"unsaturatedethers" such as vinyl methyl ether, vinyl ethyl ether, allyl epoxy propyl ether; (methyl) acrylonitrile, α-chloroacrylonitrile, dicyandiamide "Cyanide vinyl compound" such as ethylene; "unsaturated guanamine" such as (meth) acrylamide, α-chloropropenylamine or N-2-hydroxyethyl (meth) acrylamide; "Unsaturated quinone imines" such as maleimide, N-phenyl maleimide, N-cyclohexylmethyleneimine, etc.; 1,3-butadiene, "Aliphatic conjugated dienes" such as isoprene and chloroprene (chlorine); polystyrene, poly(methyl) methacrylate, poly(meth) acrylate-n-butyl ester, poly A macromonomer having a mono(meth)acrylonitrile group at the end of a polymer molecular chain such as a siloxane or the like; the structural unit derived from such an unsaturated monomer may contain one type or two or more types.

In the following, exemplified compounds 1-1 to 1-8 and 2 to 20 of (B-2) binder resin are shown. (B-2) The binder resin is not limited to such an exemplary compound.

(B-2) The weight average molecular weight of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 50,000, still more preferably in the range of 10,000 to 40,000. When it is in this range, the developability and linearity of the formed pattern will become favorable.

In the colored photosensitive resin composition of the present invention, the content of the (B-2) binder resin is preferably in the range of 10% by mass to 50% by mass based on the solid content of the colored photosensitive resin composition. More preferably, it is in the range of 15% by mass to 40% by mass.

The colored photosensitive resin composition of the present invention contains two adhesive resins of (B-1) binder resin and (B-2) binder resin as described above, but (B-1) binder resin and (B-2) The content ratio of the binder resin on a mass basis must be from 3:7 to 7:3, preferably from 4:6 to 6:4. When the content ratio is within the above range, the heat resistance of the formed cured film becomes good, and the effect of suppressing generation of wrinkles after post-baking can be effectively suppressed.

Therefore, within the range of the content of each of the above-mentioned binder resins, the content ratio of the (B-1) binder resin and the (B-2) binder resin on a mass basis is adjusted to be 3:7 to 7:3. The scope.

The colored photosensitive resin composition of the present invention may contain a resin having a structure other than the above (B-1) binder resin and (B-2) binder resin having a specific component in the present invention. (B-1) a resin other than the binder resin and the (B-2) binder resin, as long as it functions as a binder for the colorant, and when the color filter is manufactured, The developer to be used in the development treatment step is particularly preferably a solvent which is soluble in the alkaline developer, and is preferably an acrylate copolymer having a carboxyl group, particularly an ethylenic bond having one or more carboxyl groups. A copolymer of an unsaturated monomer with another copolymerizable ethylenically unsaturated monomer.

In the present invention, specific examples of the resin which can be used in combination with the structure other than the above (B-1) binder resin and (B-2) binder resin are exemplified by (meth)acrylic acid/(meth)acrylic acid. a methyl ester copolymer, a (meth)acrylic acid/benzyl methacrylate copolymer, a (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl methacrylate copolymer, (meth)acrylic acid/methyl (meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/methyl (meth)acrylate/polymethyl methacrylate macromonomer copolymer, Methyl)acrylic acid/benzyl methacrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/benzyl methacrylate/polymethyl methacrylate macromonomer copolymer, (Meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / polystyrene macromonomer copolymer, (meth)acrylic acid / (meth)acrylic acid 2-hydroxyethyl Ester / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, and the like.

Further, a resin containing an epoxy ring or an oxetane ring such as styrene/methacrylic acid/methacrylic acid tricyclo[5.2.1.0 ^2,6 ]decane-8-yl can also be used. Ester/glycidyl methacrylate copolymer, styrene/acrylic acid/acrylic tricyclo [5.2.1.0 ^2,6 ]decane-8-yl ester/glycidyl acrylate copolymer, benzyl methacrylate /methacrylic acid/3-(methacryloxymethyl)oxetane/tert-butyl methacrylate copolymer, benzyl methacrylate/methacrylic acid/3-(methacrylic acid)醯oxymethyl)-3-ethyloxetane/styrene copolymer, butadiene/styrene/methacrylic acid/methacrylic acid tricyclo[5.2.1.0 ^2,6 ]decane-8 -Base ester / Glycidyl methacrylate copolymer, butadiene / methacrylic acid / trimethacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester / glycidyl methacrylate Copolymer, styrene/methacrylic acid/trimethyl methacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester/methacrylic acid-6,7-epoxyheptyl ester copolymer, styrene/ Acrylic acid/maleic anhydride/-6,7-epoxyheptyl methacrylate copolymer, Tertiary butyl acrylate / acrylic acid / maleic anhydride / methacrylic acid-6,7-epoxyheptyl ester copolymer, styrene / methacrylic acid / methyl methacrylate / methacrylic acid propylene Ester copolymer, p-methoxystyrene/methacrylic acid/cyclohexyl acrylate/glycidyl methacrylate copolymer.

<(C) Polymerizable Compound>

The colored photosensitive resin composition of the present invention contains (C) a polymerizable compound.

The polymerizable compound which can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond selected from at least one, preferably having two or more terminal ethylenically unsaturated bonds. Compound. These compound groups are widely known in the industrial field, and in the present invention, these can be used without particular limitation. These are, for example, chemical forms of monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of the monomer and the copolymer thereof may be exemplified by an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid (maleic acid), etc.), or The esters and guanamines are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyamine compound.

Further, an addition reaction product of an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a thiol group, and a monofunctional or polyfunctional isocyanate or epoxy group, and Dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, and the like. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an isocyanate group or an electrophilic substituent such as an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and having an addition reaction product A substituted carboxylic acid ester such as a halogen group or a toluenesulfonyloxy group or a decylamine and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable. Further, as another example, a compound group using an unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid may also be used.

In the present specification, acrylate and methacrylate are collectively referred to as "(meth) acrylate".

Specific examples of the monomer of the aliphatic polyol compound and the ester of the unsaturated carboxylic acid are as follows: "(meth) acrylate" includes: ethylene glycol di(meth)acrylate Ester, triethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate , neopentyl glycol di(meth)acrylate, trimethylolpropane tris(meth)acrylate, trimethylolpropane tris((meth)acryloxypropyl)ether, tris(methyl) ) Trimethylolethane acrylate, hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, two Pentaerythritol (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, five ( Dipentaerythritol methyl methacrylate, di neopentyl hexa(meth) acrylate, sorbitol triacrylate, sorbitol tetra(meth)acrylate, sorbitol penta(meth)acrylate, Hexa(meth)acrylic acid Pear alcohol ester, tris(meth) propylene methoxyethyl ester, polyester (meth) acrylate oligomer, modified by EO (ethylene oxide) Tris(meth)acrylate, bisphenol A di(meth)acrylate, EO modification of bis(meth)acrylic acid bisphenol A, trimethylolpropane tri(meth)acrylate, trishydroxy Methylpropane tris((meth)acryloxypropyl)ether, trimethylolethane tris(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol diacrylate , neopentyl glycol (meth)acrylate, neopentyl tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, neopentyl methacrylate EO modified, six Dipentaerythritol acrylate modified EO and the like.

"Iconic acid ester" includes: ethylene glycol di-conconate, propylene glycol di-conconate, 1,3-butylene glycol di-conconate, 1,4-butylene glycol di-conconate , Icylene tetramethylene glycol ester, diconcanic acid pentaerythritol ester, tetraconcanic acid sorbitol ester, and the like. "crotonate" includes: ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, neopentyl glycol dicrotonate, sorbitol tetracrotonate, and the like. "Isocrotonate" includes ethylene glycol diisocrotonate, neopentyl glycol diisocrotonate, and sorbitol tetraisocrotonate. "maleate" includes: ethylene glycol maleate, triethylene glycol dimaleate, pentaerythritol dimaleate, tetrabutylene Sorbitol ester and the like.

Examples of the other esters are also suitable for use, for example, the aliphatic alcohol esters disclosed in Japanese Patent Publication No. Sho 51-47334, and JP-A-57-196231, or JP-A-59-5240 The aromatic group-containing group disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. And so on.

Further, specific examples of the monomer of the aliphatic polyamine compound and the decylamine of the unsaturated carboxylic acid include: methylene bis-acrylamide, methylene bis-methyl acrylamide, 1,6-hexa Methyl bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, di-ethyltriamine propylene amide, hydrazinium bis decylamine, hydrazino bis methacryl Amidoxime and the like. Other examples of the preferred amide-based monomer are those having a cyclohexylene structure as disclosed in Japanese Patent Publication No. Sho 54-21726.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and a specific example thereof is disclosed in, for example, Japanese Patent Publication No. Sho 48-41708. a polyisocyanate compound having two or more isocyanate groups in one molecule and having ethylene having two or more polymerizable vinyl groups in one molecule by addition of a vinyl monomer having a hydroxyl group represented by the following formula (V) A carbamic acid ester compound or the like.

General formula (V)

CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH(V)

(However, R ⁴ and R ⁵ each independently represent H or CH ₃ ).

Further, the urethane acrylates disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. A urethane having an ethylene oxide-based skeleton as disclosed in Japanese Patent Publication No. Sho 62-39417, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 Compound classes are also suitable. In addition, the amine group structure or the sulfide structure in the molecule is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. When a polymerizable compound is added, a photopolymerizable composition having a very excellent light-sensing rate can be obtained.

Other examples are the polyester acrylates disclosed in each of the publications of Japanese Patent Publication No. Sho-48-64183, JP-A-49-43191, and Japanese Patent Publication No. Sho 52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate having an epoxy resin and (meth)acrylic acid. In addition, a specific unsaturated compound disclosed in Japanese Patent Publication No. Sho 46-43946, Japanese Patent Publication No. Hei. No. 1-40337, and Japanese Patent Publication No. Hei. No. Hei. A vinylphosphonic acid-based compound or the like as disclosed in Japanese Patent Publication No. 25493. Further, a structure containing a perfluoroalkyl group as disclosed in Japanese Laid-Open Patent Publication No. 61-22048 is also suitably used.

Further, a commercially available product is preferably a urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.); DPHA (Nippon Chemical Co., Ltd. (Nippon) Kayaku Co., Ltd.); UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.).

Further, it can also be used as a photocurable monomer and oligomer in Nippon Secchaku Kyokai Shi [Journal of the Adhesion Society of Japan], Vol. 20, No. 7, pp. 300 to 308 (1984). The person introduced by the object.

In the colored photosensitive resin composition of the present invention, a preferred mode of the (C) polymerizable compound is to use a compound containing 5 or more and 15 or less polymerizable groups in the molecule and 1 or more and 4 in the molecule. A mixture of the following polymerizable groups of compounds. The compound containing 5 or more and 15 or less polymerizable groups in the molecule, and the compound containing one or more or four or less polymerizable groups in the molecule are preferably the following compounds.

Examples of the "compound having 5 or more and 15 or less polymerizable groups in the molecule" include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and five. Sorbitol (meth)acrylate, sorbitan hexa(meth)acrylate, and U-6HA, U-15HA, UA-32P, UA-7200 (the above is Shin-Nakamura Chemical Co., Ltd.), TO-2248, 2349, 1382 (the above is manufactured by Toagos Corporation). Further, examples thereof include oligo(meth)acrylic acid neopentyl glycol ester, oligo(1,4-butylene methacrylate), oligo(meth)acrylic acid 1,6-hexanediol ester, and oligo( Intramolecular inclusion of trimethylolpropane methyl methacrylate, neopentyl glycol (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate 5 or more compounds of 15 or less (meth) acrylate groups, but in the case of such oligos, the molecular weight is preferably in the range of 1,000 to 5,000.

The "compound containing one or more polymerizable groups of four or less in the molecule" may be exemplified by trimethylolpropane tris(meth)acrylate and modified by trimethylolpropane PO (propylene oxide). (Meth) acrylate, tris(meth)acrylate modified with trimethylolpropane EO (ethylene oxide), neopentyl glycol tetra(meth)acrylate, new tris(meth)acrylate Pentaerythritol ester, tetrakis (meth) methacrylate, neopentyl tetra(meth) acrylate, ditrimethylolpropane tetra(methyl) acrylate, ethoxylated Pentaerythritol (meth)acrylate and the like.

When a mixture of a compound containing 5 or more and 15 or less polymerizable groups in the molecule and a compound containing one or more polymerizable groups having 1 or less in the molecule is used, 5 or more and 15 or less polymerizations are contained in the molecule. The ratio of the compound of the group to the compound containing one or more polymerizable groups of four or less in the molecule [(a compound containing five or more polymerizable groups of 15 or less in the molecule): (containing one or more in the molecule 4 The compound of the following polymerizable group)] is preferably in the range of 60:40 to 95:5, more preferably 70:30 to 90:10 in terms of mass.

(C) The total content of the polymerizable compound is preferably from 10% by mass to 60% by mass, more preferably from 15% by mass to 50% by mass based on the total solid content of the colored photosensitive resin composition layer of the present invention. %, further preferably from 18% by mass to 40% by mass.

Since it is set in this range, the heat resistance of the obtained cured film becomes good, and the surface roughening after development and the generation of wrinkles after post-baking can be effectively suppressed.

In the colored photosensitive resin composition of the present invention, the mass ratio of the (C) polymerizable compound to the (D) fluorene-based photopolymerization initiator described later is "(D) photopolymerization initiator / (C) polymerizable compound" It may be 0.1 or more and 2.0 or less, preferably 0.1 or more and 1.0 or less, and particularly preferably 0.3 or more and 0.9 or less. When it is set to the above range, the pattern formability is good and the adhesion to the substrate is excellent. Further, the exposure and the amount of the mask after development are sufficient, and the pattern peeling can be suppressed.

<(D) Lanthanide Photopolymerization Initiator>

In the (D) oxime-based photopolymerization initiator of the present invention, as long as it is a compound having an oxime ester structure and capable of initiating and promoting the polymerization of the (C) polymerizable compound, the prior art can be used without limitation. Examples thereof include an oxime ester compound and a ketoxime compound. Specifically, for example, a ketone-based photopolymerization initiator represented by the following formula (III), which is represented by the following formula (D-1), which is disclosed in JP-A-2005-220097 The photopolymerization initiator, the oxime-based photopolymerization initiator disclosed in JP-A-2006-516246, and the like, preferably from the viewpoint of curing sensitivity or coloring after post-baking. A ketone-based photopolymerization initiator represented by (III).

In the formula (D-1), X ¹ represents a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ represents -R, -OR, -COR, -SR, -CONRR', or -CN, R ² and R ³ is each independently representing -R, -OR, -COR, -SR, or -NRR'. R and R' each independently represent an alkyl group, an aryl group, an arylalkyl group, or a heterocyclic group, and the groups thereof may be one or more selected from the group consisting of a halogen atom and a heterocyclic group. Alternatively, one or more of the carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be substituted into an unsaturated bond, an ether bond, or an ester bond, and R and R' may be bonded to each other. And form a ring.

In the formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer from 0 to 5. When X is present in a complex number, the complex X is independently representing a monovalent substituent.

The valence substituent represented by the above R is preferably a non-metal atomic group represented by the following one.

The "non-metal atomic group represented by R" is an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and may have Alkylsulfinyl group of a substituent, an arylsulfinylene group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and a substituent which may have a substituent Alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, a phosphinylene group which may have a substituent, a heterocyclic group which may have a substituent, an alkylthiocarbonyl group which may have a substituent, An arylthiocarbonyl group which may have a substituent, a dialkylaminocarbonyl group which may have a substituent, a dialkylaminothiocarbonyl group which may have a substituent, and the like.

The "alkyl group which may have a substituent" is preferably an alkyl group having 1 to 30 carbon atoms, which may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group or a dodecane group. Base, octadecyl, isopropyl, isobutyl, secondary butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, Benzomethazine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylsulfanylbenzylidenemethyl, 4-phenylsulfanylbenzimidylmethyl, 4-Dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzamide Base, 3-trifluoromethylbenzimidylmethyl, 3-nitrobenzimidylmethyl, and the like.

The "aryl group which may have a substituent" is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, and 9 -phenanthryl, 1-indenyl, 5-thick tetraphenyl, 1-indenyl, 2-indenyl, 9-indenyl, triphenyl, biphenyl, o-, m-, and p- Tolyl, xylyl, o-, m-, and p-isopropylphenyl, Mesityl group, cyclopentadienyl, binaphthyl, binaphthyl, naphthyl, cycloheptatrienyl, terphenyl, dicyclopentadienyl, propylene Alkene thin group, fluorenyl group, vinyl fluorenyl group, propylene naphthyl group, fluorenyl group, fluorenyl group, hydrazino group, hydrazinyl group, hydrazinyl group, quinolinol group, phenanthryl group, hydrazine Base, base, Chrysenyl group, condensed tetraphenyl, heptaenyl, decyl, decyl, bipentaphenyl, fused pentaphenyl, phenylene, hexaphenyl, hexaphenyl, ruthenyl , mercapto, tris-naphthyl, iso-hexaphenyl, hexaphenyl, anthracenyl, fluorenyl and the like.

The "alkenyl group which may have a substituent" is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a styryl group and the like.

The "alkynyl group which may have a substituent" is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, a propynyl group and the like.

The "alkylsulfinyl group which may have a substituent" is preferably an alkylsulfinyl group having a carbon number of 1 to 20, which may, for example, be a methylsulfinyl group, an ethylsulfinyl group, or a C. Isosulfonyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl , mercaptosulfinyl, decylsulfenyl, octadecylsulfenyl, cyanomethylsulfinyl, methoxymethylsulfinyl, and the like.

The "arylsulfinyl group which may have a substituent" is preferably an arylsulfinyl group having a carbon number of 6 to 30, which may, for example, be a phenylsulfinyl group or a 1-naphthylsulfinyl group. , 2-naphthylsulfinyl, 2-chlorophenylsulfinyl, 2-methylphenylsulfinyl, 2-methoxyphenylsulfinyl, 2-butoxyphenyl Sulfosyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenylsulfinyl, 4-methylsulfanylphenylsulfinyl, 4-benzene Alkylthioalkylphenylsulfinyl, 4-dimethylaminophenylsulfinyl, and the like.

The "alkylsulfonyl group which may have a substituent" is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, which may, for example, be a methylsulfonyl group, an ethylsulfonyl group or a propylsulfonyl group. , isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, twelve Alkylsulfonyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl, perfluoroalkylsulfonyl, and the like.

The "arylsulfonyl group which may have a substituent" is preferably an arylsulfonyl group having a carbon number of 6 to 30, which may, for example, be a phenylsulfonyl group, a 1-naphthylsulfonyl group or a 2-naphthalene group. Sulfosyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorobenzene Sulfosyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyano Phenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylsulfanylphenylsulfonyl, 4-phenylsulfanylphenylsulfonyl, 4-dimethylamino Phenylsulfonyl and the like.

The "thiol group which may have a substituent" is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include, for example, an ethyl group, a propyl group, a butyl group, a trifluoromethylcarbonyl group, a amyl group, and a benzamidine group. , 1-naphthylmethyl, 2-naphthylmethyl, 4-methylsulfanylbenzylidene, 4-phenylsulfanylbenzylidene, 4-dimethylaminobenzimidamide , 4-diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzimidyl , 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyano Benzopyridinyl, 4-methoxybenzimidyl, and the like.

The "alkoxycarbonyl group which may have a substituent" is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. A hexyloxycarbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, a trifluoromethoxycarbonyl group or the like.

The "aryloxycarbonyl group which may have a substituent" is exemplified by a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenoxycarbonyl group, a 4-phenyl group. Sulfoalkylphenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethylaminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2 -methoxyphenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxycarbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrate A phenoxycarbonyl group, a 4-fluorophenoxycarbonyl group, a 4-cyanophenoxycarbonyl group, a 4-methoxyphenoxycarbonyl group or the like.

The "phosphinylene group which may have a substituent" is preferably a phosphinylene group having a total carbon number of 2 to 50, and examples thereof include, for example, a dimethylphosphinylene group, a diethylphosphinylene group, and a dipropylphosphinyl group. , diphenylphosphinyl, dimethoxyphosphinyl, diethoxyphosphinyl, benzhydrylphosphinyl, bis(2,4,6-trimethylphenyl)phosphinyl Wait.

The "heterocyclic group which may have a substituent" is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples thereof include, for example, a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thiol group, a furyl group, a piperidyl group, an isobenzofuranyl group, Ethyl (chromenyl group), Xanthenyl group, brown Base, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime Base Base, isodecyl, 3H-fluorenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quina Base, isoquinolyl, quinolyl, anthracene base, Naphthyridinyl group, quinoxalinyl, quinazolinyl, Cinnolinyl group, acridinyl, 4aH-carbazolyl, oxazolyl, β-carboline, phenanthryl, acridinyl, Perimidinyl group, morpholinyl, brown Basal Base, isothiazolyl, thiophene Basis Azyl, furazolyl, brown Basis Isochromanyl group, Alkyl group, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, hexahydropyridyl Base, porphyrin group, isoindolyl group, Quinuclidinyl group, morpholinyl, sulfur Thioxanthenyl group, etc.

The "alkylthiocarbonyl group which may have a substituent" is exemplified by, for example, methylthiocarbonyl, propylthiocarbonyl, butylthiocarbonyl, octylthiocarbonyl, decylthiocarbonyl, octadecylthiocarbonyl, trifluoro Methyl thiocarbonyl and the like.

The "arylthiocarbonyl group which may have a substituent" is exemplified by 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl, 4-methylsulfanylphenylthiocarbonyl, 4-phenylsulfanylphenyl Thiocarbonyl, 4-dimethylaminophenylthiocarbonyl, 4-diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl, 2-methylphenylthiocarbonyl, 2-methoxybenzene Thiocarbonyl, 2-butoxyphenylthiocarbonyl, 3-chlorophenylthiocarbonyl, 3-trifluoromethylphenylthiocarbonyl, 3-cyanophenylthiocarbonyl, 3-nitrophenylthiocarbonyl 4-fluorophenylthiocarbonyl, 4-cyanophenylthiocarbonyl, 4-methoxyphenylthiocarbonyl, and the like.

The "dialkylaminocarbonyl group which may have a substituent" may, for example, be a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a dipropylaminocarbonyl group or a dibutylaminocarbonyl group.

The "dialkylaminothiocarbonyl group which may have a substituent" may, for example, be a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group or a dibutylaminothiocarbonyl group.

The above R, from the viewpoint of high sensitivity, is more preferably an unsubstituted or substituted fluorenyl group, specifically, an unsubstituted or substituted ethyl fluorenyl group, propyl fluorenyl group, and benzoic acid. Sulfhydryl, toluylcarbenyl.

The substituent is, for example, a group represented by the following structural formula, and any of (d-1) (d-4) and (d-5) is preferred.

The "divalent organic group represented by the above A" may, for example, be an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cyclohexylene group which may have a substituent, and an alkynyl group which may have a substituent.

Examples of the substituent which can be introduced into the group include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a tertiary butoxy group. An alkoxycarbonyl group or an aryloxycarbonyl group such as an aryloxy group such as a phenoxy group or a p-tolyloxy group, a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group or a propyloxy group; a mercapto group such as a fluorenyloxy group such as an anthracene group, an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group or a methoxy sulfhydryl group; An alkylthio group such as an alkylsulfanyl group such as a tertiary butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group or a p-tolylsulfanyl group; an alkylamino group such as a methylamino group or a cyclohexylamino group; An arylamino group such as a dimethylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group, a phenylamino group, a p-tolylamino group or the like, a methyl group or an ethyl group. Examples of the alkyl group such as a tertiary butyl group or a dodecyl group, an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumyl group, a naphthyl group, an anthranyl group or a phenanthryl group may be mentioned. Hydroxyl, carboxyl Mercapto, thiol, sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitro, cyano, trifluoromethyl, trichloromethyl, trimethyldecyl, monobasic phosphate (phosphinico group), phosphono group, trimethylammonium group, dimethylammonium group, triphenyl benzamidine methyl fluorenyl group and the like.

Among them, the above A is preferably an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tertiary butyl group, or a tenth) from the viewpoint of improving sensitivity and suppressing coloring due to heating over time. Dialkyl) substituted alkyl, alkyl substituted by alkenyl (eg vinyl, allyl), aryl (eg phenyl, p-tolyl, xylyl, cumenyl, naphthalene) Alkyl, fluorenyl, phenanthryl, styryl) substituted alkyl.

The aryl group represented by the above Ar is preferably an aryl group having a carbon number of 6 to 30, and may have a substituent.

Specifically, Ar is exemplified by phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-fluorenyl, 9-phenanthryl, 1-fluorenyl, 5-fused tetraphenyl, 1- Indenyl, 2-indenyl, 9-fluorenyl, triphenyl, tetraphenyl, o-, m-, and p-tolyl, xylyl, o-, m-, and p-isopropyl Phenyl, And cyclopentadienyl, binaphthyl, trinaphthyl, tetratetraphthyl, cycloheptatrienyl, terphenyl, dicyclopentadienyl, alkadienyl , mercapto, vinyl fluorenyl, propylene naphthyl, thin, fluorenyl, hydrazino, hydrazinyl, hydrazinyl, quinolinol, phenanthryl, triphenylene, fluorenyl , Base, condensed tetraphenyl, heptaenyl, fluorenyl, fluorenyl, bipentyl, fused pentaphenyl, phenylene, hexaphenyl, hexaphenyl, ruthenium, fluorenyl, fluorenyl Bis-naphthyl, iso-hexaphenyl, hexa-phenyl, anthracenyl, fluorenyl and the like. Among them, a substituted or unsubstituted phenyl group is preferred from the viewpoint of improving sensitivity and suppressing coloring due to heating over time.

When the phenyl group has a substituent, the "substituent group" may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a methoxy group, an ethoxy group or a tertiary butoxy group. An alkyloxy group such as an alkoxy group, a phenoxy group, a p-tolyloxy group or the like, an alkylthio group, an ethylthio group, an ethylthio group, a tris-butylthio group or the like, or a phenylthio group. An alkoxycarbonyl or aryloxycarbonyl group such as an arylthiooxy group, a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group such as a p-tolylthiooxy group; an ethoxycarbonyl group; a mercapto group such as a decyloxy group, an ethyl fluorenyl group, a benzhydryl group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, a methoxy oxalyl group, or the like, a methyl sulfane group An alkyl group such as an alkylsulfanyl group such as a butylsulfanyl group, a phenylsulfanyl group or a p-tolylsulfanyl group; an alkyl group such as an arylsulfanyl group, a methylamino group or a cyclohexylamino group; An arylamino group such as an amine group, a dimethylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group; an arylamino group such as a phenylamino group or a p-tolylamino group; Tertiary butyl, twelve Alkyl group, hydroxyl group, carboxyl group, formyl group, thiol group, sulfo group, methanesulfonyl group, p-toluenesulfonyl group, amine group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group And a trimethyldecyl group, a monobasic phosphate group, a phosphonic acid group, a trimethyl ammonium group, a dimethyl ammonium group, a triphenyl benzamidine methyl fluorenyl group or the like.

In the general formula (III), when the structure of "SAr" formed by the Ar and the adjacent S is the structure shown below, it is preferable from the viewpoint of sensitivity.

The above-mentioned "valent substituent represented by X" may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or may have Alkoxy group of a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, a halogenated alkyl group which may have a substituent, on N An amidino group which may have a substituent, an alkyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent An arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an indenyl group which may have a substituent, an alkyl group which may have a substituent An oxycarbonyl group or an aryloxycarbonyl group, an amine carbenyl group which may have a substituent, an amine sulfonyl group which may have a substituent, an amine group which may have a substituent, a phosphinylene group which may have a substituent, may have a substituent a heterocyclic group, a halogen atom or the like.

The "alkyl group which may have a substituent" is preferably an alkyl group having 1 to 30 carbon atoms, which may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group or a dodecane group. Base, octadecyl, isopropyl, isobutyl, secondary butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, Benzomethazine methyl, 1-naphthylmethylmethyl, 2-naphthylmethylmethyl, 4-methylsulfanylbenzylidenemethyl, 4-phenylsulfanylbenzimidylmethyl, 4-Dimethylaminobenzimidylmethyl, 4-cyanobenzhydrylmethyl, 4-methylbenzimidylmethyl, 2-methylbenzimidylmethyl, 3-fluorobenzamide Base, 3-trifluoromethylbenzimidylmethyl, 3-nitrobenzimidylmethyl, and the like.

The "aryl group which may have a substituent" is preferably an aryl group having a carbon number of 6 to 30, which includes, for example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-fluorenyl group, and 9- Phenylidene, 1-indenyl, 5-thick tetraphenyl, 1-indenyl, 2-indenyl, 9-indenyl, triphenyl, tetraphenyl, o-, m-, and p-toluene Base, xylyl, o-, m-, and p-cumyl, And cyclopentadienyl, binaphthyl, trinaphthyl, tetratetraphthyl, cycloheptatrienyl, terphenyl, dicyclopentadienyl, alkadienyl , mercapto, vinyl fluorenyl, propylene naphthyl, thin, fluorenyl, hydrazino, hydrazinyl, hydrazinyl, quinolinol, phenanthryl, triphenylene, fluorenyl , Base, condensed tetraphenyl, heptaenyl, fluorenyl, fluorenyl, bipentyl, fused pentaphenyl, phenylene, hexaphenyl, hexaphenyl, ruthenium, fluorenyl, fluorenyl Bis-naphthyl, iso-hexaphenyl, hexa-phenyl, anthracenyl, fluorenyl and the like.

The "alkenyl group which may have a substituent" is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a styryl group and the like.

The "alkynyl group which may have a substituent" is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, a propynyl group and the like.

The "alkoxy group which may have a substituent" is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Isobutoxy, 2,4-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, Dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethoxy, aminocarbonylmethoxy, N,N-dibutylaminocarbonylmethoxy , N-methylaminocarbonylmethoxy, N-ethylaminocarbonylmethoxy, N-octylaminocarbonylmethoxy, N-methyl-N-benzylaminocarbonylcarbonyl Base, benzyloxy, cyanomethoxy, and the like.

The "aryloxy group which may have a substituent" is preferably an aryloxy group having a carbon number of 6 to 30, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 2-chlorophenoxy group. Base, 2-methylphenoxy, 2-methoxyphenoxy, 2-butoxyphenoxy, 3-chlorophenoxy, 3-trifluoromethylphenoxy, 3-cyanobenzene Oxyl, 3-nitrophenoxy, 4-fluorophenoxy, 4-cyanophenoxy, 4-methoxyphenoxy, 4-dimethylaminophenoxy, 4-methyl Sulfoalkylphenoxy, 4-phenylsulfanylphenoxy, and the like.

The "alkylthio group which may have a substituent" is preferably an alkylthio group having 1 to 30 carbon atoms, which may, for example, be a methylthiooxy group, an ethylthio group or a propylthio group. , isopropyl thiooxy, butyl thiooxy, isobutyl thiooxy, secondary butyl thiooxy, tert-butyl thiooxy, pentyl thiooxy, isopentyl thiooxy, Hexyl thiooxy, heptyl thiooxy, octyl thiooxy, 2-ethylhexyl thiooxy, decyl thiooxy, dodecyl thiooxy, octadecyl thiooxy, benzoyl Base thiooxy and the like.

The "arylthio group which may have a substituent" is preferably an arylthiooxy group having 6 to 30 carbon atoms, which may, for example, be a phenylthiooxy group, a 1-naphthylthiooxy group or a 2-naphthalene group. Thioryloxy, 2-chlorophenylthiooxy, 2-methylphenylthiooxy, 2-methoxyphenylthiooxy, 2-butoxyphenylthiooxy, 3-chlorobenzene Thioryloxy, 3-trifluoromethylphenylthiooxy, 3-cyanophenylthiooxy, 3-nitrophenylthiooxy, 4-fluorophenylthiooxy, 4-cyano Phenylthiooxy, 4-methoxyphenylthiooxy, 4-dimethylaminophenylthiooxy, 4-methylsulfanylphenylthiooxy, 4-phenylsulfanyl Phenylthiooxy and the like.

The "oxy group which may have a substituent" is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include an ethoxy group, a propenyloxy group, a butyloxy group, a pentyloxy group, and the like. Fluoromethylcarbonyloxy, benzylideneoxy, 1-naphthylcarbonyloxy, 2-naphthylcarbonyloxy, and the like.

The "alkylsulfide group which may have a substituent" is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, which may, for example, be a methylsulfanyl group, an ethylsulfanyl group or a propylsulfanyl group. , isopropylsulfanyl, butylsulfanyl, hexylsulfanyl, cyclohexylsulfanyl, octylsulfanyl, 2-ethylhexylsulfanyl, decylsulfanyl, ruthenium Alkylthioalkyl, octadecylsulfanyl, cyanomethylsulfanyl, methoxymethylsulfanyl, and the like.

The "arylsulfide group which may have a substituent" is preferably an arylsulfanyl group having 6 to 30 carbon atoms, which may, for example, be a phenylsulfanyl group, a 1-naphthylsulfanyl group or a 2-naphthalene group. Sulfoalkyl, 2-chlorophenylsulfanyl, 2-methylphenylsulfanyl, 2-methoxyphenylsulfanyl, 2-butoxyphenylsulfanyl, 3-chlorobenzene Sulfoalkyl, 3-trifluoromethylphenylsulfanyl, 3-cyanophenylsulfanyl, 3-nitrophenylsulfanyl, 4-fluorophenylsulfanyl, 4-cyano Phenylsulfanyl, 4-methoxyphenylsulfanyl, 4-methylsulfanylphenylsulfanyl, 4-phenylsulfanylphenylsulfanyl, 4-dimethylamino Phenylsulfanyl and the like.

The "alkylsulfinyl group which may have a substituent" is preferably an alkylsulfinyl group having a carbon number of 1 to 20, which may, for example, be a methylsulfinyl group, an ethylsulfinyl group, or a C. Isosulfonyl, isopropylsulfinyl, butylsulfinyl, hexylsulfinyl, cyclohexylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl , mercaptosulfinyl, decylsulfenyl, octadecylsulfenyl, cyanomethylsulfinyl, methoxymethylsulfinyl, and the like.

The "arylsulfinyl group which may have a substituent" is preferably an arylsulfinyl group having a carbon number of 6 to 30, which may, for example, be a phenylsulfinyl group or a 1-naphthylsulfinyl group. , 2-naphthylsulfinyl, 2-chlorophenylsulfinyl, 2-methylphenylsulfinyl, 2-methoxyphenylsulfinyl, 2-butoxyphenyl Sulfosyl, 3-chlorophenylsulfinyl, 3-trifluoromethylphenylsulfinyl, 3-cyanophenylsulfinyl, 3-nitrophenylsulfinyl, 4-fluorophenylsulfinyl, 4-cyanophenylsulfinyl, 4-methoxyphenylsulfinyl, 4-methylsulfanylphenylsulfinyl, 4-benzene Alkylthioalkylphenylsulfinyl, 4-dimethylaminophenylsulfinyl, and the like.

The "alkylsulfonyl group which may have a substituent" is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, which may, for example, be a methylsulfonyl group, an ethylsulfonyl group or a propylsulfonyl group. , isopropylsulfonyl, butylsulfonyl, hexylsulfonyl, cyclohexylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, decylsulfonyl, twelve Sulfosyl, octadecylsulfonyl, cyanomethylsulfonyl, methoxymethylsulfonyl and the like.

The "arylsulfonyl group which may have a substituent" is preferably an arylsulfonyl group having a carbon number of 6 to 30, which may, for example, be a phenylsulfonyl group, a 1-naphthylsulfonyl group or a 2-naphthalene group. Sulfosyl, 2-chlorophenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl, 2-butoxyphenylsulfonyl, 3-chlorobenzene Sulfosyl, 3-trifluoromethylphenylsulfonyl, 3-cyanophenylsulfonyl, 3-nitrophenylsulfonyl, 4-fluorophenylsulfonyl, 4-cyano Phenylsulfonyl, 4-methoxyphenylsulfonyl, 4-methylsulfanylphenylsulfonyl, 4-phenylsulfanylphenylsulfonyl, 4-dimethylamino Phenylsulfonyl and the like.

The "thiol group which may have a substituent" is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include, for example, an ethyl group, a propyl group, a butyl group, a trifluoromethylcarbonyl group, a amyl group, and a benzamidine group. , 1-naphthylmethyl, 2-naphthylmethyl, 4-methylsulfanylbenzylidene, 4-phenylsulfanylbenzylidene, 4-dimethylaminobenzimidamide , 4-diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzimidyl , 3-chlorobenzhydryl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyano Benzopyridinyl, 4-methoxybenzimidyl, and the like.

The "alkoxycarbonyl group or aryloxycarbonyl group which may have a substituent" is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having 2 to 20 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group. , propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, trifluoromethoxycarbonyl, 1-naphthyloxy Carbonyl, 2-naphthyloxycarbonyl, 4-methylsulfanylphenoxycarbonyl, 4-phenylsulfanylphenoxycarbonyl, 4-dimethylaminophenoxycarbonyl, 4-diethyl Aminophenoxycarbonyl, 2-chlorophenoxycarbonyl, 2-methylphenoxycarbonyl, 2-methoxyphenoxycarbonyl, 2-butoxyphenoxycarbonyl, 3-chlorophenoxy Carbonyl, 3-trifluoromethylphenoxycarbonyl, 3-cyanophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-cyanophenoxycarbonyl, 4- Methoxyphenoxycarbonyl and the like.

The "amine-containing mercapto group which may have a substituent" is preferably an amine carbenyl group having a total carbon number of 1 to 30, and examples thereof include N-methylaminecarbamyl group and N-ethylamine methyl sulfonyl group. N-propylamine methyl sulfhydryl, N-butylamine methyl sulfhydryl, N-hexylamine methyl sulfhydryl, N-cyclohexylamine methyl sulfhydryl, N-octylamine methyl sulfhydryl, N-decylamine Mercapto, N-octadecylamine, mercapto, N-phenylamine, mercapto, N-2-methylphenylamine, N-2-chlorophenylamine, N-, N- 2-Isopropoxyphenylaminecarbamyl, N-2-(2-ethylhexyl)phenylaminecarbamyl, N-3-chlorophenylaminecarbamyl, N-3-nitrobenzene Base amide, N-3-cyanophenylamine, fluorenyl, N-4-methoxyphenylamine, fluorenyl, N-4-cyanophenylamine, fluorenyl, N-4- Methylsulfanylphenylamine methyl sulfonyl, N-4-phenylsulfanylphenylamine methyl sulfhydryl, N-methyl-N-phenylamine methyl sulfhydryl, N,N-dimethylamine Formyl, N,N-dibutylamine, fluorenyl, N,N-diphenylamine, decyl, and the like.

The "amine-containing sulfonyl group which may have a substituent" is preferably an amine sulfonyl group having a total carbon number of from 0 to 30, and examples thereof include, for example, an amine sulfonyl group, an N-alkylamine sulfonyl group, and an N-aryl group. Aminesulfonyl, N,N-dialkylaminesulfonyl, N,N-diarylaminesulfonyl, N-alkyl-N-arylaminesulfonyl and the like. More specifically, it may, for example, be N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-butylaminesulfonyl, N-hexylaminesulfonate Mercapto, N-cyclohexylamine sulfonyl, N-octylamine sulfonyl, N-2-ethylhexylamine sulfonyl, N-decylamine sulfonyl, N-octadecylamine sulfonate Sulfhydryl, N-phenylamine sulfonyl, N-2-methylphenylamine sulfonyl, N-2-chlorophenylamine sulfonyl, N-2-methoxyphenylamine sulfonyl , N-2-isopropoxyphenylamine sulfonyl, N-3-chlorophenylamine sulfonyl, N-3-nitrophenylamine sulfonyl, N-3-cyanophenylamine Sulfonyl, N-4-methoxyphenylamine sulfonyl, N-4-cyanophenylamine sulfonyl, N-4-dimethylaminophenylamine sulfonyl, N-4 -methylsulfanylphenylamine sulfonyl, N-4-phenylsulfanylphenylamine sulfonyl, N-methyl-N-phenylamine sulfonyl, N,N-dimethyl Aminesulfonyl, N,N-dibutylaminesulfonyl, N,N-diphenylaminesulfonyl and the like.

The "amino group which may have a substituent" is preferably an amine group having a total carbon number of from 0 to 50, and examples thereof include, for example, -NH ₂ , an N-alkylamino group, an N-arylamino group, and an N-fluorenyl group. Amine, N-sulfonylamino, N,N-dialkylamino, N,N-diarylamine, N-alkyl-N-arylamine, N,N-disulfonate Amino group and the like. More specifically, it may, for example, be N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamine, N-tertiary Amino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino, N-phenylamino, N-2-methylphenylamino, N-2-chlorophenylamino, N-2-methoxyphenylamino, N- 2-Isopropoxyphenylamino, N-2-(2-ethylhexyl)phenylamino, N-3-chlorophenylamino, N-3-nitrophenylamino, N- 3-cyanophenylamino, N-3-trifluoromethylphenylamino, N-4-methoxyphenylamino, N-4-cyanophenylamino, N-4-three Fluoromethylphenylamino, N-4-methylsulfanylphenylamino, N-4-phenylsulfanylphenylamino, N-4-dimethylaminophenylamino, N-methyl-N-phenylamino, N,N-dimethylamino, N,N-diethylamino, N,N-dibutylamino, N,N-diphenylamine , N,N-diethylhydrazino, N,N-dibenridylamino, N,N-(dibutylcarbonyl)amine, N,N-(dimethylsulfonyl) Amine, N,N-(diethylsulfonyl)amine, N,N-( Sulfo acyl-butyl) amine, N, N- (diphenyl sulfonic acyl) amino, morpholinyl, 3,5-dimethyl-morpholinyl, carbazolyl and the like.

The "phosphinylene group which may have a substituent" is preferably a phosphinylene group having a total carbon number of 2 to 50, and examples thereof include, for example, a dimethylphosphinylene group, a diethylphosphinylene group, and a dipropylphosphinyl group. , diphenylphosphinyl, dimethoxyphosphinyl, diethoxyphosphinyl, benzhydrylphosphinyl, bis(2,4,6-trimethylphenyl)phosphinyl Wait.

The "heterocyclic group which may have a substituent" is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples thereof include, for example, a thienyl group, a benzo[b]thienyl group, a naphtho[2,3-b]thienyl group, a thiol group, a furyl group, a piperidyl group, an isobenzofuranyl group, Alkenyl, Base Base, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime Base Base, isodecyl, 3H-fluorenyl, fluorenyl, 1H-carbazolyl, fluorenyl, 4H-quina Base, isoquinolyl, quinolyl, anthracene base, Pyridyl, quinoxalinyl, quinazolinyl, Lolinyl, acridinyl, 4aH-carbazolyl, oxazolyl, β-carbolinyl, phenanthryl, acridinyl, Pyridyl, morpholinyl, brown Basal Base, isothiazolyl, thiophene Basis Azyl, furazolyl, brown Basis alkyl, Alkyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolinyl, piperidinyl, hexahydropyridyl Base, porphyrin group, isoindolyl group, Pyridyl, morpholinyl, sulfur Base.

The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

The "halogenated alkyl group which may have a substituent" may, for example, be a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group or a trisole. Bromomethyl group and the like.

The "nonylamine group which may have a substituent on N" may, for example, be N,N-dimethylammonium or N,N-diethylguanamine.

Further, the above-mentioned alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, may have a substituent An aryloxy group, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an anthracene group which may have a substituent, an alkylthioalkyl group which may have a substituent, may have a substituent Arylsulfanyl group, alkylsulfinyl group which may have a substituent, arylsulfinylene group which may have a substituent, alkylsulfonyl group which may have a substituent, arylsulfonyl which may have a substituent An indenyl group, a mercapto group which may have a substituent, an alkoxycarbonyl group or an aryloxycarbonyl group which may have a substituent, an amine mercapto group which may have a substituent, an amine sulfonyl group which may have a substituent, may have a substituent The amine group and the heterocyclic group which may have a substituent may be further substituted with other substituents.

Examples of the "substituent" include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a tertiary alkyl group, or a phenoxy group. An alkoxycarbonyl group or an aryloxycarbonyl group such as an aryloxy group such as a p-tolyloxy group, a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group, an ethoxycarbonyl group, a propyloxy group or a benzamidine group. a mercapto group such as an oxy group such as an oxy group, an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group or a methoxy oxalyl group; An alkylthio group such as an alkylsulfanyl group such as a thioalkyl group, a phenylsulfanyl group or a p-tolylsulfanyl group; an alkylamino group such as a methylamino group or a cyclohexylamino group; An arylamino group, a methyl group, an ethyl group, a tertiary group such as a dialkylamino group such as a arylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group; a phenylamino group; a p-tolylamino group; Examples of the alkyl group such as a butyl group or a dodecyl group, an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumyl group, a naphthyl group, an anthranyl group or a phenanthryl group may be mentioned: a hydroxyl group or a carboxyl group. Hyperthyroidism , thiol, sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitro, cyano, trifluoromethyl, trichloromethyl, trimethyldecyl, monophosphate, phosphonic acid A group, a trimethylammonium group, a dimethylammonium group, a triphenyl benzamidine methyl fluorenyl group or the like.

Among these, from the viewpoint of solvent solubility and improvement of absorption efficiency in a long wavelength region, X is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, may have The halogenated alkyl group of the substituent, the amine group which may have a substituent, or the guanamine group which may have a substituent on N, more preferably an alkyl group which may have a substituent.

Further, n in the general formula (III) is an integer representing 0 to 5, and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, from the viewpoint of easiness of synthesis.

In the general formula (III), when X is present in plural, X may be the same or different.

Specific examples of the photopolymerization initiator represented by the above formula (III) are shown below.

The compound represented by the general formula (III) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm, and more preferably has an absorption wavelength in a wavelength region of 300 nm to 380 nm. The absorbance at 308 nm and 355 nm is the highest.

The content of the (D) fluorene-based photopolymerization initiator used in the present invention is preferably 3% by mass or more and 20% by mass or less, more preferably 5 Å by mass based on the total solid content of the colored photosensitive resin composition. The range of % or more and 15% by mass or less is more preferably in the range of 10% by mass or more and 15% by mass or less.

In the color-sensitive photosensitive resin composition of the present invention, in addition to the above (D) fluorene-based photopolymerization initiator, it may contain (D) fluorene-based photopolymerization initiation as long as it does not impair the scope of the present invention. The agent is another photopolymerization initiator of a different structure [hereinafter, referred to as "(D-2) other photopolymerization initiator"].

(D-2) Other photopolymerization initiator having a different structure from (D) an oxime-based photopolymerization initiator is not limited as long as it is a compound capable of initiating and promoting polymerization of the (C) polymerizable compound. Use previous learners. Specific examples thereof include a fluorene-based photopolymerization initiator, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxidic compound, and an azo group. a compound, a coumarin compound, an azide compound, a metallocene compound, an organoboric acid compound, a disulfonic acid compound, a phosphonium salt compound, a mercaptophosphine (oxide) compound, or the like.

The "role-based photopolymerization initiator" which can be used as the (D-2) other photopolymerization initiator is, for example, a hexaarylbiimidazole compound. The "hexaarylbiimidazole-based compound" is exemplified by, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2' - bis(2-chlorophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4 , 4',5,5'-indole (4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5' - 肆(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-indole (4-phenoxy) Carbonylphenyl)biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-fluorene (4-ethoxycarbonylphenyl)-linked Imidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)-biimidazole, 2,2' - bis(2-cyanophenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-cyanophenyl) -4,4',5,5'-indole (4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5' -肆(4-methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5'-fluorene (4-ethoxycarbonylbenzene) Bis-diimidazole, 2,2'-bis(2-methylphenyl)-4,4 ,5,5'-indole (4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'-indole (4- Methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'-indole (4-ethoxycarbonylphenyl)biimidazole , 2,2'-bis(2-ethylphenyl)-4,4',5,5'-indole (4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2- Phenylphenyl)-4,4',5,5'-indole (4-methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-phenylphenyl)-4,4' ,5,5'-indole (4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-indole (4- Phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(4-methoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)biimidazole, 2,2'-bis(2-chlorobenzene -4,4',5,5'-tetra-(3,4-dimethoxyphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole , 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'- (2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dicyanophenyl)-4, 4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4,6-tricyanophenyl)-4,4',5,5'-tetraphenyl-II Imidazole, 2,2'-bis(2,4-dimethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4,6- Trimethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-diethylphenyl)-4,4',5,5 '-Tetraphenyldiimidazole, 2,2'-bis(2,4,6-triethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2' - bis(2,4-diphenylphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4,6-triphenylphenyl) -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, and the like.

Among the above, particularly preferred compounds are: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, the Baotu Valley Chemical Industry ( B-CIM), 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra-(3,4-dimethoxybenzene) manufactured by Hodogaya Chemical Co., Ltd. Bis-diimidazole (for example, HABI 1311 manufactured by Shiberuheguna, Japan), 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole (for example, black gold (Kurogane Kasei Co., Ltd.)).

Further, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxidation compound, an azo compound, a coumarin compound, an azide compound, or a metallocene compound Specific examples of the organoboric acid compound, the disulfonic acid compound, the phosphonium salt compound, and the mercaptophosphine (oxide) compound are exemplified by "Bull Chem. Soc. Japan" in Jolin et al. 42, 2924 (1969), USA. Japanese Patent Publication No. 3,905,815, Japanese Patent Publication No. Sho 46-4605, Japanese Patent Laid-Open Publication No. SHO-48-36281, Japanese Patent Laid-Open No. Sho 55-32070, JP-A-60-239736 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -298339, MP Hutt, "Journal of Heterocyclic Chemistry", 1 (No. 3), (1970), Japanese Patent Publication No. 6-29285, U.S. Patent No. 3,479,185, the same as No. 4,311,783, and No. 4,622,286 Wait Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2000-131837, Japanese Laid-Open Patent Publication No. 2002-107916, No. 2764769, Japanese Patent Application No. 2000-310808, and the like, and Kunz, Martin "Rad Tech '98. Proceeding April 19 -22,1998,Chicago, et al., Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. JP-A-H07-306527, JP-A-7-292014, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japan Special Open 2000-66385 The said exposing light in the Japanese Patent Laid-Open No. 2000-80068, Japanese Unexamined Patent Publication No. 2004-534797 and other polymerization initiators.

In the present invention, the content of the (D-2) other photopolymerization initiator is preferably 100 parts by mass or less based on 100 parts by mass of the content of the (D) fluorene-based photopolymerization initiator. Further, the total amount of the photopolymerization initiator [(D) + (D-2)] with respect to the total solid content of the colored photosensitive resin composition is preferably in the range of 5 mass% to 20 mass%, more It is preferably in the range of 5 mass% to 15 mass%, and more preferably in the range of 10 mass% to 15 mass%.

Further, when a compound having no absorption at an exposure wavelength is used as the (D) specific polymerization initiator or (D-2) other photopolymerization initiator, it is preferred to use a compound having absorption at an exposure wavelength as a sensitization. Agent. The sensitizer will be explained later.

<(E) Solvent>

The colored photosensitive resin composition of the present invention contains (E) a solvent and can be prepared by using (E) a solvent. Further, the above pigment dispersion composition is also prepared by using (E) a solvent.

The solvent (E) may, for example, be an "ester" such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate or butyric acid. Propyl ester, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate , methoxyethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. Alkyl 3-oxypropionates" (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxypropane) "2-ethyloxypropionate alkyl esters" such as ethyl acetate, etc., methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (for example, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- Methyl oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, and 2-ethoxy-2- A Ethyl propyl propionate, etc., methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate, methyl 2-oxobutanoate, 2-side Ethyl oxybutyrate, 1,3-butylene glycol diacetate, etc.; "ethers" such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl Ether, tri-propylene glycol mono-n-butyl ether, propylene glycol phenyl ether, methyl sarbutazone acetate, ethyl celecoxib acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl acetate Ether ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol diacetate, propylene glycol n-butyl ether ester, propylene glycol phenyl ether acetate , dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol-n-butyl ether acetate, triacetate acetate Propylene glycol methyl ether ester; etc.; "alkoxyalkyl acetates", such as 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, acetic acid 2- Methoxypentyl ester, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate Ester, 3-methyl-4-methoxypentyl acetate, etc.; "ketones" such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; "alcohols" For example, ethanol, isopropanol, etc.; "aromatic hydrocarbons" such as toluene, xylene, and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl sarbutazone acetate, ethyl lactate, diethylene glycol dimethyl ether, Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate , propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and the like.

(E) The solvent may be used alone or in combination of two or more.

The colored photosensitive resin composition of the present invention may contain other components such as (F) a sensitizer, a surfactant, and a thermosetting resin, as needed.

<(F) sensitizer>

The colored photosensitive resin composition of the present invention preferably uses a compound having absorption at an exposure wavelength as a sensitizer to improve the initiation efficiency of the (D) fluorene-based photopolymerization initiator. The exposure of the wavelength of the (D) oxime-based photopolymerization initiator component or the polymerization reaction of the polymerizable compound caused by the sensitizer can be promoted by exposure of a wavelength absorbable by the sensitizer.

Examples of such sensitizers include a conventional spectral sensitizing dye or a dye, or a dye or pigment which absorbs light and interacts with a photopolymerization initiator.

In the present invention, preferred spectroscopic sensitizing dyes or dyes which can be used as sensitizers are: polynuclear aromatics (for example, ruthenium, osmium, and benzene); Classes (eg, fluorescent yellow, blush, red algae, rose red B, rose Bengal); cyanines (eg, thiocarbocyanine, oxacarbocyanine); merocyanoids ( For example, anthocyanins, carbonyl anthocyanins); Classes (such as thiazide, methylene blue, toluidine blue); acridines (such as acridine orange, chloroflavin, acridine flavin); phthalocyanines (such as phthalocyanine, metal phthalocyanine); porphyrins Classes (eg, tetraphenylporphyrins, porphyrins substituted with a central metal); chlorophylls (eg, chlorophyll, chlorophyllin, chlorophyll substituted by a central metal); metal complexes; terpenoids (eg, hydrazine); Horn sharks (such as horn sharks). Among them, a "thiol compound" which will be described in detail below is preferred.

The thiol compound has an effect of further increasing the sensitivity of the photopolymerization initiator to the actinic radiation or suppressing polymerization inhibition of the polymerizable compound due to oxygen.

Examples of the "thiol compound" include ethylene glycol dithiopropionate (EGTP), butylene dithiopropionate (BDTP), trimethylolpropane propionate (TMTP), and thiopropyl sulfide. "Difunctional thiol compound" such as neopentyl glycolate (PETP); 2-hydrothiobenzothiazole, 2-hydrothiobenzoate Monofunctional sulfur such as azole, 2-hydrothiobenzimidazole, 2-hydrothio-4(3H)-quinazoline, β-hydrothionaphthalene, N-phenyl-hydrothiobenzimidazole Alcohol compound".

In particular, from the viewpoint of stability over time and solubility in a solvent, a monofunctional thiol compound is preferred.

The content of the thiol compound in the colored photosensitive resin composition of the present invention is based on the quality of the total solid content of the photosensitive resin composition from the viewpoint of increasing the curing rate by the equilibrium between the polymerization growth rate and the chain transfer. It is preferably in the range of 0.5% by mass to 10% by mass, more preferably in the range of 0.5% by mass to 5% by mass.

<Other additives>

The colored photosensitive resin composition of the present invention may contain other additives as needed in addition to the component (A) to the component (E) and the component (F) which are preferred components. In the following, any additive will be described.

(surfactant)

The colored photosensitive resin composition of the present invention may contain a surfactant.

When the pigment concentration is increased, the thixotropy of the coating liquid is generally increased. Therefore, it is easy to form a colored photosensitive resin composition layer (colored layer coating film) by coating or transferring a colored photosensitive resin composition on a substrate. The film thickness is not uniform. In addition, in particular, when the colored photosensitive resin composition layer (colored layer coating film) is formed by the slit coating method, it is important that the coating liquid for forming the photosensitive resin composition layer before drying is leveled. A coating film of uniform thickness is formed. Therefore, it is preferred to contain a suitable surfactant in the colored photosensitive resin composition. The surfactants described in JP-A-2003-337424 and JP-A-11-133600 are suitable.

A surfactant such as a nonionic surfactant, a fluorine-based surfactant, a quinone-based surfactant, or the like may be added to the surfactant for improving the coating property.

The "nonionic surfactant" is preferably, for example, a polyoxyethylene glycol, a polyoxypropylene glycol, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl aryl ether, or a polyoxygen. Vinyl alkyl esters, polyoxypropylene alkyl ethers, polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, etc. Nonionic surfactants".

Specifically, it includes: polyoxyalkylene glycols such as polyoxyethylene diol and polyoxypropylene diol; polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, polyoxyethylene oleyl ether Such as "polyoxyalkylene alkyl ethers"; polyoxyethylene octyl phenyl ether, polyoxyethylene - polystyrene ether, polyoxyethylene trityl phenyl ether, polyoxyethylene - propylene polystyrene "Polyoxyethylene aryl ethers" such as alkyl ethers and polyoxyethylene nonylphenyl ethers; polyoxyalkylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate "Non-ionic surfactants such as sorbitan fatty acid esters and polyoxyalkylene sorbitan fatty acid esters".

Specific examples include, for example, Adekapluronic, Adekanol, Tetronic (above ADEKA), EMULGEN, RHEODOL (above Kao Corporation), ELEMINOL, NONIPOL OCTAPOL, DODECAPOL, NEWPOL (above is Sanyo Chemical Co., Ltd.), PAIONIN (Takemoto Oil & Fat Co., Ltd.), NISSAN NONION (Japanese Oils and Fats) ) (made by NOF Corporation) and the like. These commercially available persons can be used as appropriate. A preferred HLB value (Hydrophile-Lipophile Balance) is from 8 to 20, more preferably from 10 to 17.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkyl group at a site of at least one of a terminal, a main chain and a side chain.

Specific commercial products can be listed, for example, MEGAFACE F142D, with F172, with F173, with F176, with F177, with F183, with F780, with F781, with F782, with F784, with F552, with F554, with R30, with R08 (above is DIC (DIC)), FLUORAD FC-135, FC-170C, FC-430, and FC-431 (above is Sumitomo 3M Co., Ltd.) )), SURFLON S-112, the same S-113, the same S-131, the same S-141, the same S-145, the same S-382, the same SC-101, the same SC-102, the same SC-103, the same SC-104, the same SC-105, the same SC-106 (above is Asahi Glass Co., Ltd.), EFTOP EF351, the same 352, the same 801, the same 802 (the above is JEMCO (share) (made by JEMCO Co., Ltd.) and the like.

Examples of the "lanthanum surfactant" include TORAY SILICONE DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032. SF-8428, the same DC-57, the same DC-190 (above is Toray-Dow Corning Silicone Co.), TSF-4440, TSF-4300, TSF-4445, TSF -4446, TSF-4460, TSF-4452 (The above is GE-Toshiba Silicone Co., Ltd.) and the like.

Among these, preferred surfactants in the present invention are MEGAFACE F780, F78, F782, F784, F552, and F554 (above DIC).

The surfactant is preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 0.5 parts by mass or less, per 100 parts by mass of the colored photosensitive resin composition. When the amount of the surfactant used is more than 5 parts by mass, streaks or surface roughness are likely to occur at the time of coating drying, and the smoothness is deteriorated.

(thermosetting resin)

The colored photosensitive resin composition of the present invention is a thermosetting resin containing an epoxy resin, an oxetane resin, or the like as needed.

The epoxy resin includes: a bisphenol A type, a cresol novolak type, a biphenyl type, an alicyclic epoxy compound, and the like.

For example, "bisphenol A type" is exemplified by: EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF- 170, etc. (The above is manufactured by Tohto Kasei Co., Ltd.), DENACOL EX-1101, EX-1102, EX-1103, etc. (The above is manufactured by Nagase ChemteX Corp.), PLACCEL GL- 61. GL-62, G101, G102 (The above is manufactured by Daicel Chemical Industries, Ltd.) and the like. Other examples include bisphenol F type and bisphenol S type similar to these. Further, an epoxy acrylate such as Ebecryl 3700, 3701, 600 (the above is DAICEL-UCB (manufactured by DAICEL-UCB Company Ltd.)) can also be used.

The "cresol novolac type" includes: EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above is Dongdu Chemical Co., Ltd.), DENACOL EM-125, etc. (The above is Changchun Huacheng "Biphenyl type" includes: 3,5,3',5'-tetramethyl-4,4'-diepoxypropyl biphenyl.

"Cycloaliphatic epoxy compound" includes: CELLOXIDE 2021, 2081, 2083, 2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above manufactured by Daicel Chemical), SUNTOHVTO ST -3000, ST-4000, ST-5080, ST-5100, etc. (above is Dongdu Chemical System). In addition, it is also possible to use a non-polymeric epoxy resin such as EPOTOHTO YH-434, YH-434L, or a bisphenol A type epoxy resin modified by a dimer acid.

Among these epoxy resins, a novolac type epoxy compound and an alicyclic epoxy compound are preferable, and those having an epoxy equivalent of from 180 to 250 are particularly preferred. Examples of such materials include EPICLON N-660, N-670, N-680, N-690, YDCN-704L (above, DIC) and EHPE 3150 (manufactured by Daicel Chemical Co., Ltd.).

As the "oxetane resin", ARON OXETANE OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610, OX-SQ, PNOX (the above is manufactured by Toagosei Co., Ltd.) can be used.

Further, the oxetane resin may be used alone or in combination with an acrylate copolymer, an epoxy resin, and a maleimide resin. In particular, when it is used in combination with an epoxy resin, it is highly reactive with heat generated by ultraviolet laser exposure, which is preferable from the viewpoint of adhesion to a substrate.

In the present invention, the content of the epoxy resin and the oxetane resin in the colored photosensitive resin composition is preferably from 0.5 to 15 by mass based on the total solid content of the colored photosensitive resin composition. % is preferably from 1 to 10% by mass from the viewpoint of both the solubility to the alkali and the adhesion to the substrate.

(organic carboxylic acid)

In order to promote the alkali solubility of the uncured portion and to further improve the developability of the colored photosensitive resin composition, an organic carboxylic acid may be added, and a low molecular weight organic carboxylic acid having a molecular weight of 1,000 or less is preferable. Specific examples thereof include, for example, formic acid (amic acid), acetic acid (acetic acid), propionic acid, butyric acid (butyric acid), valeric acid (shikimic acid), trimethylacetic acid, caproic acid, diethyl acetic acid, and heptanoic acid. "Aromatic monocarboxylic acid" such as octanoic acid; oxalic acid (oxalic acid), malonic acid, succinic acid (succinic acid), glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , azelaic acid (lipe acid), barium diacid (tridecanedioic acid), methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid , "aliphatic dicarboxylic acid" such as citraconic acid; "aliphatic tricarboxylic acid" such as 1,2,3-propanetricarboxylic acid, aconitic acid, and capricinic acid; benzoic acid, o-toluic acid, and cumin "aromatic monocarboxylic acid" such as acid, 2,3-dimethylbenzoic acid or 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), pyromellitic acid (1,2,3,5-benzenetetracarboxylic acid), pyrophoric acid "Aromatic polycarboxylic acid" such as (1,2,4,5-benzenetetracarboxylic acid); phenylacetic acid, phenoxyacetic acid, methoxy Phenoxyacetic acid, hydrogen ato acid, hydrogen cinnamic acid, mandelic acid (phenylglycolic acid), phenyl succinic acid, atopic acid, cinnamic acid, cinnamic acid acetic acid, coumaric acid, umbrella acid, etc. carboxylic acid.

(decane coupling agent)

In the colored photosensitive resin composition of the present invention, a decane coupling agent can be used from the viewpoint of further improving the adhesion to the substrate.

The decane coupling agent is preferably one having an alkoxyalkyl group as a hydrolyzable group capable of chemically bonding with an inorganic material. Further, it is preferred to have a group which exhibits affinity with an interaction or bond formation with an organic resin, and these groups preferably have a (meth)acryl fluorenyl group, a phenyl group, a thiol group, and a ring. An oxypropyl group or an oxetanyl group, preferably having a (meth) acrylonitrile group or an epoxy propyl group.

That is, the decane coupling agent used in the present invention is preferably a compound having an alkoxyalkyl group, a (meth) acryl fluorenyl group or an epoxy group, and specifically, it may be exemplified by the following structure (A) Alkyl fluorenyl-trimethoxydecane compound, glycidyl-trimethoxydecane compound, and the like.

The amount of the decane coupling agent to be added is preferably from 0.2% by mass to 5.0% by mass, more preferably 0.5% by mass, based on the total solid content of the coloring photosensitive resin composition used in the present invention. 3.0% by mass.

(polymerization inhibitor)

In the present invention, in order to suppress unnecessary thermal polymerization of the polymerizable compound in the production or storage of the colored photosensitive resin composition, it is preferred to add a small amount of the thermal polymerization inhibitor.

Examples of the "thermal polymerization inhibitor" which can be used in the present invention include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, tert-butyl catechol, Benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine first sulfonium salt, brown Thiophene Wait.

The amount of the thermal polymerization inhibitor added is preferably from 0.01% by mass to 5% by mass based on the coloring photosensitive resin composition.

Further, a higher fatty acid derivative such as rosin or decylamine may be added to prevent polymerization inhibition due to oxygen, if necessary, and may be biased to the surface of the photosensitive layer in a drying process after coating. The amount of the higher fatty acid derivative added is preferably from 0.5% by mass to 10% by mass based on the coloring photosensitive resin composition.

(Plasticizer)

Further, in the present invention, an inorganic filler or a plasticizer may be added to improve the physical properties of the colored photosensitive resin composition.

"Plasticizer" includes: for example, dioctyl phthalate, di-dodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, trimethyl phenol The ester, dioctyl adipate, dibutyl sebacate, triethylene glyceryl, and the like may be added in an amount of 10% by mass or less based on the total mass of the (C) polymerizable compound and the binder resin.

The colored photosensitive resin composition of the present invention can be cured by a conventional exposure method in which exposure by ultraviolet light can be cured with high sensitivity and high adhesion to a substrate can be exhibited. The ultraviolet light exposure method can be either a laser exposure method or a proximity exposure method, and is preferably a laser exposure method from the viewpoint of suppressing surface reticulation. The colored photosensitive resin composition of the present invention is a colored pattern suitable for use in a color filter.

<<Pattern forming method, color filter, and manufacturing method thereof》

The colored photosensitive resin composition and pattern forming method of the present invention are suitable for a color filter for a liquid crystal display device. Hereinafter, a pattern forming method using the colored photosensitive resin composition of the present invention will be described as a method of forming a pattern in a method of producing a color filter for a liquid crystal display device, but the present invention is not limited. For this method.

A pattern forming method according to the present invention, comprising: a coloring layer forming step of forming a coloring layer by applying a colored photosensitive resin composition of the present invention to a substrate; and patterning the colored layer by ultraviolet light laser An exposure step of forming a latent image by exposure; and a developing step of developing the patterned color layer by forming the latent image to form a pattern. Further, a step of baking the colored layer (prebaking step), and a step of baking the developed colored layer (baking step) may be provided as needed. Sometimes, these steps are collectively referred to as "pattern forming steps."

[Coloring layer forming step]

The color layer forming step in the present invention is a step of imparting a coloring layer to the colored photosensitive resin composition of the present invention on a substrate.

The substrate is, for example, an alkali-free glass, a soda-lime glass, a borosilicate glass, a quartz glass, or the like which adheres to the transparent conductive film, or a photoelectric conversion element used for a solid-state image sensor or the like. Substrate. Also, a plastic substrate can be used. It is preferable to form the black matrix into a lattice shape or the like using these substrates, and to form a colored pattern on the vacant portion of the lattice.

On such a substrate, an undercoat layer may be provided to improve adhesion to the upper layer, prevent diffusion of the substance, or planarize the surface of the substrate, as needed. Since the effect of the present invention can be more apparent, the substrate is preferably large (about 1 metre or more on one side).

A method of forming a coloring layer on a substrate and imparting the coloring photosensitive resin composition of the present invention to the substrate is applicable to various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing. The method of application of the coating method. From the viewpoint of accuracy and speed, slit coating is preferred in the coating method.

Further, a method of transferring a coating film formed on the temporary support by the above-described coating method onto the substrate can also be applied.

Regarding the transfer method, the paragraph code [0096], [0036] to [0051], or JP-A-2006-47592, paragraph number [0096] of JP-A-2006-23696 is also suitably used in the present invention. ] to the manufacturing method disclosed in [0108].

In order to obtain a sufficient color reproduction region and a sufficient luminance of the panel, the coloring layer in the present invention is preferably formed to have a film thickness after drying of from 0.5 μm to 3.0 μm, more preferably from 1.5 μm to 2.5 μm.

[Drying step]

After the end of the coloring photosensitive resin composition as described above, a drying step of drying the solvent by vacuum drying (VCD) may be carried out. Further, the coating film on the substrate may be further dried by heating (prebaking) to obtain a colored layer.

The prebaking temperature of the coating film is preferably from 60 ° C to 140 ° C, more preferably from 80 ° C to 120 ° C. Further, the prebaking time is preferably from 30 seconds to 300 seconds, more preferably from 80 seconds to 200 seconds.

[Exposure step]

The exposure step in the present invention is a step of subjecting the colored layer to a pattern-like exposure by ultraviolet light exposure to harden an exposed region to form a latent image. According to the exposure step of the present invention, in the patterned exposed region of the colored photosensitive resin composition, (D) the initiation species generated by the specific polymerization initiator occurs, and (C) polymerization hardening of the polymerizable compound is carried out. The reaction forms a pattern including a hardened region and an uncured region.

The laser excitation medium is a laser including a crystal, a glass, a liquid, a pigment, a gas, and the like, and a laser having an oscillation wavelength in an ultraviolet region, such as a solid laser, a liquid laser, a gas laser, or a semiconductor laser, can be used. Among them, from the viewpoint of the output power of the laser and the oscillation wavelength, a solid laser or a gas laser is preferable.

The exposure wavelength of the ultraviolet laser used in the present invention is preferably in the range of 300 nm to 380 nm, more preferably 310 nm, from the viewpoint of satisfying the sensitivity of the photosensitive wavelength of the colored photosensitive resin composition. The 360 nm range is particularly suitable for laser exposure at 355 nm.

Specifically, it is particularly suitable for the third highest order of Nd:YAG laser (Neodymium: Yttrium-Aluminum-Garnet Laser) with a large output power and a relatively inexpensive solid laser. Order wave (355 nm), or XeCl (308 nm), XeF (353 nm) of excimer laser light.

Further, the exposure amount of the exposed object (pattern) may be in the range of 1 mJ/cm ² to 100 mJ/cm ² , more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² . When the amount of exposure is in this range, it is preferable from the viewpoint of productivity of pattern formation.

From the viewpoint of productivity, the ultraviolet laser used in the present invention is preferably a pulsed laser which can oscillate at a frequency of 20 Hz to 2000 Hz.

The exposure apparatus to be used in the present invention is not particularly limited, and a commercially available EGIS (manufactured by V Technology Co., Ltd.) or DF2200G (manufactured by Dainippon Screen Mfg. Co., Ltd.) can be used. )Wait. It is also suitable to use a device other than the above.

Ultraviolet lasers have good parallelism of light. Pattern exposure can be performed without using a mask during exposure, but the shape of the pattern is affected by the shape and contour of the output light. Therefore, it is preferable to use a mask to expose the pattern to increase the linearity of the pattern.

[Development Step]

In the developing step of the present invention, the coloring layer which is cured in the exposed region to form a latent image is developed, and the unexposed portion is removed to form a pattern. The exposed region through the ultraviolet light laser has been hardened into a pattern, and in the development process, the alkali-developing treatment is performed, so that the unirradiated portion (unhardened portion) of the exposure step is eluted in the aqueous alkali solution to be removed. The pattern is formed by leaving only the photohardened portion.

The developer is an organic alkali developer or an inorganic alkali developer or a mixture thereof.

Examples of the "alkaline agent" used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, Organic bases such as dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dioxinbicyclo-[5.4.0]-7-undecene The basic compound is diluted with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on the alkaline aqueous solution, which is suitable as a developing solution. Further, in the case of using a developing solution containing such an alkaline aqueous solution, it is usually washed (washed) with pure water after development.

The developing temperature is preferably from 20 ° C to 35 ° C, more preferably from 23 ° C to 30 ° C. The development time is preferably from 30 seconds to 120 seconds, more preferably from 40 seconds to 90 seconds. Among these, a preferable combination of the developing temperature and the developing time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C and 40 seconds to 80 seconds at a temperature of 30 ° C.

Further, the spray pressure is preferably from 0.01 MPa to 0.5 MPa, more preferably from 0.05 MPa to 0.3 MPa, particularly preferably from 0.1 MPa to 0.3 MPa. By appropriately selecting these conditions, the shape of the pattern can be arbitrarily designed into a rectangular shape or a forward tapered shape.

[post-baking step]

In the present invention, it is preferred to provide a baking step after baking the developed colored layer to make the hardening of the colored photosensitive resin composition complete. The baking method can be carried out by heating the substrate having the pattern after development and washing, using a heating method such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine, in a continuous or batch manner.

The baking conditions are preferably from 150 ° C to 260 ° C, more preferably from 180 ° C to 260 ° C, most preferably from 200 ° C to 240 ° C. The baking time is preferably from 10 minutes to 150 minutes, more preferably from 20 minutes to 120 minutes, and most preferably from 20 minutes to 90 minutes.

Furthermore, when forming a color pattern of a plurality of hue of an RGB three-color phase, a light-shielding layer, or the like, the cycle of forming, exposing, developing, and baking the colored layer may be repeated only in accordance with the desired number of hue, or may be After the hue is formed, the formation of the colored layer, exposure and development are carried out, and finally, the entire hue is collectively baked. Thereby, a color filter having a colored pixel including a desired hue can be obtained.

"Liquid Crystal Display Device"

The color filter of the present invention is a liquid crystal display device which is suitable for manufacturing a liquid crystal display device and which uses the color filter manufactured by the pattern forming method of the present invention to display a high quality image.

The definition of the display device or the description of each display device is disclosed, for example, in "Electronic display device (Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd.) published in 1990) "Display device (Sumiyo Ibuki, Sangyo Tosho Publishing Co., Ltd., published in the first year of the year)" and so on. Further, the liquid crystal display device has been disclosed, for example, in "Second Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Industrial Research Association (2014)"). The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "Second Generation Liquid Crystal Display Technology".

Among them, the color filter for a liquid crystal display device is particularly effective for a liquid crystal display device of a color TFT (color thin film transistor) type. A liquid crystal display device of a color TFT type has been disclosed, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Shuppan Co., Ltd., 1996)". Further, the present invention is also applicable to a horizontal electric field driving method such as IPS (In-Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment). Liquid crystal display device with expanded viewing angle, or STN (Super Twisted Nematic), TN (Twisted Nematic: Twisted Nematic), VA (Vertical Alignment: Vertical Alignment), IPS, OCS (optical) Compensated bending type: Optically Compensated Bend), FFS (Boundary Electric Field Switching Wide Angle Viewing Technology Type: Fringe Field Switching), and R-OCB (Reflective Optically Compensated Bend). The image display methods for such images are described in, for example, "EL (Electro-Excise), PDP (Plastic Display), LCD Display - Technology and Market Trends - (Research Study Division, Toray Research Center) Of Toray Research Center, Inc., published in 2001), page 43 et al.

The liquid crystal display device includes, in addition to the color filter, various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film. The color filter for liquid crystal display elements of the present invention is a liquid crystal display device which can be applied to such a conventional member. The components for such are described in, for example, "'94 Liquid Crystal Display Peripherals ‧Chemicals Markets (Kentaro Shima, CMC (CMC Publishing Co., Ltd.), published in 1994) "The status and future prospects of the liquid crystal-related market in 2003 (Volume 2) (Ryokichi Omote, Fuji Chimera Research Institute, Inc., 2003).

The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et al.); or Monthly Display (Monthly DISPLAY), December 2005, pages 18 to 24 (Hiroyasu Shima) , same as pages 25 to 30 (Takaaki Yagi) and so on.

If the color filter manufactured by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a conventional three-wavelength tube of a cold cathode tube, high contrast can be achieved, but further by red The green and blue LED (light-emitting diode) light source (RGB-LED) is used as a backlight to provide a liquid crystal display device having high luminance and high color reproducibility.

"Embodiment"

Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following embodiments unless it departs from the gist of the invention. In addition, unless otherwise stated, "%" and "parts" are based on quality.

<Synthesis Example 1: Synthesis of allyl-containing alkali-soluble resin 1 [(B-2) binder resin]>

In a 200 ml three-necked flask equipped with a stirring bar with a stirring blade, a reflux condenser, and a thermometer, 54 g of 1-methoxy-2-propanol was fed and heated to 70 ° C under a nitrogen stream. 10.07 g of allyl methacrylate, 1.93 g of methacrylic acid, and 0.185 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator were dissolved in 54 g of 1-la The solution in oxy-2-propanol was added dropwise to the three-necked flask using a plunger pump for 2.5 hours. After the dropwise addition was completed, the mixture was further stirred at 70 ° C for 2 hours. After the end of the heating, 1 liter of water was added to reprecipitate. The precipitate was filtered and dried under vacuum to obtain 9 g (yield: 75%) of a polymer compound.

In a 10 ml measuring flask, 0.01 g of the obtained polymer was weighed as a measurement sample of a weight average molecular weight, about 8 ml of tetrahydrofuran was added, and after dissolving at room temperature, the total amount was adjusted to 10 ml. The solution was measured using gel permeation chromatography (GPC). As a result, the weight average molecular weight of the alkali-soluble resin 1 (allyl methacrylate/methacrylic acid copolymer, molar ratio = 80/20, the following structure) was 35,000.

<Synthesis Example 2: Binder Resin B-1-1>

7.83 parts of dipentaerythritol tert-(3-hydrothiopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd., the following structure], and 15.57 parts The compound (A-1) having the absorbing site described below and having a carbon-carbon double bond was dissolved in 93.60 parts of dimethylformamide and heated to 70 ° C under a nitrogen gas stream. 0.06 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added thereto and heated. 3 hours. Further, 0.06 part of V-65 was added, and the reaction was carried out at 70 ° C for 3 hours under a nitrogen gas stream. Next, it was cooled to room temperature to obtain a 20% solution of the reaction product of DPMP and Compound A-1.

Further, 23.4 parts of a 20% solution of the above reaction product, and 18 parts of a mixture solution of methyl methacrylate (MMA; monomer) and 2 parts of methacrylic acid were heated to 80 ° C under a nitrogen gas stream. After adding 0.007 parts of 2,2'-azobis(diisobutyronitrile) [AIBN, Wako Pure Chemical Industries, Ltd.] and heating for 3 hours, 0.007 parts of AIBN was further added under a nitrogen stream. The reaction was carried out at 80 ° C for 3 hours. Then, it was cooled to room temperature and diluted with acetone. After reprecipitation using an excess amount of methanol, the mixture was vacuum dried to obtain 19 parts of a solid of the polymer compound of the present invention (B-1-1: polystyrene-equivalent weight average molecular weight: 32,000) as shown below. In addition, in the following formula (B-1-1), the content ratio of the structural unit contained in the polymer skeleton is p ¹ :p ² =90:10 in mass conversion.

[Example 1] (Modulation of coloring photosensitive resin composition) (1-1. Modulation of Pigment Dispersion 1)

The pigment dispersion 1 was prepared in the following manner. That is, the components described below were mixed using a homogenizer at a number of revolutions of 3,000 rpm for 3 hours to prepare a mixed solution, and a bead disperser nanoparticle dispersing device using 0.1 mmφ zirconia beads ( Kotobuki Industries Co., Ltd.) was subjected to an 8-hour dispersion treatment.

(1-2. Modulation of photosensitive resin composition)

To the obtained pigment dispersion liquid 1 of 39.2 parts, a component of the following composition was further added, and the mixture was stirred and mixed to prepare a photosensitive resin composition for blue (B).

[Examples 2 to 15, Comparative Examples 1 to 6]

In addition to the (B-1) binder resin, the coloring agent (A), and the type and content of the (D) fluorene-based photopolymerization initiator used in the coloring photosensitive resin composition of the first embodiment, and (B-2) The coloring resin compositions of Examples 2 to 15 and Comparative Examples 1 to 6 were prepared in the same manner except that the content ratio of the binder resin was changed to those described in the following Tables 1 to 7.

Further, the numerical value of the (C) polymerizable compound disclosed in the following table is the number of functional groups representing the polymerizable compound to be used, and the "ratio" is a polymerizable compound representing five or more functional groups, and one to four functional groups. The content ratio of the compound.

- Evaluation of coloring photosensitive resin composition - (formation of pictographic pixels) The colored photosensitive resin compositions of Examples 1 to 15 and Comparative Examples 1 to 6 obtained as described above were coated on the surface of an alkali-free glass substrate (Corning Incorporated, 1737, 550 mm × 660 mm). After coating with a slit coater (Hirata Corp., HC-6000), prebaking was carried out in a clean oven at 90 ° C for 120 seconds to form a film having a film thickness of 2.0 μm. (Colored layer) A substrate with a coating film was obtained. (Coloring layer forming step) Next, the laser exposure apparatus uses the EGIS (manufactured by V Technology, the third higher order wave of the YAG laser (355 nm), and the pulse width of 6 ns) to pass the surface of the photosensitive resin composition layer (colored layer) through the mask. On the other hand, pulse irradiation of about 1 mJ/cm ^{2 was performed} 20 times to harden the exposed portion. (exposure step). Then, the substrate was developed using a developing device (manufactured by Hitachi High-Technologies Corp.), and a potassium hydroxide-based developing solution CDK-1 (Fuji Film Electronic Materials Co., Ltd.) .)) 1.0% developer (1 part by mass of CDK-1 diluted with 99 parts by mass of pure water, 25 ° C), set the spray pressure to 0.20 MPa and develop for 50 seconds to pure water. After washing, it is air-dried (development step). Then, post-baking was carried out in a clean oven at 230 ° C for 30 minutes to form a blue striped pixel array on the substrate. (evaluation of line width sensitivity)

A mask having a line width and a pitch of 20 μm in width was used, and a gap between the surface of the photosensitive resin composition layer on the substrate on which the coating film was attached and the mask was set to 200 μm, and was 20 mJ/cm ² . Exposure is exposed. The above-described development, washing, air drying, and post-baking treatment are applied to the exposed substrate obtained as described above. The obtained line pattern was observed with an optical microscope, and the line width was measured and evaluated on the following basis:

A: 30 μm or more

B: 27 μm or more and less than 30 μm

C: 25 μm or more and less than 27 μm

D: less than 25μm

E: No pattern can be formed, or peeled off and cannot be evaluated.

(evaluation of linearity)

The line pattern obtained by the evaluation of the line width sensitivity was observed with an optical microscope (200 times), and the linearity of the line width (the unevenness) was evaluated by the following criteria:

Evaluation basis

A: No jagged, no gap, straight line

B: Although there are a few differences, the line is mostly straight.

C: Jagged and a line deviation of about 2 μm

D: jagged and a line deviation of about 5 μm

E: No pattern can be formed, or peeled off and cannot be evaluated.

(Evaluation of heat resistance)

The substrate obtained by the evaluation of the online wide sensitivity was additionally baked in a clean oven at 240 ° C for 60 minutes, and was measured using a spectrophotometer MCPD-2000 manufactured by Otsuka Electronics Co., Ltd. Add color change before and after baking (ΔE*ab). Here, the term "ΔE*ab" means a color difference in the L*a*b* color system. The color change ΔE*ab is evaluated on the basis of the following criteria:

Evaluation basis

5: ΔE ^* ab is 0 or more and less than 1.0

4.5: ΔE ^* ab is 1.0 or more and less than 2.0

4: ΔE ^* ab is 2.0 or more and less than 3..0

3.5: ΔE ^* ab is 3.0 or more and less than 3.5

3: ΔE ^* ab is 3.5 or more and less than 4.0

2.5: ΔE ^* ab is 4.0 or more and less than 5.0

2: ΔE ^* ab is 5.0 or more

1: There is peeling off.

(evaluation of wrinkles)

The substrate obtained by the evaluation of the line width sensitivity was baked in a clean oven at 230 ° C for 30 minutes, and the color pattern of the coloring pattern before and after baking was observed with an optical microscope (magnification: 200 times), and evaluated on the following basis. :

Evaluation basis

○: No wrinkles were observed

△: weak wrinkles are generated

X: Produces strong wrinkles.

(Comprehensive Evaluation)

The overall line width sensitivity, linearity, and heat resistance were evaluated on the basis of the following criteria. The results are summarized in Table 8.

Evaluation basis

5: Very good

4.5: Excellent

4: No problem in general use

3.5: Although the performance is slightly worse, but no problem

3: The level of reluctance in general use

2.5: slightly lower than the limit and there is a problem

2: Performance is not enough to be used

1: Level that cannot be assessed.

As is clear from Table 8, the colored photosensitive resin compositions of Examples 1 to 15 of the present invention have a good line width sensitivity, are excellent in linearity of the obtained pattern, and have a color change even if the colored pattern is heated. The wrinkle generation after post-baking is also suppressed, so that a good coloring pattern can be obtained.

On the other hand, Comparative Example 1 which does not contain the (B-1) binder resin of the present invention, and Comparative Example 2 which uses an initiator other than the (D) fluorene-based photopolymerization initiator are lines of line width sensitivity and pattern (B-2) Comparative Example 3 in which the content of the binder resin was excessive, the wrinkles after post-baking were remarkable; (B-1) Adhesive resin In Comparative Example 4 in which the content was excessive, and Comparative Example 5 in which the (B-2) binder resin was not contained, any of the line width sensitivity, the linearity, and the wrinkles were inferior to those of the examples. Further, Comparative Example 6 using (D) an initiator other than the fluorene-based photopolymerization initiator and a sensitizer in combination was used, and the linearity of the line width and the linearity of the pattern were inferior.

Claims (9)

A colored photosensitive resin composition comprising at least: (A) a colorant, (B-1) a binder resin represented by the following formula (I) and having at least one acidic group, and (B-2) a binder resin represented by the following formula (II) and a binder resin having a structural unit having an acidic group, (C) a polymerizable compound, (D) an oxime-based photopolymerization initiator, and (E) a solvent, and wherein (B-1) The binder resin and the (B-2) binder resin have a content ratio of 3:7 to 7:3 on a mass basis, and the (C) polymerizable compound contains 5 or more and 15 in the molecule. a compound of the following polymerizable group and a compound containing one or more compounds having four or less polymerizable groups in the molecule, and a compound containing five or more and 15 or less polymerizable groups in the molecule and one or more molecules in the molecule. Ratio of the following polymerizable group compounds (compounds containing 5 or more and 15 or less polymerizable groups in the molecule): (compounds containing one or more polymerizable groups of 4 or less in the molecule), converted by mass For the range of 60:40 to 95:5: In the formula (I), R ³ represents a (m+n) valent organic linking group, R ⁴ and R ⁵ each independently represent a single bond or a divalent organic linking group, and A ² represents at least one selected from the group consisting of organic Pigment structure, heterocyclic structure, acidic group, group having a basic nitrogen atom, ureido group, urethane group, group having a coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxyalkyl group The epoxy group, the isocyanate group, and the partial structure of the hydroxyl group are one of the organic groups, and the n of A ² and R ⁴ may be the same or different, m is 1 to 8, and n is 2 to 9, m +n is 3 to 10, P ² is a polymer skeleton, and m 2 of P ² and R ⁵ may be the same or different; In the formula (II), R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group, and R ¹⁶ represents a hydrogen atom or a methyl group. The colored photosensitive resin composition of the first aspect of the invention, wherein the (D) fluorene-based photopolymerization initiator is a ketoxime-based photopolymerization initiator represented by the following formula (III): In the formula (III), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, n is an integer from 0 to 5, and when X is present in plural, the complex X Yes can be the same or different. The colored photosensitive resin composition of claim 1 or 2, which is used for ultraviolet laser exposure. A pattern forming method comprising: Or a coloring layer forming step of forming a colored photosensitive resin composition on the substrate to form a coloring layer, an exposure step of patterning the colored layer to expose the exposed region by ultraviolet laser exposure, and The developing step of forming a pattern by unexposed portions of the colored layer is developed and removed. The pattern forming method of claim 4, wherein the ultraviolet laser has an exposure wavelength in a range of 300 nm to 380 nm. The pattern forming method of claim 4, wherein the ultraviolet laser is a pulsed laser oscillating at a frequency of 20 Hz to 2000 Hz. A method of producing a color filter, comprising the step of forming a colored pattern on a substrate according to the pattern forming method of claim 4 of the patent application. A color filter manufactured according to the method of producing a color filter according to claim 7 of the patent application. A display device comprising the color filter of item 8 of the patent application.